WO2022124222A1 - Composition, film, organic photoelectric conversion element, and photodetection element - Google Patents
Composition, film, organic photoelectric conversion element, and photodetection element Download PDFInfo
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- WO2022124222A1 WO2022124222A1 PCT/JP2021/044424 JP2021044424W WO2022124222A1 WO 2022124222 A1 WO2022124222 A1 WO 2022124222A1 JP 2021044424 W JP2021044424 W JP 2021044424W WO 2022124222 A1 WO2022124222 A1 WO 2022124222A1
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- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000005929 isobutyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])OC(*)=O 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 150000004658 ketimines Chemical class 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- ZHDORMMHAKXTPT-UHFFFAOYSA-N n-benzoylbenzamide Chemical group C=1C=CC=CC=1C(=O)NC(=O)C1=CC=CC=C1 ZHDORMMHAKXTPT-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004708 n-butylthio group Chemical group C(CCC)S* 0.000 description 1
- 125000006610 n-decyloxy group Chemical group 0.000 description 1
- AIDQCFHFXWPAFG-UHFFFAOYSA-N n-formylformamide Chemical group O=CNC=O AIDQCFHFXWPAFG-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004718 n-hexylthio group Chemical group C(CCCCC)S* 0.000 description 1
- 125000006609 n-nonyloxy group Chemical group 0.000 description 1
- 125000006608 n-octyloxy group Chemical group 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004712 n-pentylthio group Chemical group C(CCCC)S* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004706 n-propylthio group Chemical group C(CC)S* 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
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- 150000004866 oxadiazoles Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
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- 125000001148 pentyloxycarbonyl group Chemical group 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
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- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
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- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
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- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
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- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
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- 239000004814 polyurethane Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
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- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical group CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical class C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
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- 239000005060 rubber Substances 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000007764 slot die coating Methods 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
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- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- 238000010345 tape casting Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005579 tetracene group Chemical group 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
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- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical compound C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000005034 trifluormethylthio group Chemical group FC(S*)(F)F 0.000 description 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
Definitions
- the present invention relates to a composition, a film, an organic photoelectric conversion element, and a photodetection element.
- Photoelectric conversion elements containing organic films are attracting attention, for example, as extremely useful power generation devices from the viewpoint of energy saving and reduction of carbon dioxide emissions, or as photodetectors of highly sensitive optical sensors for near infrared rays.
- compositions for forming an active layer of an organic photoelectric conversion element a composition containing a p-type semiconductor material, a fullerene compound which is an n-type semiconductor material, and a predetermined additive is known (Patent Document). 1). It is disclosed that it is effective to add a polymer other than a semiconductor material to the composition as a means for obtaining a composition having a viscous physical characteristic suitable for the coating film forming step of the active layer in the production of an organic electronic device.
- an optical sensor including a photoelectric conversion element, a patterned electrode, an active layer, etc. are usually laminated on one substrate, and a plurality of photoelectric conversion elements are arranged on one substrate.
- a device with a similar structure is used.
- the active layer is required to have a certain thickness in order to suppress a dark current that causes noise in the sensor performance, and to have a uniform film thickness so that the characteristics of each element do not vary.
- the spin coating method is often used as a method for easily producing an active layer having a uniform film thickness.
- the inventors attempted to form an active layer by a spin coating method using a composition containing an additive with reference to Patent Document 1. As a result, a desired uniform and thick active layer was obtained, but the device contained many defective elements having an abnormally high dark current, and the dark current characteristics varied greatly among the elements contained in the device. It turned out.
- composition capable of producing an organic photoelectric conversion element having a small variation in dark current characteristics; a film capable of being produced from the composition; an organic photoelectric conversion element containing the film; and a photodetection element including the organic photoelectric conversion element. Desired.
- the present inventors can solve the above-mentioned problems by forming an active layer using a composition containing a specific p-type semiconductor material and an insulating material in combination. And completed the present invention. That is, the present invention provides the following.
- a composition containing a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent A composition in which the p-type semiconductor material contains a polymer containing a structural unit represented by the following formula (I).
- Ar 1 and Ar 2 each independently represent a trivalent aromatic heterocyclic group which may have a substituent.
- Z represents a group represented by the following formulas (Z-1) to (Z-4).
- R is Hydrogen atom, Halogen atom, Alkyl groups, which may have substituents, Cycloalkyl groups, which may have substituents, An alkenyl group which may have a substituent, Cycloalkenyl groups, which may have substituents, An alkynyl group, which may have a substituent, A cycloalkynyl group which may have a substituent, Aryl groups, which may have substituents, Alkyloxy groups, which may have substituents, Cycloalkyloxy groups, which may have substituents, Aryloxy groups, which may have substituents, Alkylthio groups, which may have substituents, Cycloalkylthio groups, which may have substituents, An arylthio group, which may have a substituent, A monovalent heterocyclic group which may have a substituent, Substituted amino groups, which may have substituents, Imine residues, which may have substituents, An arylthio group, which may have a substitu
- R a and R b are independent of each other. Hydrogen atom, Alkyl groups, which may have substituents, Cycloalkyl groups, which may have substituents, Aryl groups, which may have substituents, Alkyloxy groups, which may have substituents, Cycloalkyloxy groups, which may have substituents, Represents an aryloxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent.
- the two Rs may be the same or different. ))
- R i1 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms.
- R i2 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a group represented by the following formula (III-1), a group represented by the formula (III-2), or a group represented by the formula (III-2). Represents the group represented by 3).
- Each of the plurality of Ri2a independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms.
- R i2b represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- R i2c represents an alkyl group having 1 to 20 carbon atoms.
- R i2c represents an alkyl group having 1 to 20 carbon atoms.
- a p-type semiconductor material, an n-type semiconductor material, and an insulating material are included.
- a film in which the p-type semiconductor material contains a polymer containing a structural unit represented by the following formula (I).
- Ar 1 and Ar 2 each independently represent a trivalent aromatic heterocyclic group which may have a substituent.
- Z represents a group represented by the following formulas (Z-1) to (Z-4).
- R is Hydrogen atom, Halogen atom, Alkyl groups, which may have substituents, Cycloalkyl groups, which may have substituents, An alkenyl group which may have a substituent, Cycloalkenyl groups, which may have substituents, An alkynyl group, which may have a substituent, A cycloalkynyl group which may have a substituent, Aryl groups, which may have substituents, Alkyloxy groups, which may have substituents, Cycloalkyloxy groups, which may have substituents, Aryloxy groups, which may have substituents, Alkylthio groups, which may have substituents, Cycloalkylthio groups, which may have substituents, An arylthio group, which may have a substituent, A monovalent heterocyclic group which may have a substituent, Substituted amino groups, which may have substituents, Imine residues, which may have substituents, An arylthio group, which may have a substitu
- R a and R b are independent of each other. Hydrogen atom, Alkyl groups, which may have substituents, Cycloalkyl groups, which may have substituents, Aryl groups, which may have substituents, Alkyloxy groups, which may have substituents, Cycloalkyloxy groups, which may have substituents, Represents an aryloxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent. In the formulas (Z-1) to (Z-4), the two Rs may be the same or different. ))) [5] An organic photoelectric conversion element including the first electrode, the film according to [4], and the second electrode in this order. [6] A photodetector including the organic photoelectric conversion element according to [5].
- a composition capable of producing an organic photoelectric conversion element having a small variation in dark current characteristics a film capable of being produced from the composition; an organic photoelectric conversion element containing the film; including the organic photoelectric conversion element.
- a photodetector is provided.
- FIG. 1 is a diagram schematically showing a configuration example of a photoelectric conversion element.
- FIG. 2 is a diagram schematically showing a configuration example of an image detection unit.
- FIG. 3 is a diagram schematically showing a configuration example of the fingerprint detection unit.
- FIG. 4 is a diagram schematically showing a configuration example of an image detection unit for an X-ray image pickup apparatus.
- FIG. 5 is a diagram schematically showing a configuration example of a vein detection unit for a vein authentication device.
- FIG. 6 is a diagram schematically showing a configuration example of an image detection unit for an indirect type TOF type distance measuring device.
- the “polymer compound” means a polymer having a molecular weight distribution and having a polystyrene-equivalent number average molecular weight of 1 ⁇ 10 3 or more and 1 ⁇ 108 or less.
- the structural units contained in the polymer are 100 mol% in total.
- the "constituent unit” means a unit of the structure of the polymer.
- the "hydrogen atom” may be a light hydrogen atom or a deuterium atom.
- halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.
- substituents include halogen atom, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group, alkyloxy group, cycloalkyloxy group, alkylthio group, cycloalkylthio group, aryl group, Examples thereof include an aryloxy group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an acidimide group, a substituted oxycarbonyl group, a cyano group, an alkylsulfonyl group, and a nitro group. ..
- alkyl group may be linear or branched.
- the alkyl group may have a substituent.
- the number of carbon atoms of the alkyl group does not include the number of carbon atoms of the substituent, and is usually 1 to 50, preferably 1 to 30, and more preferably 1 to 20.
- alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 3-methylbutyl group, 2-ethylbutyl group, n.
- alkyl having a substituent examples include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a 3-phenylpropyl group and a 3- (4-methylphenyl) group.
- examples thereof include a propyl group, a 3- (3,5-dihexylphenyl) propyl group and a 6-ethyloxyhexyl group.
- the "cycloalkyl group” may be a monocyclic group or a polycyclic group.
- the cycloalkyl group may have a substituent.
- the number of carbon atoms of the cycloalkyl group does not include the number of carbon atoms of the substituent and is usually 3 to 30, preferably 3 to 20.
- cycloalkyl groups include alkyl groups having no substituents such as cyclopentyl group, cyclohexyl group, cycloheptyl group and adamantyl group, and the hydrogen atom in these groups is an alkyl group, an alkyloxy group and an aryl group.
- a group substituted with a substituent such as a fluorine atom is an alkyl group having no substituents such as cyclopentyl group, cyclohexyl group, cycloheptyl group and adamantyl group, and the hydrogen atom in these groups is an alkyl group, an alkyloxy group and an aryl group.
- a group substituted with a substituent such as a fluorine atom.
- cycloalkyl group having a substituent examples include a methylcyclohexyl group and an ethylcyclohexyl group.
- alkenyl group may be linear or branched.
- the alkenyl group may have a substituent.
- the number of carbon atoms of the alkenyl group does not include the number of carbon atoms of the substituent and is usually 2 to 30, preferably 2 to 20.
- alkenyl groups include vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, 3-butenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 5-hexenyl group, Examples thereof include an alkenyl group having no substituent such as a 7-octenyl group, and a group in which a hydrogen atom in these groups is substituted with a substituent such as an alkyloxy group, an aryl group or a fluorine atom.
- the "cycloalkenyl group” may be a monocyclic group or a polycyclic group.
- the cycloalkenyl group may have a substituent.
- the number of carbon atoms of the cycloalkenyl group does not include the number of carbon atoms of the substituent and is usually 3 to 30, preferably 3 to 20.
- cycloalkenyl groups are cycloalkenyl groups having no substituents such as cyclohexenyl groups, and the hydrogen atom in these groups is a substituent such as an alkyl group, an alkyloxy group, an aryl group or a fluorine atom. Examples include substituted groups.
- Examples of the cycloalkenyl group having a substituent include a methylcyclohexenyl group and an ethylcyclohexenyl group.
- alkynyl group may be linear or branched.
- the alkynyl group may have a substituent.
- the number of carbon atoms of the alkynyl group does not include the number of carbon atoms of the substituent and is usually 2 to 30, preferably 2 to 20.
- alkynyl groups include ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4-pentynyl group, 1-hexynyl group, 5-hexynyl group and the like.
- alkynyl groups include ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4-pentynyl group, 1-hexynyl group, 5-hexynyl group and the like.
- alkynyl group having no substituent and a group in which the hydrogen atom in these groups is substituted with a substituent such as an alkyloxy group, an aryl group or a fluorine atom.
- the "cycloalkynyl group” may be a monocyclic group or a polycyclic group.
- the cycloalkynyl group may have a substituent.
- the number of carbon atoms of the cycloalkynyl group does not include the number of carbon atoms of the substituent and is usually 4 to 30, preferably 4 to 20.
- cycloalkynyl groups include cycloalkynyl groups that do not have substituents such as cyclohexynyl groups, and hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkyloxy groups, aryl groups, and fluorine atoms. The group that was made is mentioned.
- Examples of the cycloalkynyl group having a substituent include a methylcyclohexynyl group and an ethylcyclohexynyl group.
- alkyloxy group may be linear or branched.
- the alkyloxy group may have a substituent.
- the number of carbon atoms of the alkyloxy group does not include the number of carbon atoms of the substituent and is usually 1 to 30, preferably 1 to 20.
- alkyloxy groups include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-Heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, 3,7-dimethyloctyloxy group, 3-heptyldodecyloxy group, lauryloxy group, etc.
- Examples thereof include an alkyloxy group having no substituent and a group in which the hydrogen atom in these groups is substituted with a substituent such as an alkyloxy group, an aryl group or a fluorine atom.
- the cycloalkyl group contained in the "cycloalkyloxy group” may be a monocyclic group or a polycyclic group.
- the cycloalkyloxy group may have a substituent.
- the number of carbon atoms of the cycloalkyloxy group does not include the number of carbon atoms of the substituent and is usually 3 to 30, preferably 3 to 20.
- cycloalkyloxy group examples include a cycloalkyloxy group having no substituent such as a cyclopentyloxy group, a cyclohexyloxy group and a cycloheptyloxy group, and a hydrogen atom in these groups is a fluorine atom, an alkyl group and the like. Examples thereof include groups substituted with the substituents of.
- alkylthio group may be linear or branched.
- the alkylthio group may have a substituent.
- the number of carbon atoms of the alkylthio group does not include the number of carbon atoms of the substituent and is usually 1 to 30, preferably 1 to 20.
- n-hexylthio group n-heptylthio group, n-octylthio group, 2-ethylhexylthio group, n-nonylthio group, n-decylthio group, 3,7-dimethyloctylthio group, 3-heptyldodecylthio group, laurylthio group, And a trifluoromethylthio group.
- the cycloalkyl group contained in the "cycloalkylthio group” may be a monocyclic group or a polycyclic group.
- the cycloalkylthio group may have a substituent.
- the number of carbon atoms of the cycloalkylthio group does not include the number of carbon atoms of the substituent and is usually 3 to 30, preferably 3 to 20.
- cycloalkylthio group that may have a substituent is a cyclohexylthio group.
- the "p-valent aromatic carbocyclic group” means the remaining atomic group obtained by removing p hydrogen atoms directly bonded to the carbon atom constituting the ring from the aromatic hydrocarbon which may have a substituent. do.
- the p-valent aromatic carbocyclic group may further have a substituent.
- Aryl group means a monovalent aromatic carbocyclic group.
- the aryl group may have a substituent.
- the number of carbon atoms of the aryl group does not include the number of carbon atoms of the substituent and is usually 6 to 60, preferably 6 to 48.
- aryl groups include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthrasenyl group, 2-anthrasenyl group, 9-anthrasenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, An aryl group having no substituent such as a 2-fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, a 2-phenylphenyl group, a 3-phenylphenyl group, a 4-phenylphenyl group, and hydrogen in these groups. Examples thereof include a group in which an atom is substituted with a substituent such as an alkyl group, an alkyloxy group, an aryl group or a fluorine atom.
- the "aryloxy group” may have a substituent.
- the number of carbon atoms of the aryloxy group does not include the number of carbon atoms of the substituent and is usually 6 to 60, preferably 6 to 48.
- aryloxy group examples include a substituent such as a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthrasenyloxy group, a 9-anthrasenyloxy group and a 1-pyrenyloxy group.
- substituents such as a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthrasenyloxy group, a 9-anthrasenyloxy group and a 1-pyrenyloxy group.
- substituent such as a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthrasenyloxy group, a 9-anthrasenyloxy group and a 1-pyrenyloxy group.
- substituent such as an alkyl group, an alkyloxy group, or a fluor
- the "arylthio group” may have a substituent.
- the number of carbon atoms of the arylthio group does not include the number of carbon atoms of the substituent and is usually 6 to 60, preferably 6 to 48.
- arylthio groups that may have substituents are phenylthio groups, C1-C12 alkyloxyphenylthio groups, C1-C12 alkylphenylthio groups, 1-naphthylthio groups, 2-naphthylthio groups, and pentafluorophenyls.
- the thio group is mentioned. "C1 to C12” indicates that the number of carbon atoms of the group described immediately after that is 1 to 12. Further, “Cm to Cn” indicates that the number of carbon atoms of the group described immediately after that is m to n. The same applies to the following.
- a "p-valent heterocyclic group” (p represents an integer of 1 or more) is a hydrogen directly bonded to a carbon atom or a hetero atom constituting a ring from a heterocyclic compound which may have a substituent. It means the remaining atomic group excluding p hydrogen atoms among the atoms.
- the "p-valent heterocyclic group” includes a "p-valent aromatic heterocyclic group”.
- the "p-valent aromatic heterocyclic group” is a p of hydrogen atoms directly bonded to a carbon atom or a hetero atom constituting a ring from an aromatic heterocyclic compound which may have a substituent. It means the remaining atomic group excluding one hydrogen atom.
- Aromatic heterocyclic compounds include, in addition to compounds in which the heterocycle itself exhibits aromaticity, compounds in which the heterocycle itself has an aromatic ring condensed, even if the heterocycle itself does not exhibit aromaticity.
- aromatic heterocyclic compounds specific examples of the compound in which the heterocycle itself exhibits aromaticity include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, and triazine. , Pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphol.
- aromatic heterocyclic compounds specific examples of compounds in which the heterocycle itself does not exhibit aromaticity and the aromatic ring is fused to the heterocycle include phenoxazine, phenothiazine, dibenzoborol, and dibenzosyrol. And benzopyran.
- the p-valent heterocyclic group may have a substituent.
- the number of carbon atoms of the p-valent heterocyclic group does not include the number of carbon atoms of the substituent and is usually 2 to 60, preferably 2 to 20.
- monovalent heterocyclic groups include monovalent aromatic heterocyclic groups (eg, thienyl group, pyrrolyl group, frill group, pyridyl group, quinolyl group, isoquinolyl group, pyrimidinyl group, triazinyl group) and monovalent.
- monovalent aromatic heterocyclic groups eg, thienyl group, pyrrolyl group, frill group, pyridyl group, quinolyl group, isoquinolyl group, pyrimidinyl group, triazinyl group
- non-aromatic heterocyclic groups eg, piperidyl group, piperazyl group
- groups in which the hydrogen atom in these groups is substituted with a substituent such as an alkyl group, an alkyloxy group or a fluorine atom.
- Substituted amino group means an amino group having a substituent.
- an alkyl group, an aryl group and a monovalent heterocyclic group are preferable.
- the number of carbon atoms of the substituted amino group is usually 2 to 30, not including the number of carbon atoms of the substituent.
- substituted amino groups include dialkylamino groups (eg, dimethylamino group, diethylamino group), diarylamino groups (eg, diphenylamino group, bis (4-methylphenyl) amino group, bis (4-tert-butylphenyl). ) Amino group, bis (3,5-di-tert-butylphenyl) amino group).
- the "acyl group” may have a substituent.
- the number of carbon atoms of the acyl group does not include the number of carbon atoms of the substituent and is usually 2 to 20, preferably 2 to 18.
- Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.
- the "imine residue” means the remaining atomic group obtained by removing one hydrogen atom directly bonded to the carbon atom or the nitrogen atom constituting the carbon atom-nitrogen atom double bond from the imine compound.
- the "imine compound” means an organic compound having a carbon atom-nitrogen atom double bond in the molecule.
- imine compounds include compounds in which the hydrogen atom bonded to the carbon atom-nitrogen atom double bond in aldimine, ketimine, and aldimine is replaced with an alkyl group or the like.
- the number of carbon atoms of the imine residue is usually 2 to 20, preferably 2 to 18.
- Examples of imine residues include groups represented by the following structural formulas.
- the "amide group” means the remaining atomic group obtained by removing one hydrogen atom bonded to a nitrogen atom from the amide.
- the number of carbon atoms of the amide group is usually 1 to 20, preferably 1 to 18.
- Specific examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group and a dibenzamide group. , Ditrifluoroacetamide group, and dipentafluorobenzamide group.
- the “acidimide group” means the remaining atomic group obtained by removing one hydrogen atom bonded to a nitrogen atom from the acidimide.
- the number of carbon atoms of the acidimide group is usually 4 to 20.
- Specific examples of the acidimide group include a group represented by the following structural formula.
- R' represents an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group, which may have a substituent.
- the number of carbon atoms of the substituted oxycarbonyl group is usually 2 to 60, preferably 2 to 48, not including the number of carbon atoms of the substituent.
- substituted oxycarbonyl group examples include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group, and a hexyloxycarbonyl group.
- alkylsulfonyl group may be linear or branched.
- the alkylsulfonyl group may have a substituent.
- the number of carbon atoms of the alkylsulfonyl group is usually 1 to 30, not including the number of carbon atoms of the substituent.
- Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a dodecylsulfonyl group.
- ⁇ -conjugated system means a system in which ⁇ electrons are delocalized to multiple bonds.
- (meth) acrylic includes acrylics, methacrylics, and combinations thereof.
- composition contains a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent, and the p-type semiconductor material is a structural unit represented by the formula (I). Contains a polymer containing. By using such a composition, an organic photoelectric conversion element having a small variation in dark current characteristics can be manufactured.
- the present invention is not limited.
- the concentration and viscosity physical characteristics of the composition can be appropriately adjusted, and the thickness becomes uniform at the time of coating. A coating film can be manufactured.
- the solid content concentration and viscosity of the composition are increased by adding the insulating material, it is considered that the aggregation of the p-type semiconductor material and the n-type semiconductor material is likely to proceed in the process of applying and drying the composition.
- the active layer containing a polymer which is a p-type semiconductor material having such a molecular structure, contains large crystals of the p-type semiconductor material, and pinholes and local thinning occur from the crystals. Will be done.
- the polymer containing the structural unit represented by the formula (I), which is a p-type semiconductor material, contained in the composition of the present invention has an asymmetric molecular structure.
- the polymer does not easily crystallize and exists as fine particles in the active layer.
- defects such as minute pinholes and thinning due to large particles in the composition are unlikely to occur in the active layer obtained from the composition of the present invention, and the device obtained from the composition of the present invention. Is presumed to have excellent uniformity of dark current characteristics.
- the p-type semiconductor material and the n-type semiconductor material may be dissolved or dispersed.
- the p-type semiconductor material and the n-type semiconductor material are preferably at least partially dissolved, or more preferably completely dissolved.
- the p-type semiconductor material according to the present embodiment includes a polymer containing a structural unit represented by the following formula (I).
- the polymer containing the structural unit represented by the formula (I) is also referred to as a polymer (1).
- the p-type semiconductor material may contain only one kind of the polymer (1), or may contain two or more kinds of the polymer (1). Further, the polymer (1) may contain only one kind of the structural unit represented by the formula (I), or may contain two or more kinds.
- Ar 1 and Ar 2 each independently represent a trivalent aromatic heterocyclic group which may have a substituent.
- Z represents a group represented by the following formulas (Z-1) to (Z-4).
- R is Hydrogen atom, Halogen atom, Alkyl groups, which may have substituents, Cycloalkyl groups, which may have substituents, An alkenyl group which may have a substituent, Cycloalkenyl groups, which may have substituents, An alkynyl group, which may have a substituent, A cycloalkynyl group which may have a substituent, Aryl groups, which may have substituents, Alkyloxy groups, which may have substituents, Cycloalkyloxy groups, which may have substituents, Aryloxy groups, which may have substituents, Alkylthio groups, which may have substituents, Cycloalkylthio groups, which may have substituents, An arylthio group, which may have a substituent, A monovalent heterocyclic group which may have a substituent, Substituted amino groups, which may have substituents, Imine residues, which may have substituents, An arylthio group, which may have a substitu
- R a and R b are independent of each other.
- the two Rs may be the same or different.
- aromatic heterocycles constituting a trivalent aromatic heterocyclic group represented by Ar 1 or Ar 2 include an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a thiophene ring, a pyrrole ring, and a phosphor.
- Z is preferably a group represented by the formula (Z-1) or (Z-2).
- R in the formulas (Z-1) to (Z-4) is preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom or a carbon. It is an alkyl group having 1 to 40 atoms, more preferably a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, and still more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. These groups may have substituents.
- a plurality of R's may be the same as each other or may be different from each other.
- the structural unit represented by the formula (I) is preferably the structural unit represented by the following formula (I-1) or (I-2).
- a plurality of R's may be the same as or different from each other.
- a structural unit in which X 1 and X 2 are sulfur atoms and Z 1 and Z 2 are groups represented by C (R)-is preferable.
- Examples of the structural unit (I-1) include the structural units represented by the following formulas (I-1-1) to (I-1-14).
- R has the same definition as in the formulas (Z-1) to (Z-4).
- a plurality of R's may be the same as or different from each other.
- the structural unit represented by the formula (I-1-1) is preferable.
- Examples of the structural unit (I-2) include the structural units represented by the following formulas (I-2-1) to (I-2-14).
- R has the same definition as in the formulas (Z-1) to (Z-4).
- a plurality of R's may be the same as or different from each other.
- the structural unit represented by the formula (I-2-1) is preferable.
- the polymer (1) preferably contains a structural unit represented by the formula (I) in addition to the structural unit represented by the formula (I).
- the polymer (1) may contain only one type of structural unit represented by the formula (IV), or may contain two or more types.
- Ar 3 represents a divalent aromatic heterocyclic group.
- the number of carbon atoms of the divalent aromatic heterocyclic group represented by Ar 3 is usually 2 to 60, preferably 4 to 60, and more preferably 4 to 20.
- the divalent aromatic heterocyclic group represented by Ar 3 may have a substituent.
- the structural unit represented by the formula (IV) the structural unit represented by any of the following formulas (IV-1) to (IV-8) is preferable.
- X1, X2, Z1, Z2 and R are the same as the definitions in formulas (I- 1 ) and (I-2).
- the two Rs may be the same or different.
- the two Rs are preferably independently hydrogen atoms, alkyl groups, or halogen atoms, more preferably hydrogen atoms or halogen atoms at the same time, and even more preferably. At the same time, it is a halogen atom.
- both X 1 and X 2 in the formulas (IV-1) to (IV-8) are sulfur atoms.
- divalent aromatic heterocyclic group represented by Ar 3 examples include groups represented by the following formulas (101) to (190) and groups in which these groups are substituted with substituents. ..
- substituents a halogen atom and an alkyl group are preferable.
- the group represented by the formula (148) or the formula (190) is preferable.
- R has the same meaning as described above.
- the plurality of Rs may be the same or different from each other.
- the total amount of the structural unit represented by the formula (I) and the structural unit represented by the formula (IV) in the polymer (1) is 100 mol% based on the amount of all the structural units contained in the polymer (1). Then, it is preferably 20 mol% to 100 mol%, and since it can improve the charge transport property as a p-type semiconductor material, it is more preferably 40 mol% to 100 mol%, and further preferably 50 mol. % To 100 mol%.
- the polymer (1) does not contain the structural unit represented by the formula (IV)
- the polymer (1) contains any of the following combinations of structural units. -Combination of the structural unit represented by the formula (I-2) and the structural unit represented by the formula (IV-6) -The structural unit represented by the formula (I-2) and the table by the formula (IV-8). Combination of building blocks
- the polymer (1) contains any of the following combinations of structural units. -Combination of the structural unit represented by the formula (I-2-1) and the structural unit represented by the formula (148) -The structural unit represented by the formula (I-2-1) and the table by the formula (190). Combination of building blocks
- polymers (1) which is a p-type semiconductor material in the present embodiment include polymers represented by the following formulas (P-1) to (P-2).
- the weight ratio of the polymer (1) in the p-type semiconductor material is preferably 20% by weight or more, more preferably 40% by weight or more, still more preferably 50% by weight or more, usually 100% by weight or less, and 100% by weight. May be%.
- the composition of the present embodiment may optionally contain other compounds as the p-type semiconductor material in addition to the above-mentioned polymer (1).
- examples of other compounds that are p-type semiconductor materials include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives, polythiophene and its derivatives. , Polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, polyfluorene and its derivatives.
- the composition according to the present embodiment may optionally contain only one kind or a plurality of kinds of other compounds in addition to the polymer (1) as the p-type semiconductor material.
- the composition according to this embodiment contains an n-type semiconductor material.
- the composition according to the present embodiment may contain only one kind of compound or may contain a plurality of kinds of compounds as the n-type semiconductor material.
- Various compounds are known as n-type semiconductor materials, and they can be used as the n-type semiconductor material according to the present embodiment.
- the semiconductor material contained in the composition functions as a p-type semiconductor material or an n-type semiconductor material can be relatively determined from the value of the HOMO energy level or the value of the LUMO energy of the selected compound. ..
- the relationship between the energy level values of HOMO and LUMO of the p-type semiconductor material and the energy level values of HOMO and LUMO of the n-type semiconductor material is such that the film produced from the composition has a desired function (for example, photoelectric conversion). It can be appropriately set within the range in which the function (function, light detection function) is exhibited.
- the n-type semiconductor material according to this embodiment may be a low molecular weight compound or a high molecular weight compound.
- n-type semiconductor materials electron-accepting compounds
- fullerene such as C60 fullerene and its derivatives, oxadiazole derivatives, anthracinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and Examples thereof include tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, 8-hydroxyquinolin and metal complexes of its derivatives, and phenanthrene derivatives such as basocproin.
- the composition may contain a fullerene or a fullerene derivative as an n-type semiconductor material.
- fullerenes include C 60 fullerenes, C 70 fullerenes, C 76 fullerenes, C 78 fullerenes, and C 84 fullerenes.
- fullerene derivatives include compounds represented by the following formulas (F-1) to (F-4).
- RX represents an alkyl group, an aryl group, a monovalent heterocyclic group, or a group having an ester structure. A plurality of RXs may be the same as or different from each other.
- RY represents an alkyl group or an aryl group. A plurality of RYs may be the same as or different from each other.
- Examples of the monovalent heterocyclic group represented by RX include a thienyl group, a pyrrolyl group, a frill group, a pyridyl group, a quinolyl group, and an isoquinolyl group.
- Examples of the group having an ester structure represented by RX include a group represented by the formula (E-1).
- u1 represents an integer of 1 to 6
- u2 represents an integer of 0 to 6
- RZ represents an alkyl group, an aryl group or a monovalent heterocyclic group.
- C60 fullerene derivatives include the following compounds.
- R has the same meaning as described above.
- Examples of the C70 fullerene derivative include the following compounds.
- fullerene derivative examples include [6,6] -phenyl-C61 butyrate methyl ester (C60PCBM, [6,6] -Phenyl C61 butyric acid methyl ester), [6,6] -phenyl-C71 butyrate methyl ester (6,6] -phenyl-C71 butyrate methyl ester (6,6) -phenyl-C71 butyrate methyl ester.
- the n-type semiconductor material according to the present embodiment may contain a compound that is neither fullerene nor a derivative of fullerene.
- a compound that is neither fullerene nor a derivative of fullerene is also referred to as a non-fullerene compound.
- the n-type semiconductor material preferably contains a compound represented by the following formula (V).
- V A 1 -B 10 -A 2 (V)
- a 1 and A 2 each independently represent an electron-withdrawing group
- B 10 represents a group containing a ⁇ -conjugated system.
- T represents a carbocycle which may have a substituent or a heterocycle which may have a substituent.
- the carbocycle and the heterocycle may be a monocyclic ring or a condensed ring. When these rings have a plurality of substituents, the plurality of substituents may be the same or different.
- An example of a carbocycle that may have a substituent that is T is an aromatic carbocycle, preferably an aromatic carbocycle.
- Specific examples of the carbocycle which may have a substituent which is T include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring, and a benzene ring is preferable.
- naphthalene ring and a phenanthrene ring more preferably a benzene ring and a naphthalene ring, and further preferably a benzene ring. These rings may have substituents.
- heterocycle which may have a substituent which is T is an aromatic heterocycle, and an aromatic heterocycle is preferable.
- Specific examples of the heterocycle which may have a substituent which is T include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, and a thiazole ring.
- a thienothiophene ring preferably a thiophene ring, a pyridine ring, a pyrazine ring, a thiazole ring, and a thienothiophene ring, and more preferably a thiophene ring. These rings may have substituents.
- Examples of the substituent that the carbocycle or heterocycle which is T may have include a halogen atom, an alkyl group, an alkyloxy group, an aryl group, and a monovalent heterocyclic group, preferably a fluorine atom and /. Alternatively, it is an alkyl group having 1 to 6 carbon atoms.
- X 7 is a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent, an alkyloxy group which may have a substituent, an aryl group which may have a substituent or a group. Represents a monovalent heterocyclic group.
- R a1 , R a2 , R a3 , R a4 , and R a5 independently have a hydrogen atom, an alkyl group which may have a substituent, a halogen atom, and an alkyl which may have a substituent.
- Ra6 and Ra7 each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and a substituent.
- each of the plurality of Ra 10 independently represents a hydrogen atom or a substituent, and preferably represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent.
- R a3 , R a4 , and R a5 are independently synonymous with the above, and preferably each of them independently has an alkyl group or an aryl which may have a substituent. Represents a group.
- the n-type semiconductor material is preferably a compound represented by the following formula (VI).
- a 1 and A 2 each independently represent an electron-withdrawing group.
- the examples and preferred examples of A 1 and A 2 are the same as the examples described and preferred examples of A 1 and A 2 in the above formula (V).
- the divalent carbocyclic group which may have a substituent and the divalent heterocyclic group which may have a substituent represented by S 1 and S 2 may be a fused ring. ..
- the divalent carbocyclic group or the divalent heterocyclic group has a plurality of substituents, the plurality of substituents may be the same or different.
- n1 and n2 each independently represent an integer of 0 or more, preferably independently represent 0 or 1, and more preferably represent 0 or 1 at the same time.
- divalent carbocyclic groups include divalent aromatic carbocyclic groups.
- divalent heterocyclic groups include divalent aromatic heterocyclic groups.
- the divalent aromatic carbocyclic group or the divalent aromatic heterocyclic group is a fused ring, all of the rings constituting the fused ring may be a fused ring having aromaticity, and only a part thereof may be a fused ring. It may be a fused ring having aromaticity.
- S 1 and S 2 include groups represented by any of the formulas (101) to (190) given as examples of the divalent aromatic heterocyclic group represented by Ar 3 already described. And groups in which the hydrogen atom in these groups is substituted with a substituent.
- S 1 and S 2 preferably independently represent a group represented by the following formula (s-1) or (s-2).
- X3 represents an oxygen atom or a sulfur atom.
- R a10 is as defined above.
- S 1 and S 2 are preferably independently represented by a group represented by the formula (142), the formula (148), or the formula (184), or the hydrogen atom in these groups is substituted with a substituent.
- a group more preferably a group in which one hydrogen atom in the group represented by the above formula (142) or the formula (184) or the group represented by the formula (184) is substituted with an alkyloxy group. be.
- B 11 is a fused ring group having two or more structures selected from the group consisting of a carbocyclic structure and a heterocyclic structure, and is a fused ring group that does not contain an ortho-peri condensed structure, and has a substituent. Represents a fused ring group that may be present.
- the fused ring group represented by B 11 may contain a structure obtained by condensing two or more structures that are identical to each other.
- the condensed ring group represented by B 11 has a plurality of substituents
- the plurality of substituents may be the same or different.
- Examples of the carbon ring structure that can form the fused ring group represented by B 11 include a ring structure represented by the following formula (Cy1) or formula (Cy2).
- Examples of the heterocyclic structure that can form the fused ring group represented by B 11 include a ring structure represented by any of the following formulas (Cy3) to (Cy10).
- B 11 is preferably a fused ring group having two or more structures selected from the group consisting of the structures represented by the formulas (Cy1) to (Cy10). It is a condensed ring group that does not contain a condensed structure and may have a substituent. B 11 may include a structure in which two or more of the same structures are condensed among the structures represented by the formulas (Cy1) to (Cy10).
- B 11 is more preferably a fused ring group having two or more structures selected from the group consisting of the structures represented by the formulas (Cy1) to (Cy6) and the formula (Cy8), and is an ortho-peri condensation. It is a condensed ring group that does not contain a structure and may have a substituent.
- the substituent which the fused ring group of B 11 may have may preferably have an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. It is an alkyloxy group which may have a substituent and a monovalent heterocyclic group which may have a substituent.
- the aryl group that the fused ring group represented by B 11 may have may be substituted with, for example, an alkyl group.
- the groups represented by the following formulas (b- 1 ) to (b-14) and the hydrogen atom in these groups are substituents (preferably, substituents).
- the fused ring group of B 11 is a group represented by the following formula (b-4), or an alkyl group in which the hydrogen atom in these groups is a substituent (preferably, an alkyl group which may have a substituent).
- a group substituted with an aryl group which may have a substituent, an alkyloxy group which may have a substituent, or a monovalent heterocyclic group which may have a substituent) is preferable.
- the group represented by the following formula (b-4) is more preferable.
- R a10 is as defined above.
- each of the plurality of Ra10s may independently have an alkyl group or a substituent which may preferably have a substituent. It is an aryl group.
- Examples of the compound represented by the formula (V) or the formula (VI) include a compound represented by the following formula.
- R is as defined above, and X represents an alkyl group which may have a hydrogen atom, a halogen atom, a cyano group or a substituent.
- R is preferably a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent or an alkyloxy group which may have a substituent. ..
- Examples of the compound represented by the formula (V) or (VI) include the compound represented by the following formula N-1.
- the n-type semiconductor material is preferably a compound containing a perylenetetracarboxylic acid diimide structure.
- the compound containing a perylenetetracarboxylic acid diimide structure as a non-fullerene compound include a compound represented by the following formula.
- R is as defined above.
- a plurality of Rs may be the same as or different from each other.
- the n-type semiconductor material preferably contains a compound represented by the following formula (VII).
- the compound represented by the following formula (VII) is a non-fullerene compound containing a perylenetetracarboxylic acid diimide structure.
- R 1 has a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, and even if it has a substituent.
- a good alkyloxy group, a cycloalkyloxy group which may have a substituent, an aryl group which may have a substituent, or a monovalent aromatic heterocyclic group which may have a substituent. show.
- a plurality of R 1s may be the same or different from each other.
- each of the plurality of R 1s is an alkyl group which may independently have a substituent.
- R 2 is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkyloxy group which may have a substituent, and a substituent.
- a plurality of R 2s may be the same or different.
- the composition of this embodiment contains an insulating material.
- the insulating material means a material that is neither a conductor nor a semiconductor.
- the insulating material has an electrical resistivity of 1 ⁇ 107 ⁇ ⁇ m or more at 20 ° C. Insulating materials are usually not involved in the photoelectric conversion process.
- the insulating material is preferably an organic compound, more preferably an organic polymer.
- the insulating material may contain only one type of organic compound, or may contain a combination of two or more types.
- organic compounds are known as insulating materials and can be used in the composition of the present embodiment.
- organic polymers that are insulating materials include polyolefins (eg polyethylene, polypropylene, poly (1-butene), polyisobutylene), poly (aromatic vinyl) (eg, polystyrene and its derivatives), poly (meth).
- examples thereof include methyl acrylate, polyester, vinyl polycarboxylate, polyvinyl acetal, polycarbonate, polyurethane, polyarylate, polyamide, polyimide, cellulose and derivatives thereof, polysiloxane, rubber, and thermoplastic elastomer.
- the organic polymer that can be contained in the insulating material may be a homopolymer or a copolymer.
- the insulating material preferably contains a polymer containing a structural unit represented by the following formula (II).
- the polymer containing the structural unit represented by the formula (II) is also referred to as a polymer (2).
- the polymer (2) may contain only one type of the structural unit represented by the formula (II), or may contain a combination of two or more types.
- R i1 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms
- R i2 is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms, described below. It represents a group represented by the formula (III-1), a group represented by the formula (III-2), or a group represented by the formula (III-3).
- Ri2a represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms.
- Ri2b represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- Ri2c represents an alkyl group having 1 to 20 carbon atoms.
- R i1 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and further preferably a hydrogen atom.
- R i2a is preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms, and further preferably. Is a hydrogen atom.
- R i2b is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and further preferably a methyl group.
- R i2c is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and further preferably a methyl group.
- R i2 is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a group represented by the formulas (III-1) to (III-3), and more preferably a hydrogen atom and carbon.
- the polymer (2) has a structural unit in which R i2 is an alkyl group having 1 to 20 carbon atoms in the formula (II) and R i2 in the formula (II) is the formula (III-1). It is preferable to include one or more structural units selected from the group consisting of the structural units represented, and polystyrene or a styrene unit and a structural unit in which Ri2 is represented by the formula (III-1) in the formula (II). It is more preferable that the polymer contains the polymer. In another embodiment, the polymer (2) preferably contains a structural unit in which Ri2 is represented by the formula (III-2) in the formula (II), and more preferably contains a methyl methacrylate unit.
- the content of the polymer (2) in the insulating material is preferably 70% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight or more, particularly preferably 95% by weight or more, and usually 100% by weight. % Or less, and may be 100% by weight.
- the insulating material may contain only one type of the polymer (2), or may contain a combination of two or more types.
- the polymer (2) may contain any structural unit in addition to the structural unit represented by the formula (II).
- arbitrary building blocks include alkaziene units (eg, 1,3-butadiene units, isoprene units).
- the polymer (2) can be produced by a conventionally known production method. Further, as the polymer (2), a commercially available product can also be used.
- the insulating material is a material that dissolves in an amount of 0.1% by weight or more at 25 ° C. with respect to the solvent used in the composition of the present invention. More preferably, the insulating material is the polymer (2), which is a polymer that dissolves in an amount of 0.1% by weight or more at 25 ° C. with respect to the solvent used in the composition of the present invention.
- the weight average molecular weight (Mw) of the organic polymer that can be contained in the insulating material is not particularly limited, but is preferably 1,000,000 or less, more preferably 500,000 or less, and further, from the viewpoint of solubility in a solvent. It is preferably 200,000 or less.
- the insulating material according to the present embodiment are polystyrene-block-poly (ethylene-ran-butylene) -block-polystyrene (weight average molecular weight: 118,000 or less), polystyrene (weight average molecular weight: 35,000), polystyrene-block-.
- examples thereof include polyisoprene-block-polystyrene (number average molecular weight 1900) and poly (methyl methacrylate).
- the content of the insulating material in the composition is, for example, 0.5% by weight or more or 0.1% by weight or more, for example, 5% by weight or less or 1% by weight or less.
- the total weight of the p-type semiconductor material, the n-type semiconductor material, the insulating material, and the solvent in the composition is 100% by weight.
- the insulating material is dissolved in the composition, and it is more preferable that the insulating material is completely dissolved.
- the weight ratio of the insulating material to the p-type semiconductor material (insulating material / p-type semiconductor material) in the composition is, for example, 1/10 or more or 1/5 or more, for example, 1/3 or less or 1/2 or less. ..
- composition according to this embodiment contains a solvent.
- the composition may contain only one type of solvent, or may contain a combination of two or more types.
- the composition according to the present embodiment preferably contains the first solvent described below, and may optionally further contain a second solvent.
- the solvent may be selected in consideration of the solubility in the selected p-type semiconductor material and the n-type semiconductor material, and the characteristics (boiling point, etc.) corresponding to the drying conditions when forming the film.
- the first solvent is preferably an aromatic hydrocarbon (hereinafter, simply referred to as an aromatic hydrocarbon) or an alkyl halide solvent which may have a substituent (for example, an alkyl group or a halogen atom).
- the first solvent is preferably selected in consideration of the solubility of the selected p-type semiconductor material and n-type semiconductor material.
- aromatic hydrocarbon as the first solvent examples include toluene, xylene (eg, o-xylene, m-xylene, p-xylene), trimethylbenzene (eg, mesitylene, 1,2,4-trimethylbenzene). )), Butylbenzene (eg n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (eg 1-methylnaphthalene), tetralin, indan, chlorobenzene and dichlorobenzene (1,2-dichlorobenzene) ).
- xylene eg, o-xylene, m-xylene, p-xylene
- trimethylbenzene eg, mesitylene, 1,2,4-trimethylbenzene.
- Butylbenzene eg n-butylbenzene, sec-butylbenzene, tert-buty
- alkyl halide solvent examples include chloroform.
- the first solvent may be composed of only one kind of aromatic hydrocarbon or may be composed of two or more kinds of aromatic hydrocarbons.
- the first solvent is preferably composed of only one aromatic hydrocarbon.
- the first solvent is preferably toluene, o-xylene, m-xylene, p-xylene, mesitylene, pseudocumene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, tetraline, indane, chlorobenzene, etc. Includes one or more selected from the group consisting of o-dichlorobenzene and chloroform.
- the second solvent is preferably a solvent selected from the viewpoint of enhancing the solubility of the n-type semiconductor material.
- the second solvent include ketone solvents (eg, acetone, methyl ethyl ketone, cyclohexanone, acetophenone, propiophenone), ester solvents (eg, ethyl acetate, butyl acetate, phenyl acetate, ethyl cellsolve acetate, methyl benzoate, benzoic acid). Butylate, benzyl benzoate).
- the weight ratio of the first solvent to the second solvent determines the solubility of the p-type semiconductor material and the n-type semiconductor material. From the viewpoint of improvement, it is preferably in the range of 85/15 to 99/1.
- the total weight of the solvent contained in the composition is preferably 90% by weight or more from the viewpoint of further improving the solubility of the p-type semiconductor material and the n-type semiconductor material when the total weight of the composition is 100% by weight. , More preferably 92% by weight or more, still more preferably 95% by weight or more, and increase the concentration of the p-type semiconductor material and the n-type semiconductor material in the coating liquid to facilitate the formation of a layer having a certain thickness or more. From the viewpoint, it is preferably 99.9% by weight or less.
- the composition may further contain any third solvent in addition to the above-mentioned first solvent and any second solvent.
- any third solvent is preferably 5% by weight or less, more preferably 3% by weight or less, still more preferable. Is 1% by weight or less.
- a solvent having a boiling point higher than that of the second solvent is preferable.
- the composition according to the present embodiment may contain, in addition to the above-mentioned p-type semiconductor material, n-type semiconductor material, insulating material, and solvent, any component as long as the object and effect of the present invention are not impaired. good.
- optional components are UV absorbers, antioxidants, sensitizers to sensitize the ability to generate charge by absorbed light, and photostabilizers to increase stability from UV light. Can be mentioned.
- the total content of the optional components in the composition is preferably 10% by weight or less, more preferably 5% by weight or less, and usually 0% by weight or more.
- the total concentration of the p-type semiconductor material and the n-type semiconductor material in the composition can be any suitable concentration depending on the required thickness of the active layer.
- the total concentration of the p-type semiconductor material and the n-type semiconductor material is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 10% by weight or less, and more preferably 5% by weight.
- % Or less more preferably 0.01% by weight or more and 20% by weight or less, further preferably 0.01% by weight or more and 10% by weight or less, still more preferably 0.01% by weight or more and 5% by weight or less, particularly preferably. It is 0.1% by weight or more and 5% by weight or less.
- the weight ratio of the p-type semiconductor material to the n-type semiconductor material (p-type semiconductor material / n-type semiconductor material) in the composition is preferably 1/9 or more, more preferably 1/5 or more, still more preferably 1/3.
- the above is preferably 9/1 or less, more preferably 5/1 or less, still more preferably 3/1 or less.
- Total content ratio of p-type semiconductor material, n-type semiconductor material, and insulating material The total content ratio of the p-type semiconductor material, the n-type semiconductor material, and the insulating material in the composition can be appropriately set according to, for example, the type of coating method, the viscosity of the component used, and the like.
- the total content of the p-type semiconductor material, the n-type semiconductor material, and the insulating material in the composition is not particularly limited as long as they can be dissolved in the composition, but is preferably 1% by weight or more, more preferably 2. By weight% or more, more preferably 3% by weight or more, preferably 20% by weight or less, more preferably 10% by weight or less, still more preferably 7% by weight or less.
- the composition can be produced by a conventionally known method.
- the first solvent and the second solvent are mixed to prepare a mixed solvent, and the p-type semiconductor material, the n-type semiconductor material, and the mixed solvent are used as the mixed solvent.
- Method of adding insulating material, p-type semiconductor material and insulating material are added to the first solvent, n-type semiconductor material is added to the second solvent, and then the first solvent and the second solvent to which each material is added are added. It can be manufactured by a mixing method or the like.
- the solvent and the p-type semiconductor material, the n-type semiconductor material, and the insulating material may be heated to a temperature equal to or lower than the boiling point of the solvent and mixed.
- the obtained mixture may be filtered using a filter, and the obtained filtrate may be used as a composition.
- a filter for example, a filter formed of a fluororesin such as polytetrafluoroethylene (PTFE) can be used.
- composition can be suitably used as an ink for forming a film containing a p-type semiconductor material, an n-type semiconductor material, and an insulating material by a coating method.
- ink means a liquid material used in a coating method, and is not limited to a colored liquid material.
- coating method includes a method of forming a film (layer) using a liquid material, for example, a slot die coating method, a slit coating method, a knife coating method, a spin coating method, a casting method, and a microgravure coating method.
- the film according to the embodiment of the present invention includes a polymer (1) as a p-type semiconductor material, an n-type semiconductor material, and an insulating material.
- the film containing the polymer (1) as the p-type semiconductor material, the n-type semiconductor material, and the insulating material is also referred to as “film A”.
- Examples of the polymer (1) as a p-type semiconductor material and preferred examples, examples of n-type semiconductor materials and preferred examples, and examples of insulating materials and preferred examples are described in Item [1. Composition] is the same as the example described.
- the preferable range of the weight ratio (p-type semiconductor material / n-type semiconductor material) of the p-type semiconductor material to the n-type semiconductor material in the film according to the present embodiment may be the same as the preferable range of the weight ratio in the composition. can.
- the preferable range of the weight ratio of the insulating material to the p-type semiconductor material (insulating material / p-type semiconductor material) in the film according to the present embodiment can be the same as the preferable range of the weight ratio in the composition.
- the thickness of the film according to the present embodiment can be appropriately set according to the function of the target film.
- the thickness of the film according to the present embodiment is preferably 100 nm or more, more preferably 150 nm or more, further preferably 200 nm or more, preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, still more preferably 1 ⁇ m or less.
- the film according to this embodiment can be manufactured by any method.
- the film according to this embodiment can be produced by a method including the following steps.
- Step (1) A step of applying the composition to a coating target to form a coating film.
- Step (2) A step of drying the coating film. The steps (1) and (2) are usually performed in this order.
- the composition is a composition containing a polymer (1) as a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent.
- a polymer (1) as a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent.
- the composition the preferred composition already exemplified can be used.
- examples of objects to which the composition is applied include an electrode, an electron transport layer, and a hole transport layer.
- Any coating method can be used as a method for applying the composition to the coating target.
- the method of applying the composition to the coating target in the step (1) include the above-exemplified coating method, and the spin coating method is preferable because it is easy to obtain a coating film having a uniform thickness.
- Step (2) By drying the coating film, the solvent normally contained in the coating film is removed.
- methods for drying the coating film include a method of directly heating with a hot plate in an atmosphere of an inert gas such as nitrogen gas, a hot air drying method, an infrared heating drying method, a flash lamp annealing drying method, and a vacuum drying method. Drying methods such as the method and combinations thereof can be mentioned.
- the drying conditions such as the drying temperature and the drying treatment time can be set to any suitable conditions in consideration of the boiling point of the solvent contained in the composition, the thickness of the coating film, and the like.
- the film manufacturing method according to the present embodiment may include any step in addition to the steps (1) and (2).
- the photoelectric conversion element according to the embodiment of the present invention includes a first electrode, the film A, and a second electrode in this order.
- the film A can usually function as an active layer.
- the first electrode is an electrode that causes a positive charge to flow out to an external circuit
- the second electrode is an electrode that allows a positive charge to flow in from the external circuit.
- FIG. 1 is a diagram schematically showing a configuration example of a photoelectric conversion element.
- the photoelectric conversion element 10 is provided on the support substrate 11.
- the photoelectric conversion element 10 is attached to a first electrode 12 provided in contact with the support substrate 11, a hole transport layer 13 provided in contact with the first electrode 12, and a hole transport layer 13.
- the active layer 14 provided in contact with the active layer 14, the electron transport layer 15 provided in contact with the active layer 14, and the second electrode 16 provided in contact with the electron transport layer 15 are provided.
- the sealing member 17 is further provided so as to be in contact with the second electrode 16.
- the photoelectric conversion element is usually formed on a substrate (support substrate). Further, it may be further sealed by a substrate (sealing substrate). Usually, one of a pair of electrodes consisting of a first electrode and a second electrode is formed on the substrate.
- the material of the substrate is not particularly limited as long as it is a material that does not chemically change when forming a layer containing an organic compound.
- the substrate material examples include glass, plastic, polymer film, and silicon.
- the electrode on the opposite side of the electrode provided on the opaque substrate side is a transparent or translucent electrode. ..
- the photoelectric conversion element includes a first electrode and a second electrode, which are a pair of electrodes. It is preferable that at least one of the first electrode and the second electrode is a transparent or translucent electrode in order to allow light to enter.
- transparent or translucent electrode materials include conductive metal oxide films and translucent metal thin films. Specifically, indium oxide, zinc oxide, tin oxide, and conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), and NESA, which are composites thereof, gold, platinum, and silver. Copper is mentioned. As a transparent or translucent electrode material, ITO, IZO, and tin oxide are preferable. Further, as the electrode, a transparent conductive film using an organic compound such as polyaniline and its derivative, polythiophene and its derivative as a material may be used. The transparent or translucent electrode may be the first electrode or the second electrode.
- the other electrode may be an electrode having low light transmission.
- materials for electrodes having low light transmission include metals and conductive polymers.
- Specific examples of materials for electrodes with low light transmission include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, ittrium, indium, cerium, samarium, and europium.
- Metals such as rubidium and itterbium, and two or more alloys of these, or one or more of these metals, gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin.
- Examples include alloys with one or more metals selected from the group consisting of, graphite, graphite interlayer compounds, polyaniline and its derivatives, polythiophene and its derivatives.
- Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.
- the photoelectric conversion element of this embodiment has the film A as an active layer.
- the active layer which is the membrane A, according to the present embodiment has a bulk heterojunction type structure, and includes a polymer (1) as a p-type semiconductor material, an n-type semiconductor material, and an insulating material. Examples of the polymer (1) as a p-type semiconductor material and preferred examples, examples of n-type semiconductor materials and preferred examples, and examples of insulating materials and preferred examples are described in Item [1. Composition] is the same as the example described.
- the preferable range of the weight ratio (p-type semiconductor material / n-type semiconductor material) of the p-type semiconductor material to the n-type semiconductor material in the active layer can be the same as the preferable range of the weight ratio in the composition.
- the preferable range of the weight ratio of the insulating material to the p-type semiconductor material (insulating material / p-type semiconductor material) in the active layer can be the same as the preferable range of the weight ratio in the composition.
- the thickness of the active layer is not particularly limited.
- the thickness of the active layer can be arbitrarily set in consideration of the balance between the suppression of the dark current and the extraction of the generated photocurrent.
- the thickness of the active layer is preferably 100 nm or more, more preferably 150 nm or more, still more preferably 200 nm or more, particularly from the viewpoint of further reducing the dark current.
- the thickness of the active layer is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and further preferably 1 ⁇ m or less.
- the photoelectric conversion element of the present embodiment has, for example, a charge transport layer (electron transport layer, hole transport layer, electron injection layer, etc.) as a component for improving characteristics such as photoelectric conversion efficiency. It is preferable to have an intermediate layer (buffer layer) such as a hole injection layer).
- a charge transport layer electron transport layer, hole transport layer, electron injection layer, etc.
- an intermediate layer buffer layer such as a hole injection layer.
- Examples of materials used for the intermediate layer include metals such as calcium, inorganic oxide semiconductors such as molybdenum oxide and zinc oxide, and PEDOT (poly (3,4-ethylenedioxythiophene)) and PSS (poly (poly (3,4-ethylenedioxythiophene)). 4-styrene sulfonate)) and a mixture (PEDOT: PSS) can be mentioned.
- the photoelectric conversion element preferably includes a hole transport layer between the first electrode and the active layer.
- the hole transport layer has a function of transporting holes from the active layer to the electrode.
- the photoelectric conversion element may not include a hole transport layer.
- the hole transport layer provided in contact with the first electrode may be particularly referred to as a hole injection layer.
- the hole transport layer (hole injection layer) provided in contact with the first electrode has a function of promoting the injection of holes into the first electrode.
- the hole transport layer (hole injection layer) may be in contact with the active layer.
- the hole transport layer contains a hole transport material.
- hole-transporting materials include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing structural units having aromatic amine residues, CuSCN, CuI, NiO, tungsten oxide (WO 3 ) and molybdenum oxide. (MoO 3 ) can be mentioned.
- the intermediate layer can be formed by a conventionally known arbitrary suitable forming method.
- the intermediate layer can be formed by a coating method similar to the vacuum vapor deposition method or the active layer forming method.
- the intermediate layer is a hole transport layer and an electron transport layer
- the substrate support substrate
- the first electrode the hole transport layer
- the active layer the electron transport layer
- the second the substrate
- the photoelectric conversion element of the present embodiment preferably includes an electron transport layer as an intermediate layer between the second electrode and the active layer.
- the electron transport layer has a function of transporting electrons from the active layer to the second electrode.
- the electron transport layer may be in contact with the second electrode.
- the electron transport layer may be in contact with the active layer.
- the electron transport layer provided in contact with the second electrode may be particularly referred to as an electron injection layer.
- the electron transport layer (electron injection layer) provided in contact with the second electrode has a function of promoting the injection of electrons generated in the active layer into the second electrode.
- the electron transport layer contains an electron transport material.
- the electron transporting material include polyalkyleneimine and its derivatives, polymer compounds containing a fluorene structure, metals such as calcium, and metal oxides.
- polyalkyleneimines and derivatives thereof include alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, and octyleneimine, particularly having 2 to 8 carbon atoms.
- alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, and octyleneimine, particularly having 2 to 8 carbon atoms.
- examples thereof include polymers obtained by polymerizing one or more of 2 to 4 alkyleneimines by a conventional method, and polymers obtained by reacting them with various compounds to chemically modify them.
- polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE) are preferable.
- polymer compounds containing a fluorene structure examples include poly [(9,9-bis (3'-(N, N-dimethylamino) propyl) -2,7-fluorene) -ortho-2,7- (9). , 9'-Dioctylfluorene)] (PFN) and PFN-P2.
- metal oxides examples include zinc oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, titanium oxide and niobium oxide.
- a metal oxide containing zinc is preferable, and zinc oxide is particularly preferable.
- Examples of other electron-transporting materials include poly (4-vinylphenol) and perylenemidi.
- the photoelectric conversion element of the present embodiment further includes a sealing member and is a sealed body sealed by such a sealing member.
- a sealing member Any suitable conventionally known member can be used as the sealing member.
- the sealing member include a combination of a glass substrate which is a substrate (sealing substrate) and a sealing material (adhesive) such as a UV curable resin.
- the sealing member may be a sealing layer having a layer structure of one or more layers.
- Examples of the layer constituting the sealing layer include a gas barrier layer and a gas barrier film.
- the sealing layer is preferably formed of a material having a property of blocking water (water vapor barrier property) or a property of blocking oxygen (oxygen barrier property).
- suitable materials for the sealing layer include polyethylene trifluoride, polyethylene trifluoride chloride (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, ethylene-vinyl alcohol copolymer and the like.
- PCTFE polyethylene trifluoride
- PCTFE polyethylene trifluoride chloride
- polyimide polycarbonate
- polyethylene terephthalate polyethylene terephthalate
- alicyclic polyolefin ethylene-vinyl alcohol copolymer and the like.
- organic materials silicon oxide, silicon nitride, aluminum oxide, and inorganic materials such as diamond-like carbon.
- the sealing member is usually composed of a material that can withstand the heat treatment that can be carried out when the photoelectric conversion element is applied, for example, when it is incorporated into the device of the application example described later.
- the photoelectric conversion element of the present embodiment can be manufactured by any method.
- the photoelectric conversion element of the present embodiment can be manufactured by combining a forming method suitable for the material selected for forming the constituent elements.
- a photoelectric conversion having a structure in which a substrate (supporting substrate), a first electrode, a hole transport layer, a film A as an active layer, an electron transport layer, and a second electrode are in contact with each other in this order.
- a method of manufacturing the element will be described.
- a support substrate provided with the first electrode is prepared. Further, a substrate provided with a conductive thin film formed of the electrode material described above is obtained from the market, and if necessary, the conductive thin film is patterned to form the first electrode. A support substrate provided with the first electrode can be prepared.
- the method for forming the first electrode when the first electrode is formed on the support substrate is not particularly limited.
- the first electrode has a structure in which the material already described should be formed of the first electrode by any conventionally known suitable method such as a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and a coating method (a configuration in which the first electrode is formed. For example, it can be formed on a support substrate, an active layer, a hole transport layer).
- the method for manufacturing a photoelectric conversion element may include a step of forming a hole transport layer (hole injection layer) provided between the active layer and the first electrode.
- the method of forming the hole transport layer is not particularly limited. From the viewpoint of simplifying the step of forming the hole transport layer, it is preferable to form the hole transport layer by a conventionally known and arbitrary suitable coating method.
- the hole transport layer can be formed, for example, by a coating method using a coating liquid containing the material and solvent of the hole transport layer already described or a vacuum vapor deposition method.
- a film A as an active layer is formed on the hole transport layer.
- the film A can be formed by any suitable conventionally known forming step.
- the membrane A as an active layer can be produced by a coating method using the above composition.
- Membrane A as an active layer is [2. It can be formed by the same method as the method for producing a film described in [Membrane].
- the above composition containing the polymer (1) as the p-type semiconductor material, the n-type semiconductor material, the insulating material, and the solvent is applied onto the hole transport layer to form a coating film.
- the film A as an active layer can be formed by a step including a step of drying the coating film.
- the method for manufacturing a photoelectric conversion element of the present embodiment includes a step of forming an electron transport layer (electron injection layer) provided on the active layer.
- the method of forming the electron transport layer is not particularly limited. From the viewpoint of simplifying the process of forming the electron transport layer, it is preferable to form the electron transport layer by a conventionally known arbitrary suitable vacuum vapor deposition method.
- the method for forming the second electrode is not particularly limited.
- the material of the above-exemplified electrode is formed on the electron transport layer by any conventionally known suitable method such as a coating method, a vacuum vapor deposition method, a sputtering method, an ion plating method, and a plating method. be able to.
- the photoelectric conversion element of the present embodiment is manufactured.
- a conventionally known arbitrary suitable encapsulant (adhesive) and substrate (encapsulating substrate) are used.
- a sealing material such as a UV curable resin is applied onto the support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and then the sealing material is used to bond them without gaps before selection.
- Applications of the photoelectric conversion element of this embodiment include a photodetection element and a solar cell. More specifically, in the photoelectric conversion element of the present embodiment, a light current is passed by irradiating light from the transparent or translucent electrode side in a state where a voltage (reverse bias voltage) is applied between the electrodes. It can be operated as a photodetection element (optical sensor). It can also be used as an image sensor by integrating a plurality of photodetecting elements. As described above, the photoelectric conversion element of the present embodiment can be particularly suitably used as a photodetection element.
- the photoelectric conversion element of the present embodiment can generate photovoltaic power between the electrodes by being irradiated with light, and can be operated as a solar cell.
- a solar cell module can also be obtained by integrating a plurality of photoelectric conversion elements.
- the photoelectric conversion element according to the present embodiment is suitably applied as a photodetection element to a detection unit provided in various electronic devices such as a workstation, a personal computer, a personal digital assistant, an entrance / exit management system, a digital camera, and a medical device. can do.
- the photoelectric conversion element of the present embodiment includes, for example, an image detection unit (for example, an image sensor such as an X-ray sensor) for a solid-state image pickup device such as an X-ray image pickup device and a CMOS image sensor, and a fingerprint, which are included in the above-exemplified electronic device.
- a detection unit for example, a near-infrared sensor
- a biometric information authentication device that detects a predetermined feature of a part of a living body such as a detection unit, a face detection unit, a vein detection unit, and an iris detection unit, and an optical biosensor such as a pulse oximeter. It can be suitably applied to a detection unit or the like.
- the photoelectric conversion element of the present embodiment can be suitably applied as an image detection unit for a solid-state imaging device, and further to a Time-of-flight (TOF) type distance measuring device (TOF type distance measuring device).
- TOF Time-of-flight
- the distance is measured by receiving the reflected light reflected by the light source from the light source by the photoelectric conversion element. Specifically, the flight time until the irradiation light emitted from the light source is reflected by the measurement target and returned as the reflected light is detected, and the distance to the measurement target is obtained.
- the TOF type includes a direct TOF method and an indirect TOF method.
- the direct TOF method the difference between the time when the light is emitted from the light source and the time when the reflected light is received by the photoelectric conversion element is directly measured, and in the indirect TOF method, the change in the charge accumulation amount depending on the flight time is converted into the time change.
- the distance measurement principle used in the indirect TOF method to obtain the flight time by accumulating charge is a continuous wave (especially sinusoidal) modulation method in which the flight time is obtained from the phase of the emitted light from the light source and the reflected light reflected by the measurement target. And the pulse modulation method.
- an image detection unit for a solid-state image pickup device an image detection unit for an X-ray image pickup device, and a biometric authentication device (for example, a fingerprint authentication device or a vein).
- a biometric authentication device for example, a fingerprint authentication device or a vein.
- FIG. 2 is a diagram schematically showing a configuration example of an image detection unit for a solid-state image sensor.
- the image detection unit 1 comprises a CMOS transistor substrate 20, an interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20, and a photoelectric conversion according to an embodiment of the present invention provided on the interlayer insulating film 30. It is provided so as to penetrate the element 10 and the interlayer insulating film 30, and is provided so as to cover the interlayer wiring portion 32 that electrically connects the CMOS transistor substrate 20 and the photoelectric conversion element 10 and the photoelectric conversion element 10.
- the sealing layer 40 and the color filter 50 provided on the sealing layer 40 are provided.
- the CMOS transistor substrate 20 is provided with a conventionally known arbitrary suitable configuration in a mode according to the design.
- the CMOS transistor substrate 20 includes transistors, capacitors, etc. formed within the thickness of the substrate, and includes functional elements such as a CMOS transistor circuit (MOS transistor circuit) for realizing various functions.
- MOS transistor circuit CMOS transistor circuit
- Examples of the functional element include a floating diffusion, a reset transistor, an output transistor, and a selection transistor.
- CMOS transistor substrate 20 With such functional elements, wiring, etc., a signal readout circuit and the like are built in the CMOS transistor substrate 20.
- the interlayer insulating film 30 can be made of any conventionally known and arbitrarily suitable insulating material such as silicon oxide and an insulating resin.
- the interlayer wiring portion 32 can be made of, for example, any conventionally known suitable conductive material (wiring material) such as copper and tungsten.
- the interlayer wiring portion 32 may be, for example, an in-hole wiring formed at the same time as the formation of the wiring layer, or an embedded plug formed separately from the wiring layer.
- the sealing layer 40 is made of any conventionally known suitable material, provided that the permeation of harmful substances such as oxygen and water that may functionally deteriorate the photoelectric conversion element 10 can be prevented or suppressed. Can be done.
- the sealing layer 40 can have the same configuration as the sealing member 17 described above.
- a primary color filter that is made of any suitable material known conventionally and that corresponds to the design of the image detection unit 1 can be used.
- a complementary color filter that can be thinner than the primary color filter can also be used.
- Complementary color filters include, for example, three types (yellow, cyan, magenta), three types (yellow, cyan, transparent), three types (yellow, transparent, magenta), and three types (transparent, cyan, magenta). Color filters that combine types can be used. These can be arbitrarily arranged according to the design of the photoelectric conversion element 10 and the CMOS transistor substrate 20, provided that color image data can be generated.
- the light received by the photoelectric conversion element 10 via the color filter 50 is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10, and the light received signal outside the photoelectric conversion element 10 via the electrode, that is, an image pickup target. It is output as an electric signal corresponding to.
- the light receiving signal output from the photoelectric conversion element 10 is input to the CMOS transistor substrate 20 via the interlayer wiring unit 32, and is read out by the signal readout circuit built in the CMOS transistor substrate 20, which is not shown.
- Image information based on the imaging target is generated by signal processing by any suitable conventionally known functional unit.
- FIG. 3 is a diagram schematically showing a configuration example of a fingerprint detection unit integrally configured with a display device.
- the display device 2 of the mobile information terminal includes a fingerprint detection unit 100 including the photoelectric conversion element 10 according to the embodiment of the present invention as a main component, and a display panel provided on the fingerprint detection unit 100 and displaying a predetermined image. It is equipped with a unit 200.
- the fingerprint detection unit 100 is provided in an area corresponding to the display area 200a of the display panel unit 200.
- the display panel unit 200 is integrally laminated above the fingerprint detection unit 100.
- the fingerprint detection unit 100 may be provided corresponding to only the part of the display area 200a.
- the fingerprint detection unit 100 includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs an essential function.
- the fingerprint detection unit 100 desired any suitable conventionally known member such as a protective film (projection film), a support substrate, a sealing substrate, a sealing member, a barrier film, a bandpass filter, and an infrared cut film (not shown). It can be provided in a manner corresponding to the design so that the characteristics can be obtained.
- the configuration of the image detection unit already described can also be adopted.
- the photoelectric conversion element 10 may be included in the display area 200a in any manner.
- a plurality of photoelectric conversion elements 10 may be arranged in a matrix.
- the photoelectric conversion element 10 is provided on the support substrate 11, and the support substrate 11 is provided with electrodes (first electrode or second electrode) in a matrix, for example.
- the light received by the photoelectric conversion element 10 is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10, and the light received signal outside the photoelectric conversion element 10 via the electrode, that is, electricity corresponding to the captured fingerprint. It is output as a signal.
- the display panel unit 200 is configured as an organic electroluminescence display panel (organic EL display panel) including a touch sensor panel.
- the display panel unit 200 may be configured by, for example, instead of the organic EL display panel, a display panel having an arbitrary suitable conventionally known configuration such as a liquid crystal display panel including a light source such as a backlight.
- the display panel unit 200 is provided on the fingerprint detection unit 100 already described.
- the display panel unit 200 includes an organic electroluminescence element (organic EL element) 220 as a functional unit that performs an essential function.
- the display panel unit 200 is further optionally suitable such as a substrate such as a conventionally known glass substrate (support substrate 210 or a sealing substrate 240), a sealing member, a barrier film, a polarizing plate such as a circular polarizing plate, and a touch sensor panel 230.
- Suitable conventionally known members may be provided in a manner corresponding to the desired characteristics.
- the organic EL element 220 is used as a light source for pixels in the display region 200a and also as a light source for fingerprint imaging in the fingerprint detection unit 100.
- the fingerprint detection unit 100 detects a fingerprint using the light emitted from the organic EL element 220 of the display panel unit 200. Specifically, the light emitted from the organic EL element 220 passes through a component existing between the organic EL element 220 and the photoelectric conversion element 10 of the fingerprint detection unit 100, and is displayed within the display area 200a. It is reflected by the skin (finger surface) of the fingertips of the fingers placed so as to be in contact with the surface of the panel portion 200. At least a part of the light reflected by the finger surface passes through the components existing between them and is received by the photoelectric conversion element 10, and is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10. Then, image information about the fingerprint on the finger surface is constructed from the converted electric signal.
- the portable information terminal provided with the display device 2 performs fingerprint authentication by comparing the obtained image information with the fingerprint data for fingerprint authentication recorded in advance by an arbitrary suitable step known conventionally.
- FIG. 4 is a diagram schematically showing a configuration example of an image detection unit for an X-ray image pickup apparatus.
- the image detection unit 1 for the X-ray image pickup apparatus is provided on the CMOS transistor substrate 20, the interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20, and the interlayer insulating film 30 of the present invention.
- the photoelectric conversion element 10 according to the embodiment, the interlayer wiring portion 32 which is provided so as to penetrate the interlayer insulating film 30 and electrically connects the CMOS transistor substrate 20 and the photoelectric conversion element 10, and the photoelectric conversion element 10
- a sealing layer 40 provided so as to cover the sealing layer 40, a reflecting layer 44 provided so as to cover the scintillator 42 and the scintillator 42 provided on the sealing layer 40, and a reflective layer 44 provided so as to cover the reflective layer 44. It is provided with a protective layer 46 that is provided.
- the CMOS transistor substrate 20 is provided with a conventionally known arbitrary suitable configuration in a mode according to the design.
- the CMOS transistor substrate 20 includes transistors, capacitors, etc. formed within the thickness of the substrate, and includes functional elements such as a CMOS transistor circuit (MOS transistor circuit) for realizing various functions.
- MOS transistor circuit CMOS transistor circuit
- Examples of the functional element include a floating diffusion, a reset transistor, an output transistor, and a selection transistor.
- CMOS transistor substrate 20 With such functional elements, wiring, etc., a signal readout circuit and the like are built in the CMOS transistor substrate 20.
- the interlayer insulating film 30 can be made of any conventionally known and arbitrarily suitable insulating material such as silicon oxide and an insulating resin.
- the interlayer wiring portion 32 can be made of, for example, any conventionally known suitable conductive material (wiring material) such as copper and tungsten.
- the interlayer wiring portion 32 may be, for example, an in-hole wiring formed at the same time as the formation of the wiring layer, or an embedded plug formed separately from the wiring layer.
- the sealing layer 40 is made of any conventionally known suitable material, provided that the permeation of harmful substances such as oxygen and water that may functionally deteriorate the photoelectric conversion element 10 can be prevented or suppressed. Can be done.
- the sealing layer 40 can have the same configuration as the sealing member 17 described above.
- the scintillator 42 can be made of any conventionally known and arbitrarily suitable material corresponding to the design of the image detection unit 1 for the X-ray image pickup apparatus.
- suitable materials for the scintillator 42 are inorganic crystals of inorganic materials such as CsI (cesium iodide), NaI (sodium iodide), ZnS (zinc sulfide), GOS (gadrinium acid sulfide), and GSO (gadrinium silicate).
- Organic crystals of organic materials such as anthracene, naphthalene, and stilben, organic liquids in which organic materials such as diphenyloxazole (PPO) and terphenyl (TP) are dissolved in organic solvents such as toluene, xylene, and dioxane, and xenone and helium. Gas, plastic, etc. can be used.
- the above components correspond to the design of the photoelectric conversion element 10 and the CMOS transistor substrate 20 on the condition that the X-rays incident by the scintillator 42 can be converted into light having a wavelength centered on the visible region to generate image data. Any suitable arrangement can be made.
- the reflective layer 44 reflects the light converted by the scintillator 42.
- the reflective layer 44 can reduce the loss of converted light and increase the detection sensitivity. Further, the reflective layer 44 can also block light directly incident from the outside.
- the protective layer 46 can be made of any suitable material known conventionally, provided that the permeation of harmful substances such as oxygen and water that may functionally deteriorate the scintillator 42 can be prevented or suppressed.
- the scintillator 42 When radiation energy such as X-rays and ⁇ -rays is incident on the scintillator 42, the scintillator 42 absorbs the radiation energy and converts it into light (fluorescence) having a wavelength in the ultraviolet to infrared region centered on the visible region. Then, the light converted by the scintillator 42 is received by the photoelectric conversion element 10.
- the light received by the photoelectric conversion element 10 via the scintillator 42 is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10, and the light received signal is transmitted to the outside of the photoelectric conversion element 10 via the electrode. That is, it is output as an electric signal corresponding to the image pickup target.
- the radiation energy (X-ray) to be detected may be incident from either the scintillator 42 side or the photoelectric conversion element 10 side.
- the light receiving signal output from the photoelectric conversion element 10 is input to the CMOS transistor substrate 20 via the interlayer wiring unit 32, and is read out by the signal readout circuit built in the CMOS transistor substrate 20, which is not shown.
- Image information based on the imaging target is generated by signal processing by any suitable conventionally known functional unit.
- FIG. 5 is a diagram schematically showing a configuration example of a vein detection unit for a vein authentication device.
- the vein detection unit 300 for the finger vein recognition device includes a cover unit 306 that defines an insertion unit 310 into which a finger (eg, one or more fingertips, fingers and palm) to be measured at the time of measurement is inserted, and a cover.
- a glass substrate 302 that is arranged so as to face each other with the substrate 11 and the support substrate 11 and the photoelectric conversion element 10 interposed therebetween, separated from the cover portion 306 at a predetermined distance, and defines the insertion portion 306 together with the cover portion 306. It is composed of.
- the light source unit 304 shows a transmission type photographing method in which the light source unit 304 is integrally configured with the cover unit 306 so as to be separated from the photoelectric conversion element 10 with the measurement target interposed therebetween.
- the light source unit 304 does not necessarily have to be located on the cover unit 306 side.
- the light from the light source unit 304 can be efficiently irradiated to the measurement target, for example, a reflection type photographing method in which the measurement target is irradiated from the photoelectric conversion element 10 side may be used.
- the vein detection unit 300 includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs an essential function.
- the vein detection unit 300 is an optional conventionally known member such as a protective film (projection film), a sealing member, a barrier film, a bandpass filter, a near-infrared transmission filter, a visible light cut film, a finger rest guide, etc. (not shown). Can be provided in a manner corresponding to the design so as to obtain the desired characteristics.
- the configuration of the image detection unit 1 described above can also be adopted for the vein detection unit 300.
- the photoelectric conversion element 10 can be included in any embodiment.
- a plurality of photoelectric conversion elements 10 may be arranged in a matrix.
- the photoelectric conversion element 10 is provided on the support substrate 11, and the support substrate 11 is provided with electrodes (first electrode or second electrode) in a matrix, for example.
- the light received by the photoelectric conversion element 10 is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10, and the light received signal outside the photoelectric conversion element 10 via the electrode, that is, the electricity corresponding to the imaged vein. It is output as a signal.
- the measurement target may or may not be in contact with the glass substrate 302 on the photoelectric conversion element 10 side.
- the vein detection unit 300 detects the vein pattern to be measured by using the light emitted from the light source unit 304. Specifically, the light radiated from the light source unit 304 passes through the measurement target and is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10. Then, the image information of the vein pattern to be measured is constructed from the converted electrical signal.
- vein recognition is performed by comparing the obtained image information with the vein data for vein recognition recorded in advance by an arbitrary suitable step known conventionally.
- FIG. 6 is a diagram schematically showing a configuration example of an image detection unit for an indirect type TOF type distance measuring device.
- the image detection unit 400 for a TOF type distance measuring device is provided on the CMOS transistor substrate 20, the interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20, and the interlayer insulating film 30 of the present invention. It is provided so as to cover the photoelectric conversion element 10 according to the embodiment, two floating diffusion layers 402 arranged apart from each other so as to sandwich the photoelectric conversion element 10, and the photoelectric conversion element 10 and the floating diffusion layer 402. It includes an insulating layer 40 and two photogates 404 provided on the insulating layer 40 and arranged apart from each other.
- CMOS transistor substrate 20 and the floating diffusion layer 402 are electrically connected by an interlayer wiring portion 32 provided so as to penetrate the interlayer insulating film 30.
- the interlayer insulating film 30 can be made of any conventionally known and arbitrarily suitable insulating material such as silicon oxide and an insulating resin.
- the interlayer wiring portion 32 can be made of, for example, any conventionally known suitable conductive material (wiring material) such as copper and tungsten.
- the interlayer wiring portion 32 may be, for example, an in-hole wiring formed at the same time as the formation of the wiring layer, or an embedded plug formed separately from the wiring layer.
- the insulating layer 40 can have any conventionally known and arbitrarily suitable configuration such as a field oxide film composed of silicon oxide.
- the photogate 404 can be made of any conventionally known suitable material such as polysilicon.
- the image detection unit 400 for a TOF type distance measuring device includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs an essential function.
- the image detection unit 400 for a TOF type distance measuring device is any suitable conventional image detection unit 400 such as a protective film (projection film), a support substrate, a sealing substrate, a sealing member, a barrier film, a bandpass filter, and an infrared cut film (not shown).
- a known member may be provided in a manner corresponding to a design such that a desired characteristic can be obtained.
- Two photogates 404 are provided between the photoelectric conversion element 10 and the floating diffusion layer 402, and by alternately applying pulses, the signal charges generated by the photoelectric conversion element 10 are transferred to the two floating diffusion layers 402. It is transferred to either, and the charge is accumulated in the floating diffusion layer 402.
- the optical pulse arrives so as to spread evenly with respect to the timing of opening the two photo gates 404, the amount of electric charge accumulated in the two floating diffusion layers 402 becomes equal.
- the optical pulse arrives at the other photogate 404 with a delay with respect to the timing at which the optical pulse arrives at one photogate 404, there is a difference in the amount of charge accumulated in the two floating diffusion layers 402.
- the amount of light received by the photoelectric conversion element 10 is converted into an electric signal as the difference between the amounts of electric charges stored in the two floating diffusion layers 402, and the received signal outside the photoelectric conversion element 10, that is, the electricity corresponding to the measurement target. It is output as a signal.
- the light receiving signal output from the floating diffusion layer 402 is input to the CMOS transistor substrate 20 via the interlayer wiring unit 32, and is read out by the signal readout circuit built in the CMOS transistor substrate 20, which is not shown.
- signal processing by any suitable conventionally known functional unit, distance information based on the measurement target is generated.
- the organic photoelectric conversion element of the present embodiment may have a photodetection function capable of converting the irradiated light into an electric signal according to the amount of received light and outputting it to an external circuit via an electrode. Therefore, the photodetection element according to the embodiment of the present invention may have a photodetection function by including the organic photoelectric conversion element.
- the photodetection element of the present embodiment may be the organic photoelectric conversion element itself, or may include a functional element for voltage control or the like in addition to the organic photoelectric conversion element.
- p-type semiconductor material electron-donating compound
- n-type semiconductor material electron-accepting compound
- insulating material compound not involved in the photoelectric conversion process
- P-type semiconductor material The following polymers P-1 to P-4, which are polymer compounds, were used as the p-type semiconductor material.
- the polymer compound (polymer) P-1 which is a p-type semiconductor material, was synthesized and used with reference to the method described in International Publication No. 2013/051676.
- the polymer compound (polymer) P-2 which is a p-type semiconductor material, was synthesized and used with reference to the method described in International Publication No. 2011/052709.
- As the polymer compound (polymer) P-3 which is a p-type semiconductor material, PDTSTPD (trade name, manufactured by 1-material) was obtained from the market and used.
- PBDTTPD trade name, manufactured by 1-material
- N-type semiconductor material The following compounds N-1 to N-2 were used as the n-type semiconductor material.
- compound N-1 which is an n-type semiconductor material
- Coi8DFIC trade name, manufactured by 1-material
- E100 trade name, manufactured by Frontier Carbon Co., Ltd.
- compound Z-1 which is an insulating material
- Polystyrene-block-poly (ethylene-ran-butyrene) -block-polystyrene weight average molecular weight Mw 118000 or less, manufactured by Aldrich
- the compound Z-2 was obtained from the market and used Polystyrene-block-polyisoprene-block-polystyrene (number average molecular weight Mn 1900, manufactured by Aldrich).
- solubility of insulating material in solvent was evaluated as follows. Tetralin was used as the first solvent, butyl benzoate was used as the second solvent, and the weight ratio of the first solvent to the second solvent was 97: 3, and a mixed solvent was prepared. To 99 parts by weight of the mixed solvent, 1 part by weight of the compound Z-1 or Z-2 as an insulating material was added, and the mixture was stirred at 60 ° C. for 1 hour. After cooling to 25 ° C., the mixture after stirring was visually observed to confirm whether or not the insulating material remained undissolved. When there was no undissolved residue of the insulating material, the solubility in the mixed solvent was regarded as "good".
- the solubility in tetralin was also evaluated in the same manner as the evaluation of the solubility in the mixed solvent except that the mixed solvent was changed to the tetralin single solvent.
- the evaluation results are shown in the table below. It was found that the insulating materials Z-1 to Z-2 are materials that are dissolved in the mixed solvent or tetralin at 25 ° C. in an amount of 0.1% by weight or more.
- a composition as an ink was prepared using compound Z-1 or Z-2 as an insulating material.
- the polymer compound (polymer) P-1 which is a p-type semiconductor material has a concentration of 1% by weight based on the total weight of the ink
- the compound N-1 which is an n-type semiconductor material was added so as to have a concentration of 1% by weight based on the total weight of the ink
- compound Z-1 as an insulating material was added so as to have a concentration of 0.5% by weight based on the total weight of the ink.
- the mixture was stirred at 60 ° C. for 8 hours to obtain a mixed solution.
- the obtained mixed solution was filtered using a filter to obtain ink I-1.
- Preparation Example 2 Preparation of Ink I-2 ⁇ A tetralin solvent was used instead of the mixed solvent. -Compound N-2, which is an n-type semiconductor material, was used instead of compound N-1, and compound N-2 was added to the tetralin solvent so as to have a concentration of 2% by weight based on the total weight of the ink. -Compound Z-2, which is an insulating material, was used instead of Compound Z-1, and Compound Z-2 was added to the tetralin solvent so as to have a concentration of 1% by weight based on the total weight of the ink. Ink I-2 was obtained by operating in the same manner as in Preparation Example 1 except for the above items.
- Preparation Example 3 Preparation of Ink I-3 ⁇ A tetralin solvent was used instead of the mixed solvent. -A polymer compound (polymer) P-2, which is a p-type semiconductor material, was used instead of the polymer P-1. -Compound N-2, which is an n-type semiconductor material, was used instead of compound N-1, and compound N-2 was added to the tetralin solvent so as to have a concentration of 2% by weight based on the total weight of the ink. -Compound Z-2 was added to the tetralin solvent so as to have a concentration of 1% by weight based on the total weight of the ink. Ink I-3 was obtained by operating in the same manner as in Preparation Example 1 except for the above items.
- a glass substrate having a thickness of 50 nm and formed into a plurality of linear shapes (hereinafter referred to as stripes) in which a thin film of ITO (first electrode) is arranged so as to be separated from each other in parallel is prepared.
- the glass substrate was subjected to ozone UV treatment as a surface treatment.
- a coating film of Ink I-1 was formed on an ITO thin film by a spin coating method, and then heat-treated for 10 minutes using a hot plate heated to 100 ° C. under a nitrogen gas atmosphere to dry the active layer. 1 was formed.
- the thickness of the formed active layer was about 500 nm.
- a calcium (Ca) layer was formed on the formed active layer 1 with a thickness of about 5 nm to form an electron transport layer.
- a metal mask was used when forming the Ca layer so that the striped ITO thin film intersects with the Ca layer.
- a silver (Ag) layer was formed on the formed electron transport layer to a thickness of about 60 nm to form a second electrode.
- a metal mask was used when forming the Ag layer so that the striped ITO thin film intersects with the Ag layer.
- the unit of the portion where the thin film of ITO and the Ca layer and the Ag layer overlap when viewed from the thickness direction is a pixel, and 6 pixels are formed on one substrate.
- the effective area of the pixel is the area of the portion where the ITO thin film and the Ca layer and the Ag layer overlap each other when viewed from the thickness direction.
- the photoelectric conversion element was manufactured on a glass substrate by the above steps.
- the obtained structure was used as sample 1.
- a UV curable sealant as a sealing material was applied onto a glass substrate as a support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and the glass substrate as a sealing substrate was bonded. .. Next, this was irradiated with UV light, and the photoelectric conversion element was sealed in the gap between the support substrate and the sealing substrate. As a result, a sealed body of the photoelectric conversion element was obtained.
- the planar shape of the photoelectric conversion element sealed in the gap between the support substrate and the sealing substrate when viewed from the thickness direction was a square of 2 mm ⁇ 2 mm.
- the dark current values of the other 5 pixels are all within 10 times the lowest value of the dark current at a voltage of -8V among the 6 pixels in one substrate, the dark current will vary. The degree was evaluated as “Good”. On the other hand, if the dark current value exceeds 10 times the lowest value among the other 5 pixels, the degree of variation in the dark current is evaluated as "bad".
- Table 3 shows the evaluation results of the variation in dark current of Example 1.
- Example 2 (1) Manufacture of photoelectric conversion element and its encapsulant The photoelectric conversion element and its encapsulant were manufactured as follows.
- a glass substrate having an ITO thin film (second electrode) formed in stripes with a thickness of 50 nm was prepared by a sputtering method, and the glass substrate was subjected to ozone UV treatment as a surface treatment.
- PEIE polyethyleneimine ethoxylate
- Aldrich trade name polyethyleneimine, 80% ethoxylated solution, weight average molecular weight 110,000
- ultrapure water 1000 times was applied for forming an electron transport layer. It was used as a liquid and was applied onto an ITO thin film of a glass substrate treated with ozone UV by a spin coating method to form a coating film.
- the glass substrate on which the coating film was formed was heat-treated at 100 ° C. for 10 minutes using a hot plate to cure the formed coating film, whereby an electron transport layer was placed on the ITO thin film, which is the second electrode.
- PEIE polyethyleneimine ethoxylate
- the ink (I-2) was formed into a coating film on an ITO thin film by a spin coating method, and then heat-treated for 10 minutes using a hot plate heated to 100 ° C. in a nitrogen gas atmosphere to dry it. ,
- the active layer 2 was formed.
- the thickness of the formed active layer was about 500 nm.
- MoO 3 molybdenum oxide
- a metal mask was used when forming the MoO 3 layer so that the striped ITO thin film intersects with the MoO 3 layer.
- a silver (Ag) layer was formed with a thickness of about 60 nm on the formed hole transport layer to serve as the first electrode.
- a metal mask was used when forming the Ag layer so that the striped ITO thin film intersects with the Ag layer.
- the unit of the portion where the ITO thin film and the MoO 3 layer and the Ag layer overlap when viewed from the thickness direction is a pixel, and 6 pixels are formed on one substrate.
- the effective area of the pixel is the area of the portion where the ITO thin film, the MoO 3 layer, and the Ag layer overlap each other when viewed from the thickness direction.
- the photoelectric conversion element was manufactured on a glass substrate by the above steps.
- the obtained structure was used as sample 2.
- a UV curable sealant as a sealing material was applied onto a glass substrate as a support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and the glass substrate as a sealing substrate was bonded. .. Next, this was irradiated with UV light, and the photoelectric conversion element was sealed in the gap between the support substrate and the sealing substrate. As a result, a sealed body of the photoelectric conversion element was obtained.
- the planar shape of the photoelectric conversion element sealed in the gap between the support substrate and the sealing substrate when viewed from the thickness direction was a square of 2 mm ⁇ 2 mm.
- Example 3 An ink (I-3) was used instead of the ink (I-2), and the rotation speed in the spin coating method was adjusted so that a film thickness of 500 nm could be obtained to obtain the active layer 3. Except for this, a sealed body of the photoelectric conversion element was manufactured in the same manner as in Example 2 described above, and the variation in dark current was evaluated. The evaluation results are shown in Table 3.
- the compositions containing the polymer represented by the formula (I) as the p-type semiconductor material, the n-type semiconductor material, the insulating material, and the solvent (inks (I-1) to (I)).
- the elements (samples 1 to 3) according to Examples 1 to 3 in which the active layer was formed from -3)) have good evaluation results of variations in dark current.
- Comparative Examples 1 and 2 in which the active layer was formed from the composition (inks (C-1) to (C-2)) containing no polymer represented by the formula (I) as the p-type semiconductor material.
- Such elements (samples 4 to 5) had poor evaluation results of variations in dark current.
- the inks (C-1) and (C-2) according to Comparative Examples 1 and 2 are the insulating material Z-2, similarly to the inks (I-2) and (I-3) according to Examples 2 and 3. including.
- Comparative Examples 1 and 2 since the evaluation result of the variation in dark current is poor, some kind of mutual interaction between the polymer represented by the formula (I) as the p-type semiconductor material and the insulating material. It is inferred that the action is occurring. It is presumed that such an interaction affects the dissolution state of each component, the process of drying the active layer, and the like, which in turn affects the film thickness distribution of the active layer.
- the above inference does not limit the present invention.
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Abstract
The present invention addresses the problem of providing a composition with which it is possible to produce an organic photoelectric conversion element having little variation in characteristics. The present invention is a composition including a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent, wherein the p-type semiconductor material includes a polymer including a structural unit represented by formula (I). (In formula (I), Ar1 and Ar2 each independently represent a trivalent aromatic heterocyclic group that may have a substituent. Z represents a group represented by formulas (Z-1) to (Z-4). (In formulas (Z-1) to (Z-4), R represents a hydrogen atom or the like, and the two Rs in each of formulas (Z-1) to (Z-4) may be the same or different.))
Description
本発明は、組成物、膜、有機光電変換素子、及び光検出素子に関する。
The present invention relates to a composition, a film, an organic photoelectric conversion element, and a photodetection element.
有機膜を含む光電変換素子は、例えば、省エネルギー、二酸化炭素の排出量の低減の観点から極めて有用な発電デバイスとして、あるいは近赤外線に対する高感度な光センサーの光検出素子として、注目されている。
Photoelectric conversion elements containing organic films are attracting attention, for example, as extremely useful power generation devices from the viewpoint of energy saving and reduction of carbon dioxide emissions, or as photodetectors of highly sensitive optical sensors for near infrared rays.
有機光電変換素子の活性層を形成するための組成物として、p型半導体材料と、n型半導体材料であるフラーレン化合物と、所定の添加剤とを含有する組成物が知られている(特許文献1)。有機電子デバイスの製造における、活性層の塗布製膜工程に適した粘度物性の組成物を得る手段として、組成物に半導体材料以外のポリマーを添加することが有効であると開示されている。
As a composition for forming an active layer of an organic photoelectric conversion element, a composition containing a p-type semiconductor material, a fullerene compound which is an n-type semiconductor material, and a predetermined additive is known (Patent Document). 1). It is disclosed that it is effective to add a polymer other than a semiconductor material to the composition as a means for obtaining a composition having a viscous physical characteristic suitable for the coating film forming step of the active layer in the production of an organic electronic device.
一方、光電変換素子を含む光センサーの製造においては、通常、一枚の基板上に、パターン状の電極、活性層等が積層されて、一枚の基板上に複数の光電変換素子が配置された構造を有するデバイスが使われる。ここで活性層には、センサー性能においてノイズとなる暗電流を抑制するために、ある程度の厚さと、素子ごとの特性にバラつきが生じないように、膜厚の均一性とが求められる。膜厚の均一な活性層を簡便に製造する方法として、スピンコート法が用いられることが多い。
発明者らは、特許文献1を参考に添加剤を含む組成物を用い、スピンコート法により活性層の製膜を試みた。その結果、所望とする均一で厚い活性層が得られたが、デバイスに暗電流が異常に高い不良素子が多く含まれ、デバイスに含まれる素子間で、暗電流特性に大きなばらつきが生じていることが分かった。 On the other hand, in the manufacture of an optical sensor including a photoelectric conversion element, a patterned electrode, an active layer, etc. are usually laminated on one substrate, and a plurality of photoelectric conversion elements are arranged on one substrate. A device with a similar structure is used. Here, the active layer is required to have a certain thickness in order to suppress a dark current that causes noise in the sensor performance, and to have a uniform film thickness so that the characteristics of each element do not vary. The spin coating method is often used as a method for easily producing an active layer having a uniform film thickness.
The inventors attempted to form an active layer by a spin coating method using a composition containing an additive with reference toPatent Document 1. As a result, a desired uniform and thick active layer was obtained, but the device contained many defective elements having an abnormally high dark current, and the dark current characteristics varied greatly among the elements contained in the device. It turned out.
発明者らは、特許文献1を参考に添加剤を含む組成物を用い、スピンコート法により活性層の製膜を試みた。その結果、所望とする均一で厚い活性層が得られたが、デバイスに暗電流が異常に高い不良素子が多く含まれ、デバイスに含まれる素子間で、暗電流特性に大きなばらつきが生じていることが分かった。 On the other hand, in the manufacture of an optical sensor including a photoelectric conversion element, a patterned electrode, an active layer, etc. are usually laminated on one substrate, and a plurality of photoelectric conversion elements are arranged on one substrate. A device with a similar structure is used. Here, the active layer is required to have a certain thickness in order to suppress a dark current that causes noise in the sensor performance, and to have a uniform film thickness so that the characteristics of each element do not vary. The spin coating method is often used as a method for easily producing an active layer having a uniform film thickness.
The inventors attempted to form an active layer by a spin coating method using a composition containing an additive with reference to
したがって、暗電流特性のばらつきの小さい有機光電変換素子を製造しうる、組成物;当該組成物から製造されうる膜;当該膜を含む有機光電変換素子;当該有機光電変換素子を含む光検出素子が求められる。
Therefore, a composition capable of producing an organic photoelectric conversion element having a small variation in dark current characteristics; a film capable of being produced from the composition; an organic photoelectric conversion element containing the film; and a photodetection element including the organic photoelectric conversion element. Desired.
本発明者らは、前記課題を解決すべく鋭意検討した結果、特定のp型半導体材料と、絶縁材料とを組み合わせて含む組成物を用いて活性層を形成することで、前記課題を解決できることを見出し、本発明を完成した。すなわち、本発明は、以下を提供する。
As a result of diligent studies to solve the above-mentioned problems, the present inventors can solve the above-mentioned problems by forming an active layer using a composition containing a specific p-type semiconductor material and an insulating material in combination. And completed the present invention. That is, the present invention provides the following.
[1] p型半導体材料と、n型半導体材料と、絶縁材料と、溶媒とを含む組成物であって、
前記p型半導体材料が、下記式(I)で表される構成単位を含む重合体を含む、組成物。 [1] A composition containing a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent.
A composition in which the p-type semiconductor material contains a polymer containing a structural unit represented by the following formula (I).
前記p型半導体材料が、下記式(I)で表される構成単位を含む重合体を含む、組成物。 [1] A composition containing a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent.
A composition in which the p-type semiconductor material contains a polymer containing a structural unit represented by the following formula (I).
Ar1及びAr2は、それぞれ独立して、置換基を有していてもよい3価の芳香族複素環基を表す。
Zは、下記式(Z-1)~式(Z-4)で表される基を表す。
Ar 1 and Ar 2 each independently represent a trivalent aromatic heterocyclic group which may have a substituent.
Z represents a group represented by the following formulas (Z-1) to (Z-4).
Rは、
水素原子、
ハロゲン原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアルケニル基、
置換基を有していてもよいシクロアルケニル基、
置換基を有していてもよいアルキニル基、
置換基を有していてもよいシクロアルキニル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいシクロアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、
置換基を有していてもよいアルキルチオ基、
置換基を有していてもよいシクロアルキルチオ基、
置換基を有していてもよいアリールチオ基、
置換基を有していてもよい1価の複素環基、
置換基を有していてもよい置換アミノ基、
置換基を有していてもよいイミン残基、
置換基を有していてもよいアミド基、
置換基を有していてもよい酸イミド基、
置換基を有していてもよい置換オキシカルボニル基、
シアノ基、
ニトロ基、
-C(=O)-Raで表される基、又は
-SO2-Rbで表される基を表し、
Ra及びRbは、それぞれ独立して、
水素原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいシクロアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、又は
置換基を有していてもよい1価の複素環基を表す。
式(Z-1)~式(Z-4)中、2つあるRは同一であっても異なっていてもよい。))
[2] 前記絶縁材料が、前記溶媒に25℃で0.1重量%以上溶解する材料である、[1]に記載の組成物。
[3] 前記絶縁材料が、下記式(II)で表される構成単位を含む重合体を含む、[1]又は[2]に記載の組成物。
R is
Hydrogen atom,
Halogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
An alkenyl group which may have a substituent,
Cycloalkenyl groups, which may have substituents,
An alkynyl group, which may have a substituent,
A cycloalkynyl group which may have a substituent,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Aryloxy groups, which may have substituents,
Alkylthio groups, which may have substituents,
Cycloalkylthio groups, which may have substituents,
An arylthio group, which may have a substituent,
A monovalent heterocyclic group which may have a substituent,
Substituted amino groups, which may have substituents,
Imine residues, which may have substituents,
An amide group which may have a substituent,
An acidimide group, which may have a substituent,
Substituted oxycarbonyl group, which may have a substituent,
Cyano group,
Nitro group,
Represents a group represented by -C (= O) -R a or a group represented by -SO 2 -R b .
R a and R b are independent of each other.
Hydrogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Represents an aryloxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent.
In the formulas (Z-1) to (Z-4), the two Rs may be the same or different. )))
[2] The composition according to [1], wherein the insulating material is a material that dissolves in the solvent at 25 ° C. in an amount of 0.1% by weight or more.
[3] The composition according to [1] or [2], wherein the insulating material contains a polymer containing a structural unit represented by the following formula (II).
Ri1は、水素原子、ハロゲン原子、又は炭素原子数1~20のアルキル基を表し、
Ri2は、水素原子、ハロゲン原子、炭素原子数1~20のアルキル基、下記式(III-1)で表される基、式(III-2)で表される基、又は式(III-3)で表される基を表す。
R i1 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms.
R i2 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a group represented by the following formula (III-1), a group represented by the formula (III-2), or a group represented by the formula (III-2). Represents the group represented by 3).
複数あるRi2aは、それぞれ独立して、水素原子、ハロゲン原子、又は炭素原子数1~20のアルキル基を表す。)
Each of the plurality of Ri2a independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms. )
Ri2bは、水素原子又は炭素原子数1~20のアルキル基を表す。)
R i2b represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. )
Ri2cは、炭素原子数1~20のアルキル基を表す。))
[4] p型半導体材料と、n型半導体材料と、絶縁材料とを含み、
前記p型半導体材料が、下記式(I)で表される構成単位を含む重合体を含む、膜。
R i2c represents an alkyl group having 1 to 20 carbon atoms. )))
[4] A p-type semiconductor material, an n-type semiconductor material, and an insulating material are included.
A film in which the p-type semiconductor material contains a polymer containing a structural unit represented by the following formula (I).
Ar1及びAr2は、それぞれ独立して、置換基を有していてもよい3価の芳香族複素環基を表す。
Zは、下記式(Z-1)~式(Z-4)で表される基を表す。
Ar 1 and Ar 2 each independently represent a trivalent aromatic heterocyclic group which may have a substituent.
Z represents a group represented by the following formulas (Z-1) to (Z-4).
Rは、
水素原子、
ハロゲン原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアルケニル基、
置換基を有していてもよいシクロアルケニル基、
置換基を有していてもよいアルキニル基、
置換基を有していてもよいシクロアルキニル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいシクロアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、
置換基を有していてもよいアルキルチオ基、
置換基を有していてもよいシクロアルキルチオ基、
置換基を有していてもよいアリールチオ基、
置換基を有していてもよい1価の複素環基、
置換基を有していてもよい置換アミノ基、
置換基を有していてもよいイミン残基、
置換基を有していてもよいアミド基、
置換基を有していてもよい酸イミド基、
置換基を有していてもよい置換オキシカルボニル基、
シアノ基、
ニトロ基、
-C(=O)-Raで表される基、又は
-SO2-Rbで表される基を表し、
Ra及びRbは、それぞれ独立して、
水素原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいシクロアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、又は
置換基を有していてもよい1価の複素環基を表す。
式(Z-1)~式(Z-4)中、2つあるRは同一であっても異なっていてもよい。))
[5] 第一の電極と、[4]に記載の膜と、第二の電極とをこの順で含む、有機光電変換素子。
[6] [5]に記載の有機光電変換素子を含む、光検出素子。
R is
Hydrogen atom,
Halogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
An alkenyl group which may have a substituent,
Cycloalkenyl groups, which may have substituents,
An alkynyl group, which may have a substituent,
A cycloalkynyl group which may have a substituent,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Aryloxy groups, which may have substituents,
Alkylthio groups, which may have substituents,
Cycloalkylthio groups, which may have substituents,
An arylthio group, which may have a substituent,
A monovalent heterocyclic group which may have a substituent,
Substituted amino groups, which may have substituents,
Imine residues, which may have substituents,
An amide group which may have a substituent,
An acidimide group, which may have a substituent,
Substituted oxycarbonyl group, which may have a substituent,
Cyano group,
Nitro group,
Represents a group represented by -C (= O) -R a or a group represented by -SO 2 -R b .
R a and R b are independent of each other.
Hydrogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Represents an aryloxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent.
In the formulas (Z-1) to (Z-4), the two Rs may be the same or different. )))
[5] An organic photoelectric conversion element including the first electrode, the film according to [4], and the second electrode in this order.
[6] A photodetector including the organic photoelectric conversion element according to [5].
本発明によれば、暗電流特性のばらつきの小さい有機光電変換素子を製造しうる、組成物;当該組成物から製造されうる膜;当該膜を含む有機光電変換素子;当該有機光電変換素子を含む光検出素子が提供される。
According to the present invention, a composition capable of producing an organic photoelectric conversion element having a small variation in dark current characteristics; a film capable of being produced from the composition; an organic photoelectric conversion element containing the film; including the organic photoelectric conversion element. A photodetector is provided.
[共通する用語の説明]
以下の説明において共通して用いられる用語等についてまず説明する。
「高分子化合物」とは、分子量分布を有し、ポリスチレン換算の数平均分子量が、1×103以上1×108以下である重合体を意味する。なお、重合体に含まれる構成単位は、合計100モル%である。 [Explanation of common terms]
First, terms commonly used in the following description will be described.
The “polymer compound” means a polymer having a molecular weight distribution and having a polystyrene-equivalent number average molecular weight of 1 × 10 3 or more and 1 × 108 or less. The structural units contained in the polymer are 100 mol% in total.
以下の説明において共通して用いられる用語等についてまず説明する。
「高分子化合物」とは、分子量分布を有し、ポリスチレン換算の数平均分子量が、1×103以上1×108以下である重合体を意味する。なお、重合体に含まれる構成単位は、合計100モル%である。 [Explanation of common terms]
First, terms commonly used in the following description will be described.
The “polymer compound” means a polymer having a molecular weight distribution and having a polystyrene-equivalent number average molecular weight of 1 × 10 3 or more and 1 × 108 or less. The structural units contained in the polymer are 100 mol% in total.
「構成単位」とは、重合体が有する構造の単位を意味する。
The "constituent unit" means a unit of the structure of the polymer.
「水素原子」は、軽水素原子であっても、重水素原子であってもよい。
The "hydrogen atom" may be a light hydrogen atom or a deuterium atom.
「ハロゲン原子」の例としては、フッ素原子、塩素原子、臭素原子、及びヨウ素原子が挙げられる。
Examples of "halogen atoms" include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.
「置換基を有していてもよい」態様には、化合物又は基を構成するすべての水素原子が無置換の場合、及び1個以上の水素原子の一部又は全部が置換基によって置換されている場合の両方の態様が含まれる。
In the "may have substituents" embodiment, all hydrogen atoms constituting the compound or group are unsubstituted, and some or all of one or more hydrogen atoms are substituted with the substituents. Both aspects, if any, are included.
置換基の例としては、ハロゲン原子、アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アルキニル基、シクロアルキニル基、アルキルオキシ基、シクロアルキルオキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、1価の複素環基、置換アミノ基、アシル基、イミン残基、アミド基、酸イミド基、置換オキシカルボニル基、シアノ基、アルキルスルホニル基、及びニトロ基が挙げられる。
Examples of substituents include halogen atom, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group, alkyloxy group, cycloalkyloxy group, alkylthio group, cycloalkylthio group, aryl group, Examples thereof include an aryloxy group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an acidimide group, a substituted oxycarbonyl group, a cyano group, an alkylsulfonyl group, and a nitro group. ..
「アルキル基」は、直鎖状でもあってもよく、分岐状であってもよい。アルキル基は、置換基を有していてもよい。アルキル基の炭素原子数は、置換基の炭素原子数を含まないで、通常1~50、好ましくは1~30、より好ましくは1~20である。
The "alkyl group" may be linear or branched. The alkyl group may have a substituent. The number of carbon atoms of the alkyl group does not include the number of carbon atoms of the substituent, and is usually 1 to 50, preferably 1 to 30, and more preferably 1 to 20.
アルキル基の例としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基、n-ペンチル基、3-メチルブチル基、2-エチルブチル基、n-ヘキシル基、n-ヘプチル基、n-オクチル基、2-エチルヘキシル基、3-プロピルヘプチル基、n-デシル基、3,7-ジメチルオクチル基、3-ヘプチルドデシル基、2-エチルオクチル基、2-ヘキシルデシル基、ドデシル基、n-テトラデシル基、ヘキサデシル墓、オクタデシル基、エイコシル基などの、置換基を有さないアルキル基、及びこれらの基における水素原子が、アルキルオキシ基、アリール基、フッ素原子などの置換基で置換された基が挙げられる。
Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 3-methylbutyl group, 2-ethylbutyl group, n. -Hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, 3-propylheptyl group, n-decyl group, 3,7-dimethyloctyl group, 3-heptyl dodecyl group, 2-ethyloctyl group, Alkyl groups having no substituents such as 2-hexyldecyl group, dodecyl group, n-tetradecyl group, hexadecyl tomb, octadecyl group and eicosyl group, and the hydrogen atom in these groups are alkyloxy group, aryl group, etc. Examples thereof include a group substituted with a substituent such as a fluorine atom.
置換基を有するアルキルの具体例としては、トリフルオロメチル基、ペンタフルオロエチル基、パーフルオロブチル基、パーフルオロヘキシル基、パーフルオロオクチル基、3-フェニルプロピル基、3-(4-メチルフェニル)プロピル基、3-(3,5-ジヘキシルフェニル)プロピル基、6-エチルオキシヘキシル基が挙げられる。
Specific examples of the alkyl having a substituent include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a 3-phenylpropyl group and a 3- (4-methylphenyl) group. Examples thereof include a propyl group, a 3- (3,5-dihexylphenyl) propyl group and a 6-ethyloxyhexyl group.
「シクロアルキル基」は、単環の基であってもよく、多環の基であってもよい。シクロアルキル基は、置換基を有していてもよい。シクロアルキル基の炭素原子数は、置換基の炭素原子数を含まないで、通常3~30であり、好ましくは3~20である。
The "cycloalkyl group" may be a monocyclic group or a polycyclic group. The cycloalkyl group may have a substituent. The number of carbon atoms of the cycloalkyl group does not include the number of carbon atoms of the substituent and is usually 3 to 30, preferably 3 to 20.
シクロアルキル基の例としては、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、アダマンチル基などの、置換基を有さないアルキル基、及びこれらの基における水素原子が、アルキル基、アルキルオキシ基、アリール基、フッ素原子などの置換基で置換された基が挙げられる。
Examples of cycloalkyl groups include alkyl groups having no substituents such as cyclopentyl group, cyclohexyl group, cycloheptyl group and adamantyl group, and the hydrogen atom in these groups is an alkyl group, an alkyloxy group and an aryl group. , A group substituted with a substituent such as a fluorine atom.
置換基を有するシクロアルキル基の具体例としては、メチルシクロヘキシル基、エチルシクロヘキシル基が挙げられる。
Specific examples of the cycloalkyl group having a substituent include a methylcyclohexyl group and an ethylcyclohexyl group.
「アルケニル基」は、直鎖状でもあってもよく、分岐状であってもよい。アルケニル基は、置換基を有していてもよい。アルケニル基の炭素原子数は、置換基の炭素原子数を含まないで、通常2~30であり、好ましくは2~20である。
The "alkenyl group" may be linear or branched. The alkenyl group may have a substituent. The number of carbon atoms of the alkenyl group does not include the number of carbon atoms of the substituent and is usually 2 to 30, preferably 2 to 20.
アルケニル基の例としては、ビニル基、1-プロペニル基、2-プロペニル基、2-ブテニル基、3-ブテニル基、3-ペンテニル基、4-ペンテニル基、1-ヘキセニル基、5-ヘキセニル基、7-オクテニル基などの、置換基を有さないアルケニル基、及びこれらの基における水素原子が、アルキルオキシ基、アリール基、フッ素原子などの置換基で置換された基が挙げられる。
Examples of alkenyl groups include vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, 3-butenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 5-hexenyl group, Examples thereof include an alkenyl group having no substituent such as a 7-octenyl group, and a group in which a hydrogen atom in these groups is substituted with a substituent such as an alkyloxy group, an aryl group or a fluorine atom.
「シクロアルケニル基」は、単環の基であってもよく、多環の基であってもよい。シクロアルケニル基は、置換基を有していてもよい。シクロアルケニル基の炭素原子数は、置換基の炭素原子数を含まないで、通常3~30であり、好ましくは3~20である。
The "cycloalkenyl group" may be a monocyclic group or a polycyclic group. The cycloalkenyl group may have a substituent. The number of carbon atoms of the cycloalkenyl group does not include the number of carbon atoms of the substituent and is usually 3 to 30, preferably 3 to 20.
シクロアルケニル基の例としては、シクロヘキセニル基などの、置換基を有さないシクロアルケニル基、及びこれらの基における水素原子が、アルキル基、アルキルオキシ基、アリール基、フッ素原子などの置換基で置換された基が挙げられる。
Examples of cycloalkenyl groups are cycloalkenyl groups having no substituents such as cyclohexenyl groups, and the hydrogen atom in these groups is a substituent such as an alkyl group, an alkyloxy group, an aryl group or a fluorine atom. Examples include substituted groups.
置換基を有するシクロアルケニル基の例としては、メチルシクロヘキセニル基、及びエチルシクロヘキセニル基が挙げられる。
Examples of the cycloalkenyl group having a substituent include a methylcyclohexenyl group and an ethylcyclohexenyl group.
「アルキニル基」は、直鎖状であってもよく、分岐状であってもよい。アルキニル基は、置換基を有していてもよい。アルキニル基の炭素原子数は、置換基の炭素原子数を含まないで、通常2~30であり、好ましくは2~20である。
The "alkynyl group" may be linear or branched. The alkynyl group may have a substituent. The number of carbon atoms of the alkynyl group does not include the number of carbon atoms of the substituent and is usually 2 to 30, preferably 2 to 20.
アルキニル基の例としては、エチニル基、1-プロピニル基、2-プロピニル基、2-ブチニル基、3-ブチニル基、3-ペンチニル基、4-ペンチニル基、1-ヘキシニル基、5-ヘキシニル基などの、置換基を有さないアルキニル基、及びこれらの基における水素原子が、アルキルオキシ基、アリール基、フッ素原子などの置換基で置換された基が挙げられる。
Examples of alkynyl groups include ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4-pentynyl group, 1-hexynyl group, 5-hexynyl group and the like. Examples thereof include an alkynyl group having no substituent and a group in which the hydrogen atom in these groups is substituted with a substituent such as an alkyloxy group, an aryl group or a fluorine atom.
「シクロアルキニル基」は、単環の基であってもよく、多環の基であってもよい。シクロアルキニル基は、置換基を有していてもよい。シクロアルキニル基の炭素原子数は、置換基の炭素原子数を含まないで、通常4~30であり、好ましくは4~20である。
The "cycloalkynyl group" may be a monocyclic group or a polycyclic group. The cycloalkynyl group may have a substituent. The number of carbon atoms of the cycloalkynyl group does not include the number of carbon atoms of the substituent and is usually 4 to 30, preferably 4 to 20.
シクロアルキニル基の例としては、シクロヘキシニル基などの置換基を有さないシクロアルキニル基、及びこれらの基における水素原子が、アルキル基、アルキルオキシ基、アリール基、フッ素原子などの置換基で置換された基が挙げられる。
Examples of cycloalkynyl groups include cycloalkynyl groups that do not have substituents such as cyclohexynyl groups, and hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkyloxy groups, aryl groups, and fluorine atoms. The group that was made is mentioned.
置換基を有するシクロアルキニル基の例としては、メチルシクロヘキシニル基、及びエチルシクロヘキシニル基が挙げられる。
Examples of the cycloalkynyl group having a substituent include a methylcyclohexynyl group and an ethylcyclohexynyl group.
「アルキルオキシ基」は、直鎖状であってもよく、分岐状であってもよい。アルキルオキシ基は、置換基を有していてもよい。アルキルオキシ基の炭素原子数は、置換基の炭素原子数を含まないで、通常1~30であり、好ましくは1~20である。
The "alkyloxy group" may be linear or branched. The alkyloxy group may have a substituent. The number of carbon atoms of the alkyloxy group does not include the number of carbon atoms of the substituent and is usually 1 to 30, preferably 1 to 20.
アルキルオキシ基の例としては、メトキシ基、エトキシ基、n-プロピルオキシ基、イソプロピルオキシ基、n-ブチルオキシ基、イソブチルオキシ基、tert-ブチルオキシ基、n-ペンチルオキシ基、n-ヘキシルオキシ基、n-ヘプチルオキシ基、n-オクチルオキシ基、2-エチルヘキシルオキシ基、n-ノニルオキシ基、n-デシルオキシ基、3,7-ジメチルオクチルオキシ基、3-ヘプチルドデシルオキシ基、ラウリルオキシ基などの、置換基を有さないアルキルオキシ基、及びこれらの基における水素原子が、アルキルオキシ基、アリール基、フッ素原子等の置換基で置換された基が挙げられる。
Examples of alkyloxy groups include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-Heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, 3,7-dimethyloctyloxy group, 3-heptyldodecyloxy group, lauryloxy group, etc. Examples thereof include an alkyloxy group having no substituent and a group in which the hydrogen atom in these groups is substituted with a substituent such as an alkyloxy group, an aryl group or a fluorine atom.
「シクロアルキルオキシ基」が有するシクロアルキル基は、単環の基であってもよく、多環の基であってもよい。シクロアルキルオキシ基は、置換基を有していてもよい。シクロアルキルオキシ基の炭素原子数は、置換基の炭素原子数を含まないで、通常3~30であり、好ましくは3~20である。
The cycloalkyl group contained in the "cycloalkyloxy group" may be a monocyclic group or a polycyclic group. The cycloalkyloxy group may have a substituent. The number of carbon atoms of the cycloalkyloxy group does not include the number of carbon atoms of the substituent and is usually 3 to 30, preferably 3 to 20.
シクロアルキルオキシ基の例としては、シクロペンチルオキシ基、シクロヘキシルオキシ基、シクロヘプチルオキシ基などの、置換基を有さないシクロアルキルオキシ基、及びこれらの基における水素原子が、フッ素原子、アルキル基などの置換基で置換された基が挙げられる。
Examples of the cycloalkyloxy group include a cycloalkyloxy group having no substituent such as a cyclopentyloxy group, a cyclohexyloxy group and a cycloheptyloxy group, and a hydrogen atom in these groups is a fluorine atom, an alkyl group and the like. Examples thereof include groups substituted with the substituents of.
「アルキルチオ基」は、直鎖状であってもよく、分岐状であってもよい。アルキルチオ基は、置換基を有していてもよい。アルキルチオ基の炭素原子数は、置換基の炭素原子数を含まないで、通常1~30であり、好ましくは1~20である。
The "alkylthio group" may be linear or branched. The alkylthio group may have a substituent. The number of carbon atoms of the alkylthio group does not include the number of carbon atoms of the substituent and is usually 1 to 30, preferably 1 to 20.
置換基を有していてもよいアルキルチオ基の例としては、メチルチオ基、エチルチオ基、n-プロピルチオ基、イソプロピルチオ基、n-ブチルチオ基、イソブチルチオ基、tert-ブチルチオ基、n-ペンチルチオ基、n-ヘキシルチオ基、n-ヘプチルチオ基、n-オクチルチオ基、2-エチルヘキシルチオ基、n-ノニルチオ基、n-デシルチオ基、3,7-ジメチルオクチルチオ基、3-ヘプチルドデシルチオ基、ラウリルチオ基、及びトリフルオロメチルチオ基が挙げられる。
Examples of alkylthio groups that may have a substituent include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a tert-butylthio group, an n-pentylthio group, and the like. n-hexylthio group, n-heptylthio group, n-octylthio group, 2-ethylhexylthio group, n-nonylthio group, n-decylthio group, 3,7-dimethyloctylthio group, 3-heptyldodecylthio group, laurylthio group, And a trifluoromethylthio group.
「シクロアルキルチオ基」が有するシクロアルキル基は、単環の基であってもよく、多環の基であってもよい。シクロアルキルチオ基は、置換基を有していてもよい。シクロアルキルチオ基の炭素原子数は、置換基の炭素原子数を含まないで、通常3~30であり、好ましくは3~20である。
The cycloalkyl group contained in the "cycloalkylthio group" may be a monocyclic group or a polycyclic group. The cycloalkylthio group may have a substituent. The number of carbon atoms of the cycloalkylthio group does not include the number of carbon atoms of the substituent and is usually 3 to 30, preferably 3 to 20.
置換基を有していてもよいシクロアルキルチオ基の例としては、シクロヘキシルチオ基が挙げられる。
An example of a cycloalkylthio group that may have a substituent is a cyclohexylthio group.
「p価の芳香族炭素環基」とは、置換基を有していてもよい芳香族炭化水素から環を構成する炭素原子に直接結合する水素原子p個を除いた残りの原子団を意味する。p価の芳香族炭素環基は、置換基を更に有していてもよい。
The "p-valent aromatic carbocyclic group" means the remaining atomic group obtained by removing p hydrogen atoms directly bonded to the carbon atom constituting the ring from the aromatic hydrocarbon which may have a substituent. do. The p-valent aromatic carbocyclic group may further have a substituent.
「アリール基」は、1価の芳香族炭素環基を意味する。アリール基は置換基を有していてもよい。アリール基の炭素原子数は、置換基の炭素原子数を含まないで、通常6~60であり、好ましくは6~48である。
"Aryl group" means a monovalent aromatic carbocyclic group. The aryl group may have a substituent. The number of carbon atoms of the aryl group does not include the number of carbon atoms of the substituent and is usually 6 to 60, preferably 6 to 48.
アリール基の例としては、フェニル基、1-ナフチル基、2-ナフチル基、1-アントラセニル基、2-アントラセニル基、9-アントラセニル基、1-ピレニル基、2-ピレニル基、4-ピレニル基、2-フルオレニル基、3-フルオレニル基、4-フルオレニル基、2-フェニルフェニル基、3-フェニルフェニル基、4-フェニルフェニル基などの、置換基を有さないアリール基、及びこれらの基における水素原子が、アルキル基、アルキルオキシ基、アリール基、フッ素原子などの置換基で置換された基が挙げられる。
Examples of aryl groups include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthrasenyl group, 2-anthrasenyl group, 9-anthrasenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, An aryl group having no substituent such as a 2-fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, a 2-phenylphenyl group, a 3-phenylphenyl group, a 4-phenylphenyl group, and hydrogen in these groups. Examples thereof include a group in which an atom is substituted with a substituent such as an alkyl group, an alkyloxy group, an aryl group or a fluorine atom.
「アリールオキシ基」は、置換基を有していてもよい。アリールオキシ基の炭素原子数は、置換基の炭素原子数を含まないで、通常6~60であり、好ましくは6~48である。
The "aryloxy group" may have a substituent. The number of carbon atoms of the aryloxy group does not include the number of carbon atoms of the substituent and is usually 6 to 60, preferably 6 to 48.
アリールオキシ基の例としては、フェノキシ基、1-ナフチルオキシ基、2-ナフチルオキシ基、1-アントラセニルオキシ基、9-アントラセニルオキシ基、1-ピレニルオキシ基などの、置換基を有さないアリールオキシ基、及びこれらの基における水素原子が、アルキル基、アルキルオキシ基、フッ素原子などの置換基で置換された基が挙げられる。
Examples of the aryloxy group include a substituent such as a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthrasenyloxy group, a 9-anthrasenyloxy group and a 1-pyrenyloxy group. Examples thereof include an aryloxy group that does not have an aryloxy group, and a group in which the hydrogen atom in these groups is substituted with a substituent such as an alkyl group, an alkyloxy group, or a fluorine atom.
「アリールチオ基」は、置換基を有していてもよい。アリールチオ基の炭素原子数は、置換基の炭素原子数を含まないで、通常6~60であり、好ましくは6~48である。
The "arylthio group" may have a substituent. The number of carbon atoms of the arylthio group does not include the number of carbon atoms of the substituent and is usually 6 to 60, preferably 6 to 48.
置換基を有していてもよいアリールチオ基の例としては、フェニルチオ基、C1~C12アルキルオキシフェニルチオ基、C1~C12アルキルフェニルチオ基、1-ナフチルチオ基、2-ナフチルチオ基、及びペンタフルオロフェニルチオ基が挙げられる。「C1~C12」は、その直後に記載された基の炭素原子数が1~12であることを示す。さらに、「Cm~Cn」は、その直後に記載された基の炭素原子数がm~nであることを示す。以下も同様である。
Examples of arylthio groups that may have substituents are phenylthio groups, C1-C12 alkyloxyphenylthio groups, C1-C12 alkylphenylthio groups, 1-naphthylthio groups, 2-naphthylthio groups, and pentafluorophenyls. The thio group is mentioned. "C1 to C12" indicates that the number of carbon atoms of the group described immediately after that is 1 to 12. Further, "Cm to Cn" indicates that the number of carbon atoms of the group described immediately after that is m to n. The same applies to the following.
「p価の複素環基」(pは、1以上の整数を表す。)は、置換基を有していてもよい複素環式化合物から環を構成する炭素原子又はヘテロ原子に直接結合する水素原子のうちのp個の水素原子を除いた残りの原子団を意味する。「p価の複素環基」には、「p価の芳香族複素環基」が含まれる。「p価の芳香族複素環基」は、置換基を有していてもよい芳香族複素環式化合物から、環を構成する炭素原子又はヘテロ原子に直接結合している水素原子のうちのp個の水素原子を除いた残りの原子団を意味する。
A "p-valent heterocyclic group" (p represents an integer of 1 or more) is a hydrogen directly bonded to a carbon atom or a hetero atom constituting a ring from a heterocyclic compound which may have a substituent. It means the remaining atomic group excluding p hydrogen atoms among the atoms. The "p-valent heterocyclic group" includes a "p-valent aromatic heterocyclic group". The "p-valent aromatic heterocyclic group" is a p of hydrogen atoms directly bonded to a carbon atom or a hetero atom constituting a ring from an aromatic heterocyclic compound which may have a substituent. It means the remaining atomic group excluding one hydrogen atom.
芳香族複素環式化合物には、複素環自体が芳香族性を示す化合物に加えて、複素環自体は芳香族性を示さなくとも、複素環に芳香環が縮環している化合物が包含される。
Aromatic heterocyclic compounds include, in addition to compounds in which the heterocycle itself exhibits aromaticity, compounds in which the heterocycle itself has an aromatic ring condensed, even if the heterocycle itself does not exhibit aromaticity. To.
芳香族複素環式化合物のうち、複素環自体が芳香族性を示す化合物の具体例としては、オキサジアゾール、チアジアゾール、チアゾール、オキサゾール、チオフェン、ピロール、ホスホール、フラン、ピリジン、ピラジン、ピリミジン、トリアジン、ピリダジン、キノリン、イソキノリン、カルバゾール、及びジベンゾホスホールが挙げられる。
Among the aromatic heterocyclic compounds, specific examples of the compound in which the heterocycle itself exhibits aromaticity include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, and triazine. , Pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphol.
芳香族複素環式化合物のうち、複素環自体が芳香族性を示さず、複素環に芳香環が縮環している化合物の具体例としては、フェノキサジン、フェノチアジン、ジベンゾボロール、ジベンゾシロール、及びベンゾピランが挙げられる。
Among aromatic heterocyclic compounds, specific examples of compounds in which the heterocycle itself does not exhibit aromaticity and the aromatic ring is fused to the heterocycle include phenoxazine, phenothiazine, dibenzoborol, and dibenzosyrol. And benzopyran.
p価の複素環基は、置換基を有していてもよい。p価の複素環基の炭素原子数は、置換基の炭素原子数を含まないで、通常2~60であり、好ましくは2~20である。
The p-valent heterocyclic group may have a substituent. The number of carbon atoms of the p-valent heterocyclic group does not include the number of carbon atoms of the substituent and is usually 2 to 60, preferably 2 to 20.
1価の複素環基の例としては、1価の芳香族複素環基(例、チエニル基、ピロリル基、フリル基、ピリジル基、キノリル基、イソキノリル基、ピリミジニル基、トリアジニル基)、1価の非芳香族複素環基(例、ピペリジル基、ピペラジル基)、及びこれらの基における水素原子が、アルキル基、アルキルオキシ基、フッ素原子などの置換基で置換された基が挙げられる。
Examples of monovalent heterocyclic groups include monovalent aromatic heterocyclic groups (eg, thienyl group, pyrrolyl group, frill group, pyridyl group, quinolyl group, isoquinolyl group, pyrimidinyl group, triazinyl group) and monovalent. Examples thereof include non-aromatic heterocyclic groups (eg, piperidyl group, piperazyl group) and groups in which the hydrogen atom in these groups is substituted with a substituent such as an alkyl group, an alkyloxy group or a fluorine atom.
「置換アミノ基」は、置換基を有するアミノ基を意味する。アミノ基が有する置換基としては、アルキル基、アリール基、及び1価の複素環基が好ましい。置換アミノ基の炭素原子数は、置換基の炭素原子数を含めないで、通常2~30である。
"Substituted amino group" means an amino group having a substituent. As the substituent contained in the amino group, an alkyl group, an aryl group and a monovalent heterocyclic group are preferable. The number of carbon atoms of the substituted amino group is usually 2 to 30, not including the number of carbon atoms of the substituent.
置換アミノ基の例としては、ジアルキルアミノ基(例、ジメチルアミノ基、ジエチルアミノ基)、ジアリールアミノ基(例、ジフェニルアミノ基、ビス(4-メチルフェニル)アミノ基、ビス(4-tert-ブチルフェニル)アミノ基、ビス(3,5-ジ-tert-ブチルフェニル)アミノ基)が挙げられる。
Examples of substituted amino groups include dialkylamino groups (eg, dimethylamino group, diethylamino group), diarylamino groups (eg, diphenylamino group, bis (4-methylphenyl) amino group, bis (4-tert-butylphenyl). ) Amino group, bis (3,5-di-tert-butylphenyl) amino group).
「アシル基」は、置換基を有していてもよい。アシル基の炭素原子数は、置換基の炭素原子数を含めないで、通常2~20であり、好ましくは2~18である。アシル基の具体例としては、アセチル基、プロピオニル基、ブチリル基、イソブチリル基、ピバロイル基、ベンゾイル基、トリフルオロアセチル基、及びペンタフルオロベンゾイル基が挙げられる。
The "acyl group" may have a substituent. The number of carbon atoms of the acyl group does not include the number of carbon atoms of the substituent and is usually 2 to 20, preferably 2 to 18. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.
「イミン残基」とは、イミン化合物から、炭素原子-窒素原子二重結合を構成する炭素原子又は窒素原子に直接結合する水素原子を1個除いた残りの原子団を意味する。「イミン化合物」とは、分子内に、炭素原子-窒素原子二重結合を有する有機化合物を意味する。イミン化合物の例としては、アルジミン、ケチミン、及びアルジミン中の炭素原子-窒素原子二重結合を構成する窒素原子に結合している水素原子が、アルキル基などで置換された化合物が挙げられる。
The "imine residue" means the remaining atomic group obtained by removing one hydrogen atom directly bonded to the carbon atom or the nitrogen atom constituting the carbon atom-nitrogen atom double bond from the imine compound. The "imine compound" means an organic compound having a carbon atom-nitrogen atom double bond in the molecule. Examples of imine compounds include compounds in which the hydrogen atom bonded to the carbon atom-nitrogen atom double bond in aldimine, ketimine, and aldimine is replaced with an alkyl group or the like.
イミン残基の炭素原子数は、通常2~20であり、好ましくは2~18である。イミン残基の例としては、下記の構造式で表される基が挙げられる。
The number of carbon atoms of the imine residue is usually 2 to 20, preferably 2 to 18. Examples of imine residues include groups represented by the following structural formulas.
「アミド基」とは、アミドから窒素原子に結合した水素原子を1個除いた残りの原子団を意味する。アミド基の炭素原子数は、通常1~20であり、好ましくは1~18である。アミド基の具体例としては、ホルムアミド基、アセトアミド基、プロピオアミド基、ブチロアミド基、ベンズアミド基、トリフルオロアセトアミド基、ペンタフルオロベンズアミド基、ジホルムアミド基、ジアセトアミド基、ジプロピオアミド基、ジブチロアミド基、ジベンズアミド基、ジトリフルオロアセトアミド基、及びジペンタフルオロベンズアミド基が挙げられる。
The "amide group" means the remaining atomic group obtained by removing one hydrogen atom bonded to a nitrogen atom from the amide. The number of carbon atoms of the amide group is usually 1 to 20, preferably 1 to 18. Specific examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group and a dibenzamide group. , Ditrifluoroacetamide group, and dipentafluorobenzamide group.
「酸イミド基」とは、酸イミドから窒素原子に結合した水素原子を1個除いた残りの原子団を意味する。酸イミド基の炭素原子数は、通常4~20である。酸イミド基の具体例としては、下記の構造式で表される基が挙げられる。
The "acidimide group" means the remaining atomic group obtained by removing one hydrogen atom bonded to a nitrogen atom from the acidimide. The number of carbon atoms of the acidimide group is usually 4 to 20. Specific examples of the acidimide group include a group represented by the following structural formula.
「置換オキシカルボニル基」とは、R’-O-(C=O)-で表される基を意味する。
ここで、R’は、アルキル基、シクロアルキル基、アリール基、アリールアルキル基、又は1価の複素環基を表し、これらは置換基を有していてもよい。 The "substituted oxycarbonyl group" means a group represented by R'-O- (C = O)-.
Here, R'represents an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group, which may have a substituent.
ここで、R’は、アルキル基、シクロアルキル基、アリール基、アリールアルキル基、又は1価の複素環基を表し、これらは置換基を有していてもよい。 The "substituted oxycarbonyl group" means a group represented by R'-O- (C = O)-.
Here, R'represents an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group, which may have a substituent.
置換オキシカルボニル基の炭素原子数は、置換基の炭素原子数を含めないで、通常2~60であり、好ましくは2~48である。
The number of carbon atoms of the substituted oxycarbonyl group is usually 2 to 60, preferably 2 to 48, not including the number of carbon atoms of the substituent.
置換オキシカルボニル基の具体例としては、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、イソプロポキシカルボニル基、ブトキシカルボニル基、イソブトキシカルボニル基、tert-ブトキシカルボニル基、ペンチルオキシカルボニル基、ヘキシルオキシカルボニル基、シクロヘキシルオキシカルボニル基、ヘプチルオキシカルボニル基、オクチルオキシカルボニル基、2-エチルヘキシルオキシカルボニル基、ノニルオキシカルボニル基、デシルオキシカルボニル基、3,7-ジメチルオクチルオキシカルボニル基、ドデシルオキシカルボニル基、トリフルオロメトキシカルボニル基、ペンタフルオロエトキシカルボニル基、パーフルオロブトキシカルボニル基、パーフルオロヘキシルオキシカルボニル基、パーフルオロオクチルオキシカルボニル基、フェノキシカルボニル基、ナフトキシカルボニル基、及びピリジルオキシカルボニル基が挙げられる。
Specific examples of the substituted oxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group, and a hexyloxycarbonyl group. Group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, tri Examples thereof include a fluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, a perfluorobutoxycarbonyl group, a perfluorohexyloxycarbonyl group, a perfluorooctyloxycarbonyl group, a phenoxycarbonyl group, a naphthoxycarbonyl group, and a pyridyloxycarbonyl group.
「アルキルスルホニル基」は、直鎖状でもあってもよく、分岐状であってもよい。アルキルスルホニル基は、置換基を有していてもよい。アルキルスルホニル基の炭素原子数は、置換基の炭素原子数を含めないで、通常1~30である。アルキルスルホニル基の具体例としては、メチルスルホニル基、エチルスルホニル基、及びドデシルスルホニル基が挙げられる。
The "alkylsulfonyl group" may be linear or branched. The alkylsulfonyl group may have a substituent. The number of carbon atoms of the alkylsulfonyl group is usually 1 to 30, not including the number of carbon atoms of the substituent. Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a dodecylsulfonyl group.
化学式に付される「*」は、結合手を表す。
The "*" attached to the chemical formula represents the bond.
「π共役系」とは、π電子が複数の結合に非局在化している系を意味する。
The "π-conjugated system" means a system in which π electrons are delocalized to multiple bonds.
用語「(メタ)アクリル」は、アクリル、メタクリル、及びその組み合わせを包含する。
The term "(meth) acrylic" includes acrylics, methacrylics, and combinations thereof.
[1.組成物]
本発明の一実施形態に係る組成物は、p型半導体材料と、n型半導体材料と、絶縁材料と、溶媒とを含み、前記p型半導体材料が、式(I)で表される構成単位を含む重合体を含む。かかる組成物を用いることによって、暗電流特性のばらつきの小さい有機光電変換素子を製造することができる。 [1. Composition]
The composition according to one embodiment of the present invention contains a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent, and the p-type semiconductor material is a structural unit represented by the formula (I). Contains a polymer containing. By using such a composition, an organic photoelectric conversion element having a small variation in dark current characteristics can be manufactured.
本発明の一実施形態に係る組成物は、p型半導体材料と、n型半導体材料と、絶縁材料と、溶媒とを含み、前記p型半導体材料が、式(I)で表される構成単位を含む重合体を含む。かかる組成物を用いることによって、暗電流特性のばらつきの小さい有機光電変換素子を製造することができる。 [1. Composition]
The composition according to one embodiment of the present invention contains a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent, and the p-type semiconductor material is a structural unit represented by the formula (I). Contains a polymer containing. By using such a composition, an organic photoelectric conversion element having a small variation in dark current characteristics can be manufactured.
本発明の組成物で暗電流特性のばらつきが抑制される機構について、詳細は不明であるものの、次のような機構が考えられるが、本発明を限定するものではない。本発明の組成物では、光電変換効果には直接関与しない絶縁材料を添加剤として含むことで、組成物の濃度及び粘度物性を適正に調製することができ、塗布の際に均一な厚さの塗布膜を製造することができる。その反面、絶縁材料を加えることで組成物の固形分濃度及び粘度が高くなるため、組成物を塗布及び乾燥させる過程において、p型半導体材料及びn型半導体材料の凝集が進行し易くなると考えらえる。とりわけ、p型半導体材料として用いられるポリマーは、光吸収性及び電荷輸送性の観点から、π共役が連続した平面的な且つ対称な分子構造を有する化合物が多い。そのため、塗布及び乾燥の過程において、結晶化および結晶成長が進行し易いと考えられる。そのような分子構造を持つp型半導体材料であるポリマーを含む活性層では、p型半導体材料の大きな結晶が含まれ、それを起点としたピンホールや局所的な薄膜化が生じていると推測される。
一方、本発明の組成物に含まれる、p型半導体材料である式(I)で表される構成単位を含む重合体は、非対称な分子構造を持つ。そのため、塗布及び乾燥工程において、当該重合体は結晶化が進行しにくく、微細粒子として活性層中に存在すると考えられる。その結果、組成物中の大きな粒子に起因した微小なピンホールや薄膜化などの欠陥は、本発明の組成物から得られる活性層では生じにくいと考えられ、本発明の組成物から得られる素子は、暗電流特性の均一性が優れていると推察される。 Although the details of the mechanism for suppressing the variation in dark current characteristics in the composition of the present invention are unknown, the following mechanism can be considered, but the present invention is not limited. In the composition of the present invention, by including an insulating material that is not directly involved in the photoelectric conversion effect as an additive, the concentration and viscosity physical characteristics of the composition can be appropriately adjusted, and the thickness becomes uniform at the time of coating. A coating film can be manufactured. On the other hand, since the solid content concentration and viscosity of the composition are increased by adding the insulating material, it is considered that the aggregation of the p-type semiconductor material and the n-type semiconductor material is likely to proceed in the process of applying and drying the composition. Eh. In particular, many polymers used as p-type semiconductor materials have a planar and symmetric molecular structure in which π-conjugation is continuous from the viewpoint of light absorption and charge transportability. Therefore, it is considered that crystallization and crystal growth are likely to proceed in the process of coating and drying. It is presumed that the active layer containing a polymer, which is a p-type semiconductor material having such a molecular structure, contains large crystals of the p-type semiconductor material, and pinholes and local thinning occur from the crystals. Will be done.
On the other hand, the polymer containing the structural unit represented by the formula (I), which is a p-type semiconductor material, contained in the composition of the present invention has an asymmetric molecular structure. Therefore, in the coating and drying steps, it is considered that the polymer does not easily crystallize and exists as fine particles in the active layer. As a result, it is considered that defects such as minute pinholes and thinning due to large particles in the composition are unlikely to occur in the active layer obtained from the composition of the present invention, and the device obtained from the composition of the present invention. Is presumed to have excellent uniformity of dark current characteristics.
一方、本発明の組成物に含まれる、p型半導体材料である式(I)で表される構成単位を含む重合体は、非対称な分子構造を持つ。そのため、塗布及び乾燥工程において、当該重合体は結晶化が進行しにくく、微細粒子として活性層中に存在すると考えられる。その結果、組成物中の大きな粒子に起因した微小なピンホールや薄膜化などの欠陥は、本発明の組成物から得られる活性層では生じにくいと考えられ、本発明の組成物から得られる素子は、暗電流特性の均一性が優れていると推察される。 Although the details of the mechanism for suppressing the variation in dark current characteristics in the composition of the present invention are unknown, the following mechanism can be considered, but the present invention is not limited. In the composition of the present invention, by including an insulating material that is not directly involved in the photoelectric conversion effect as an additive, the concentration and viscosity physical characteristics of the composition can be appropriately adjusted, and the thickness becomes uniform at the time of coating. A coating film can be manufactured. On the other hand, since the solid content concentration and viscosity of the composition are increased by adding the insulating material, it is considered that the aggregation of the p-type semiconductor material and the n-type semiconductor material is likely to proceed in the process of applying and drying the composition. Eh. In particular, many polymers used as p-type semiconductor materials have a planar and symmetric molecular structure in which π-conjugation is continuous from the viewpoint of light absorption and charge transportability. Therefore, it is considered that crystallization and crystal growth are likely to proceed in the process of coating and drying. It is presumed that the active layer containing a polymer, which is a p-type semiconductor material having such a molecular structure, contains large crystals of the p-type semiconductor material, and pinholes and local thinning occur from the crystals. Will be done.
On the other hand, the polymer containing the structural unit represented by the formula (I), which is a p-type semiconductor material, contained in the composition of the present invention has an asymmetric molecular structure. Therefore, in the coating and drying steps, it is considered that the polymer does not easily crystallize and exists as fine particles in the active layer. As a result, it is considered that defects such as minute pinholes and thinning due to large particles in the composition are unlikely to occur in the active layer obtained from the composition of the present invention, and the device obtained from the composition of the present invention. Is presumed to have excellent uniformity of dark current characteristics.
組成物中、p型半導体材料及びn型半導体材料は溶解していても分散していてもよい。
p型半導体材料及びn型半導体材料は、好ましくは少なくとも一部が溶解しているか、より好ましくは全部が溶解している。 In the composition, the p-type semiconductor material and the n-type semiconductor material may be dissolved or dispersed.
The p-type semiconductor material and the n-type semiconductor material are preferably at least partially dissolved, or more preferably completely dissolved.
p型半導体材料及びn型半導体材料は、好ましくは少なくとも一部が溶解しているか、より好ましくは全部が溶解している。 In the composition, the p-type semiconductor material and the n-type semiconductor material may be dissolved or dispersed.
The p-type semiconductor material and the n-type semiconductor material are preferably at least partially dissolved, or more preferably completely dissolved.
[1.1.p型半導体材料]
本実施形態に係るp型半導体材料は、下記式(I)で表される構成単位を含む重合体を含む。以下、式(I)で表される構成単位を含む重合体を、重合体(1)ともいう。p型半導体材料は、重合体(1)を一種のみ含んでいてもよく、二種以上含んでいてもよい。
また、重合体(1)は、式(I)で表される構成単位を、一種のみ含んでいてもよく、二種以上含んでいてもよい。 [1.1. p-type semiconductor material]
The p-type semiconductor material according to the present embodiment includes a polymer containing a structural unit represented by the following formula (I). Hereinafter, the polymer containing the structural unit represented by the formula (I) is also referred to as a polymer (1). The p-type semiconductor material may contain only one kind of the polymer (1), or may contain two or more kinds of the polymer (1).
Further, the polymer (1) may contain only one kind of the structural unit represented by the formula (I), or may contain two or more kinds.
本実施形態に係るp型半導体材料は、下記式(I)で表される構成単位を含む重合体を含む。以下、式(I)で表される構成単位を含む重合体を、重合体(1)ともいう。p型半導体材料は、重合体(1)を一種のみ含んでいてもよく、二種以上含んでいてもよい。
また、重合体(1)は、式(I)で表される構成単位を、一種のみ含んでいてもよく、二種以上含んでいてもよい。 [1.1. p-type semiconductor material]
The p-type semiconductor material according to the present embodiment includes a polymer containing a structural unit represented by the following formula (I). Hereinafter, the polymer containing the structural unit represented by the formula (I) is also referred to as a polymer (1). The p-type semiconductor material may contain only one kind of the polymer (1), or may contain two or more kinds of the polymer (1).
Further, the polymer (1) may contain only one kind of the structural unit represented by the formula (I), or may contain two or more kinds.
式(I)中、Ar1及びAr2は、それぞれ独立して、置換基を有していてもよい3価の芳香族複素環基を表す。
Zは、下記式(Z-1)~式(Z-4)で表される基を表す。 In formula (I), Ar 1 and Ar 2 each independently represent a trivalent aromatic heterocyclic group which may have a substituent.
Z represents a group represented by the following formulas (Z-1) to (Z-4).
Zは、下記式(Z-1)~式(Z-4)で表される基を表す。 In formula (I), Ar 1 and Ar 2 each independently represent a trivalent aromatic heterocyclic group which may have a substituent.
Z represents a group represented by the following formulas (Z-1) to (Z-4).
式(Z-1)~(Z-4)中、Rは、
水素原子、
ハロゲン原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアルケニル基、
置換基を有していてもよいシクロアルケニル基、
置換基を有していてもよいアルキニル基、
置換基を有していてもよいシクロアルキニル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいシクロアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、
置換基を有していてもよいアルキルチオ基、
置換基を有していてもよいシクロアルキルチオ基、
置換基を有していてもよいアリールチオ基、
置換基を有していてもよい1価の複素環基、
置換基を有していてもよい置換アミノ基、
置換基を有していてもよいイミン残基、
置換基を有していてもよいアミド基、
置換基を有していてもよい酸イミド基、
置換基を有していてもよい置換オキシカルボニル基、
シアノ基、
ニトロ基、
-C(=O)-Raで表される基、又は
-SO2-Rbで表される基を表し、
Ra及びRbは、それぞれ独立して、
水素原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいシクロアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、又は
置換基を有していてもよい1価の複素環基を表す。
式(Z-1)~式(Z-4)中、2つあるRは同一であっても異なっていてもよい。 In the formulas (Z-1) to (Z-4), R is
Hydrogen atom,
Halogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
An alkenyl group which may have a substituent,
Cycloalkenyl groups, which may have substituents,
An alkynyl group, which may have a substituent,
A cycloalkynyl group which may have a substituent,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Aryloxy groups, which may have substituents,
Alkylthio groups, which may have substituents,
Cycloalkylthio groups, which may have substituents,
An arylthio group, which may have a substituent,
A monovalent heterocyclic group which may have a substituent,
Substituted amino groups, which may have substituents,
Imine residues, which may have substituents,
An amide group which may have a substituent,
An acidimide group, which may have a substituent,
Substituted oxycarbonyl group, which may have a substituent,
Cyano group,
Nitro group,
Represents a group represented by -C (= O) -R a or a group represented by -SO 2 -R b .
R a and R b are independent of each other.
Hydrogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Represents an aryloxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent.
In the formulas (Z-1) to (Z-4), the two Rs may be the same or different.
水素原子、
ハロゲン原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアルケニル基、
置換基を有していてもよいシクロアルケニル基、
置換基を有していてもよいアルキニル基、
置換基を有していてもよいシクロアルキニル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいシクロアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、
置換基を有していてもよいアルキルチオ基、
置換基を有していてもよいシクロアルキルチオ基、
置換基を有していてもよいアリールチオ基、
置換基を有していてもよい1価の複素環基、
置換基を有していてもよい置換アミノ基、
置換基を有していてもよいイミン残基、
置換基を有していてもよいアミド基、
置換基を有していてもよい酸イミド基、
置換基を有していてもよい置換オキシカルボニル基、
シアノ基、
ニトロ基、
-C(=O)-Raで表される基、又は
-SO2-Rbで表される基を表し、
Ra及びRbは、それぞれ独立して、
水素原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいシクロアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、又は
置換基を有していてもよい1価の複素環基を表す。
式(Z-1)~式(Z-4)中、2つあるRは同一であっても異なっていてもよい。 In the formulas (Z-1) to (Z-4), R is
Hydrogen atom,
Halogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
An alkenyl group which may have a substituent,
Cycloalkenyl groups, which may have substituents,
An alkynyl group, which may have a substituent,
A cycloalkynyl group which may have a substituent,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Aryloxy groups, which may have substituents,
Alkylthio groups, which may have substituents,
Cycloalkylthio groups, which may have substituents,
An arylthio group, which may have a substituent,
A monovalent heterocyclic group which may have a substituent,
Substituted amino groups, which may have substituents,
Imine residues, which may have substituents,
An amide group which may have a substituent,
An acidimide group, which may have a substituent,
Substituted oxycarbonyl group, which may have a substituent,
Cyano group,
Nitro group,
Represents a group represented by -C (= O) -R a or a group represented by -SO 2 -R b .
R a and R b are independent of each other.
Hydrogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Represents an aryloxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent.
In the formulas (Z-1) to (Z-4), the two Rs may be the same or different.
Ar1又はAr2により表される3価の芳香族複素環基を構成する芳香族複素環の例としては、オキサジアゾール環、チアジアゾール環、チアゾール環、オキサゾール環、チオフェン環、ピロール環、ホスホール環、フラン環、ピリジン環、ピラジン環、ピリミジン環、トリアジン環、ピリダジン環、キノリン環、イソキノリン環、カルバゾール環、及びジベンゾホスホール環、並びに、フェノキサジン環、フェノチアジン環、ジベンゾボロール環、ジベンゾシロール環、及びベンゾピラン環が挙げられる。これらの環は、置換基を有していてもよい。
Examples of aromatic heterocycles constituting a trivalent aromatic heterocyclic group represented by Ar 1 or Ar 2 include an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a thiophene ring, a pyrrole ring, and a phosphor. Ring, furan ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyridazine ring, quinoline ring, isoquinoline ring, carbazole ring, and dibenzophosphor ring, as well as phenoxazine ring, phenothiazine ring, dibenzobolol ring, dibenzo. Examples thereof include a silol ring and a benzopyran ring. These rings may have substituents.
Zは、好ましくは、式(Z-1)又は(Z-2)で表される基である。
Z is preferably a group represented by the formula (Z-1) or (Z-2).
式(Z-1)~(Z-4)中のRは、好ましくは水素原子、アルキル基、又はアリール基であり、より好ましくは水素原子又はアルキル基であり、更に好ましくは、水素原子又は炭素原子数1~40のアルキル基であり、更に好ましくは水素原子又は炭素原子数1~30のアルキル基であり、更に好ましくは水素原子又は炭素原子数1~20のアルキル基である。これらの基は、置換基を有していてもよい。複数存在するRは、互いに同一でも、異なっていてもよい。
R in the formulas (Z-1) to (Z-4) is preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom or a carbon. It is an alkyl group having 1 to 40 atoms, more preferably a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, and still more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. These groups may have substituents. A plurality of R's may be the same as each other or may be different from each other.
一実施形態において、式(I)で表される構成単位としては、下記式(I-1)又は(I-2)で表される構成単位が好ましい。
In one embodiment, the structural unit represented by the formula (I) is preferably the structural unit represented by the following formula (I-1) or (I-2).
式(I-1)及び式(I-2)中、X1及びX2は、それぞれ独立して、硫黄原子又は酸素原子であり、Z1及びZ2は、それぞれ独立して、=C(R)-で表される基又は窒素原子であり、Rは、式(Z-1)~(Z-4)における定義と同じである。複数存在するRは、互いに同一であっても異なっていてもよい。
In formulas (I-1) and (I-2), X 1 and X 2 are independent sulfur atoms or oxygen atoms, and Z 1 and Z 2 are independent, respectively, = C ( R)-is a group or nitrogen atom represented by-, and R has the same definition as in the formulas (Z-1) to (Z-4). A plurality of R's may be the same as or different from each other.
式(I-1)で表される構成単位としては、X1及びX2が硫黄原子であり、Z1及びZ2が=C(R)-で表される基である構成単位が好ましい。Z1及びZ2としての=C(R)-で表される基におけるRは、好ましくは水素原子である。
式(I-2)で表される構成単位としては、X1及びX2が硫黄原子であり、Z1及びZ2が=C(R)-で表される基である構成単位が好ましい。Z1及びZ2としての=C(R)-で表される基におけるRは、好ましくは水素原子である。 As the structural unit represented by the formula (I-1), a structural unit in which X 1 and X 2 are sulfur atoms and Z 1 and Z 2 are groups represented by = C (R) − is preferable. R in the group represented by = C (R)-as Z 1 and Z 2 is preferably a hydrogen atom.
As the structural unit represented by the formula (I-2), a structural unit in which X 1 and X 2 are sulfur atoms and Z 1 and Z 2 are groups represented by = C (R)-is preferable. R in the group represented by = C (R)-as Z 1 and Z 2 is preferably a hydrogen atom.
式(I-2)で表される構成単位としては、X1及びX2が硫黄原子であり、Z1及びZ2が=C(R)-で表される基である構成単位が好ましい。Z1及びZ2としての=C(R)-で表される基におけるRは、好ましくは水素原子である。 As the structural unit represented by the formula (I-1), a structural unit in which X 1 and X 2 are sulfur atoms and Z 1 and Z 2 are groups represented by = C (R) − is preferable. R in the group represented by = C (R)-as Z 1 and Z 2 is preferably a hydrogen atom.
As the structural unit represented by the formula (I-2), a structural unit in which X 1 and X 2 are sulfur atoms and Z 1 and Z 2 are groups represented by = C (R)-is preferable. R in the group represented by = C (R)-as Z 1 and Z 2 is preferably a hydrogen atom.
構成単位(I-1)の例として、下記式(I-1-1)~(I-1-14)で表される構成単位が挙げられる。下記式(I-1-1)~(I-1-14)中、Rは、式(Z-1)~(Z-4)における定義と同じである。複数存在するRは、互いに同一であっても異なっていてもよい。
中でも、式(I-1-1)で表される構成単位が好ましい。 Examples of the structural unit (I-1) include the structural units represented by the following formulas (I-1-1) to (I-1-14). In the following formulas (I-1-1) to (I-1-14), R has the same definition as in the formulas (Z-1) to (Z-4). A plurality of R's may be the same as or different from each other.
Above all, the structural unit represented by the formula (I-1-1) is preferable.
中でも、式(I-1-1)で表される構成単位が好ましい。 Examples of the structural unit (I-1) include the structural units represented by the following formulas (I-1-1) to (I-1-14). In the following formulas (I-1-1) to (I-1-14), R has the same definition as in the formulas (Z-1) to (Z-4). A plurality of R's may be the same as or different from each other.
Above all, the structural unit represented by the formula (I-1-1) is preferable.
構成単位(I-2)の例として、下記式(I-2-1)~(I-2-14)で表される構成単位が挙げられる。下記式(I-2-1)~(I-2-14)中、Rは、式(Z-1)~(Z-4)における定義と同じである。複数存在するRは、互いに同一であっても異なっていてもよい。
中でも、式(I-2-1)で表される構成単位が好ましい。 Examples of the structural unit (I-2) include the structural units represented by the following formulas (I-2-1) to (I-2-14). In the following formulas (I-2-1) to (I-2-14), R has the same definition as in the formulas (Z-1) to (Z-4). A plurality of R's may be the same as or different from each other.
Above all, the structural unit represented by the formula (I-2-1) is preferable.
中でも、式(I-2-1)で表される構成単位が好ましい。 Examples of the structural unit (I-2) include the structural units represented by the following formulas (I-2-1) to (I-2-14). In the following formulas (I-2-1) to (I-2-14), R has the same definition as in the formulas (Z-1) to (Z-4). A plurality of R's may be the same as or different from each other.
Above all, the structural unit represented by the formula (I-2-1) is preferable.
重合体(1)は、好ましくは、式(I)で表される構成単位に加えて、更に式(IV)で表される構成単位を含む。重合体(1)は、式(IV)で表される構成単位を一種のみ含んでいてもよく、二種以上含んでいてもよい。
The polymer (1) preferably contains a structural unit represented by the formula (I) in addition to the structural unit represented by the formula (I). The polymer (1) may contain only one type of structural unit represented by the formula (IV), or may contain two or more types.
-Ar3- (IV)
-Ar 3- (IV)
式(IV)中、Ar3は2価の芳香族複素環基を表す。
In formula (IV), Ar 3 represents a divalent aromatic heterocyclic group.
Ar3で表される2価の芳香族複素環基の炭素原子数は、通常2~60であり、好ましくは4~60であり、より好ましくは4~20である。Ar3で表される2価の芳香族複素環基は置換基を有していてもよい。
式(IV)で表される構成単位としては、下記式(IV-1)~(IV-8)のいずれかで表される構成単位が好ましい。 The number of carbon atoms of the divalent aromatic heterocyclic group represented by Ar 3 is usually 2 to 60, preferably 4 to 60, and more preferably 4 to 20. The divalent aromatic heterocyclic group represented by Ar 3 may have a substituent.
As the structural unit represented by the formula (IV), the structural unit represented by any of the following formulas (IV-1) to (IV-8) is preferable.
式(IV)で表される構成単位としては、下記式(IV-1)~(IV-8)のいずれかで表される構成単位が好ましい。 The number of carbon atoms of the divalent aromatic heterocyclic group represented by Ar 3 is usually 2 to 60, preferably 4 to 60, and more preferably 4 to 20. The divalent aromatic heterocyclic group represented by Ar 3 may have a substituent.
As the structural unit represented by the formula (IV), the structural unit represented by any of the following formulas (IV-1) to (IV-8) is preferable.
式(IV-1)~式(IV-8)中、X1、X2、Z1、Z2及びRは、式(I-1)及び式(I-2)における定義と同じである。Rが2つある場合、2つあるRは、同一であっても異なっていてもよい。
式(IV-6)中、2つのRは、好ましくは、それぞれ独立して、水素原子、アルキル基、又はハロゲン原子であり、より好ましくは、同時に水素原子又はハロゲン原子であり、更に好ましくは、同時にハロゲン原子である。 In formulas (IV- 1 ) to (IV - 8), X1, X2, Z1, Z2 and R are the same as the definitions in formulas (I- 1 ) and (I-2). When there are two Rs, the two Rs may be the same or different.
In formula (IV-6), the two Rs are preferably independently hydrogen atoms, alkyl groups, or halogen atoms, more preferably hydrogen atoms or halogen atoms at the same time, and even more preferably. At the same time, it is a halogen atom.
式(IV-6)中、2つのRは、好ましくは、それぞれ独立して、水素原子、アルキル基、又はハロゲン原子であり、より好ましくは、同時に水素原子又はハロゲン原子であり、更に好ましくは、同時にハロゲン原子である。 In formulas (IV- 1 ) to (IV - 8), X1, X2, Z1, Z2 and R are the same as the definitions in formulas (I- 1 ) and (I-2). When there are two Rs, the two Rs may be the same or different.
In formula (IV-6), the two Rs are preferably independently hydrogen atoms, alkyl groups, or halogen atoms, more preferably hydrogen atoms or halogen atoms at the same time, and even more preferably. At the same time, it is a halogen atom.
原料化合物の入手性の観点から、式(IV-1)~式(IV-8)中のX1及びX2は、いずれも硫黄原子であることが好ましい。
From the viewpoint of availability of the raw material compound, it is preferable that both X 1 and X 2 in the formulas (IV-1) to (IV-8) are sulfur atoms.
Ar3で表される2価の芳香族複素環基の具体例としては、下記式(101)~式(190)で表される基及びこれらの基が置換基により置換された基が挙げられる。置換基としては、ハロゲン原子及びアルキル基が好ましい。中でも、式(148)又は式(190)で表される基が好ましい。
Specific examples of the divalent aromatic heterocyclic group represented by Ar 3 include groups represented by the following formulas (101) to (190) and groups in which these groups are substituted with substituents. .. As the substituent, a halogen atom and an alkyl group are preferable. Of these, the group represented by the formula (148) or the formula (190) is preferable.
式(101)~式(190)中、Rは前記と同義である。Rが複数ある場合、複数あるRは、互いに同一であっても異なっていてもよい。
In equations (101) to (190), R has the same meaning as described above. When there are a plurality of Rs, the plurality of Rs may be the same or different from each other.
重合体(1)における、式(I)で表される構成単位及び式(IV)で表される構成単位の合計量は、重合体(1)が含むすべての構成単位の量を100モル%とすると、好ましくは20モル%~100モル%であり、p型半導体材料としての電荷輸送性を向上させることができるので、より好ましくは40モル%~100モル%であり、更に好ましくは50モル%~100モル%である。ここで、重合体(1)が、式(IV)で表される構成単位を含まない場合は、式(I)で表される構成単位及び式(IV)で表される構成単位の合計量は、式(I)で表される構成単位の量とする。
The total amount of the structural unit represented by the formula (I) and the structural unit represented by the formula (IV) in the polymer (1) is 100 mol% based on the amount of all the structural units contained in the polymer (1). Then, it is preferably 20 mol% to 100 mol%, and since it can improve the charge transport property as a p-type semiconductor material, it is more preferably 40 mol% to 100 mol%, and further preferably 50 mol. % To 100 mol%. Here, when the polymer (1) does not contain the structural unit represented by the formula (IV), the total amount of the structural unit represented by the formula (I) and the structural unit represented by the formula (IV). Is the amount of the structural unit represented by the formula (I).
好ましくは、重合体(1)は、下記構成単位の組み合わせのいずれかを含む。
・式(I-2)で表される構成単位及び式(IV-6)で表される構成単位の組み合わせ・式(I-2)で表される構成単位及び式(IV-8)で表される構成単位の組み合わせ Preferably, the polymer (1) contains any of the following combinations of structural units.
-Combination of the structural unit represented by the formula (I-2) and the structural unit represented by the formula (IV-6) -The structural unit represented by the formula (I-2) and the table by the formula (IV-8). Combination of building blocks
・式(I-2)で表される構成単位及び式(IV-6)で表される構成単位の組み合わせ・式(I-2)で表される構成単位及び式(IV-8)で表される構成単位の組み合わせ Preferably, the polymer (1) contains any of the following combinations of structural units.
-Combination of the structural unit represented by the formula (I-2) and the structural unit represented by the formula (IV-6) -The structural unit represented by the formula (I-2) and the table by the formula (IV-8). Combination of building blocks
より好ましくは、重合体(1)は、下記構成単位の組み合わせのいずれかを含む。
・式(I-2-1)で表される構成単位及び式(148)で表される構成単位の組み合わせ
・式(I-2-1)で表される構成単位及び式(190)で表される構成単位の組み合わせ More preferably, the polymer (1) contains any of the following combinations of structural units.
-Combination of the structural unit represented by the formula (I-2-1) and the structural unit represented by the formula (148) -The structural unit represented by the formula (I-2-1) and the table by the formula (190). Combination of building blocks
・式(I-2-1)で表される構成単位及び式(148)で表される構成単位の組み合わせ
・式(I-2-1)で表される構成単位及び式(190)で表される構成単位の組み合わせ More preferably, the polymer (1) contains any of the following combinations of structural units.
-Combination of the structural unit represented by the formula (I-2-1) and the structural unit represented by the formula (148) -The structural unit represented by the formula (I-2-1) and the table by the formula (190). Combination of building blocks
本実施形態におけるp型半導体材料である重合体(1)の具体例としては、下記式(P-1)~(P-2)で表される重合体が挙げられる。
Specific examples of the polymer (1) which is a p-type semiconductor material in the present embodiment include polymers represented by the following formulas (P-1) to (P-2).
p型半導体材料における重合体(1)の重量割合は、好ましくは20重量%以上、より好ましくは40重量%以上、更に好ましくは50重量%以上であり、通常100重量%以下であり、100重量%であってもよい。
The weight ratio of the polymer (1) in the p-type semiconductor material is preferably 20% by weight or more, more preferably 40% by weight or more, still more preferably 50% by weight or more, usually 100% by weight or less, and 100% by weight. May be%.
本実施形態の組成物は、p型半導体材料として、前記の重合体(1)に加えて、任意で他の化合物を含んでいてもよい。
p型半導体材料である他の化合物の例としては、ポリビニルカルバゾール及びその誘導体、ポリシラン及びその誘導体、側鎖又は主鎖に芳香族アミン構造を含むポリシロキサン誘導体、ポリアニリン及びその誘導体、ポリチオフェン及びその誘導体、ポリピロール及びその誘導体、ポリフェニレンビニレン及びその誘導体、ポリチエニレンビニレン及びその誘導体、ポリフルオレン及びその誘導体が挙げられる。本実施形態に係る組成物は、p型半導体材料として、重合体(1)に加えて、任意に、他の化合物を一種のみ含んでいても、複数種含んでいてもよい。 The composition of the present embodiment may optionally contain other compounds as the p-type semiconductor material in addition to the above-mentioned polymer (1).
Examples of other compounds that are p-type semiconductor materials include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives, polythiophene and its derivatives. , Polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, polyfluorene and its derivatives. The composition according to the present embodiment may optionally contain only one kind or a plurality of kinds of other compounds in addition to the polymer (1) as the p-type semiconductor material.
p型半導体材料である他の化合物の例としては、ポリビニルカルバゾール及びその誘導体、ポリシラン及びその誘導体、側鎖又は主鎖に芳香族アミン構造を含むポリシロキサン誘導体、ポリアニリン及びその誘導体、ポリチオフェン及びその誘導体、ポリピロール及びその誘導体、ポリフェニレンビニレン及びその誘導体、ポリチエニレンビニレン及びその誘導体、ポリフルオレン及びその誘導体が挙げられる。本実施形態に係る組成物は、p型半導体材料として、重合体(1)に加えて、任意に、他の化合物を一種のみ含んでいても、複数種含んでいてもよい。 The composition of the present embodiment may optionally contain other compounds as the p-type semiconductor material in addition to the above-mentioned polymer (1).
Examples of other compounds that are p-type semiconductor materials include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives, polythiophene and its derivatives. , Polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, polyfluorene and its derivatives. The composition according to the present embodiment may optionally contain only one kind or a plurality of kinds of other compounds in addition to the polymer (1) as the p-type semiconductor material.
[1.2.n型半導体材料]
本実施形態に係る組成物は、n型半導体材料を含む。本実施形態に係る組成物は、n型半導体材料として、一種の化合物のみを含んでいても、複数種の化合物を含んでいてもよい。n型半導体材料として、多種の化合物が公知であり、それらを本実施形態に係るn型半導体材料として用いることができる。 [1.2. n-type semiconductor material]
The composition according to this embodiment contains an n-type semiconductor material. The composition according to the present embodiment may contain only one kind of compound or may contain a plurality of kinds of compounds as the n-type semiconductor material. Various compounds are known as n-type semiconductor materials, and they can be used as the n-type semiconductor material according to the present embodiment.
本実施形態に係る組成物は、n型半導体材料を含む。本実施形態に係る組成物は、n型半導体材料として、一種の化合物のみを含んでいても、複数種の化合物を含んでいてもよい。n型半導体材料として、多種の化合物が公知であり、それらを本実施形態に係るn型半導体材料として用いることができる。 [1.2. n-type semiconductor material]
The composition according to this embodiment contains an n-type semiconductor material. The composition according to the present embodiment may contain only one kind of compound or may contain a plurality of kinds of compounds as the n-type semiconductor material. Various compounds are known as n-type semiconductor materials, and they can be used as the n-type semiconductor material according to the present embodiment.
組成物に含まれる半導体材料が、p型半導体材料及びn型半導体材料のうちのいずれとして機能するかは、選択された化合物のHOMOエネルギーレベルの値又はLUMOエネルギーの値から相対的に決定し得る。p型半導体材料のHOMO及びLUMOのエネルギーレベルの値と、n型半導体材料のHOMO及びLUMOのエネルギーレベルの値との関係は、組成物から製造される膜が、所望の機能(例えば、光電変換機能、光検出機能)を発揮する範囲に適宜設定することができる。
Whether the semiconductor material contained in the composition functions as a p-type semiconductor material or an n-type semiconductor material can be relatively determined from the value of the HOMO energy level or the value of the LUMO energy of the selected compound. .. The relationship between the energy level values of HOMO and LUMO of the p-type semiconductor material and the energy level values of HOMO and LUMO of the n-type semiconductor material is such that the film produced from the composition has a desired function (for example, photoelectric conversion). It can be appropriately set within the range in which the function (function, light detection function) is exhibited.
本実施形態に係るn型半導体材料は、低分子化合物であっても高分子化合物であってもよい。n型半導体材料(電子受容性化合物)の例としては、C60フラーレン等のフラーレン及びその誘導体、オキサジアゾール誘導体、アントラキノジメタン及びその誘導体、ベンゾキノン及びその誘導体、ナフトキノン及びその誘導体、アントラキノン及びその誘導体、テトラシアノアントラキノジメタン及びその誘導体、フルオレノン誘導体、ジフェニルジシアノエチレン及びその誘導体、ジフェノキノン誘導体、8-ヒドロキシキノリン及びその誘導体の金属錯体、並びに、バソクプロイン等のフェナントレン誘導体が挙げられる。
The n-type semiconductor material according to this embodiment may be a low molecular weight compound or a high molecular weight compound. Examples of n-type semiconductor materials ( electron-accepting compounds) include fullerene such as C60 fullerene and its derivatives, oxadiazole derivatives, anthracinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and Examples thereof include tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, 8-hydroxyquinolin and metal complexes of its derivatives, and phenanthrene derivatives such as basocproin.
一実施形態において、組成物は、n型半導体材料としてフラーレン又はフラーレン誘導体を含んでいてもよい。
フラーレンの例としては、C60フラーレン、C70フラーレン、C76フラーレン、C78フラーレン、及びC84フラーレンが挙げられる。 In one embodiment, the composition may contain a fullerene or a fullerene derivative as an n-type semiconductor material.
Examples of fullerenes include C 60 fullerenes, C 70 fullerenes, C 76 fullerenes, C 78 fullerenes, and C 84 fullerenes.
フラーレンの例としては、C60フラーレン、C70フラーレン、C76フラーレン、C78フラーレン、及びC84フラーレンが挙げられる。 In one embodiment, the composition may contain a fullerene or a fullerene derivative as an n-type semiconductor material.
Examples of fullerenes include C 60 fullerenes, C 70 fullerenes, C 76 fullerenes, C 78 fullerenes, and C 84 fullerenes.
フラーレン誘導体の例としては、下記式(F-1)~式(F-4)で表される化合物が挙げられる。
Examples of fullerene derivatives include compounds represented by the following formulas (F-1) to (F-4).
式(F-1)~式(F-4)中、
RXは、アルキル基、アリール基、1価の複素環基、又はエステル構造を有する基を表す。複数あるRXは、互いに同一であっても異なっていてもよい。
RYは、アルキル基、又はアリール基を表す。複数あるRYは、互いに同一であっても異なっていてもよい。 In equations (F-1) to (F-4),
RX represents an alkyl group, an aryl group, a monovalent heterocyclic group, or a group having an ester structure. A plurality of RXs may be the same as or different from each other.
RY represents an alkyl group or an aryl group. A plurality of RYs may be the same as or different from each other.
RXは、アルキル基、アリール基、1価の複素環基、又はエステル構造を有する基を表す。複数あるRXは、互いに同一であっても異なっていてもよい。
RYは、アルキル基、又はアリール基を表す。複数あるRYは、互いに同一であっても異なっていてもよい。 In equations (F-1) to (F-4),
RX represents an alkyl group, an aryl group, a monovalent heterocyclic group, or a group having an ester structure. A plurality of RXs may be the same as or different from each other.
RY represents an alkyl group or an aryl group. A plurality of RYs may be the same as or different from each other.
RXで表される1価の複素環基の例としては、チエニル基、ピロリル基、フリル基、ピリジル基、キノリル基、及びイソキノリル基が挙げられる。
Examples of the monovalent heterocyclic group represented by RX include a thienyl group, a pyrrolyl group, a frill group, a pyridyl group, a quinolyl group, and an isoquinolyl group.
RXで表されるエステル構造を有する基の例としては、式(E-1)で表される基が挙げられる。
Examples of the group having an ester structure represented by RX include a group represented by the formula (E-1).
(式中、u1は、1~6の整数を表し、u2は、0~6の整数を表し、RZは、アルキル基、アリール基又は1価の複素環基を表す。)
(In the formula, u1 represents an integer of 1 to 6, u2 represents an integer of 0 to 6, and RZ represents an alkyl group, an aryl group or a monovalent heterocyclic group.)
C60フラーレン誘導体の例としては、下記の化合物が挙げられる。式中、Rは前記と同義である。
Examples of C60 fullerene derivatives include the following compounds. In the formula, R has the same meaning as described above.
C70フラーレン誘導体の例としては、下記の化合物が挙げられる。
Examples of the C70 fullerene derivative include the following compounds.
フラーレン誘導体の具体例としては、[6,6]-フェニル-C61酪酸メチルエステル(C60PCBM、[6,6]-Phenyl C61 butyric acid methyl ester)、[6,6]-フェニル-C71酪酸メチルエステル(C70PCBM、[6,6]-Phenyl C71 butyric acid methyl ester)、[6,6」-フェニル-C85酪酸メチルエステル(C84PCBM、[6,6]-Phenyl C85 butyric acid methyl ester)、及び[6,6]-チエニル-C61酪酸メチルエステル([6,6]-Thienyl C61 butyric acid methyl ester)が挙げられる。
Specific examples of the fullerene derivative include [6,6] -phenyl-C61 butyrate methyl ester (C60PCBM, [6,6] -Phenyl C61 butyric acid methyl ester), [6,6] -phenyl-C71 butyrate methyl ester (6,6] -phenyl-C71 butyrate methyl ester (6,6) -phenyl-C71 butyrate methyl ester. C70PCBM, [6,6] -Phenyl C71 butyric acid methyl ester), [6,6] -phenyl-C85 butyrate methyl ester (C84PCBM, [6,6] -Phenyl C85 butyric acid methyl ester), and [6,6] ] -Thienyl-C61 butyrate methyl ester ([6,6] -Thienyl C61 butyric acid methyl ester) can be mentioned.
本実施形態に係るn型半導体材料は、フラーレン及びフラーレンの誘導体のいずれでもない化合物を含んでいてもよい。以下、フラーレン及びフラーレンの誘導体のいずれでもない化合物を非フラーレン化合物ともいう。
The n-type semiconductor material according to the present embodiment may contain a compound that is neither fullerene nor a derivative of fullerene. Hereinafter, a compound that is neither fullerene nor a derivative of fullerene is also referred to as a non-fullerene compound.
一実施形態において、n型半導体材料は、下記式(V)で表される化合物を含むことが好ましい。
A1-B10-A2 (V)
In one embodiment, the n-type semiconductor material preferably contains a compound represented by the following formula (V).
A 1 -B 10 -A 2 (V)
A1-B10-A2 (V)
In one embodiment, the n-type semiconductor material preferably contains a compound represented by the following formula (V).
A 1 -B 10 -A 2 (V)
式(V)中、
A1及びA2は、それぞれ独立して、電子求引性の基を表し、B10は、π共役系を含む基を表す。 In equation (V),
A 1 and A 2 each independently represent an electron-withdrawing group, and B 10 represents a group containing a π-conjugated system.
A1及びA2は、それぞれ独立して、電子求引性の基を表し、B10は、π共役系を含む基を表す。 In equation (V),
A 1 and A 2 each independently represent an electron-withdrawing group, and B 10 represents a group containing a π-conjugated system.
A1及びA2である電子求引性の基の例としては、-CH=C(-CN)2で表される基、及び下記式(a-1)~式(a-9)で表される基が挙げられる。
Examples of electron-withdrawing groups such as A 1 and A 2 are groups represented by -CH = C (-CN) 2 and tables represented by the following formulas (a-1) to (a-9). The group to be done is mentioned.
式(a-1)~式(a-7)中、
Tは、置換基を有していてもよい炭素環、又は置換基を有していてもよい複素環を表す。炭素環及び複素環は、単環であってもよく、縮合環であってもよい。これらの環が置換基を複数有する場合、複数ある置換基は、同一であっても異なっていてもよい。 In equations (a-1) to (a-7),
T represents a carbocycle which may have a substituent or a heterocycle which may have a substituent. The carbocycle and the heterocycle may be a monocyclic ring or a condensed ring. When these rings have a plurality of substituents, the plurality of substituents may be the same or different.
Tは、置換基を有していてもよい炭素環、又は置換基を有していてもよい複素環を表す。炭素環及び複素環は、単環であってもよく、縮合環であってもよい。これらの環が置換基を複数有する場合、複数ある置換基は、同一であっても異なっていてもよい。 In equations (a-1) to (a-7),
T represents a carbocycle which may have a substituent or a heterocycle which may have a substituent. The carbocycle and the heterocycle may be a monocyclic ring or a condensed ring. When these rings have a plurality of substituents, the plurality of substituents may be the same or different.
Tである置換基を有していてもよい炭素環の例としては、芳香族炭素環が挙げられ、好ましくは芳香族炭素環である。Tである置換基を有していてもよい炭素環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、テトラセン環、ペンタセン環、ピレン環、及びフェナントレン環が挙げられ、好ましくはベンゼン環、ナフタレン環、及びフェナントレン環であり、より好ましくはベンゼン環及びナフタレン環であり、さらに好ましくはベンゼン環である。これらの環は、置換基を有していてもよい。
An example of a carbocycle that may have a substituent that is T is an aromatic carbocycle, preferably an aromatic carbocycle. Specific examples of the carbocycle which may have a substituent which is T include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring, and a benzene ring is preferable. It is a naphthalene ring and a phenanthrene ring, more preferably a benzene ring and a naphthalene ring, and further preferably a benzene ring. These rings may have substituents.
Tである置換基を有していてもよい複素環の例としては、芳香族複素環が挙げられ、好ましくは芳香族複素環である。Tである置換基を有していてもよい複素環の具体例としては、ピリジン環、ピリダジン環、ピリミジン環、ピラジン環、ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、及びチエノチオフェン環が挙げられ、好ましくはチオフェン環、ピリジン環、ピラジン環、チアゾール環、及びチエノチオフェン環であり、より好ましくはチオフェン環である。これらの環は、置換基を有していてもよい。
An example of a heterocycle which may have a substituent which is T is an aromatic heterocycle, and an aromatic heterocycle is preferable. Specific examples of the heterocycle which may have a substituent which is T include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, and a thiazole ring. And a thienothiophene ring, preferably a thiophene ring, a pyridine ring, a pyrazine ring, a thiazole ring, and a thienothiophene ring, and more preferably a thiophene ring. These rings may have substituents.
Tである炭素環又は複素環が有し得る置換基の例としては、ハロゲン原子、アルキル基、アルキルオキシ基、アリール基、及び1価の複素環基が挙げられ、好ましくはフッ素原子、及び/又は炭素原子数1~6のアルキル基である。
Examples of the substituent that the carbocycle or heterocycle which is T may have include a halogen atom, an alkyl group, an alkyloxy group, an aryl group, and a monovalent heterocyclic group, preferably a fluorine atom and /. Alternatively, it is an alkyl group having 1 to 6 carbon atoms.
X4、X5、及びX6は、それぞれ独立して、酸素原子、硫黄原子、アルキリデン基、又は=C(-CN)2で表される基を表し、好ましくは、酸素原子、硫黄原子、又は=C(-CN)2で表される基である。
X 4 , X 5 and X 6 independently represent an oxygen atom, a sulfur atom, an alkylidene group, or a group represented by = C (-CN) 2 , preferably an oxygen atom, a sulfur atom, and the like. Or, it is a group represented by = C (-CN) 2 .
X7は、水素原子、ハロゲン原子、シアノ基、置換基を有していてもよいアルキル基、置換基を有していてもよいアルキルオキシ基、置換基を有していてもよいアリール基又は1価の複素環基を表す。
X 7 is a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent, an alkyloxy group which may have a substituent, an aryl group which may have a substituent or a group. Represents a monovalent heterocyclic group.
Ra1、Ra2、Ra3、Ra4、及びRa5は、それぞれ独立して、水素原子、置換基を有していてもよいアルキル基、ハロゲン原子、置換基を有していてもよいアルキルオキシ基、置換基を有していてもよいアリール基又は1価の複素環基を表し、好ましくは、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基である。
R a1 , R a2 , R a3 , R a4 , and R a5 independently have a hydrogen atom, an alkyl group which may have a substituent, a halogen atom, and an alkyl which may have a substituent. Represents an oxy group, an aryl group which may have a substituent or a monovalent heterocyclic group, and preferably an alkyl group which may have a substituent or an aryl group which may have a substituent. Is.
式(a-8)及び式(a-9)中、Ra6及びRa7は、それぞれ独立して、水素原子、ハロゲン原子、置換基を有していてもよいアルキル基、置換基を有していてもよいシクロアルキル基、置換基を有していてもよいアルキルオキシ基、置換基を有していてもよいシクロアルキルオキシ基、置換基を有していてもよい1価の芳香族炭素環基、又は置換基を有していてもよい1価の芳香族複素環基を表し、複数あるRa6及びRa7は、同一であっても異なっていてもよい。
In the formulas (a-8) and (a-9), Ra6 and Ra7 each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and a substituent. A cycloalkyl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, and a monovalent aromatic carbon which may have a substituent. It represents a monovalent aromatic heterocyclic group which may have a ring group or a substituent, and a plurality of Ra 6 and Ra 7 may be the same or different.
A1及びA2である電子求引性の基としては、下記の式(a-1-1)~式(a-1-4)並びに式(a-6-1)及び式(a-7-1)のいずれかで表される基が好ましく、式(a-1-1)で表される基がより好ましい。ここで、複数あるRa10は、それぞれ独立して、水素原子又は置換基を表し、好ましくは水素原子、ハロゲン原子、シアノ基、又は置換基を有していてもよいアルキル基を表す。Ra3、Ra4、及びRa5は、それぞれ独立して、前記と同義であり、好ましくはそれぞれ独立して置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表す。
The following formulas (a-1-1) to (a-1-4), as well as formulas (a-6-1) and formulas (a-7) are used as the basis of the electron-withdrawing properties of A 1 and A 2 . The group represented by any one of -1) is preferable, and the group represented by the formula (a-1-1) is more preferable. Here, each of the plurality of Ra 10 independently represents a hydrogen atom or a substituent, and preferably represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. R a3 , R a4 , and R a5 are independently synonymous with the above, and preferably each of them independently has an alkyl group or an aryl which may have a substituent. Represents a group.
B10であるπ共役系を含む基の例としては、後述する式(VI)で表される化合物における、-(S1)n1-B11-(S2)n2-で表される基が挙げられる。
As an example of a group containing a π-conjugated system of B 10 , the group represented by-(S 1 ) n1 -B 11- (S 2 ) n2- in the compound represented by the formula (VI) described later is Can be mentioned.
一実施形態において、n型半導体材料は、下記式(VI)で表される化合物であることが好ましい。
A1-(S1)n1-B11-(S2)n2-A2 (VI)
In one embodiment, the n-type semiconductor material is preferably a compound represented by the following formula (VI).
A 1- (S 1 ) n1 -B 11- (S 2 ) n2 -A 2 (VI)
A1-(S1)n1-B11-(S2)n2-A2 (VI)
In one embodiment, the n-type semiconductor material is preferably a compound represented by the following formula (VI).
A 1- (S 1 ) n1 -B 11- (S 2 ) n2 -A 2 (VI)
式(VI)中、A1及びA2は、それぞれ独立して、電子求引性の基を表す。A1及びA2の例及び好ましい例は、前記式(V)におけるA1及びA2について説明した例及び好ましい例と同様である。
In formula (VI), A 1 and A 2 each independently represent an electron-withdrawing group. The examples and preferred examples of A 1 and A 2 are the same as the examples described and preferred examples of A 1 and A 2 in the above formula (V).
S1及びS2は、それぞれ独立して、置換基を有していてもよい2価の炭素環基、置換基を有していてもよい2価の複素環基、-C(Rs1)=C(Rs2)-で表される基(ここで、Rs1及びRs2は、それぞれ独立して、水素原子、又は置換基(好ましくは、水素原子、ハロゲン原子、置換基を有していてもよいアルキル基、又は置換基を有していてもよい1価の複素環基を表す。)、又は-C≡C-で表される基を表す。
S 1 and S 2 are independently a divalent carbocyclic group which may have a substituent and a divalent heterocyclic group which may have a substituent, -C (R s1 ). = Group represented by C (R s2 )-(where R s1 and R s2 each independently have a hydrogen atom or a substituent (preferably a hydrogen atom, a halogen atom, a substituent). Represents a monovalent heterocyclic group which may have an alkyl group which may have a substituent or a substituent), or a group represented by −C≡C−.
S1及びS2により表される、置換基を有していてもよい2価の炭素環基及び置換基を有していてもよい2価の複素環基は、縮合環であってもよい。2価の炭素環基又は2価の複素環基が、複数の置換基を有する場合、複数ある置換基は、同一であっても異なっていてもよい。
The divalent carbocyclic group which may have a substituent and the divalent heterocyclic group which may have a substituent represented by S 1 and S 2 may be a fused ring. .. When the divalent carbocyclic group or the divalent heterocyclic group has a plurality of substituents, the plurality of substituents may be the same or different.
式(VI)中、n1及びn2は、それぞれ独立して、0以上の整数を表し、好ましくはそれぞれ独立して、0又は1を表し、より好ましくは、同時に0又は1を表す。
In the formula (VI), n1 and n2 each independently represent an integer of 0 or more, preferably independently represent 0 or 1, and more preferably represent 0 or 1 at the same time.
2価の炭素環基の例としては、2価の芳香族炭素環基が挙げられる。
2価の複素環基の例としては、2価の芳香族複素環基が挙げられる。
2価の芳香族炭素環基又は2価の芳香族複素環基が縮合環である場合、縮合環を構成する環の全部が芳香族性を有する縮合環であってもよく、一部のみが芳香族性を有する縮合環であってもよい。 Examples of divalent carbocyclic groups include divalent aromatic carbocyclic groups.
Examples of divalent heterocyclic groups include divalent aromatic heterocyclic groups.
When the divalent aromatic carbocyclic group or the divalent aromatic heterocyclic group is a fused ring, all of the rings constituting the fused ring may be a fused ring having aromaticity, and only a part thereof may be a fused ring. It may be a fused ring having aromaticity.
2価の複素環基の例としては、2価の芳香族複素環基が挙げられる。
2価の芳香族炭素環基又は2価の芳香族複素環基が縮合環である場合、縮合環を構成する環の全部が芳香族性を有する縮合環であってもよく、一部のみが芳香族性を有する縮合環であってもよい。 Examples of divalent carbocyclic groups include divalent aromatic carbocyclic groups.
Examples of divalent heterocyclic groups include divalent aromatic heterocyclic groups.
When the divalent aromatic carbocyclic group or the divalent aromatic heterocyclic group is a fused ring, all of the rings constituting the fused ring may be a fused ring having aromaticity, and only a part thereof may be a fused ring. It may be a fused ring having aromaticity.
S1及びS2の例としては、既に説明したAr3で表される2価の芳香族複素環基の例として挙げられた式(101)~(190)のいずれかで表される基、及びこれらの基における水素原子が置換基で置換された基が挙げられる。
Examples of S 1 and S 2 include groups represented by any of the formulas (101) to (190) given as examples of the divalent aromatic heterocyclic group represented by Ar 3 already described. And groups in which the hydrogen atom in these groups is substituted with a substituent.
S1及びS2は、好ましくは、それぞれ独立して、下記式(s-1)又は(s-2)で表される基を表す。
S 1 and S 2 preferably independently represent a group represented by the following formula (s-1) or (s-2).
式(s-1)及び(s-2)中、
X3は、酸素原子又は硫黄原子を表す。
Ra10は、前記定義のとおりである。 In equations (s-1) and (s-2),
X3 represents an oxygen atom or a sulfur atom.
R a10 is as defined above.
X3は、酸素原子又は硫黄原子を表す。
Ra10は、前記定義のとおりである。 In equations (s-1) and (s-2),
X3 represents an oxygen atom or a sulfur atom.
R a10 is as defined above.
S1及びS2は、好ましくは、それぞれ独立して、式(142)、式(148)、若しくは式(184)で表される基、又はこれらの基における水素原子が置換基で置換された基であり、より好ましくは、前記式(142)若しくは式(184)で表される基、又は式(184)で表される基における1つの水素原子が、アルキルオキシ基で置換された基である。
S 1 and S 2 are preferably independently represented by a group represented by the formula (142), the formula (148), or the formula (184), or the hydrogen atom in these groups is substituted with a substituent. A group, more preferably a group in which one hydrogen atom in the group represented by the above formula (142) or the formula (184) or the group represented by the formula (184) is substituted with an alkyloxy group. be.
B11は、炭素環構造及び複素環構造からなる群から選択された2以上の構造の縮合環基であり、かつオルト-ペリ縮合構造を含まない縮合環基であり、かつ置換基を有していてもよい縮合環基を表す。
B 11 is a fused ring group having two or more structures selected from the group consisting of a carbocyclic structure and a heterocyclic structure, and is a fused ring group that does not contain an ortho-peri condensed structure, and has a substituent. Represents a fused ring group that may be present.
B11で表される縮合環基は、互いに同一である2以上の構造を縮合した構造を含んでいてもよい。
The fused ring group represented by B 11 may contain a structure obtained by condensing two or more structures that are identical to each other.
B11で表される縮合環基が複数の置換基を有する場合、複数ある置換基は、同一であっても異なっていてもよい。
When the condensed ring group represented by B 11 has a plurality of substituents, the plurality of substituents may be the same or different.
B11で表される縮合環基を構成し得る炭素環構造の例としては、下記式(Cy1)又は式(Cy2)で表される環構造が挙げられる。
Examples of the carbon ring structure that can form the fused ring group represented by B 11 include a ring structure represented by the following formula (Cy1) or formula (Cy2).
B11で表される縮合環基を構成し得る複素環構造の例としては、下記式(Cy3)~式(Cy10)のいずれかで表される環構造が挙げられる。
Examples of the heterocyclic structure that can form the fused ring group represented by B 11 include a ring structure represented by any of the following formulas (Cy3) to (Cy10).
式(VI)中、B11は、好ましくは、前記式(Cy1)~式(Cy10)で表される構造からなる群から選択された2以上の構造の縮合環基であって、オルト-ペリ縮合構造を含まない縮合環基であり、かつ置換基を有していてもよい縮合環基である。B11は、式(Cy1)~式(Cy10)で表される構造のうち、2以上の同一の構造が縮合した構造を含んでいてもよい。
In formula (VI), B 11 is preferably a fused ring group having two or more structures selected from the group consisting of the structures represented by the formulas (Cy1) to (Cy10). It is a condensed ring group that does not contain a condensed structure and may have a substituent. B 11 may include a structure in which two or more of the same structures are condensed among the structures represented by the formulas (Cy1) to (Cy10).
B11は、より好ましくは、式(Cy1)~式(Cy6)及び式(Cy8)で表される構造からなる群から選択された2以上の構造の縮合環基であって、オルト-ペリ縮合構造を含まない縮合環基であり、かつ置換基を有していてもよい縮合環基である。
B 11 is more preferably a fused ring group having two or more structures selected from the group consisting of the structures represented by the formulas (Cy1) to (Cy6) and the formula (Cy8), and is an ortho-peri condensation. It is a condensed ring group that does not contain a structure and may have a substituent.
B11である縮合環基が有していてもよい置換基は、好ましくは置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルキルオキシ基、及び置換基を有していてもよい1価の複素環基である。B11で表される縮合環基が有していてもよいアリール基は、例えば、アルキル基により置換されていてもよい。
The substituent which the fused ring group of B 11 may have may preferably have an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. It is an alkyloxy group which may have a substituent and a monovalent heterocyclic group which may have a substituent. The aryl group that the fused ring group represented by B 11 may have may be substituted with, for example, an alkyl group.
B11である縮合環基の例としては、下記式(b-1)~式(b-14)で表される基、及びこれらの基における水素原子が、置換基(好ましくは、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルキルオキシ基、又は置換基を有していてもよい1価の複素環基)で置換された基が挙げられる。
B11である縮合環基としては、下記式(b-4)で表される基、又はこれらの基における水素原子が、置換基(好ましくは、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルキルオキシ基、又は置換基を有していてもよい1価の複素環基)で置換された基が好ましく、下記式(b-4)で表される基がより好ましい。 As an example of the fused ring group of B11, the groups represented by the following formulas (b- 1 ) to (b-14) and the hydrogen atom in these groups are substituents (preferably, substituents). An alkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, or a monovalent heterocyclic group which may have a substituent. ) Substituted groups.
The fused ring group of B 11 is a group represented by the following formula (b-4), or an alkyl group in which the hydrogen atom in these groups is a substituent (preferably, an alkyl group which may have a substituent). A group substituted with an aryl group which may have a substituent, an alkyloxy group which may have a substituent, or a monovalent heterocyclic group which may have a substituent) is preferable. The group represented by the following formula (b-4) is more preferable.
B11である縮合環基としては、下記式(b-4)で表される基、又はこれらの基における水素原子が、置換基(好ましくは、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルキルオキシ基、又は置換基を有していてもよい1価の複素環基)で置換された基が好ましく、下記式(b-4)で表される基がより好ましい。 As an example of the fused ring group of B11, the groups represented by the following formulas (b- 1 ) to (b-14) and the hydrogen atom in these groups are substituents (preferably, substituents). An alkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, or a monovalent heterocyclic group which may have a substituent. ) Substituted groups.
The fused ring group of B 11 is a group represented by the following formula (b-4), or an alkyl group in which the hydrogen atom in these groups is a substituent (preferably, an alkyl group which may have a substituent). A group substituted with an aryl group which may have a substituent, an alkyloxy group which may have a substituent, or a monovalent heterocyclic group which may have a substituent) is preferable. The group represented by the following formula (b-4) is more preferable.
式(b-1)~式(b-14)中、
Ra10は、前記定義のとおりである。
式(b-1)~式(b-14)中、複数あるRa10は、それぞれ独立して、好ましくは置換基を有していてもよいアルキル基、又は置換基を有していてもよいアリール基である。 In equations (b-1) to (b-14),
R a10 is as defined above.
In the formulas (b-1) to (b-14), each of the plurality of Ra10s may independently have an alkyl group or a substituent which may preferably have a substituent. It is an aryl group.
Ra10は、前記定義のとおりである。
式(b-1)~式(b-14)中、複数あるRa10は、それぞれ独立して、好ましくは置換基を有していてもよいアルキル基、又は置換基を有していてもよいアリール基である。 In equations (b-1) to (b-14),
R a10 is as defined above.
In the formulas (b-1) to (b-14), each of the plurality of Ra10s may independently have an alkyl group or a substituent which may preferably have a substituent. It is an aryl group.
式(V)又は式(VI)で表される化合物の例としては、下記式で表される化合物が挙げられる。
Examples of the compound represented by the formula (V) or the formula (VI) include a compound represented by the following formula.
上記式中、Rは、前記定義のとおりであり、Xは、水素原子、ハロゲン原子、シアノ基又は置換基を有していてもよいアルキル基を表す。
上記式中、Rは、好ましくは水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基又は置換基を有していてもよいアルキルオキシ基である。 In the above formula, R is as defined above, and X represents an alkyl group which may have a hydrogen atom, a halogen atom, a cyano group or a substituent.
In the above formula, R is preferably a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent or an alkyloxy group which may have a substituent. ..
上記式中、Rは、好ましくは水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基又は置換基を有していてもよいアルキルオキシ基である。 In the above formula, R is as defined above, and X represents an alkyl group which may have a hydrogen atom, a halogen atom, a cyano group or a substituent.
In the above formula, R is preferably a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent or an alkyloxy group which may have a substituent. ..
式(V)又は(VI)で表される化合物としては、下記の式N-1で表される化合物が挙げられる。
Examples of the compound represented by the formula (V) or (VI) include the compound represented by the following formula N-1.
一実施形態において、n型半導体材料は、ペリレンテトラカルボン酸ジイミド構造を含む化合物であることが好ましい。非フラーレン化合物としてのペリレンテトラカルボン酸ジイミド構造を含む化合物の例としては、下記式で表される化合物が挙げられる。
In one embodiment, the n-type semiconductor material is preferably a compound containing a perylenetetracarboxylic acid diimide structure. Examples of the compound containing a perylenetetracarboxylic acid diimide structure as a non-fullerene compound include a compound represented by the following formula.
式中、Rは、前記定義のとおりである。複数あるRは、互いに同一であっても異なっていてもよい。
In the formula, R is as defined above. A plurality of Rs may be the same as or different from each other.
一実施形態において、n型半導体材料は、好ましくは、下記式(VII)で表される化合物を含む。下記式(VII)で表される化合物は、ペリレンテトラカルボン酸ジイミド構造を含む非フラーレン化合物である。
In one embodiment, the n-type semiconductor material preferably contains a compound represented by the following formula (VII). The compound represented by the following formula (VII) is a non-fullerene compound containing a perylenetetracarboxylic acid diimide structure.
前記式(VII)中、R1は、水素原子、ハロゲン原子、置換基を有していてもよいアルキル基、置換基を有していてもよいシクロアルキル基、置換基を有していてもよいアルキルオキシ基、置換基を有していてもよいシクロアルキルオキシ基、置換基を有していてもよいアリール基、又は置換基を有していてもよい1価の芳香族複素環基を表す。複数あるR1は互いに同一であっても異なっていてもよい。
In the above formula (VII), R 1 has a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, and even if it has a substituent. A good alkyloxy group, a cycloalkyloxy group which may have a substituent, an aryl group which may have a substituent, or a monovalent aromatic heterocyclic group which may have a substituent. show. A plurality of R 1s may be the same or different from each other.
好ましくは、複数あるR1は、それぞれ独立して、置換基を有していてもよいアルキル基である。
Preferably, each of the plurality of R 1s is an alkyl group which may independently have a substituent.
R2は、水素原子、ハロゲン原子、置換基を有していてもよいアルキル基、置換基を有していてもよいシクロアルキル基、置換基を有していてもよいアルキルオキシ基、置換基を有していてもよいシクロアルキルオキシ基、置換基を有していてもよいアリール基、又は置換基を有していてもよい1価の芳香族複素環基を表す。複数あるR2は同一であっても異なっていてもよい。
R 2 is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkyloxy group which may have a substituent, and a substituent. Represents a cycloalkyloxy group which may have a substituent, an aryl group which may have a substituent, or a monovalent aromatic heterocyclic group which may have a substituent. A plurality of R 2s may be the same or different.
[1.3.絶縁材料]
本実施形態の組成物は、絶縁材料を含む。ここで、絶縁材料とは、導電体及び半導体のいずれでもない材料を意味する。通常、絶縁材料は、20℃における電気抵抗率が1×107Ω・m以上である。絶縁材料は、通常光電変換過程に関与しない。 [1.3. Insulation material]
The composition of this embodiment contains an insulating material. Here, the insulating material means a material that is neither a conductor nor a semiconductor. Generally, the insulating material has an electrical resistivity of 1 × 107 Ω · m or more at 20 ° C. Insulating materials are usually not involved in the photoelectric conversion process.
本実施形態の組成物は、絶縁材料を含む。ここで、絶縁材料とは、導電体及び半導体のいずれでもない材料を意味する。通常、絶縁材料は、20℃における電気抵抗率が1×107Ω・m以上である。絶縁材料は、通常光電変換過程に関与しない。 [1.3. Insulation material]
The composition of this embodiment contains an insulating material. Here, the insulating material means a material that is neither a conductor nor a semiconductor. Generally, the insulating material has an electrical resistivity of 1 × 107 Ω · m or more at 20 ° C. Insulating materials are usually not involved in the photoelectric conversion process.
絶縁材料は、好ましくは有機化合物であり、より好ましくは有機重合体である。絶縁材料は、有機化合物を一種のみ含んでいてもよく、二種以上の組み合わせで含んでいてもよい。
The insulating material is preferably an organic compound, more preferably an organic polymer. The insulating material may contain only one type of organic compound, or may contain a combination of two or more types.
絶縁材料として、各種有機化合物が公知であり、本実施形態の組成物に用い得る。
絶縁材料である有機重合体の例としては、ポリオレフィン(例、ポリエチレン、ポリプロピレン、ポリ(1-ブテン)、ポリイソブチレン)、ポリ(芳香族ビニル)(例、ポリスチレン及びその誘導体)、ポリ(メタ)アクリル酸メチル、ポリエステル、ポリカルボン酸ビニル、ポリビニルアセタール、ポリカーボネート、ポリウレタン、ポリアリレート、ポリアミド、ポリイミド、セルロース及びその誘導体、ポリシロキサン、ゴム、並びに熱可塑性エラストマーが挙げられる。絶縁材料に含まれ得る有機重合体は、単独重合体であってもよく共重合体であってもよい。 Various organic compounds are known as insulating materials and can be used in the composition of the present embodiment.
Examples of organic polymers that are insulating materials include polyolefins (eg polyethylene, polypropylene, poly (1-butene), polyisobutylene), poly (aromatic vinyl) (eg, polystyrene and its derivatives), poly (meth). Examples thereof include methyl acrylate, polyester, vinyl polycarboxylate, polyvinyl acetal, polycarbonate, polyurethane, polyarylate, polyamide, polyimide, cellulose and derivatives thereof, polysiloxane, rubber, and thermoplastic elastomer. The organic polymer that can be contained in the insulating material may be a homopolymer or a copolymer.
絶縁材料である有機重合体の例としては、ポリオレフィン(例、ポリエチレン、ポリプロピレン、ポリ(1-ブテン)、ポリイソブチレン)、ポリ(芳香族ビニル)(例、ポリスチレン及びその誘導体)、ポリ(メタ)アクリル酸メチル、ポリエステル、ポリカルボン酸ビニル、ポリビニルアセタール、ポリカーボネート、ポリウレタン、ポリアリレート、ポリアミド、ポリイミド、セルロース及びその誘導体、ポリシロキサン、ゴム、並びに熱可塑性エラストマーが挙げられる。絶縁材料に含まれ得る有機重合体は、単独重合体であってもよく共重合体であってもよい。 Various organic compounds are known as insulating materials and can be used in the composition of the present embodiment.
Examples of organic polymers that are insulating materials include polyolefins (eg polyethylene, polypropylene, poly (1-butene), polyisobutylene), poly (aromatic vinyl) (eg, polystyrene and its derivatives), poly (meth). Examples thereof include methyl acrylate, polyester, vinyl polycarboxylate, polyvinyl acetal, polycarbonate, polyurethane, polyarylate, polyamide, polyimide, cellulose and derivatives thereof, polysiloxane, rubber, and thermoplastic elastomer. The organic polymer that can be contained in the insulating material may be a homopolymer or a copolymer.
絶縁材料は、好ましくは、下記式(II)で表される構成単位を含む重合体を含む。以下、式(II)で表される構成単位を含む重合体を、重合体(2)ともいう。重合体(2)は、式(II)で表される構成単位を、一種のみ含んでいてもよく、二種以上の組み合わせで含んでいてもよい。
The insulating material preferably contains a polymer containing a structural unit represented by the following formula (II). Hereinafter, the polymer containing the structural unit represented by the formula (II) is also referred to as a polymer (2). The polymer (2) may contain only one type of the structural unit represented by the formula (II), or may contain a combination of two or more types.
式(II)中、Ri1は、水素原子、ハロゲン原子、又は炭素原子数1~20のアルキル基を表し、Ri2は、水素原子、ハロゲン原子、炭素原子数1~20のアルキル基、下記式(III-1)で表される基、式(III-2)で表される基、又は式(III-3)で表される基を表す。
In formula (II), R i1 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms, and R i2 is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms, described below. It represents a group represented by the formula (III-1), a group represented by the formula (III-2), or a group represented by the formula (III-3).
前記式(III-1)中、Ri2aは、水素原子、ハロゲン原子、又は炭素原子数1~20のアルキル基を表す。
前記式(III-2)中、Ri2bは、水素原子又は炭素原子数1~20のアルキル基を表す。
前記式(III-3)中、Ri2cは、炭素原子数1~20のアルキル基を表す。 In the formula (III-1), Ri2a represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms.
In the above formula (III-2), Ri2b represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
In the above formula (III-3), Ri2c represents an alkyl group having 1 to 20 carbon atoms.
前記式(III-2)中、Ri2bは、水素原子又は炭素原子数1~20のアルキル基を表す。
前記式(III-3)中、Ri2cは、炭素原子数1~20のアルキル基を表す。 In the formula (III-1), Ri2a represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms.
In the above formula (III-2), Ri2b represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
In the above formula (III-3), Ri2c represents an alkyl group having 1 to 20 carbon atoms.
Ri1は、好ましくは水素原子又は炭素原子数1~10のアルキル基であり、より好ましくは水素原子又は炭素原子数1~5のアルキル基であり、更に好ましくは、水素原子である。
R i1 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and further preferably a hydrogen atom.
Ri2aは、好ましくは水素原子、ハロゲン原子、又は炭素原子数1~10のアルキル基であり、より好ましくは、水素原子、ハロゲン原子、又は炭素原子数1~5のアルキル基であり、更に好ましくは水素原子である。
R i2a is preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms, and further preferably. Is a hydrogen atom.
Ri2bは、好ましくは炭素原子数1~10のアルキル基であり、より好ましくは炭素原子数1~5のアルキル基であり、更に好ましくはメチル基である。
R i2b is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and further preferably a methyl group.
Ri2cは、好ましくは炭素原子数1~10のアルキル基であり、より好ましくは炭素原子数1~5のアルキル基であり、更に好ましくはメチル基である。
R i2c is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and further preferably a methyl group.
Ri2は、好ましくは、水素原子、炭素原子数1~20のアルキル基、又は式(III-1)~式(III-3)で表される基であり、より好ましくは、水素原子、炭素原子数1~10のアルキル基、又は式(III-1)~式(III-3)で表される基であり、更に好ましくは、炭素原子数1~5のアルキル基、又は式(III-1)~式(III-3)で表される基である。
R i2 is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a group represented by the formulas (III-1) to (III-3), and more preferably a hydrogen atom and carbon. An alkyl group having 1 to 10 atoms, or a group represented by the formulas (III-1) to (III-3), more preferably an alkyl group having 1 to 5 carbon atoms, or a formula (III-). 1) -A group represented by the formula (III-3).
一実施形態において、重合体(2)は、式(II)において、Ri2が炭素原子数1~20のアルキル基である構成単位及び式(II)においてRi2が式(III-1)で表される構成単位からなる群より選択される一種以上の構成単位を含むことが好ましく、ポリスチレン、又はスチレン単位及び式(II)においてRi2が式(III-1)で表される構成単位を含む重合体であることがより好ましい。
別の実施形態において、重合体(2)は、式(II)においてRi2が式(III-2)で表される構成単位を含むことが好ましく、メチルメタクリレート単位を含むことがより好ましい。 In one embodiment, the polymer (2) has a structural unit in which R i2 is an alkyl group having 1 to 20 carbon atoms in the formula (II) and R i2 in the formula (II) is the formula (III-1). It is preferable to include one or more structural units selected from the group consisting of the structural units represented, and polystyrene or a styrene unit and a structural unit in which Ri2 is represented by the formula (III-1) in the formula (II). It is more preferable that the polymer contains the polymer.
In another embodiment, the polymer (2) preferably contains a structural unit in which Ri2 is represented by the formula (III-2) in the formula (II), and more preferably contains a methyl methacrylate unit.
別の実施形態において、重合体(2)は、式(II)においてRi2が式(III-2)で表される構成単位を含むことが好ましく、メチルメタクリレート単位を含むことがより好ましい。 In one embodiment, the polymer (2) has a structural unit in which R i2 is an alkyl group having 1 to 20 carbon atoms in the formula (II) and R i2 in the formula (II) is the formula (III-1). It is preferable to include one or more structural units selected from the group consisting of the structural units represented, and polystyrene or a styrene unit and a structural unit in which Ri2 is represented by the formula (III-1) in the formula (II). It is more preferable that the polymer contains the polymer.
In another embodiment, the polymer (2) preferably contains a structural unit in which Ri2 is represented by the formula (III-2) in the formula (II), and more preferably contains a methyl methacrylate unit.
絶縁材料中の重合体(2)の含有率は、好ましくは70重量%以上、より好ましくは80重量%以上、更に好ましくは90重量%以上、特に好ましくは95重量%以上であり、通常100重量%以下であり、100重量%であってもよい。絶縁材料は、重合体(2)を一種のみ含んでいてもよく、二種以上の組み合わせで含んでいてもよい。
The content of the polymer (2) in the insulating material is preferably 70% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight or more, particularly preferably 95% by weight or more, and usually 100% by weight. % Or less, and may be 100% by weight. The insulating material may contain only one type of the polymer (2), or may contain a combination of two or more types.
重合体(2)は、式(II)で表される構成単位に加えて、任意の構成単位を含んでいてもよい。任意の構成単位の例としては、アルカジエン単位(例、1,3-ブタジエン単位、イソプレン単位)が挙げられる。
The polymer (2) may contain any structural unit in addition to the structural unit represented by the formula (II). Examples of arbitrary building blocks include alkaziene units (eg, 1,3-butadiene units, isoprene units).
重合体(2)は、従前公知の製造方法により製造できる。また、重合体(2)として、市販品を使用することもできる。
The polymer (2) can be produced by a conventionally known production method. Further, as the polymer (2), a commercially available product can also be used.
好ましくは、絶縁材料は、本発明の組成物に用いられる溶媒に対して25℃において0.1重量%以上溶解する材料である。
より好ましくは、絶縁材料は、重合体(2)であって、本発明の組成物に用いられる溶媒に対して25℃において0.1重量%以上溶解する重合体である。 Preferably, the insulating material is a material that dissolves in an amount of 0.1% by weight or more at 25 ° C. with respect to the solvent used in the composition of the present invention.
More preferably, the insulating material is the polymer (2), which is a polymer that dissolves in an amount of 0.1% by weight or more at 25 ° C. with respect to the solvent used in the composition of the present invention.
より好ましくは、絶縁材料は、重合体(2)であって、本発明の組成物に用いられる溶媒に対して25℃において0.1重量%以上溶解する重合体である。 Preferably, the insulating material is a material that dissolves in an amount of 0.1% by weight or more at 25 ° C. with respect to the solvent used in the composition of the present invention.
More preferably, the insulating material is the polymer (2), which is a polymer that dissolves in an amount of 0.1% by weight or more at 25 ° C. with respect to the solvent used in the composition of the present invention.
絶縁材料に含まれ得る有機重合体の重量平均分子量(Mw)は、特に限定されないが、溶媒への溶解性の観点から、好ましくは1,000,000以下、より好ましくは500,000以下、更に好ましくは200,000以下である。
The weight average molecular weight (Mw) of the organic polymer that can be contained in the insulating material is not particularly limited, but is preferably 1,000,000 or less, more preferably 500,000 or less, and further, from the viewpoint of solubility in a solvent. It is preferably 200,000 or less.
本実施形態に係る絶縁材料の具体例として、ポリスチレン-block-ポリ(エチレン-ran-ブチレン)-block-ポリスチレン(重量平均分子量:118000以下)、ポリスチレン(重量平均分子量:35000)、ポリスチレン-block-ポリイソプレン-block-ポリスチレン(数平均分子量 1900)、及びポリ(メチルメタクリレート)が挙げられる。
Specific examples of the insulating material according to the present embodiment are polystyrene-block-poly (ethylene-ran-butylene) -block-polystyrene (weight average molecular weight: 118,000 or less), polystyrene (weight average molecular weight: 35,000), polystyrene-block-. Examples thereof include polyisoprene-block-polystyrene (number average molecular weight 1900) and poly (methyl methacrylate).
組成物中の絶縁材料の含有量は、例えば0.5重量%以上又は0.1重量%以上であり、例えば5重量%以下又は1重量%以下である。ここで、組成物における、p型半導体材料、n型半導体材料、絶縁材料、及び溶媒の総重量を100重量%とする。
The content of the insulating material in the composition is, for example, 0.5% by weight or more or 0.1% by weight or more, for example, 5% by weight or less or 1% by weight or less. Here, the total weight of the p-type semiconductor material, the n-type semiconductor material, the insulating material, and the solvent in the composition is 100% by weight.
絶縁材料は、組成物中において、少なくとも一部が溶解していることが好ましく、全部が溶解していることがより好ましい。
It is preferable that at least a part of the insulating material is dissolved in the composition, and it is more preferable that the insulating material is completely dissolved.
組成物における、絶縁材料のp型半導体材料に対する重量比(絶縁材料/p型半導体材料)は、例えば1/10以上又は1/5以上であり、例えば1/3以下又は1/2以下である。
The weight ratio of the insulating material to the p-type semiconductor material (insulating material / p-type semiconductor material) in the composition is, for example, 1/10 or more or 1/5 or more, for example, 1/3 or less or 1/2 or less. ..
[1.4.溶媒]
本実施形態に係る組成物は、溶媒を含む。組成物は、溶媒を一種のみ含んでいてもよく、二種以上の組み合わせで含んでいてもよい。
本実施形態に係る組成物は、好ましくは下記に述べる第1溶媒を含み、任意で更に第2溶媒を含み得る。 [1.4. solvent]
The composition according to this embodiment contains a solvent. The composition may contain only one type of solvent, or may contain a combination of two or more types.
The composition according to the present embodiment preferably contains the first solvent described below, and may optionally further contain a second solvent.
本実施形態に係る組成物は、溶媒を含む。組成物は、溶媒を一種のみ含んでいてもよく、二種以上の組み合わせで含んでいてもよい。
本実施形態に係る組成物は、好ましくは下記に述べる第1溶媒を含み、任意で更に第2溶媒を含み得る。 [1.4. solvent]
The composition according to this embodiment contains a solvent. The composition may contain only one type of solvent, or may contain a combination of two or more types.
The composition according to the present embodiment preferably contains the first solvent described below, and may optionally further contain a second solvent.
(第1溶媒)
溶媒は、選択されたp型半導体材料及びn型半導体材料に対する溶解性、膜を形成する際の乾燥条件に対応するための特性(沸点など)を考慮して選択してよい。 (First solvent)
The solvent may be selected in consideration of the solubility in the selected p-type semiconductor material and the n-type semiconductor material, and the characteristics (boiling point, etc.) corresponding to the drying conditions when forming the film.
溶媒は、選択されたp型半導体材料及びn型半導体材料に対する溶解性、膜を形成する際の乾燥条件に対応するための特性(沸点など)を考慮して選択してよい。 (First solvent)
The solvent may be selected in consideration of the solubility in the selected p-type semiconductor material and the n-type semiconductor material, and the characteristics (boiling point, etc.) corresponding to the drying conditions when forming the film.
第1溶媒は、置換基(例えば、アルキル基、ハロゲン原子)を有していてもよい芳香族炭化水素(以下、単に芳香族炭化水素という。)又はハロゲン化アルキル溶媒であることが好ましい。第1溶媒は、選択されたp型半導体材料及びn型半導体材料の溶解性を考慮して選択することが好ましい。
The first solvent is preferably an aromatic hydrocarbon (hereinafter, simply referred to as an aromatic hydrocarbon) or an alkyl halide solvent which may have a substituent (for example, an alkyl group or a halogen atom). The first solvent is preferably selected in consideration of the solubility of the selected p-type semiconductor material and n-type semiconductor material.
第1溶媒である芳香族炭化水素としては、例えば、トルエン、キシレン(例、o-キシレン、m-キシレン、p-キシレン)、トリメチルベンゼン(例、メシチレン、1,2,4-トリメチルベンゼン(プソイドクメン))、ブチルベンゼン(例、n-ブチルベンゼン、sec-ブチルベンゼン、tert-ブチルベンゼン)、メチルナフタレン(例、1-メチルナフタレン)、テトラリン、インダン、クロロベンゼン及びジクロロベンゼン(1,2-ジクロロベンゼン)が挙げられる。
Examples of the aromatic hydrocarbon as the first solvent include toluene, xylene (eg, o-xylene, m-xylene, p-xylene), trimethylbenzene (eg, mesitylene, 1,2,4-trimethylbenzene). )), Butylbenzene (eg n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (eg 1-methylnaphthalene), tetralin, indan, chlorobenzene and dichlorobenzene (1,2-dichlorobenzene) ).
第1溶媒であるハロゲン化アルキル溶媒としては、例えば、クロロホルムが挙げられる。
Examples of the alkyl halide solvent as the first solvent include chloroform.
第1溶媒は1種のみの芳香族炭化水素から構成されていても、2種以上の芳香族炭化水素から構成されていてもよい。第1溶媒は、1種のみの芳香族炭化水素から構成されることが好ましい。
The first solvent may be composed of only one kind of aromatic hydrocarbon or may be composed of two or more kinds of aromatic hydrocarbons. The first solvent is preferably composed of only one aromatic hydrocarbon.
第1溶媒は、好ましくは、トルエン、o-キシレン、m-キシレン、p-キシレン、メシチレン、プソイドクメン、n-ブチルベンゼン、sec-ブチルベンゼン、tert-ブチルベンゼン、メチルナフタレン、テトラリン、インダン、クロロベンゼン、o-ジクロロベンゼン及びクロロホルムからなる群から選択される1種以上を含む。
The first solvent is preferably toluene, o-xylene, m-xylene, p-xylene, mesitylene, pseudocumene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, tetraline, indane, chlorobenzene, etc. Includes one or more selected from the group consisting of o-dichlorobenzene and chloroform.
(第2溶媒)
第2溶媒は、特にn型半導体材料の溶解性を高める観点から選択される溶媒であることが好ましい。第2溶媒の例としては、ケトン溶媒(例、アセトン、メチルエチルケトン、シクロヘキサノン、アセトフェノン、プロピオフェノン)、エステル溶媒(例、酢酸エチル、酢酸ブチル、酢酸フェニル、エチルセルソルブアセテート、安息香酸メチル、安息香酸ブチル、安息香酸ベンジル)が挙げられる。 (Second solvent)
The second solvent is preferably a solvent selected from the viewpoint of enhancing the solubility of the n-type semiconductor material. Examples of the second solvent include ketone solvents (eg, acetone, methyl ethyl ketone, cyclohexanone, acetophenone, propiophenone), ester solvents (eg, ethyl acetate, butyl acetate, phenyl acetate, ethyl cellsolve acetate, methyl benzoate, benzoic acid). Butylate, benzyl benzoate).
第2溶媒は、特にn型半導体材料の溶解性を高める観点から選択される溶媒であることが好ましい。第2溶媒の例としては、ケトン溶媒(例、アセトン、メチルエチルケトン、シクロヘキサノン、アセトフェノン、プロピオフェノン)、エステル溶媒(例、酢酸エチル、酢酸ブチル、酢酸フェニル、エチルセルソルブアセテート、安息香酸メチル、安息香酸ブチル、安息香酸ベンジル)が挙げられる。 (Second solvent)
The second solvent is preferably a solvent selected from the viewpoint of enhancing the solubility of the n-type semiconductor material. Examples of the second solvent include ketone solvents (eg, acetone, methyl ethyl ketone, cyclohexanone, acetophenone, propiophenone), ester solvents (eg, ethyl acetate, butyl acetate, phenyl acetate, ethyl cellsolve acetate, methyl benzoate, benzoic acid). Butylate, benzyl benzoate).
(第1溶媒及び第2溶媒の重量比)
組成物が、第1溶媒及び第2溶媒を含む場合、第1溶媒の第2溶媒に対する重量比(第1溶媒/第2溶媒)は、p型半導体材料及びn型半導体材料の溶解性をより向上させる観点から、85/15~99/1の範囲とすることが好ましい。 (Weight ratio of first solvent and second solvent)
When the composition contains the first solvent and the second solvent, the weight ratio of the first solvent to the second solvent (first solvent / second solvent) determines the solubility of the p-type semiconductor material and the n-type semiconductor material. From the viewpoint of improvement, it is preferably in the range of 85/15 to 99/1.
組成物が、第1溶媒及び第2溶媒を含む場合、第1溶媒の第2溶媒に対する重量比(第1溶媒/第2溶媒)は、p型半導体材料及びn型半導体材料の溶解性をより向上させる観点から、85/15~99/1の範囲とすることが好ましい。 (Weight ratio of first solvent and second solvent)
When the composition contains the first solvent and the second solvent, the weight ratio of the first solvent to the second solvent (first solvent / second solvent) determines the solubility of the p-type semiconductor material and the n-type semiconductor material. From the viewpoint of improvement, it is preferably in the range of 85/15 to 99/1.
(組成物における溶媒の重量百分率)
組成物に含まれる溶媒の総重量は、組成物の全重量を100重量%としたときに、p型半導体材料及びn型半導体材料の溶解性をより向上させる観点から、好ましくは90重量%以上、より好ましくは92重量%以上、更に好ましくは95重量%以上であり、塗布液中のp型半導体材料及びn型半導体材料の濃度を高くして一定の厚さ以上の層を形成し易くする観点から、好ましくは99.9重量%以下である。 (Weight percentage of solvent in composition)
The total weight of the solvent contained in the composition is preferably 90% by weight or more from the viewpoint of further improving the solubility of the p-type semiconductor material and the n-type semiconductor material when the total weight of the composition is 100% by weight. , More preferably 92% by weight or more, still more preferably 95% by weight or more, and increase the concentration of the p-type semiconductor material and the n-type semiconductor material in the coating liquid to facilitate the formation of a layer having a certain thickness or more. From the viewpoint, it is preferably 99.9% by weight or less.
組成物に含まれる溶媒の総重量は、組成物の全重量を100重量%としたときに、p型半導体材料及びn型半導体材料の溶解性をより向上させる観点から、好ましくは90重量%以上、より好ましくは92重量%以上、更に好ましくは95重量%以上であり、塗布液中のp型半導体材料及びn型半導体材料の濃度を高くして一定の厚さ以上の層を形成し易くする観点から、好ましくは99.9重量%以下である。 (Weight percentage of solvent in composition)
The total weight of the solvent contained in the composition is preferably 90% by weight or more from the viewpoint of further improving the solubility of the p-type semiconductor material and the n-type semiconductor material when the total weight of the composition is 100% by weight. , More preferably 92% by weight or more, still more preferably 95% by weight or more, and increase the concentration of the p-type semiconductor material and the n-type semiconductor material in the coating liquid to facilitate the formation of a layer having a certain thickness or more. From the viewpoint, it is preferably 99.9% by weight or less.
組成物は、前記の第1溶媒及び任意の第2溶媒に加えて、更に任意の第3溶媒を含んでいてもよい。塗布液に含まれる全溶媒の合計重量を100重量%とした場合に、任意の第3溶媒の含有率は、好ましくは5重量%以下であり、より好ましくは3重量%以下であり、更に好ましくは1重量%以下である。任意の第3溶媒としては、第2溶媒より沸点が高い溶媒が好ましい。
The composition may further contain any third solvent in addition to the above-mentioned first solvent and any second solvent. When the total weight of all the solvents contained in the coating liquid is 100% by weight, the content of any third solvent is preferably 5% by weight or less, more preferably 3% by weight or less, still more preferable. Is 1% by weight or less. As the arbitrary third solvent, a solvent having a boiling point higher than that of the second solvent is preferable.
[1.5.任意の成分]
本実施形態に係る組成物は、前記のp型半導体材料、n型半導体材料、絶縁材料、及び溶媒に加えて、本発明の目的及び効果を損なわない限度において、任意の成分を含んでいてもよい。任意の成分の例としては、紫外線吸収剤、酸化防止剤、吸収した光により電荷を発生させる機能を増感するためのため増感剤、及び紫外線からの安定性を増すための光安定剤が挙げられる。
組成物における任意成分の合計の含有量は、好ましくは10重量%以下、より好ましくは5重量%以下であり、通常0重量%以上である。 [1.5. Any ingredient]
The composition according to the present embodiment may contain, in addition to the above-mentioned p-type semiconductor material, n-type semiconductor material, insulating material, and solvent, any component as long as the object and effect of the present invention are not impaired. good. Examples of optional components are UV absorbers, antioxidants, sensitizers to sensitize the ability to generate charge by absorbed light, and photostabilizers to increase stability from UV light. Can be mentioned.
The total content of the optional components in the composition is preferably 10% by weight or less, more preferably 5% by weight or less, and usually 0% by weight or more.
本実施形態に係る組成物は、前記のp型半導体材料、n型半導体材料、絶縁材料、及び溶媒に加えて、本発明の目的及び効果を損なわない限度において、任意の成分を含んでいてもよい。任意の成分の例としては、紫外線吸収剤、酸化防止剤、吸収した光により電荷を発生させる機能を増感するためのため増感剤、及び紫外線からの安定性を増すための光安定剤が挙げられる。
組成物における任意成分の合計の含有量は、好ましくは10重量%以下、より好ましくは5重量%以下であり、通常0重量%以上である。 [1.5. Any ingredient]
The composition according to the present embodiment may contain, in addition to the above-mentioned p-type semiconductor material, n-type semiconductor material, insulating material, and solvent, any component as long as the object and effect of the present invention are not impaired. good. Examples of optional components are UV absorbers, antioxidants, sensitizers to sensitize the ability to generate charge by absorbed light, and photostabilizers to increase stability from UV light. Can be mentioned.
The total content of the optional components in the composition is preferably 10% by weight or less, more preferably 5% by weight or less, and usually 0% by weight or more.
[1.6.p型半導体材料、n型半導体材料、及び絶縁材料の含有割合]
(組成物におけるp型半導体材料及びn型半導体材料の濃度)
組成物における、p型半導体材料及びn型半導体材料の合計の濃度は、必要とされる活性層の厚さに応じて、任意好適な濃度とすることができる。p型半導体材料及びn型半導体材料の合計の濃度は、好ましくは0.01重量%以上、より好ましくは0.1重量%以上であり、好ましくは10重量%以下であり、より好ましくは5重量%以下であり、更に好ましくは0.01重量%以上20重量%以下、更に好ましくは0.01重量%以上10重量%以下、更に好ましくは0.01重量%以上5重量%以下、特に好ましくは0.1重量%以上5重量%以下である。 [1.6. Content ratio of p-type semiconductor material, n-type semiconductor material, and insulating material]
(Concentration of p-type semiconductor material and n-type semiconductor material in the composition)
The total concentration of the p-type semiconductor material and the n-type semiconductor material in the composition can be any suitable concentration depending on the required thickness of the active layer. The total concentration of the p-type semiconductor material and the n-type semiconductor material is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 10% by weight or less, and more preferably 5% by weight. % Or less, more preferably 0.01% by weight or more and 20% by weight or less, further preferably 0.01% by weight or more and 10% by weight or less, still more preferably 0.01% by weight or more and 5% by weight or less, particularly preferably. It is 0.1% by weight or more and 5% by weight or less.
(組成物におけるp型半導体材料及びn型半導体材料の濃度)
組成物における、p型半導体材料及びn型半導体材料の合計の濃度は、必要とされる活性層の厚さに応じて、任意好適な濃度とすることができる。p型半導体材料及びn型半導体材料の合計の濃度は、好ましくは0.01重量%以上、より好ましくは0.1重量%以上であり、好ましくは10重量%以下であり、より好ましくは5重量%以下であり、更に好ましくは0.01重量%以上20重量%以下、更に好ましくは0.01重量%以上10重量%以下、更に好ましくは0.01重量%以上5重量%以下、特に好ましくは0.1重量%以上5重量%以下である。 [1.6. Content ratio of p-type semiconductor material, n-type semiconductor material, and insulating material]
(Concentration of p-type semiconductor material and n-type semiconductor material in the composition)
The total concentration of the p-type semiconductor material and the n-type semiconductor material in the composition can be any suitable concentration depending on the required thickness of the active layer. The total concentration of the p-type semiconductor material and the n-type semiconductor material is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 10% by weight or less, and more preferably 5% by weight. % Or less, more preferably 0.01% by weight or more and 20% by weight or less, further preferably 0.01% by weight or more and 10% by weight or less, still more preferably 0.01% by weight or more and 5% by weight or less, particularly preferably. It is 0.1% by weight or more and 5% by weight or less.
(p型半導体材料のn型半導体材料に対する重量比(p/n比))
組成物中のp型半導体材料のn型半導体材料に対する重量比(p型半導体材料/n型半導体材料)は、好ましくは1/9以上、より好ましくは1/5以上、更に好ましくは1/3以上であり、好ましくは9/1以下、より好ましくは5/1以下、更に好ましくは3/1以下である。 (Weight ratio of p-type semiconductor material to n-type semiconductor material (p / n ratio))
The weight ratio of the p-type semiconductor material to the n-type semiconductor material (p-type semiconductor material / n-type semiconductor material) in the composition is preferably 1/9 or more, more preferably 1/5 or more, still more preferably 1/3. The above is preferably 9/1 or less, more preferably 5/1 or less, still more preferably 3/1 or less.
組成物中のp型半導体材料のn型半導体材料に対する重量比(p型半導体材料/n型半導体材料)は、好ましくは1/9以上、より好ましくは1/5以上、更に好ましくは1/3以上であり、好ましくは9/1以下、より好ましくは5/1以下、更に好ましくは3/1以下である。 (Weight ratio of p-type semiconductor material to n-type semiconductor material (p / n ratio))
The weight ratio of the p-type semiconductor material to the n-type semiconductor material (p-type semiconductor material / n-type semiconductor material) in the composition is preferably 1/9 or more, more preferably 1/5 or more, still more preferably 1/3. The above is preferably 9/1 or less, more preferably 5/1 or less, still more preferably 3/1 or less.
(p型半導体材料、n型半導体材料、及び絶縁材料の合計の含有割合)
組成物中の、p型半導体材料、n型半導体材料、及び絶縁材料の合計の含有割合は、例えば、塗布法の種類、用いる成分の粘度などに応じて適宜設定しうる。組成物中の、p型半導体材料、n型半導体材料、及び絶縁材料の合計の含有割合は、組成物においてこれらを溶解できる範囲では特に限定しないが、好ましくは1重量%以上、より好ましくは2重量%以上、更に好ましくは3重量%以上であり、好ましくは20重量%以下、より好ましくは10重量%以下、更に好ましくは7重量%以下である。 (Total content ratio of p-type semiconductor material, n-type semiconductor material, and insulating material)
The total content ratio of the p-type semiconductor material, the n-type semiconductor material, and the insulating material in the composition can be appropriately set according to, for example, the type of coating method, the viscosity of the component used, and the like. The total content of the p-type semiconductor material, the n-type semiconductor material, and the insulating material in the composition is not particularly limited as long as they can be dissolved in the composition, but is preferably 1% by weight or more, more preferably 2. By weight% or more, more preferably 3% by weight or more, preferably 20% by weight or less, more preferably 10% by weight or less, still more preferably 7% by weight or less.
組成物中の、p型半導体材料、n型半導体材料、及び絶縁材料の合計の含有割合は、例えば、塗布法の種類、用いる成分の粘度などに応じて適宜設定しうる。組成物中の、p型半導体材料、n型半導体材料、及び絶縁材料の合計の含有割合は、組成物においてこれらを溶解できる範囲では特に限定しないが、好ましくは1重量%以上、より好ましくは2重量%以上、更に好ましくは3重量%以上であり、好ましくは20重量%以下、より好ましくは10重量%以下、更に好ましくは7重量%以下である。 (Total content ratio of p-type semiconductor material, n-type semiconductor material, and insulating material)
The total content ratio of the p-type semiconductor material, the n-type semiconductor material, and the insulating material in the composition can be appropriately set according to, for example, the type of coating method, the viscosity of the component used, and the like. The total content of the p-type semiconductor material, the n-type semiconductor material, and the insulating material in the composition is not particularly limited as long as they can be dissolved in the composition, but is preferably 1% by weight or more, more preferably 2. By weight% or more, more preferably 3% by weight or more, preferably 20% by weight or less, more preferably 10% by weight or less, still more preferably 7% by weight or less.
[1.7.組成物の製造方法]
組成物は、従来公知の方法により製造することができる。例えば、溶媒として、前記第1溶媒及び第2溶媒を用いる場合には、第1溶媒及び第2溶媒を混合して混合溶媒を調製し、混合溶媒にp型半導体材料、n型半導体材料、及び絶縁材料を添加する方法、第1溶媒にp型半導体材料及び絶縁材料を添加し、第2溶媒にn型半導体材料を添加してから、各材料が添加された第1溶媒及び第2溶媒を混合する方法などにより、製造することができる。 [1.7. Method for producing composition]
The composition can be produced by a conventionally known method. For example, when the first solvent and the second solvent are used as the solvent, the first solvent and the second solvent are mixed to prepare a mixed solvent, and the p-type semiconductor material, the n-type semiconductor material, and the mixed solvent are used as the mixed solvent. Method of adding insulating material, p-type semiconductor material and insulating material are added to the first solvent, n-type semiconductor material is added to the second solvent, and then the first solvent and the second solvent to which each material is added are added. It can be manufactured by a mixing method or the like.
組成物は、従来公知の方法により製造することができる。例えば、溶媒として、前記第1溶媒及び第2溶媒を用いる場合には、第1溶媒及び第2溶媒を混合して混合溶媒を調製し、混合溶媒にp型半導体材料、n型半導体材料、及び絶縁材料を添加する方法、第1溶媒にp型半導体材料及び絶縁材料を添加し、第2溶媒にn型半導体材料を添加してから、各材料が添加された第1溶媒及び第2溶媒を混合する方法などにより、製造することができる。 [1.7. Method for producing composition]
The composition can be produced by a conventionally known method. For example, when the first solvent and the second solvent are used as the solvent, the first solvent and the second solvent are mixed to prepare a mixed solvent, and the p-type semiconductor material, the n-type semiconductor material, and the mixed solvent are used as the mixed solvent. Method of adding insulating material, p-type semiconductor material and insulating material are added to the first solvent, n-type semiconductor material is added to the second solvent, and then the first solvent and the second solvent to which each material is added are added. It can be manufactured by a mixing method or the like.
溶媒と、p型半導体材料、n型半導体材料、及び絶縁材料とを、溶媒の沸点以下の温度まで加温して混合してもよい。
The solvent and the p-type semiconductor material, the n-type semiconductor material, and the insulating material may be heated to a temperature equal to or lower than the boiling point of the solvent and mixed.
溶媒と、p型半導体材料、n型半導体材料、及び絶縁材料とを混合した後、得られた混合物をフィルターを用いて濾過し、得られた濾液を組成物としてよい。フィルターとしては、例えば、ポリテトラフルオロエチレン(PTFE)等のフッ素樹脂で形成されたフィルターを用いることができる。
After mixing the solvent with the p-type semiconductor material, the n-type semiconductor material, and the insulating material, the obtained mixture may be filtered using a filter, and the obtained filtrate may be used as a composition. As the filter, for example, a filter formed of a fluororesin such as polytetrafluoroethylene (PTFE) can be used.
[1.8.組成物の用途]
組成物は、塗布法によりp型半導体材料、n型半導体材料、及び絶縁材料を含む膜を形成するためのインクとして好適に用いられ得る。本明細書において、「インク」は、塗布法に用いられる液状物を意味しており、着色した液に限定されない。また、「塗布法」は、液状物を用いて膜(層)を形成する方法を包含し、例えば、スロットダイコート法、スリットコート法、ナイフコート法、スピンコート法、キャスティング法、マイクログラビアコート法、グラビアコート法、バーコート法、ロールコート法、ワイヤーバーコート法、ディップコート法、スプレーコート法、スクリーン印刷法、グラビア印刷法、フレキソ印刷法、オフセット印刷法、インクジェットコート法、ディスペンサー印刷法、ノズルコート法、及びキャピラリーコート法が挙げられる。 [1.8. Use of composition]
The composition can be suitably used as an ink for forming a film containing a p-type semiconductor material, an n-type semiconductor material, and an insulating material by a coating method. In the present specification, "ink" means a liquid material used in a coating method, and is not limited to a colored liquid material. Further, the "coating method" includes a method of forming a film (layer) using a liquid material, for example, a slot die coating method, a slit coating method, a knife coating method, a spin coating method, a casting method, and a microgravure coating method. , Gravure coating method, Bar coating method, Roll coating method, Wire bar coating method, Dip coating method, Spray coating method, Screen printing method, Gravure printing method, Flexo printing method, Offset printing method, Inkjet coating method, Dispenser printing method, The nozzle coat method and the capillary coat method can be mentioned.
組成物は、塗布法によりp型半導体材料、n型半導体材料、及び絶縁材料を含む膜を形成するためのインクとして好適に用いられ得る。本明細書において、「インク」は、塗布法に用いられる液状物を意味しており、着色した液に限定されない。また、「塗布法」は、液状物を用いて膜(層)を形成する方法を包含し、例えば、スロットダイコート法、スリットコート法、ナイフコート法、スピンコート法、キャスティング法、マイクログラビアコート法、グラビアコート法、バーコート法、ロールコート法、ワイヤーバーコート法、ディップコート法、スプレーコート法、スクリーン印刷法、グラビア印刷法、フレキソ印刷法、オフセット印刷法、インクジェットコート法、ディスペンサー印刷法、ノズルコート法、及びキャピラリーコート法が挙げられる。 [1.8. Use of composition]
The composition can be suitably used as an ink for forming a film containing a p-type semiconductor material, an n-type semiconductor material, and an insulating material by a coating method. In the present specification, "ink" means a liquid material used in a coating method, and is not limited to a colored liquid material. Further, the "coating method" includes a method of forming a film (layer) using a liquid material, for example, a slot die coating method, a slit coating method, a knife coating method, a spin coating method, a casting method, and a microgravure coating method. , Gravure coating method, Bar coating method, Roll coating method, Wire bar coating method, Dip coating method, Spray coating method, Screen printing method, Gravure printing method, Flexo printing method, Offset printing method, Inkjet coating method, Dispenser printing method, The nozzle coat method and the capillary coat method can be mentioned.
[2.膜]
本発明の一実施形態に係る膜は、p型半導体材料としての重合体(1)、n型半導体材料、及び絶縁材料を含む。以下、p型半導体材料としての重合体(1)、n型半導体材料、及び絶縁材料を含む膜を、「膜A」ともいう。
p型半導体材料としての重合体(1)の例及び好ましい例、n型半導体材料の例及び好ましい例、並びに絶縁材料の例及び好ましい例は、項目[1.組成物]において述べた例と同様である。 [2. film]
The film according to the embodiment of the present invention includes a polymer (1) as a p-type semiconductor material, an n-type semiconductor material, and an insulating material. Hereinafter, the film containing the polymer (1) as the p-type semiconductor material, the n-type semiconductor material, and the insulating material is also referred to as “film A”.
Examples of the polymer (1) as a p-type semiconductor material and preferred examples, examples of n-type semiconductor materials and preferred examples, and examples of insulating materials and preferred examples are described in Item [1. Composition] is the same as the example described.
本発明の一実施形態に係る膜は、p型半導体材料としての重合体(1)、n型半導体材料、及び絶縁材料を含む。以下、p型半導体材料としての重合体(1)、n型半導体材料、及び絶縁材料を含む膜を、「膜A」ともいう。
p型半導体材料としての重合体(1)の例及び好ましい例、n型半導体材料の例及び好ましい例、並びに絶縁材料の例及び好ましい例は、項目[1.組成物]において述べた例と同様である。 [2. film]
The film according to the embodiment of the present invention includes a polymer (1) as a p-type semiconductor material, an n-type semiconductor material, and an insulating material. Hereinafter, the film containing the polymer (1) as the p-type semiconductor material, the n-type semiconductor material, and the insulating material is also referred to as “film A”.
Examples of the polymer (1) as a p-type semiconductor material and preferred examples, examples of n-type semiconductor materials and preferred examples, and examples of insulating materials and preferred examples are described in Item [1. Composition] is the same as the example described.
本実施形態に係る膜におけるp型半導体材料のn型半導体材料に対する重量比(p型半導体材料/n型半導体材料)の好ましい範囲は、組成物における当該重量比の好ましい範囲と同様とすることができる。
The preferable range of the weight ratio (p-type semiconductor material / n-type semiconductor material) of the p-type semiconductor material to the n-type semiconductor material in the film according to the present embodiment may be the same as the preferable range of the weight ratio in the composition. can.
本実施形態に係る膜における、絶縁材料のp型半導体材料に対する重量比(絶縁材料/p型半導体材料)の好ましい範囲は、組成物における当該重量比の好ましい範囲と同様とすることができる。
The preferable range of the weight ratio of the insulating material to the p-type semiconductor material (insulating material / p-type semiconductor material) in the film according to the present embodiment can be the same as the preferable range of the weight ratio in the composition.
本実施形態に係る膜の厚さは、目的とする膜の機能に応じて適宜設定し得る。本実施形態に係る膜の厚さは、好ましくは100nm以上、より好ましくは150nm以上、更に好ましくは200nm以上であり、好ましくは10μm以下、より好ましくは5μm以下、更に好ましくは1μm以下である。
The thickness of the film according to the present embodiment can be appropriately set according to the function of the target film. The thickness of the film according to the present embodiment is preferably 100 nm or more, more preferably 150 nm or more, further preferably 200 nm or more, preferably 10 μm or less, more preferably 5 μm or less, still more preferably 1 μm or less.
本実施形態に係る膜は、任意の方法により製造し得る。例えば、本実施形態に係る膜は、下記工程を含む方法により製造し得る。
The film according to this embodiment can be manufactured by any method. For example, the film according to this embodiment can be produced by a method including the following steps.
工程(1):組成物を、塗布対象に塗布して塗膜を形成する工程。
工程(2):前記塗膜を乾燥させる工程。
前記工程(1)及び工程(2)は、通常この順で行われる。 Step (1): A step of applying the composition to a coating target to form a coating film.
Step (2): A step of drying the coating film.
The steps (1) and (2) are usually performed in this order.
工程(2):前記塗膜を乾燥させる工程。
前記工程(1)及び工程(2)は、通常この順で行われる。 Step (1): A step of applying the composition to a coating target to form a coating film.
Step (2): A step of drying the coating film.
The steps (1) and (2) are usually performed in this order.
(工程(1))
組成物は、p型半導体材料としての重合体(1)と、n型半導体材料と、絶縁材料と、溶媒とを含む組成物である。組成物として、既に例示した好ましい組成物が用いられ得る。 (Step (1))
The composition is a composition containing a polymer (1) as a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent. As the composition, the preferred composition already exemplified can be used.
組成物は、p型半導体材料としての重合体(1)と、n型半導体材料と、絶縁材料と、溶媒とを含む組成物である。組成物として、既に例示した好ましい組成物が用いられ得る。 (Step (1))
The composition is a composition containing a polymer (1) as a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent. As the composition, the preferred composition already exemplified can be used.
本実施形態に係る膜を光電変換素子の活性層として機能させる場合、組成物を塗布する対象の例としては、電極、電子輸送層、及び正孔輸送層が挙げられる。
When the film according to this embodiment functions as an active layer of a photoelectric conversion element, examples of objects to which the composition is applied include an electrode, an electron transport layer, and a hole transport layer.
組成物を塗布対象に塗布する方法としては、任意の塗布法を用いることができる。工程(1)において組成物を塗布対象に塗布する方法の例としては、前記例示の塗布法が挙げられ、中でも均一な厚さの塗膜を得やすいことから、スピンコート法が好ましい。
Any coating method can be used as a method for applying the composition to the coating target. Examples of the method of applying the composition to the coating target in the step (1) include the above-exemplified coating method, and the spin coating method is preferable because it is easy to obtain a coating film having a uniform thickness.
(工程(2))
塗膜を乾燥させることにより、通常塗膜に含まれる溶媒が除去される。塗膜を乾燥させる方法の例としては、窒素ガスなどの不活性ガス雰囲気下でホットプレートを用いて直接的に加熱する方法、熱風乾燥法、赤外線加熱乾燥法、フラッシュランプアニール乾燥法、減圧乾燥法などの乾燥法、これらの組み合わせが挙げられる。
乾燥温度、乾燥処理時間などの乾燥条件は、組成物に含まれる溶媒の沸点、塗膜の厚さなどを考慮して、任意好適な条件とすることができる。 (Step (2))
By drying the coating film, the solvent normally contained in the coating film is removed. Examples of methods for drying the coating film include a method of directly heating with a hot plate in an atmosphere of an inert gas such as nitrogen gas, a hot air drying method, an infrared heating drying method, a flash lamp annealing drying method, and a vacuum drying method. Drying methods such as the method and combinations thereof can be mentioned.
The drying conditions such as the drying temperature and the drying treatment time can be set to any suitable conditions in consideration of the boiling point of the solvent contained in the composition, the thickness of the coating film, and the like.
塗膜を乾燥させることにより、通常塗膜に含まれる溶媒が除去される。塗膜を乾燥させる方法の例としては、窒素ガスなどの不活性ガス雰囲気下でホットプレートを用いて直接的に加熱する方法、熱風乾燥法、赤外線加熱乾燥法、フラッシュランプアニール乾燥法、減圧乾燥法などの乾燥法、これらの組み合わせが挙げられる。
乾燥温度、乾燥処理時間などの乾燥条件は、組成物に含まれる溶媒の沸点、塗膜の厚さなどを考慮して、任意好適な条件とすることができる。 (Step (2))
By drying the coating film, the solvent normally contained in the coating film is removed. Examples of methods for drying the coating film include a method of directly heating with a hot plate in an atmosphere of an inert gas such as nitrogen gas, a hot air drying method, an infrared heating drying method, a flash lamp annealing drying method, and a vacuum drying method. Drying methods such as the method and combinations thereof can be mentioned.
The drying conditions such as the drying temperature and the drying treatment time can be set to any suitable conditions in consideration of the boiling point of the solvent contained in the composition, the thickness of the coating film, and the like.
本実施形態に係る膜の製造方法は、前記工程(1)及び工程(2)に加えて、任意の工程を含むものであってもよい。
The film manufacturing method according to the present embodiment may include any step in addition to the steps (1) and (2).
[3.光電変換素子]
[3.1.光電変換素子の構成]
本発明の一実施形態に係る光電変換素子は、第一の電極と、前記膜Aと、第二の電極とをこの順で含む。光電変換素子において、通常前記膜Aは、活性層として機能し得る。光電変換素子に光を照射した場合において、第一の電極は、外部回路へ正の電荷を流出させる電極であり、第二の電極は、外部回路から正の電荷が流入する電極である。
以下、図面を用いて本実施形態の光電変換素子を説明する。 [3. Photoelectric conversion element]
[3.1. Configuration of photoelectric conversion element]
The photoelectric conversion element according to the embodiment of the present invention includes a first electrode, the film A, and a second electrode in this order. In a photoelectric conversion element, the film A can usually function as an active layer. When the photoelectric conversion element is irradiated with light, the first electrode is an electrode that causes a positive charge to flow out to an external circuit, and the second electrode is an electrode that allows a positive charge to flow in from the external circuit.
Hereinafter, the photoelectric conversion element of the present embodiment will be described with reference to the drawings.
[3.1.光電変換素子の構成]
本発明の一実施形態に係る光電変換素子は、第一の電極と、前記膜Aと、第二の電極とをこの順で含む。光電変換素子において、通常前記膜Aは、活性層として機能し得る。光電変換素子に光を照射した場合において、第一の電極は、外部回路へ正の電荷を流出させる電極であり、第二の電極は、外部回路から正の電荷が流入する電極である。
以下、図面を用いて本実施形態の光電変換素子を説明する。 [3. Photoelectric conversion element]
[3.1. Configuration of photoelectric conversion element]
The photoelectric conversion element according to the embodiment of the present invention includes a first electrode, the film A, and a second electrode in this order. In a photoelectric conversion element, the film A can usually function as an active layer. When the photoelectric conversion element is irradiated with light, the first electrode is an electrode that causes a positive charge to flow out to an external circuit, and the second electrode is an electrode that allows a positive charge to flow in from the external circuit.
Hereinafter, the photoelectric conversion element of the present embodiment will be described with reference to the drawings.
図1は、光電変換素子の構成例を模式的に示す図である。
FIG. 1 is a diagram schematically showing a configuration example of a photoelectric conversion element.
図1に示されるように、光電変換素子10は、支持基板11に設けられている。光電変換素子10は、支持基板11に接するように設けられている第一の電極12と、第一の電極12に接するように設けられている正孔輸送層13と、正孔輸送層13に接するように設けられている活性層14と、活性層14に接するように設けられている電子輸送層15と、電子輸送層15に接するように設けられている第二の電極16とを備えている。この構成例では、第二の電極16に接するように封止部材17がさらに設けられている。
以下、本実施形態の光電変換素子に含まれ得る構成要素について具体的に説明する。 As shown in FIG. 1, thephotoelectric conversion element 10 is provided on the support substrate 11. The photoelectric conversion element 10 is attached to a first electrode 12 provided in contact with the support substrate 11, a hole transport layer 13 provided in contact with the first electrode 12, and a hole transport layer 13. The active layer 14 provided in contact with the active layer 14, the electron transport layer 15 provided in contact with the active layer 14, and the second electrode 16 provided in contact with the electron transport layer 15 are provided. There is. In this configuration example, the sealing member 17 is further provided so as to be in contact with the second electrode 16.
Hereinafter, the constituent elements that can be included in the photoelectric conversion element of the present embodiment will be specifically described.
以下、本実施形態の光電変換素子に含まれ得る構成要素について具体的に説明する。 As shown in FIG. 1, the
Hereinafter, the constituent elements that can be included in the photoelectric conversion element of the present embodiment will be specifically described.
(基板)
光電変換素子は、通常、基板(支持基板)上に形成される。また、さらに基板(封止基板)により封止される場合もある。基板には、通常、第一の電極及び第二の電極からなる一対の電極のうちの一方が形成される。基板の材料は、特に有機化合物を含む層を形成する際に化学的に変化しない材料であれば特に限定されない。 (substrate)
The photoelectric conversion element is usually formed on a substrate (support substrate). Further, it may be further sealed by a substrate (sealing substrate). Usually, one of a pair of electrodes consisting of a first electrode and a second electrode is formed on the substrate. The material of the substrate is not particularly limited as long as it is a material that does not chemically change when forming a layer containing an organic compound.
光電変換素子は、通常、基板(支持基板)上に形成される。また、さらに基板(封止基板)により封止される場合もある。基板には、通常、第一の電極及び第二の電極からなる一対の電極のうちの一方が形成される。基板の材料は、特に有機化合物を含む層を形成する際に化学的に変化しない材料であれば特に限定されない。 (substrate)
The photoelectric conversion element is usually formed on a substrate (support substrate). Further, it may be further sealed by a substrate (sealing substrate). Usually, one of a pair of electrodes consisting of a first electrode and a second electrode is formed on the substrate. The material of the substrate is not particularly limited as long as it is a material that does not chemically change when forming a layer containing an organic compound.
基板の材料としては、例えば、ガラス、プラスチック、高分子フィルム、シリコンが挙げられる。不透明な基板が用いられる場合には、不透明な基板側に設けられる電極とは反対側の電極(換言すると、不透明な基板から遠い側の電極)が透明又は半透明の電極とされることが好ましい。
Examples of the substrate material include glass, plastic, polymer film, and silicon. When an opaque substrate is used, it is preferable that the electrode on the opposite side of the electrode provided on the opaque substrate side (in other words, the electrode on the side far from the opaque substrate) is a transparent or translucent electrode. ..
(電極)
光電変換素子は、一対の電極である第一の電極及び第二の電極を含んでいる。第一の電極及び第二の電極のうち、少なくとも一方の電極は、光を入射させるために、透明又は半透明の電極とすることが好ましい。 (electrode)
The photoelectric conversion element includes a first electrode and a second electrode, which are a pair of electrodes. It is preferable that at least one of the first electrode and the second electrode is a transparent or translucent electrode in order to allow light to enter.
光電変換素子は、一対の電極である第一の電極及び第二の電極を含んでいる。第一の電極及び第二の電極のうち、少なくとも一方の電極は、光を入射させるために、透明又は半透明の電極とすることが好ましい。 (electrode)
The photoelectric conversion element includes a first electrode and a second electrode, which are a pair of electrodes. It is preferable that at least one of the first electrode and the second electrode is a transparent or translucent electrode in order to allow light to enter.
透明又は半透明の電極の材料の例としては、導電性の金属酸化物膜、半透明の金属薄膜が挙げられる。具体的には、酸化インジウム、酸化亜鉛、酸化スズ、及びそれらの複合体であるインジウムスズ酸化物(ITO)、インジウム亜鉛酸化物(IZO)、NESA等の導電性材料、金、白金、銀、銅が挙げられる。透明又は半透明である電極の材料としては、ITO、IZO、酸化スズが好ましい。また、電極として、ポリアニリン及びその誘導体、ポリチオフェン及びその誘導体などの有機化合物が材料として用いられる透明導電膜を用いてもよい。透明又は半透明の電極は、第一の電極であっても第二の電極であってもよい。
Examples of transparent or translucent electrode materials include conductive metal oxide films and translucent metal thin films. Specifically, indium oxide, zinc oxide, tin oxide, and conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), and NESA, which are composites thereof, gold, platinum, and silver. Copper is mentioned. As a transparent or translucent electrode material, ITO, IZO, and tin oxide are preferable. Further, as the electrode, a transparent conductive film using an organic compound such as polyaniline and its derivative, polythiophene and its derivative as a material may be used. The transparent or translucent electrode may be the first electrode or the second electrode.
一対の電極のうちの一方の電極が透明又は半透明であれば、他方の電極は光透過性の低い電極であってもよい。光透過性の低い電極の材料の例としては、金属、及び導電性高分子が挙げられる。光透過性の低い電極の材料の具体例としては、リチウム、ナトリウム、カリウム、ルビジウム、セシウム、マグネシウム、カルシウム、ストロンチウム、バリウム、アルミニウム、スカンジウム、バナジウム、亜鉛、イットリウム、インジウム、セリウム、サマリウム、ユーロピウム、テルビウム、イッテルビウム等の金属、及びこれらのうちの2種以上の合金、又は、これらのうちの1種以上の金属と、金、銀、白金、銅、マンガン、チタン、コバルト、ニッケル、タングステン及び錫からなる群から選ばれる1種以上の金属との合金、グラファイト、グラファイト層間化合物、ポリアニリン及びその誘導体、ポリチオフェン及びその誘導体が挙げられる。合金としては、マグネシウム-銀合金、マグネシウム-インジウム合金、マグネシウム-アルミニウム合金、インジウム-銀合金、リチウム-アルミニウム合金、リチウム-マグネシウム合金、リチウム-インジウム合金、及びカルシウム-アルミニウム合金が挙げられる。
If one of the pair of electrodes is transparent or translucent, the other electrode may be an electrode having low light transmission. Examples of materials for electrodes having low light transmission include metals and conductive polymers. Specific examples of materials for electrodes with low light transmission include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, ittrium, indium, cerium, samarium, and europium. Metals such as rubidium and itterbium, and two or more alloys of these, or one or more of these metals, gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin. Examples include alloys with one or more metals selected from the group consisting of, graphite, graphite interlayer compounds, polyaniline and its derivatives, polythiophene and its derivatives. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.
(活性層)
本実施形態の光電変換素子は、活性層として、前記膜Aを有する。本実施形態に係る、膜Aである活性層は、バルクヘテロジャンクション型の構造を有しており、p型半導体材料としての重合体(1)、n型半導体材料、及び絶縁材料を含む。p型半導体材料としての重合体(1)の例及び好ましい例、n型半導体材料の例及び好ましい例、並びに絶縁材料の例及び好ましい例は、項目[1.組成物]において述べた例と同様である。 (Active layer)
The photoelectric conversion element of this embodiment has the film A as an active layer. The active layer, which is the membrane A, according to the present embodiment has a bulk heterojunction type structure, and includes a polymer (1) as a p-type semiconductor material, an n-type semiconductor material, and an insulating material. Examples of the polymer (1) as a p-type semiconductor material and preferred examples, examples of n-type semiconductor materials and preferred examples, and examples of insulating materials and preferred examples are described in Item [1. Composition] is the same as the example described.
本実施形態の光電変換素子は、活性層として、前記膜Aを有する。本実施形態に係る、膜Aである活性層は、バルクヘテロジャンクション型の構造を有しており、p型半導体材料としての重合体(1)、n型半導体材料、及び絶縁材料を含む。p型半導体材料としての重合体(1)の例及び好ましい例、n型半導体材料の例及び好ましい例、並びに絶縁材料の例及び好ましい例は、項目[1.組成物]において述べた例と同様である。 (Active layer)
The photoelectric conversion element of this embodiment has the film A as an active layer. The active layer, which is the membrane A, according to the present embodiment has a bulk heterojunction type structure, and includes a polymer (1) as a p-type semiconductor material, an n-type semiconductor material, and an insulating material. Examples of the polymer (1) as a p-type semiconductor material and preferred examples, examples of n-type semiconductor materials and preferred examples, and examples of insulating materials and preferred examples are described in Item [1. Composition] is the same as the example described.
活性層におけるp型半導体材料のn型半導体材料に対する重量比(p型半導体材料/n型半導体材料)の好ましい範囲は、組成物における当該重量比の好ましい範囲と同様とすることができる。
The preferable range of the weight ratio (p-type semiconductor material / n-type semiconductor material) of the p-type semiconductor material to the n-type semiconductor material in the active layer can be the same as the preferable range of the weight ratio in the composition.
活性層における、絶縁材料のp型半導体材料に対する重量比(絶縁材料/p型半導体材料)の好ましい範囲は、組成物における当該重量比の好ましい範囲と同様とすることができる。
The preferable range of the weight ratio of the insulating material to the p-type semiconductor material (insulating material / p-type semiconductor material) in the active layer can be the same as the preferable range of the weight ratio in the composition.
本実施形態において、活性層の厚さは、特に限定されない。活性層の厚さは、暗電流の抑制と生じた光電流の取り出しとのバランスを考慮して、任意好適な厚さとすることができる。活性層の厚さは、特に暗電流をより低減する観点から、好ましくは100nm以上であり、より好ましくは150nm以上であり、更に好ましくは200nm以上である。
また、活性層の厚さは、好ましくは10μm以下であり、より好ましくは5μm以下であり、更に好ましくは1μm以下である。 In the present embodiment, the thickness of the active layer is not particularly limited. The thickness of the active layer can be arbitrarily set in consideration of the balance between the suppression of the dark current and the extraction of the generated photocurrent. The thickness of the active layer is preferably 100 nm or more, more preferably 150 nm or more, still more preferably 200 nm or more, particularly from the viewpoint of further reducing the dark current.
The thickness of the active layer is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 1 μm or less.
また、活性層の厚さは、好ましくは10μm以下であり、より好ましくは5μm以下であり、更に好ましくは1μm以下である。 In the present embodiment, the thickness of the active layer is not particularly limited. The thickness of the active layer can be arbitrarily set in consideration of the balance between the suppression of the dark current and the extraction of the generated photocurrent. The thickness of the active layer is preferably 100 nm or more, more preferably 150 nm or more, still more preferably 200 nm or more, particularly from the viewpoint of further reducing the dark current.
The thickness of the active layer is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 1 μm or less.
(中間層)
図1に示されるとおり、本実施形態の光電変換素子は、光電変換効率などの特性を向上させるための構成要素として、例えば、電荷輸送層(電子輸送層、正孔輸送層、電子注入層、正孔注入層)などの中間層(バッファー層)を備えていることが好ましい。 (Middle layer)
As shown in FIG. 1, the photoelectric conversion element of the present embodiment has, for example, a charge transport layer (electron transport layer, hole transport layer, electron injection layer, etc.) as a component for improving characteristics such as photoelectric conversion efficiency. It is preferable to have an intermediate layer (buffer layer) such as a hole injection layer).
図1に示されるとおり、本実施形態の光電変換素子は、光電変換効率などの特性を向上させるための構成要素として、例えば、電荷輸送層(電子輸送層、正孔輸送層、電子注入層、正孔注入層)などの中間層(バッファー層)を備えていることが好ましい。 (Middle layer)
As shown in FIG. 1, the photoelectric conversion element of the present embodiment has, for example, a charge transport layer (electron transport layer, hole transport layer, electron injection layer, etc.) as a component for improving characteristics such as photoelectric conversion efficiency. It is preferable to have an intermediate layer (buffer layer) such as a hole injection layer).
また、中間層に用いられる材料の例としては、カルシウムなどの金属、酸化モリブデン、酸化亜鉛などの無機酸化物半導体、及びPEDOT(ポリ(3,4-エチレンジオキシチオフェン))とPSS(ポリ(4-スチレンスルホネート))との混合物(PEDOT:PSS)が挙げられる。
Examples of materials used for the intermediate layer include metals such as calcium, inorganic oxide semiconductors such as molybdenum oxide and zinc oxide, and PEDOT (poly (3,4-ethylenedioxythiophene)) and PSS (poly (poly (3,4-ethylenedioxythiophene)). 4-styrene sulfonate)) and a mixture (PEDOT: PSS) can be mentioned.
一実施形態では、図1に示されるように、光電変換素子は、第一の電極と活性層との間に、正孔輸送層を備えることが好ましい。正孔輸送層は、活性層から電極へと正孔を輸送する機能を有する。
別の実施形態では、光電変換素子は、正孔輸送層を備えていなくてもよい。 In one embodiment, as shown in FIG. 1, the photoelectric conversion element preferably includes a hole transport layer between the first electrode and the active layer. The hole transport layer has a function of transporting holes from the active layer to the electrode.
In another embodiment, the photoelectric conversion element may not include a hole transport layer.
別の実施形態では、光電変換素子は、正孔輸送層を備えていなくてもよい。 In one embodiment, as shown in FIG. 1, the photoelectric conversion element preferably includes a hole transport layer between the first electrode and the active layer. The hole transport layer has a function of transporting holes from the active layer to the electrode.
In another embodiment, the photoelectric conversion element may not include a hole transport layer.
第一の電極に接して設けられる正孔輸送層を、特に正孔注入層という場合がある。第一の電極に接して設けられる正孔輸送層(正孔注入層)は、第一の電極への正孔の注入を促進する機能を有する。正孔輸送層(正孔注入層)は、活性層に接していてもよい。
The hole transport layer provided in contact with the first electrode may be particularly referred to as a hole injection layer. The hole transport layer (hole injection layer) provided in contact with the first electrode has a function of promoting the injection of holes into the first electrode. The hole transport layer (hole injection layer) may be in contact with the active layer.
正孔輸送層は、正孔輸送性材料を含む。正孔輸送性材料の例としては、ポリチオフェン及びその誘導体、芳香族アミン化合物、芳香族アミン残基を有する構成単位を含む高分子化合物、CuSCN、CuI、NiO、酸化タングステン(WO3)及び酸化モリブデン(MoO3)が挙げられる。
The hole transport layer contains a hole transport material. Examples of hole-transporting materials include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing structural units having aromatic amine residues, CuSCN, CuI, NiO, tungsten oxide (WO 3 ) and molybdenum oxide. (MoO 3 ) can be mentioned.
中間層は、従来公知の任意好適な形成方法により形成することができる。中間層は、真空蒸着法や活性層の形成方法と同様の塗布法により形成することができる。
The intermediate layer can be formed by a conventionally known arbitrary suitable forming method. The intermediate layer can be formed by a coating method similar to the vacuum vapor deposition method or the active layer forming method.
本実施形態にかかる光電変換素子は、中間層が正孔輸送層及び電子輸送層であって、基板(支持基板)、第一の電極、正孔輸送層、活性層、電子輸送層、第二の電極がこの順に互いに接するように積層された構成を有することが好ましい。
In the photoelectric conversion element according to the present embodiment, the intermediate layer is a hole transport layer and an electron transport layer, and the substrate (support substrate), the first electrode, the hole transport layer, the active layer, the electron transport layer, and the second. It is preferable to have a structure in which the electrodes of the above are laminated so as to be in contact with each other in this order.
図1に示されるように、本実施形態の光電変換素子は、第二の電極と活性層との間に、中間層として電子輸送層を備えていることが好ましい。電子輸送層は、活性層から第二の電極へと電子を輸送する機能を有する。電子輸送層は、第二の電極に接していてもよい。
電子輸送層は活性層に接していてもよい。 As shown in FIG. 1, the photoelectric conversion element of the present embodiment preferably includes an electron transport layer as an intermediate layer between the second electrode and the active layer. The electron transport layer has a function of transporting electrons from the active layer to the second electrode. The electron transport layer may be in contact with the second electrode.
The electron transport layer may be in contact with the active layer.
電子輸送層は活性層に接していてもよい。 As shown in FIG. 1, the photoelectric conversion element of the present embodiment preferably includes an electron transport layer as an intermediate layer between the second electrode and the active layer. The electron transport layer has a function of transporting electrons from the active layer to the second electrode. The electron transport layer may be in contact with the second electrode.
The electron transport layer may be in contact with the active layer.
第二の電極に接して設けられる電子輸送層を、特に電子注入層という場合がある。第二の電極に接して設けられる電子輸送層(電子注入層)は、活性層で発生した電子の第二の電極への注入を促進する機能を有する。
The electron transport layer provided in contact with the second electrode may be particularly referred to as an electron injection layer. The electron transport layer (electron injection layer) provided in contact with the second electrode has a function of promoting the injection of electrons generated in the active layer into the second electrode.
電子輸送層は、電子輸送性材料を含む。電子輸送性材料の例としては、ポリアルキレンイミン及びその誘導体、フルオレン構造を含む高分子化合物、カルシウムなどの金属、金属酸化物が挙げられる。
The electron transport layer contains an electron transport material. Examples of the electron transporting material include polyalkyleneimine and its derivatives, polymer compounds containing a fluorene structure, metals such as calcium, and metal oxides.
ポリアルキレンイミン及びその誘導体の例としては、エチレンイミン、プロピレンイミン、ブチレンイミン、ジメチルエチレンイミン、ペンチレンイミン、ヘキシレンイミン、ヘプチレンイミン、オクチレンイミンといった炭素原子数2~8のアルキレンイミン、特に炭素原子数2~4のアルキレンイミンの1種又は2種以上を常法により重合して得られるポリマー、並びにそれらを種々の化合物と反応させて化学的に変性させたポリマーが挙げられる。ポリアルキレンイミン及びその誘導体としては、ポリエチレンイミン(PEI)及びエトキシ化ポリエチレンイミン(PEIE)が好ましい。
Examples of polyalkyleneimines and derivatives thereof include alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, and octyleneimine, particularly having 2 to 8 carbon atoms. Examples thereof include polymers obtained by polymerizing one or more of 2 to 4 alkyleneimines by a conventional method, and polymers obtained by reacting them with various compounds to chemically modify them. As the polyalkyleneimine and its derivative, polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE) are preferable.
フルオレン構造を含む高分子化合物の例としては、ポリ[(9,9-ビス(3’-(N,N-ジメチルアミノ)プロピル)-2,7-フルオレン)-オルト-2,7-(9,9’-ジオクチルフルオレン)](PFN)及びPFN-P2が挙げられる。
Examples of polymer compounds containing a fluorene structure include poly [(9,9-bis (3'-(N, N-dimethylamino) propyl) -2,7-fluorene) -ortho-2,7- (9). , 9'-Dioctylfluorene)] (PFN) and PFN-P2.
金属酸化物の例としては、酸化亜鉛、ガリウムドープ酸化亜鉛、アルミニウムドープ酸化亜鉛、酸化チタン及び酸化ニオブが挙げられる。金属酸化物としては、亜鉛を含む金属酸化物が好ましく、中でも酸化亜鉛が好ましい。
Examples of metal oxides include zinc oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, titanium oxide and niobium oxide. As the metal oxide, a metal oxide containing zinc is preferable, and zinc oxide is particularly preferable.
その他の電子輸送性材料の例としては、ポリ(4-ビニルフェノール)、ペリレンジイミドが挙げられる。
Examples of other electron-transporting materials include poly (4-vinylphenol) and perylenemidi.
(封止部材)
本実施形態の光電変換素子は、封止部材をさらに含み、かかる封止部材により封止された封止体とすることが好ましい。
封止部材は任意好適な従来公知の部材を用いることができる。封止部材の例としては、基板(封止基板)であるガラス基板とUV硬化性樹脂などの封止材(接着剤)との組合せが挙げられる。 (Sealing member)
It is preferable that the photoelectric conversion element of the present embodiment further includes a sealing member and is a sealed body sealed by such a sealing member.
Any suitable conventionally known member can be used as the sealing member. Examples of the sealing member include a combination of a glass substrate which is a substrate (sealing substrate) and a sealing material (adhesive) such as a UV curable resin.
本実施形態の光電変換素子は、封止部材をさらに含み、かかる封止部材により封止された封止体とすることが好ましい。
封止部材は任意好適な従来公知の部材を用いることができる。封止部材の例としては、基板(封止基板)であるガラス基板とUV硬化性樹脂などの封止材(接着剤)との組合せが挙げられる。 (Sealing member)
It is preferable that the photoelectric conversion element of the present embodiment further includes a sealing member and is a sealed body sealed by such a sealing member.
Any suitable conventionally known member can be used as the sealing member. Examples of the sealing member include a combination of a glass substrate which is a substrate (sealing substrate) and a sealing material (adhesive) such as a UV curable resin.
封止部材は、1層以上の層構造である封止層であってもよい。封止層を構成する層の例としては、ガスバリア層、ガスバリア性フィルムが挙げられる。
The sealing member may be a sealing layer having a layer structure of one or more layers. Examples of the layer constituting the sealing layer include a gas barrier layer and a gas barrier film.
封止層は、水分を遮断する性質(水蒸気バリア性)又は酸素を遮断する性質(酸素バリア性)を有する材料により形成することが好ましい。封止層の材料として好適な材料の例としては、三フッ化ポリエチレン、ポリ三フッ化塩化エチレン(PCTFE)、ポリイミド、ポリカーボネート、ポリエチレンテレフタレート、脂環式ポリオレフィン、エチレン-ビニルアルコール共重合体などの有機材料、酸化ケイ素、窒化ケイ素、酸化アルミニウム、ダイヤモンドライクカーボンなどの無機材料などが挙げられる。
The sealing layer is preferably formed of a material having a property of blocking water (water vapor barrier property) or a property of blocking oxygen (oxygen barrier property). Examples of suitable materials for the sealing layer include polyethylene trifluoride, polyethylene trifluoride chloride (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, ethylene-vinyl alcohol copolymer and the like. Examples thereof include organic materials, silicon oxide, silicon nitride, aluminum oxide, and inorganic materials such as diamond-like carbon.
封止部材は、通常、光電変換素子が適用される、例えば後述する適用例のデバイスに組み込まれる際において実施され得る加熱処理に耐え得る材料により構成される。
The sealing member is usually composed of a material that can withstand the heat treatment that can be carried out when the photoelectric conversion element is applied, for example, when it is incorporated into the device of the application example described later.
[3.2.光電変換素子の製造方法]
本実施形態の光電変換素子は、任意の方法で製造しうる。本実施形態の光電変換素子は、構成要素を形成するにあたり選択された材料に好適な形成方法を組み合わせることにより製造することができる。 [3.2. Manufacturing method of photoelectric conversion element]
The photoelectric conversion element of the present embodiment can be manufactured by any method. The photoelectric conversion element of the present embodiment can be manufactured by combining a forming method suitable for the material selected for forming the constituent elements.
本実施形態の光電変換素子は、任意の方法で製造しうる。本実施形態の光電変換素子は、構成要素を形成するにあたり選択された材料に好適な形成方法を組み合わせることにより製造することができる。 [3.2. Manufacturing method of photoelectric conversion element]
The photoelectric conversion element of the present embodiment can be manufactured by any method. The photoelectric conversion element of the present embodiment can be manufactured by combining a forming method suitable for the material selected for forming the constituent elements.
以下、本発明の実施形態として、基板(支持基板)、第一の電極、正孔輸送層、活性層としての膜A、電子輸送層、第二の電極がこの順に互いに接する構成を有する光電変換素子の製造方法について説明する。
Hereinafter, as an embodiment of the present invention, a photoelectric conversion having a structure in which a substrate (supporting substrate), a first electrode, a hole transport layer, a film A as an active layer, an electron transport layer, and a second electrode are in contact with each other in this order. A method of manufacturing the element will be described.
(基板を用意する工程)
本工程では、例えば第一の電極が設けられた支持基板を用意する。また、既に説明した電極の材料により形成された導電性の薄膜が設けられた基板を市場より入手し、必要に応じて、導電性の薄膜をパターニングして第一の電極を形成することにより、第一の電極が設けられた支持基板を用意することができる。 (Process to prepare the board)
In this step, for example, a support substrate provided with the first electrode is prepared. Further, a substrate provided with a conductive thin film formed of the electrode material described above is obtained from the market, and if necessary, the conductive thin film is patterned to form the first electrode. A support substrate provided with the first electrode can be prepared.
本工程では、例えば第一の電極が設けられた支持基板を用意する。また、既に説明した電極の材料により形成された導電性の薄膜が設けられた基板を市場より入手し、必要に応じて、導電性の薄膜をパターニングして第一の電極を形成することにより、第一の電極が設けられた支持基板を用意することができる。 (Process to prepare the board)
In this step, for example, a support substrate provided with the first electrode is prepared. Further, a substrate provided with a conductive thin film formed of the electrode material described above is obtained from the market, and if necessary, the conductive thin film is patterned to form the first electrode. A support substrate provided with the first electrode can be prepared.
本実施形態にかかる光電変換素子の製造方法において、支持基板上に第一の電極を形成する場合の第一の電極の形成方法は特に限定されない。第一の電極は、既に説明した材料を、真空蒸着法、スパッタリング法、イオンプレーティング法、めっき法、塗布法などの従来公知の任意好適な方法によって、第一の電極を形成すべき構成(例、支持基板、活性層、正孔輸送層)上に形成することができる。
In the method for manufacturing a photoelectric conversion element according to the present embodiment, the method for forming the first electrode when the first electrode is formed on the support substrate is not particularly limited. The first electrode has a structure in which the material already described should be formed of the first electrode by any conventionally known suitable method such as a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and a coating method (a configuration in which the first electrode is formed. For example, it can be formed on a support substrate, an active layer, a hole transport layer).
(正孔輸送層の形成工程)
光電変換素子の製造方法は、活性層と第一の電極との間に設けられる正孔輸送層(正孔注入層)を形成する工程を含んでいてもよい。 (Process of forming hole transport layer)
The method for manufacturing a photoelectric conversion element may include a step of forming a hole transport layer (hole injection layer) provided between the active layer and the first electrode.
光電変換素子の製造方法は、活性層と第一の電極との間に設けられる正孔輸送層(正孔注入層)を形成する工程を含んでいてもよい。 (Process of forming hole transport layer)
The method for manufacturing a photoelectric conversion element may include a step of forming a hole transport layer (hole injection layer) provided between the active layer and the first electrode.
正孔輸送層の形成方法は特に限定されない。正孔輸送層の形成工程をより簡便にする観点からは、従来公知の任意好適な塗布法によって正孔輸送層を形成することが好ましい。
正孔輸送層は、例えば、既に説明した正孔輸送層の材料と溶媒とを含む塗布液を用いる塗布法や真空蒸着法により形成することができる。 The method of forming the hole transport layer is not particularly limited. From the viewpoint of simplifying the step of forming the hole transport layer, it is preferable to form the hole transport layer by a conventionally known and arbitrary suitable coating method.
The hole transport layer can be formed, for example, by a coating method using a coating liquid containing the material and solvent of the hole transport layer already described or a vacuum vapor deposition method.
正孔輸送層は、例えば、既に説明した正孔輸送層の材料と溶媒とを含む塗布液を用いる塗布法や真空蒸着法により形成することができる。 The method of forming the hole transport layer is not particularly limited. From the viewpoint of simplifying the step of forming the hole transport layer, it is preferable to form the hole transport layer by a conventionally known and arbitrary suitable coating method.
The hole transport layer can be formed, for example, by a coating method using a coating liquid containing the material and solvent of the hole transport layer already described or a vacuum vapor deposition method.
(活性層の形成工程)
本実施形態の光電変換素子の製造方法においては、正孔輸送層上に活性層としての膜Aが形成される。膜Aは、任意好適な従来公知の形成工程により形成することができる。本実施形態において、活性層としての膜Aは、前記組成物を用いる塗布法により製造されうる。 (Process of forming active layer)
In the method for manufacturing a photoelectric conversion element of the present embodiment, a film A as an active layer is formed on the hole transport layer. The film A can be formed by any suitable conventionally known forming step. In the present embodiment, the membrane A as an active layer can be produced by a coating method using the above composition.
本実施形態の光電変換素子の製造方法においては、正孔輸送層上に活性層としての膜Aが形成される。膜Aは、任意好適な従来公知の形成工程により形成することができる。本実施形態において、活性層としての膜Aは、前記組成物を用いる塗布法により製造されうる。 (Process of forming active layer)
In the method for manufacturing a photoelectric conversion element of the present embodiment, a film A as an active layer is formed on the hole transport layer. The film A can be formed by any suitable conventionally known forming step. In the present embodiment, the membrane A as an active layer can be produced by a coating method using the above composition.
活性層としての膜Aは、[2.膜]において説明した膜の製造方法と同様の方法により形成されうる。本実施形態では、p型半導体材料として重合体(1)と、n型半導体材料と、絶縁材料と、溶媒とを含む前記の組成物を、正孔輸送層上に塗布して塗膜を形成する工程、次いで、前記塗膜を乾燥させる工程を含む工程により、活性層としての膜Aが形成されうる。
Membrane A as an active layer is [2. It can be formed by the same method as the method for producing a film described in [Membrane]. In the present embodiment, the above composition containing the polymer (1) as the p-type semiconductor material, the n-type semiconductor material, the insulating material, and the solvent is applied onto the hole transport layer to form a coating film. The film A as an active layer can be formed by a step including a step of drying the coating film.
(電子輸送層の形成工程)
本実施形態の光電変換素子の製造方法は、活性層上に設けられた電子輸送層(電子注入層)を形成する工程を含んでいる。 (Process of forming electron transport layer)
The method for manufacturing a photoelectric conversion element of the present embodiment includes a step of forming an electron transport layer (electron injection layer) provided on the active layer.
本実施形態の光電変換素子の製造方法は、活性層上に設けられた電子輸送層(電子注入層)を形成する工程を含んでいる。 (Process of forming electron transport layer)
The method for manufacturing a photoelectric conversion element of the present embodiment includes a step of forming an electron transport layer (electron injection layer) provided on the active layer.
電子輸送層の形成方法は特に限定されない。電子輸送層の形成工程をより簡便にする観点からは、従来公知の任意好適な真空蒸着法によって電子輸送層を形成することが好ましい。
The method of forming the electron transport layer is not particularly limited. From the viewpoint of simplifying the process of forming the electron transport layer, it is preferable to form the electron transport layer by a conventionally known arbitrary suitable vacuum vapor deposition method.
(第二の電極の形成工程)
第二の電極の形成方法は特に限定されない。第二の電極は、例えば、上記例示の電極の材料を、塗布法、真空蒸着法、スパッタリング法、イオンプレーティング法、めっき法など従来公知の任意好適な方法によって、電子輸送層上に形成することができる。以上の工程により、本実施形態の光電変換素子が製造される。 (Step of forming the second electrode)
The method for forming the second electrode is not particularly limited. For the second electrode, for example, the material of the above-exemplified electrode is formed on the electron transport layer by any conventionally known suitable method such as a coating method, a vacuum vapor deposition method, a sputtering method, an ion plating method, and a plating method. be able to. By the above steps, the photoelectric conversion element of the present embodiment is manufactured.
第二の電極の形成方法は特に限定されない。第二の電極は、例えば、上記例示の電極の材料を、塗布法、真空蒸着法、スパッタリング法、イオンプレーティング法、めっき法など従来公知の任意好適な方法によって、電子輸送層上に形成することができる。以上の工程により、本実施形態の光電変換素子が製造される。 (Step of forming the second electrode)
The method for forming the second electrode is not particularly limited. For the second electrode, for example, the material of the above-exemplified electrode is formed on the electron transport layer by any conventionally known suitable method such as a coating method, a vacuum vapor deposition method, a sputtering method, an ion plating method, and a plating method. be able to. By the above steps, the photoelectric conversion element of the present embodiment is manufactured.
(封止体の形成工程)
封止体の形成にあたり、本実施形態では、従来公知の任意好適な封止材(接着剤)及び基板(封止基板)を用いる。具体的には、製造された光電変換素子の周辺を囲むように、支持基板上に、例えばUV硬化性樹脂などの封止材を塗布した後、封止材により隙間なく貼り合わせた後、選択された封止材に好適な、UV光の照射などの方法を用いて支持基板と封止基板との間隙に光電変換素子を封止することにより、光電変換素子の封止体を得ることができる。 (Process of forming a sealed body)
In forming the encapsulant, in the present embodiment, a conventionally known arbitrary suitable encapsulant (adhesive) and substrate (encapsulating substrate) are used. Specifically, a sealing material such as a UV curable resin is applied onto the support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and then the sealing material is used to bond them without gaps before selection. By encapsulating the photoelectric conversion element in the gap between the support substrate and the encapsulating substrate by using a method such as irradiation with UV light, which is suitable for the encapsulating material, a encapsulating body of the photoelectric conversion element can be obtained. can.
封止体の形成にあたり、本実施形態では、従来公知の任意好適な封止材(接着剤)及び基板(封止基板)を用いる。具体的には、製造された光電変換素子の周辺を囲むように、支持基板上に、例えばUV硬化性樹脂などの封止材を塗布した後、封止材により隙間なく貼り合わせた後、選択された封止材に好適な、UV光の照射などの方法を用いて支持基板と封止基板との間隙に光電変換素子を封止することにより、光電変換素子の封止体を得ることができる。 (Process of forming a sealed body)
In forming the encapsulant, in the present embodiment, a conventionally known arbitrary suitable encapsulant (adhesive) and substrate (encapsulating substrate) are used. Specifically, a sealing material such as a UV curable resin is applied onto the support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and then the sealing material is used to bond them without gaps before selection. By encapsulating the photoelectric conversion element in the gap between the support substrate and the encapsulating substrate by using a method such as irradiation with UV light, which is suitable for the encapsulating material, a encapsulating body of the photoelectric conversion element can be obtained. can.
[3.3.光電変換素子の用途]
本実施形態の光電変換素子の用途としては、光検出素子、太陽電池が挙げられる。
より具体的には、本実施形態の光電変換素子は、電極間に電圧(逆バイアス電圧)を印加した状態で、透明又は半透明の電極側から光を照射することにより、光電流を流すことができ、光検出素子(光センサー)として動作させることができる。また、光検出素子を複数集積することによりイメージセンサーとして用いることもできる。このように本実施形態の光電変換素子は、特に光検出素子として好適に用いることができる。 [3.3. Applications for photoelectric conversion elements]
Applications of the photoelectric conversion element of this embodiment include a photodetection element and a solar cell.
More specifically, in the photoelectric conversion element of the present embodiment, a light current is passed by irradiating light from the transparent or translucent electrode side in a state where a voltage (reverse bias voltage) is applied between the electrodes. It can be operated as a photodetection element (optical sensor). It can also be used as an image sensor by integrating a plurality of photodetecting elements. As described above, the photoelectric conversion element of the present embodiment can be particularly suitably used as a photodetection element.
本実施形態の光電変換素子の用途としては、光検出素子、太陽電池が挙げられる。
より具体的には、本実施形態の光電変換素子は、電極間に電圧(逆バイアス電圧)を印加した状態で、透明又は半透明の電極側から光を照射することにより、光電流を流すことができ、光検出素子(光センサー)として動作させることができる。また、光検出素子を複数集積することによりイメージセンサーとして用いることもできる。このように本実施形態の光電変換素子は、特に光検出素子として好適に用いることができる。 [3.3. Applications for photoelectric conversion elements]
Applications of the photoelectric conversion element of this embodiment include a photodetection element and a solar cell.
More specifically, in the photoelectric conversion element of the present embodiment, a light current is passed by irradiating light from the transparent or translucent electrode side in a state where a voltage (reverse bias voltage) is applied between the electrodes. It can be operated as a photodetection element (optical sensor). It can also be used as an image sensor by integrating a plurality of photodetecting elements. As described above, the photoelectric conversion element of the present embodiment can be particularly suitably used as a photodetection element.
また、本実施形態の光電変換素子は、光が照射されることにより、電極間に光起電力を発生させることができ、太陽電池として動作させることができる。光電変換素子を複数集積することにより太陽電池モジュールとすることもできる。
Further, the photoelectric conversion element of the present embodiment can generate photovoltaic power between the electrodes by being irradiated with light, and can be operated as a solar cell. A solar cell module can also be obtained by integrating a plurality of photoelectric conversion elements.
(光電変換素子の適用例)
本実施形態にかかる光電変換素子は、光検出素子として、ワークステーション、パーソナルコンピュータ、携帯情報端末、入退室管理システム、デジタルカメラ、及び医療機器などの種々の電子装置が備える検出部に好適に適用することができる。 (Application example of photoelectric conversion element)
The photoelectric conversion element according to the present embodiment is suitably applied as a photodetection element to a detection unit provided in various electronic devices such as a workstation, a personal computer, a personal digital assistant, an entrance / exit management system, a digital camera, and a medical device. can do.
本実施形態にかかる光電変換素子は、光検出素子として、ワークステーション、パーソナルコンピュータ、携帯情報端末、入退室管理システム、デジタルカメラ、及び医療機器などの種々の電子装置が備える検出部に好適に適用することができる。 (Application example of photoelectric conversion element)
The photoelectric conversion element according to the present embodiment is suitably applied as a photodetection element to a detection unit provided in various electronic devices such as a workstation, a personal computer, a personal digital assistant, an entrance / exit management system, a digital camera, and a medical device. can do.
本実施形態の光電変換素子は、上記例示の電子装置が備える、例えば、X線撮像装置及びCMOSイメージセンサーなどの固体撮像装置用のイメージ検出部(例えば、X線センサーなどのイメージセンサー)、指紋検出部、顔検出部、静脈検出部及び虹彩検出部などの生体の一部分の所定の特徴を検出する生体情報認証装置の検出部(例えば、近赤外線センサー)、パルスオキシメータなどの光学バイオセンサーの検出部などに好適に適用することができる。
The photoelectric conversion element of the present embodiment includes, for example, an image detection unit (for example, an image sensor such as an X-ray sensor) for a solid-state image pickup device such as an X-ray image pickup device and a CMOS image sensor, and a fingerprint, which are included in the above-exemplified electronic device. A detection unit (for example, a near-infrared sensor) of a biometric information authentication device that detects a predetermined feature of a part of a living body such as a detection unit, a face detection unit, a vein detection unit, and an iris detection unit, and an optical biosensor such as a pulse oximeter. It can be suitably applied to a detection unit or the like.
本実施形態の光電変換素子は、固体撮像装置用のイメージ検出部として、さらにはTime-of-flight(TOF)型距離測定装置(TOF型測距装置)に好適に適用することもできる。
The photoelectric conversion element of the present embodiment can be suitably applied as an image detection unit for a solid-state imaging device, and further to a Time-of-flight (TOF) type distance measuring device (TOF type distance measuring device).
TOF型測距装置では、光源からの放射光が測定対象物において反射された反射光を光電変換素子で受光させることにより距離を測定する。具体的には、光源から放射された照射光が測定対象物で反射して反射光として戻るまでの飛行時間を検出して測定対象物までの距離を求める。TOF型には、直接TOF方式と間接TOF方式とが存在する。直接TOF方式では光源から光を照射した時刻と反射光を光電変換素子で受光した時刻との差を直接計測し、間接TOF方式では飛行時間に依存した電荷蓄積量の変化を時間変化に換算することで距離を計測する。間接TOF方式で用いられる電荷蓄積により飛行時間を得る測距原理には、光源からの放射光と測定対象で反射される反射光との位相から飛行時間を求める連続波(特に正弦波)変調方式とパルス変調方式とがある。
In the TOF type distance measuring device, the distance is measured by receiving the reflected light reflected by the light source from the light source by the photoelectric conversion element. Specifically, the flight time until the irradiation light emitted from the light source is reflected by the measurement target and returned as the reflected light is detected, and the distance to the measurement target is obtained. The TOF type includes a direct TOF method and an indirect TOF method. In the direct TOF method, the difference between the time when the light is emitted from the light source and the time when the reflected light is received by the photoelectric conversion element is directly measured, and in the indirect TOF method, the change in the charge accumulation amount depending on the flight time is converted into the time change. By measuring the distance. The distance measurement principle used in the indirect TOF method to obtain the flight time by accumulating charge is a continuous wave (especially sinusoidal) modulation method in which the flight time is obtained from the phase of the emitted light from the light source and the reflected light reflected by the measurement target. And the pulse modulation method.
以下、本実施形態にかかる光電変換素子が好適に適用され得る検出部のうち、固体撮像装置用のイメージ検出部及びX線撮像装置用のイメージ検出部、生体認証装置(例えば指紋認証装置や静脈認証装置など)のための指紋検出部及び静脈検出部、並びにTOF型測距装置(間接TOF方式)のイメージ検出部の構成例について、図面を参照して説明する。
Hereinafter, among the detection units to which the photoelectric conversion element according to the present embodiment can be suitably applied, an image detection unit for a solid-state image pickup device, an image detection unit for an X-ray image pickup device, and a biometric authentication device (for example, a fingerprint authentication device or a vein). A configuration example of a fingerprint detection unit and a vein detection unit for (authentication device, etc.) and an image detection unit of a TOF type ranging device (indirect TOF method) will be described with reference to the drawings.
(固体撮像装置用のイメージ検出部)
図2は、固体撮像装置用のイメージ検出部の構成例を模式的に示す図である。 (Image detector for solid-state image sensor)
FIG. 2 is a diagram schematically showing a configuration example of an image detection unit for a solid-state image sensor.
図2は、固体撮像装置用のイメージ検出部の構成例を模式的に示す図である。 (Image detector for solid-state image sensor)
FIG. 2 is a diagram schematically showing a configuration example of an image detection unit for a solid-state image sensor.
イメージ検出部1は、CMOSトランジスタ基板20と、CMOSトランジスタ基板20を覆うように設けられている層間絶縁膜30と、層間絶縁膜30上に設けられている、本発明の実施形態にかかる光電変換素子10と、層間絶縁膜30を貫通するように設けられており、CMOSトランジスタ基板20と光電変換素子10とを電気的に接続する層間配線部32と、光電変換素子10を覆うように設けられている封止層40と、封止層40上に設けられているカラーフィルター50とを備えている。
The image detection unit 1 comprises a CMOS transistor substrate 20, an interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20, and a photoelectric conversion according to an embodiment of the present invention provided on the interlayer insulating film 30. It is provided so as to penetrate the element 10 and the interlayer insulating film 30, and is provided so as to cover the interlayer wiring portion 32 that electrically connects the CMOS transistor substrate 20 and the photoelectric conversion element 10 and the photoelectric conversion element 10. The sealing layer 40 and the color filter 50 provided on the sealing layer 40 are provided.
CMOSトランジスタ基板20は、従来公知の任意好適な構成を設計に応じた態様で備えている。
The CMOS transistor substrate 20 is provided with a conventionally known arbitrary suitable configuration in a mode according to the design.
CMOSトランジスタ基板20は、基板の厚さ内に形成されたトランジスタ、コンデンサなどを含み、種々の機能を実現するためのCMOSトランジスタ回路(MOSトランジスタ回路)などの機能素子を備えている。
The CMOS transistor substrate 20 includes transistors, capacitors, etc. formed within the thickness of the substrate, and includes functional elements such as a CMOS transistor circuit (MOS transistor circuit) for realizing various functions.
機能素子としては、例えば、フローティングディフュージョン、リセットトランジスタ、出力トランジスタ、選択トランジスタが挙げられる。
Examples of the functional element include a floating diffusion, a reset transistor, an output transistor, and a selection transistor.
このような機能素子、配線などにより、CMOSトランジスタ基板20には、信号読み出し回路などが作り込まれている。
With such functional elements, wiring, etc., a signal readout circuit and the like are built in the CMOS transistor substrate 20.
層間絶縁膜30は、例えば酸化シリコン、絶縁性樹脂などの従来公知の任意好適な絶縁性材料により構成することができる。層間配線部32は、例えば、銅、タングステンなどの従来公知の任意好適な導電性材料(配線材料)により構成することができる。層間配線部32は、例えば、配線層の形成と同時に形成されるホール内配線であっても、配線層とは別途形成される埋込みプラグであってもよい。
The interlayer insulating film 30 can be made of any conventionally known and arbitrarily suitable insulating material such as silicon oxide and an insulating resin. The interlayer wiring portion 32 can be made of, for example, any conventionally known suitable conductive material (wiring material) such as copper and tungsten. The interlayer wiring portion 32 may be, for example, an in-hole wiring formed at the same time as the formation of the wiring layer, or an embedded plug formed separately from the wiring layer.
封止層40は、光電変換素子10を機能的に劣化させてしまうおそれのある酸素、水などの有害物質の浸透を防止又は抑制できることを条件として、従来公知の任意好適な材料により構成することができる。封止層40は、既に説明した封止部材17と同様の構成とすることができる。
The sealing layer 40 is made of any conventionally known suitable material, provided that the permeation of harmful substances such as oxygen and water that may functionally deteriorate the photoelectric conversion element 10 can be prevented or suppressed. Can be done. The sealing layer 40 can have the same configuration as the sealing member 17 described above.
カラーフィルター50としては、従来公知の任意好適な材料により構成され、かつイメージ検出部1の設計に対応した例えば原色カラーフィルターを用いることができる。また、カラーフィルター50としては、原色カラーフィルターと比較して、厚さを薄くすることができる補色カラーフィルターを用いることもできる。補色カラーフィルターとしては、例えば(イエロー、シアン、マゼンタ)の3種類、(イエロー、シアン、透明)の3種類、(イエロー、透明、マゼンタ)の3種類、及び(透明、シアン、マゼンタ)の3種類が組み合わされたカラーフィルターを用いることができる。これらは、カラー画像データを生成できることを条件として、光電変換素子10及びCMOSトランジスタ基板20の設計に対応した任意好適な配置とすることができる。
As the color filter 50, for example, a primary color filter that is made of any suitable material known conventionally and that corresponds to the design of the image detection unit 1 can be used. Further, as the color filter 50, a complementary color filter that can be thinner than the primary color filter can also be used. Complementary color filters include, for example, three types (yellow, cyan, magenta), three types (yellow, cyan, transparent), three types (yellow, transparent, magenta), and three types (transparent, cyan, magenta). Color filters that combine types can be used. These can be arbitrarily arranged according to the design of the photoelectric conversion element 10 and the CMOS transistor substrate 20, provided that color image data can be generated.
カラーフィルター50を介して光電変換素子10が受光した光は、光電変換素子10によって、受光量に応じた電気信号に変換され、電極を介して、光電変換素子10外に受光信号、すなわち撮像対象に対応する電気信号として出力される。
The light received by the photoelectric conversion element 10 via the color filter 50 is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10, and the light received signal outside the photoelectric conversion element 10 via the electrode, that is, an image pickup target. It is output as an electric signal corresponding to.
次いで、光電変換素子10から出力された受光信号は、層間配線部32を介して、CMOSトランジスタ基板20に入力され、CMOSトランジスタ基板20に作り込まれた信号読み出し回路により読み出され、図示しないさらなる任意好適な従来公知の機能部によって信号処理されることにより、撮像対象に基づく画像情報が生成される。
Next, the light receiving signal output from the photoelectric conversion element 10 is input to the CMOS transistor substrate 20 via the interlayer wiring unit 32, and is read out by the signal readout circuit built in the CMOS transistor substrate 20, which is not shown. Image information based on the imaging target is generated by signal processing by any suitable conventionally known functional unit.
(指紋検出部)
図3は、表示装置に一体的に構成される指紋検出部の構成例を模式的に示す図である。 (Fingerprint detector)
FIG. 3 is a diagram schematically showing a configuration example of a fingerprint detection unit integrally configured with a display device.
図3は、表示装置に一体的に構成される指紋検出部の構成例を模式的に示す図である。 (Fingerprint detector)
FIG. 3 is a diagram schematically showing a configuration example of a fingerprint detection unit integrally configured with a display device.
携帯情報端末の表示装置2は、本発明の実施形態にかかる光電変換素子10を主たる構成要素として含む指紋検出部100と、当該指紋検出部100上に設けられ、所定の画像を表示する表示パネル部200とを備えている。
The display device 2 of the mobile information terminal includes a fingerprint detection unit 100 including the photoelectric conversion element 10 according to the embodiment of the present invention as a main component, and a display panel provided on the fingerprint detection unit 100 and displaying a predetermined image. It is equipped with a unit 200.
この構成例では、表示パネル部200の表示領域200aと一致する領域に指紋検出部100が設けられている。換言すると、指紋検出部100の上方に、表示パネル部200が一体的に積層されている。
In this configuration example, the fingerprint detection unit 100 is provided in an area corresponding to the display area 200a of the display panel unit 200. In other words, the display panel unit 200 is integrally laminated above the fingerprint detection unit 100.
表示領域200aのうちの一部の領域においてのみ指紋検出を行う場合には、当該一部の領域のみに対応させて指紋検出部100を設ければよい。
When fingerprint detection is performed only in a part of the display area 200a, the fingerprint detection unit 100 may be provided corresponding to only the part of the display area 200a.
指紋検出部100は、本発明の実施形態にかかる光電変換素子10を本質的な機能を奏する機能部として含む。指紋検出部100は、図示されていない保護フィルム(protection film)、支持基板、封止基板、封止部材、バリアフィルム、バンドパスフィルター、赤外線カットフィルムなどの任意好適な従来公知の部材を所望の特性が得られるような設計に対応した態様で備え得る。指紋検出部100には、既に説明したイメージ検出部の構成を採用することもできる。
The fingerprint detection unit 100 includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs an essential function. The fingerprint detection unit 100 desired any suitable conventionally known member such as a protective film (projection film), a support substrate, a sealing substrate, a sealing member, a barrier film, a bandpass filter, and an infrared cut film (not shown). It can be provided in a manner corresponding to the design so that the characteristics can be obtained. For the fingerprint detection unit 100, the configuration of the image detection unit already described can also be adopted.
光電変換素子10は、表示領域200a内において、任意の態様で含まれ得る。例えば、複数の光電変換素子10が、マトリクス状に配置されていてもよい。
The photoelectric conversion element 10 may be included in the display area 200a in any manner. For example, a plurality of photoelectric conversion elements 10 may be arranged in a matrix.
光電変換素子10は、既に説明したとおり、支持基板11に設けられており、支持基板11には、例えばマトリクス状に電極(第一の電極又は第二の電極)が設けられている。
As described above, the photoelectric conversion element 10 is provided on the support substrate 11, and the support substrate 11 is provided with electrodes (first electrode or second electrode) in a matrix, for example.
光電変換素子10が受光した光は、光電変換素子10によって、受光量に応じた電気信号に変換され、電極を介して、光電変換素子10外に受光信号、すなわち撮像された指紋に対応する電気信号として出力される。
The light received by the photoelectric conversion element 10 is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10, and the light received signal outside the photoelectric conversion element 10 via the electrode, that is, electricity corresponding to the captured fingerprint. It is output as a signal.
表示パネル部200は、この構成例では、タッチセンサーパネルを含む有機エレクトロルミネッセンス表示パネル(有機EL表示パネル)として構成されている。表示パネル部200は、例えば有機EL表示パネルの代わりに、バックライトなどの光源を含む液晶表示パネルなどの任意好適な従来公知の構成を有する表示パネルにより構成されていてもよい。
In this configuration example, the display panel unit 200 is configured as an organic electroluminescence display panel (organic EL display panel) including a touch sensor panel. The display panel unit 200 may be configured by, for example, instead of the organic EL display panel, a display panel having an arbitrary suitable conventionally known configuration such as a liquid crystal display panel including a light source such as a backlight.
表示パネル部200は、既に説明した指紋検出部100上に設けられている。表示パネル部200は、有機エレクトロルミネッセンス素子(有機EL素子)220を本質的な機能を奏する機能部として含む。表示パネル部200は、さらに任意好適な従来公知のガラス基板といった基板(支持基板210又は封止基板240)、封止部材、バリアフィルム、円偏光板などの偏光板、タッチセンサーパネル230などの任意好適な従来公知の部材を所望の特性に対応した態様で備え得る。
The display panel unit 200 is provided on the fingerprint detection unit 100 already described. The display panel unit 200 includes an organic electroluminescence element (organic EL element) 220 as a functional unit that performs an essential function. The display panel unit 200 is further optionally suitable such as a substrate such as a conventionally known glass substrate (support substrate 210 or a sealing substrate 240), a sealing member, a barrier film, a polarizing plate such as a circular polarizing plate, and a touch sensor panel 230. Suitable conventionally known members may be provided in a manner corresponding to the desired characteristics.
以上説明した構成例において、有機EL素子220は、表示領域200aにおける画素の光源として用いられるとともに、指紋検出部100における指紋の撮像のための光源としても用いられる。
In the configuration example described above, the organic EL element 220 is used as a light source for pixels in the display region 200a and also as a light source for fingerprint imaging in the fingerprint detection unit 100.
ここで、指紋検出部100の動作について簡単に説明する。
指紋認証の実行時には、表示パネル部200の有機EL素子220から放射される光を用いて指紋検出部100が指紋を検出する。具体的には、有機EL素子220から放射された光は、有機EL素子220と指紋検出部100の光電変換素子10との間に存在する構成要素を透過して、表示領域200a内である表示パネル部200の表面に接するように載置された手指の指先の皮膚(指表面)によって反射される。指表面によって反射された光のうちの少なくとも一部は、間に存在する構成要素を透過して光電変換素子10によって受光され、光電変換素子10の受光量に応じた電気信号に変換される。そして、変換された電気信号から、指表面の指紋についての画像情報が構成される。 Here, the operation of thefingerprint detection unit 100 will be briefly described.
When performing fingerprint authentication, thefingerprint detection unit 100 detects a fingerprint using the light emitted from the organic EL element 220 of the display panel unit 200. Specifically, the light emitted from the organic EL element 220 passes through a component existing between the organic EL element 220 and the photoelectric conversion element 10 of the fingerprint detection unit 100, and is displayed within the display area 200a. It is reflected by the skin (finger surface) of the fingertips of the fingers placed so as to be in contact with the surface of the panel portion 200. At least a part of the light reflected by the finger surface passes through the components existing between them and is received by the photoelectric conversion element 10, and is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10. Then, image information about the fingerprint on the finger surface is constructed from the converted electric signal.
指紋認証の実行時には、表示パネル部200の有機EL素子220から放射される光を用いて指紋検出部100が指紋を検出する。具体的には、有機EL素子220から放射された光は、有機EL素子220と指紋検出部100の光電変換素子10との間に存在する構成要素を透過して、表示領域200a内である表示パネル部200の表面に接するように載置された手指の指先の皮膚(指表面)によって反射される。指表面によって反射された光のうちの少なくとも一部は、間に存在する構成要素を透過して光電変換素子10によって受光され、光電変換素子10の受光量に応じた電気信号に変換される。そして、変換された電気信号から、指表面の指紋についての画像情報が構成される。 Here, the operation of the
When performing fingerprint authentication, the
表示装置2を備える携帯情報端末は、従来公知の任意好適なステップにより、得られた画像情報と、予め記録されていた指紋認証用の指紋データとを比較して、指紋認証を行う。
The portable information terminal provided with the display device 2 performs fingerprint authentication by comparing the obtained image information with the fingerprint data for fingerprint authentication recorded in advance by an arbitrary suitable step known conventionally.
(X線撮像装置用のイメージ検出部)
図4は、X線撮像装置用のイメージ検出部の構成例を模式的に示す図である。 (Image detector for X-ray imager)
FIG. 4 is a diagram schematically showing a configuration example of an image detection unit for an X-ray image pickup apparatus.
図4は、X線撮像装置用のイメージ検出部の構成例を模式的に示す図である。 (Image detector for X-ray imager)
FIG. 4 is a diagram schematically showing a configuration example of an image detection unit for an X-ray image pickup apparatus.
X線撮像装置用のイメージ検出部1は、CMOSトランジスタ基板20と、CMOSトランジスタ基板20を覆うように設けられている層間絶縁膜30と、層間絶縁膜30上に設けられている、本発明の実施形態にかかる光電変換素子10と、層間絶縁膜30を貫通するように設けられており、CMOSトランジスタ基板20と光電変換素子10とを電気的に接続する層間配線部32と、光電変換素子10を覆うように設けられている封止層40と、封止層40上に設けられているシンチレータ42とシンチレータ42を覆うように設けられている反射層44と、反射層44を覆うように設けられている保護層46とを備えている。
The image detection unit 1 for the X-ray image pickup apparatus is provided on the CMOS transistor substrate 20, the interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20, and the interlayer insulating film 30 of the present invention. The photoelectric conversion element 10 according to the embodiment, the interlayer wiring portion 32 which is provided so as to penetrate the interlayer insulating film 30 and electrically connects the CMOS transistor substrate 20 and the photoelectric conversion element 10, and the photoelectric conversion element 10 A sealing layer 40 provided so as to cover the sealing layer 40, a reflecting layer 44 provided so as to cover the scintillator 42 and the scintillator 42 provided on the sealing layer 40, and a reflective layer 44 provided so as to cover the reflective layer 44. It is provided with a protective layer 46 that is provided.
CMOSトランジスタ基板20は、従来公知の任意好適な構成を設計に応じた態様で備えている。
The CMOS transistor substrate 20 is provided with a conventionally known arbitrary suitable configuration in a mode according to the design.
CMOSトランジスタ基板20は、基板の厚さ内に形成されたトランジスタ、コンデンサなどを含み、種々の機能を実現するためのCMOSトランジスタ回路(MOSトランジスタ回路)などの機能素子を備えている。
The CMOS transistor substrate 20 includes transistors, capacitors, etc. formed within the thickness of the substrate, and includes functional elements such as a CMOS transistor circuit (MOS transistor circuit) for realizing various functions.
機能素子としては、例えば、フローティングディフュージョン、リセットトランジスタ、出力トランジスタ、選択トランジスタが挙げられる。
Examples of the functional element include a floating diffusion, a reset transistor, an output transistor, and a selection transistor.
このような機能素子、配線などにより、CMOSトランジスタ基板20には、信号読み出し回路などが作り込まれている。
With such functional elements, wiring, etc., a signal readout circuit and the like are built in the CMOS transistor substrate 20.
層間絶縁膜30は、例えば酸化シリコン、絶縁性樹脂などの従来公知の任意好適な絶縁性材料により構成することができる。層間配線部32は、例えば、銅、タングステンなどの従来公知の任意好適な導電性材料(配線材料)により構成することができる。層間配線部32は、例えば、配線層の形成と同時に形成されるホール内配線であっても、配線層とは別途形成される埋込みプラグであってもよい。
The interlayer insulating film 30 can be made of any conventionally known and arbitrarily suitable insulating material such as silicon oxide and an insulating resin. The interlayer wiring portion 32 can be made of, for example, any conventionally known suitable conductive material (wiring material) such as copper and tungsten. The interlayer wiring portion 32 may be, for example, an in-hole wiring formed at the same time as the formation of the wiring layer, or an embedded plug formed separately from the wiring layer.
封止層40は、光電変換素子10を機能的に劣化させてしまうおそれのある酸素、水などの有害物質の浸透を防止又は抑制できることを条件として、従来公知の任意好適な材料により構成することができる。封止層40は、既に説明した封止部材17と同様の構成とすることができる。
The sealing layer 40 is made of any conventionally known suitable material, provided that the permeation of harmful substances such as oxygen and water that may functionally deteriorate the photoelectric conversion element 10 can be prevented or suppressed. Can be done. The sealing layer 40 can have the same configuration as the sealing member 17 described above.
シンチレータ42は、X線撮像装置用のイメージ検出部1の設計に対応した従来公知の任意好適な材料により構成することができる。シンチレータ42の好適な材料の例としては、CsI(ヨウ化セシウム)やNaI(ヨウ化ナトリウム)、ZnS(硫化亜鉛)、GOS(酸硫化ガドリニウム)、GSO(ケイ酸ガドリニウム)といった無機材料の無機結晶や、アントラセン、ナフタレン、スチルベンといった有機材料の有機結晶や、トルエン、キシレン、ジオキサンといった有機溶媒にジフェニルオキサゾール(PPO)やテルフェニル(TP)などの有機材料を溶解させた有機液体、キセノンやヘリウムといった気体、プラスチックなどを用いることができる。
The scintillator 42 can be made of any conventionally known and arbitrarily suitable material corresponding to the design of the image detection unit 1 for the X-ray image pickup apparatus. Examples of suitable materials for the scintillator 42 are inorganic crystals of inorganic materials such as CsI (cesium iodide), NaI (sodium iodide), ZnS (zinc sulfide), GOS (gadrinium acid sulfide), and GSO (gadrinium silicate). , Organic crystals of organic materials such as anthracene, naphthalene, and stilben, organic liquids in which organic materials such as diphenyloxazole (PPO) and terphenyl (TP) are dissolved in organic solvents such as toluene, xylene, and dioxane, and xenone and helium. Gas, plastic, etc. can be used.
上記の構成要素は、シンチレータ42が入射したX線を可視領域を中心とした波長を有する光に変換して画像データを生成できることを条件として、光電変換素子10及びCMOSトランジスタ基板20の設計に対応した任意好適な配置とすることができる。
The above components correspond to the design of the photoelectric conversion element 10 and the CMOS transistor substrate 20 on the condition that the X-rays incident by the scintillator 42 can be converted into light having a wavelength centered on the visible region to generate image data. Any suitable arrangement can be made.
反射層44は、シンチレータ42で変換された光を反射する。反射層44は、変換された光の損失を低減し、検出感度を増大させることができる。また、反射層44は、外部から直接的に入射する光を遮断することもできる。
The reflective layer 44 reflects the light converted by the scintillator 42. The reflective layer 44 can reduce the loss of converted light and increase the detection sensitivity. Further, the reflective layer 44 can also block light directly incident from the outside.
保護層46は、シンチレータ42を機能的に劣化させてしまうおそれのある酸素、水などの有害物質の浸透を防止又は抑制できることを条件として、従来公知の任意好適な材料により構成することができる。
The protective layer 46 can be made of any suitable material known conventionally, provided that the permeation of harmful substances such as oxygen and water that may functionally deteriorate the scintillator 42 can be prevented or suppressed.
ここで、上記の構成を有するX線撮像装置用のイメージ検出部1の動作について簡単に説明する。
Here, the operation of the image detection unit 1 for the X-ray image pickup apparatus having the above configuration will be briefly described.
X線やγ線といった放射線エネルギーがシンチレータ42に入射すると、シンチレータ42は放射線エネルギーを吸収し、可視領域を中心とした紫外から赤外領域の波長の光(蛍光)に変換する。そして、シンチレータ42によって変換された光は、光電変換素子10によって受光される。
When radiation energy such as X-rays and γ-rays is incident on the scintillator 42, the scintillator 42 absorbs the radiation energy and converts it into light (fluorescence) having a wavelength in the ultraviolet to infrared region centered on the visible region. Then, the light converted by the scintillator 42 is received by the photoelectric conversion element 10.
このように、シンチレータ42を介して光電変換素子10が受光した光は、光電変換素子10によって、受光量に応じた電気信号に変換され、電極を介して、光電変換素子10外に受光信号、すなわち撮像対象に対応する電気信号として出力される。検出対象である放射線エネルギー(X線)は、シンチレータ42側、光電変換素子10側のいずれから入射させてもよい。
In this way, the light received by the photoelectric conversion element 10 via the scintillator 42 is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10, and the light received signal is transmitted to the outside of the photoelectric conversion element 10 via the electrode. That is, it is output as an electric signal corresponding to the image pickup target. The radiation energy (X-ray) to be detected may be incident from either the scintillator 42 side or the photoelectric conversion element 10 side.
次いで、光電変換素子10から出力された受光信号は、層間配線部32を介して、CMOSトランジスタ基板20に入力され、CMOSトランジスタ基板20に作り込まれた信号読み出し回路により読み出され、図示しないさらなる任意好適な従来公知の機能部によって信号処理されることにより、撮像対象に基づく画像情報が生成される。
Next, the light receiving signal output from the photoelectric conversion element 10 is input to the CMOS transistor substrate 20 via the interlayer wiring unit 32, and is read out by the signal readout circuit built in the CMOS transistor substrate 20, which is not shown. Image information based on the imaging target is generated by signal processing by any suitable conventionally known functional unit.
(静脈検出部)
図5は、静脈認証装置用の静脈検出部の構成例を模式的に示す図である。
静脈認証装置用の静脈検出部300は、測定時において測定対象である手指(例、1以上の手指の指先、手指及び掌)が挿入される挿入部310を画成するカバー部306と、カバー部306に設けられており、測定対象に光を照射する光源部304と、光源部304から照射された光を測定対象を介して受光する光電変換素子10と、光電変換素子10を支持する支持基板11と、支持基板11と光電変換素子10を挟んで対向するように配置されており、所定の距離でカバー部306から離間して、カバー部306とともに挿入部306を画成するガラス基板302から構成されている。 (Vein detector)
FIG. 5 is a diagram schematically showing a configuration example of a vein detection unit for a vein authentication device.
Thevein detection unit 300 for the finger vein recognition device includes a cover unit 306 that defines an insertion unit 310 into which a finger (eg, one or more fingertips, fingers and palm) to be measured at the time of measurement is inserted, and a cover. A support for supporting a light source unit 304 that irradiates a measurement target with light, a photoelectric conversion element 10 that receives light emitted from the light source unit 304 via the measurement target, and a photoelectric conversion element 10 provided in the unit 306. A glass substrate 302 that is arranged so as to face each other with the substrate 11 and the support substrate 11 and the photoelectric conversion element 10 interposed therebetween, separated from the cover portion 306 at a predetermined distance, and defines the insertion portion 306 together with the cover portion 306. It is composed of.
図5は、静脈認証装置用の静脈検出部の構成例を模式的に示す図である。
静脈認証装置用の静脈検出部300は、測定時において測定対象である手指(例、1以上の手指の指先、手指及び掌)が挿入される挿入部310を画成するカバー部306と、カバー部306に設けられており、測定対象に光を照射する光源部304と、光源部304から照射された光を測定対象を介して受光する光電変換素子10と、光電変換素子10を支持する支持基板11と、支持基板11と光電変換素子10を挟んで対向するように配置されており、所定の距離でカバー部306から離間して、カバー部306とともに挿入部306を画成するガラス基板302から構成されている。 (Vein detector)
FIG. 5 is a diagram schematically showing a configuration example of a vein detection unit for a vein authentication device.
The
この構成例では、光源部304は、光電変換素子10とは、使用時において測定対象を挟んで離間するように、カバー部306と一体的に構成されている透過型撮影方式を示しているが、光源部304は必ずしもカバー部306側に位置させる必要はない。
In this configuration example, the light source unit 304 shows a transmission type photographing method in which the light source unit 304 is integrally configured with the cover unit 306 so as to be separated from the photoelectric conversion element 10 with the measurement target interposed therebetween. The light source unit 304 does not necessarily have to be located on the cover unit 306 side.
光源部304からの光を、測定対象に効率的に照射できることを条件として、例えば、光電変換素子10側から測定対象を照射する反射型撮影方式としてもよい。
On the condition that the light from the light source unit 304 can be efficiently irradiated to the measurement target, for example, a reflection type photographing method in which the measurement target is irradiated from the photoelectric conversion element 10 side may be used.
静脈検出部300は、本発明の実施形態にかかる光電変換素子10を本質的な機能を奏する機能部として含む。静脈検出部300は、図示されていない保護フィルム(protection film)、封止部材、バリアフィルム、バンドパスフィルター、近赤外線透過フィルター、可視光カットフィルム、指置きガイドなどの任意好適な従来公知の部材を所望の特性が得られるような設計に対応した態様で備え得る。静脈検出部300には、既に説明したイメージ検出部1の構成を採用することもできる。
The vein detection unit 300 includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs an essential function. The vein detection unit 300 is an optional conventionally known member such as a protective film (projection film), a sealing member, a barrier film, a bandpass filter, a near-infrared transmission filter, a visible light cut film, a finger rest guide, etc. (not shown). Can be provided in a manner corresponding to the design so as to obtain the desired characteristics. The configuration of the image detection unit 1 described above can also be adopted for the vein detection unit 300.
光電変換素子10は、任意の態様で含まれ得る。例えば、複数の光電変換素子10が、マトリクス状に配置されていてもよい。
The photoelectric conversion element 10 can be included in any embodiment. For example, a plurality of photoelectric conversion elements 10 may be arranged in a matrix.
光電変換素子10は、既に説明したとおり、支持基板11に設けられており、支持基板11には、例えばマトリクス状に電極(第一の電極又は第二の電極)が設けられている。
As described above, the photoelectric conversion element 10 is provided on the support substrate 11, and the support substrate 11 is provided with electrodes (first electrode or second electrode) in a matrix, for example.
光電変換素子10が受光した光は、光電変換素子10によって、受光量に応じた電気信号に変換され、電極を介して、光電変換素子10外に受光信号、すなわち撮像された静脈に対応する電気信号として出力される。
The light received by the photoelectric conversion element 10 is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10, and the light received signal outside the photoelectric conversion element 10 via the electrode, that is, the electricity corresponding to the imaged vein. It is output as a signal.
静脈検出時(使用時)において、測定対象は、光電変換素子10側のガラス基板302に接触していても、接触していなくてもよい。
At the time of vein detection (during use), the measurement target may or may not be in contact with the glass substrate 302 on the photoelectric conversion element 10 side.
ここで、静脈検出部300の動作について簡単に説明する。
静脈検出時には、光源部304から放射される光を用いて静脈検出部300が測定対象の静脈パターンを検出する。具体的には、光源部304から放射された光は、測定対象を透過して光電変換素子10の受光量に応じた電気信号に変換される。そして、変換された電気信号から、測定対象の静脈パターンの画像情報が構成される。 Here, the operation of thevein detection unit 300 will be briefly described.
At the time of vein detection, thevein detection unit 300 detects the vein pattern to be measured by using the light emitted from the light source unit 304. Specifically, the light radiated from the light source unit 304 passes through the measurement target and is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10. Then, the image information of the vein pattern to be measured is constructed from the converted electrical signal.
静脈検出時には、光源部304から放射される光を用いて静脈検出部300が測定対象の静脈パターンを検出する。具体的には、光源部304から放射された光は、測定対象を透過して光電変換素子10の受光量に応じた電気信号に変換される。そして、変換された電気信号から、測定対象の静脈パターンの画像情報が構成される。 Here, the operation of the
At the time of vein detection, the
静脈認証装置では、従来公知の任意好適なステップにより、得られた画像情報と、予め記録されていた静脈認証用の静脈データとを比較して、静脈認証が行われる。
In the vein recognition device, vein recognition is performed by comparing the obtained image information with the vein data for vein recognition recorded in advance by an arbitrary suitable step known conventionally.
(TOF型測距装置用イメージ検出部)
図6は、間接方式のTOF型測距装置用イメージ検出部の構成例を模式的に示す図である。 (Image detector for TOF type ranging device)
FIG. 6 is a diagram schematically showing a configuration example of an image detection unit for an indirect type TOF type distance measuring device.
図6は、間接方式のTOF型測距装置用イメージ検出部の構成例を模式的に示す図である。 (Image detector for TOF type ranging device)
FIG. 6 is a diagram schematically showing a configuration example of an image detection unit for an indirect type TOF type distance measuring device.
TOF型測距装置用イメージ検出部400は、CMOSトランジスタ基板20と、CMOSトランジスタ基板20を覆うように設けられている層間絶縁膜30と、層間絶縁膜30上に設けられている、本発明の実施形態にかかる光電変換素子10と、光電変換素子10を挟むように離間して配置されている2つの浮遊拡散層402と、光電変換素子10と浮遊拡散層402を覆うように設けられている絶縁層40と、絶縁層40上に設けられており、互いに離間して配置されている2つのフォトゲート404とを備えている。
The image detection unit 400 for a TOF type distance measuring device is provided on the CMOS transistor substrate 20, the interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20, and the interlayer insulating film 30 of the present invention. It is provided so as to cover the photoelectric conversion element 10 according to the embodiment, two floating diffusion layers 402 arranged apart from each other so as to sandwich the photoelectric conversion element 10, and the photoelectric conversion element 10 and the floating diffusion layer 402. It includes an insulating layer 40 and two photogates 404 provided on the insulating layer 40 and arranged apart from each other.
離間した2つのフォトゲート404の間隙からは絶縁層40の一部分が露出しており、残余の領域は遮光部406により遮光されている。CMOSトランジスタ基板20と浮遊拡散層402とは層間絶縁膜30を貫通するように設けられている層間配線部32によって電気的に接続されている。
A part of the insulating layer 40 is exposed from the gap between the two separated photo gates 404, and the remaining area is shielded by the light-shielding portion 406. The CMOS transistor substrate 20 and the floating diffusion layer 402 are electrically connected by an interlayer wiring portion 32 provided so as to penetrate the interlayer insulating film 30.
層間絶縁膜30は、例えば酸化シリコン、絶縁性樹脂などの従来公知の任意好適な絶縁性材料により構成することができる。層間配線部32は、例えば、銅、タングステンなどの従来公知の任意好適な導電性材料(配線材料)により構成することができる。層間配線部32は、例えば、配線層の形成と同時に形成されるホール内配線であっても、配線層とは別途形成される埋込みプラグであってもよい。
The interlayer insulating film 30 can be made of any conventionally known and arbitrarily suitable insulating material such as silicon oxide and an insulating resin. The interlayer wiring portion 32 can be made of, for example, any conventionally known suitable conductive material (wiring material) such as copper and tungsten. The interlayer wiring portion 32 may be, for example, an in-hole wiring formed at the same time as the formation of the wiring layer, or an embedded plug formed separately from the wiring layer.
絶縁層40は、この構成例では、酸化シリコンにより構成されるフィールド酸化膜などの従来公知の任意好適な構成とすることができる。
In this configuration example, the insulating layer 40 can have any conventionally known and arbitrarily suitable configuration such as a field oxide film composed of silicon oxide.
フォトゲート404は、例えばポリシリコンなどの従来公知の任意好適な材料により構成することができる。
The photogate 404 can be made of any conventionally known suitable material such as polysilicon.
TOF型測距装置用イメージ検出部400は、本発明の実施形態にかかる光電変換素子10を本質的な機能を奏する機能部として含む。TOF型測距装置用イメージ検出部400は、図示されていない保護フィルム(protection film)、支持基板、封止基板、封止部材、バリアフィルム、バンドパスフィルター、赤外線カットフィルムなどの任意好適な従来公知の部材を所望の特性が得られるような設計に対応した態様で備え得る。
The image detection unit 400 for a TOF type distance measuring device includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs an essential function. The image detection unit 400 for a TOF type distance measuring device is any suitable conventional image detection unit 400 such as a protective film (projection film), a support substrate, a sealing substrate, a sealing member, a barrier film, a bandpass filter, and an infrared cut film (not shown). A known member may be provided in a manner corresponding to a design such that a desired characteristic can be obtained.
ここで、TOF型測距装置用イメージ検出部400の動作について簡単に説明する。
Here, the operation of the image detection unit 400 for the TOF type ranging device will be briefly described.
光源から光が照射され、光源からの光が測定対象より反射され、反射光を光電変換素子10で受光する。光電変換素子10と浮遊拡散層402との間には2つのフォトゲート404が設けられており、交互にパルスを加えることによって、光電変換素子10によって発生した信号電荷を2つの浮遊拡散層402のいずれかに転送し、浮遊拡散層402に電荷が蓄積される。2つのフォトゲート404を開くタイミングに対して、光パルスが等分にまたがるように到来すると、2つの浮遊拡散層402に蓄積される電荷量は等量になる。一方のフォトゲート404に光パルスが到達するタイミングに対して、他方のフォトゲート404に光パルスが遅れて到来すると、2つの浮遊拡散層402に蓄積される電荷量に差が生じる。
Light is emitted from the light source, the light from the light source is reflected from the measurement target, and the reflected light is received by the photoelectric conversion element 10. Two photogates 404 are provided between the photoelectric conversion element 10 and the floating diffusion layer 402, and by alternately applying pulses, the signal charges generated by the photoelectric conversion element 10 are transferred to the two floating diffusion layers 402. It is transferred to either, and the charge is accumulated in the floating diffusion layer 402. When the optical pulse arrives so as to spread evenly with respect to the timing of opening the two photo gates 404, the amount of electric charge accumulated in the two floating diffusion layers 402 becomes equal. When the optical pulse arrives at the other photogate 404 with a delay with respect to the timing at which the optical pulse arrives at one photogate 404, there is a difference in the amount of charge accumulated in the two floating diffusion layers 402.
浮遊拡散層402に蓄積された電荷量の差は、光パルスの遅延時間に依存する。測定対象までの距離Lは、光の往復時間tdと光の速度cを用いてL=(1/2)ctdの関係にあるので、遅延時間が2つの浮遊拡散層402の電荷量の差から推定できれば、測定対象までの距離を求めることができる。
The difference in the amount of charge stored in the floating diffusion layer 402 depends on the delay time of the optical pulse. Since the distance L to the measurement target has a relationship of L = (1/2) ctd using the round-trip time td of light and the speed c of light, the delay time is based on the difference in the amount of charge between the two floating diffusion layers 402. If it can be estimated, the distance to the measurement target can be obtained.
光電変換素子10が受光した光の受光量は、2つの浮遊拡散層402に蓄積される電荷量の差として電気信号に変換され、光電変換素子10外に受光信号、すなわち測定対象に対応する電気信号として出力される。
The amount of light received by the photoelectric conversion element 10 is converted into an electric signal as the difference between the amounts of electric charges stored in the two floating diffusion layers 402, and the received signal outside the photoelectric conversion element 10, that is, the electricity corresponding to the measurement target. It is output as a signal.
次いで、浮遊拡散層402から出力された受光信号は、層間配線部32を介して、CMOSトランジスタ基板20に入力され、CMOSトランジスタ基板20に作り込まれた信号読み出し回路により読み出され、図示しないさらなる任意好適な従来公知の機能部によって信号処理されることにより、測定対象に基づく距離情報が生成される。
Next, the light receiving signal output from the floating diffusion layer 402 is input to the CMOS transistor substrate 20 via the interlayer wiring unit 32, and is read out by the signal readout circuit built in the CMOS transistor substrate 20, which is not shown. By signal processing by any suitable conventionally known functional unit, distance information based on the measurement target is generated.
[4.光検出素子]
前記のとおり、本実施形態の有機光電変換素子は、照射された光を、受光量に応じた電気信号に変換し、電極を介して外部回路に出力しうる光検出機能を有しうる。
したがって、本発明の一実施形態に係る光検出素子は、前記有機光電変換素子を含むことにより、光検出機能を有しうる。本実施形態の光検出素子は、前記有機光電変換素子そのものであってもよく、前記有機光電変換素子に加えて、電圧制御のためなどの機能素子を含むものであってもよい。 [4. Photodetection]
As described above, the organic photoelectric conversion element of the present embodiment may have a photodetection function capable of converting the irradiated light into an electric signal according to the amount of received light and outputting it to an external circuit via an electrode.
Therefore, the photodetection element according to the embodiment of the present invention may have a photodetection function by including the organic photoelectric conversion element. The photodetection element of the present embodiment may be the organic photoelectric conversion element itself, or may include a functional element for voltage control or the like in addition to the organic photoelectric conversion element.
前記のとおり、本実施形態の有機光電変換素子は、照射された光を、受光量に応じた電気信号に変換し、電極を介して外部回路に出力しうる光検出機能を有しうる。
したがって、本発明の一実施形態に係る光検出素子は、前記有機光電変換素子を含むことにより、光検出機能を有しうる。本実施形態の光検出素子は、前記有機光電変換素子そのものであってもよく、前記有機光電変換素子に加えて、電圧制御のためなどの機能素子を含むものであってもよい。 [4. Photodetection]
As described above, the organic photoelectric conversion element of the present embodiment may have a photodetection function capable of converting the irradiated light into an electric signal according to the amount of received light and outputting it to an external circuit via an electrode.
Therefore, the photodetection element according to the embodiment of the present invention may have a photodetection function by including the organic photoelectric conversion element. The photodetection element of the present embodiment may be the organic photoelectric conversion element itself, or may include a functional element for voltage control or the like in addition to the organic photoelectric conversion element.
以下、本発明をさらに詳細に説明するために実施例を示す。本発明は以下に説明する実施例に限定されるものではない。以下の実施例は、特に断りのない限り、常温常圧の条件下で行った。また、「%」及び「部」は、特に断りのない限り、それぞれ「重量%」及び「重量部」を表す。
Hereinafter, examples will be shown in order to explain the present invention in more detail. The present invention is not limited to the examples described below. The following examples were carried out under normal temperature and pressure conditions unless otherwise specified. Further, "%" and "part" represent "% by weight" and "part by weight", respectively, unless otherwise specified.
<使用した材料>
下記実施例において使用された、p型半導体材料(電子供与性化合物)、n型半導体材料(電子受容性化合物)、及び絶縁材料(光電変換過程に関与しない化合物)は、下記のとおりである。 <Material used>
The p-type semiconductor material (electron-donating compound), n-type semiconductor material (electron-accepting compound), and insulating material (compound not involved in the photoelectric conversion process) used in the following examples are as follows.
下記実施例において使用された、p型半導体材料(電子供与性化合物)、n型半導体材料(電子受容性化合物)、及び絶縁材料(光電変換過程に関与しない化合物)は、下記のとおりである。 <Material used>
The p-type semiconductor material (electron-donating compound), n-type semiconductor material (electron-accepting compound), and insulating material (compound not involved in the photoelectric conversion process) used in the following examples are as follows.
(p型半導体材料)
p型半導体材料として、高分子化合物である下記の重合体P-1~P-4を用いた。 (P-type semiconductor material)
The following polymers P-1 to P-4, which are polymer compounds, were used as the p-type semiconductor material.
p型半導体材料として、高分子化合物である下記の重合体P-1~P-4を用いた。 (P-type semiconductor material)
The following polymers P-1 to P-4, which are polymer compounds, were used as the p-type semiconductor material.
p型半導体材料である高分子化合物(重合体)P-1は、国際公開第2013/051676号に記載の方法を参考にして合成し、使用した。
p型半導体材料である高分子化合物(重合体)P-2は、国際公開第2011/052709号に記載の方法を参考にして合成し、使用した。
p型半導体材料である高分子化合物(重合体)P-3は、PDTSTPD(商品名、1-material社製)を市場より入手して使用した。
p型半導体材料である高分子化合物(重合体)P-4は、PBDTTPD(商品名、1-material社製)を市場より入手して使用した。 The polymer compound (polymer) P-1, which is a p-type semiconductor material, was synthesized and used with reference to the method described in International Publication No. 2013/051676.
The polymer compound (polymer) P-2, which is a p-type semiconductor material, was synthesized and used with reference to the method described in International Publication No. 2011/052709.
As the polymer compound (polymer) P-3, which is a p-type semiconductor material, PDTSTPD (trade name, manufactured by 1-material) was obtained from the market and used.
As the polymer compound (polymer) P-4, which is a p-type semiconductor material, PBDTTPD (trade name, manufactured by 1-material) was obtained from the market and used.
p型半導体材料である高分子化合物(重合体)P-2は、国際公開第2011/052709号に記載の方法を参考にして合成し、使用した。
p型半導体材料である高分子化合物(重合体)P-3は、PDTSTPD(商品名、1-material社製)を市場より入手して使用した。
p型半導体材料である高分子化合物(重合体)P-4は、PBDTTPD(商品名、1-material社製)を市場より入手して使用した。 The polymer compound (polymer) P-1, which is a p-type semiconductor material, was synthesized and used with reference to the method described in International Publication No. 2013/051676.
The polymer compound (polymer) P-2, which is a p-type semiconductor material, was synthesized and used with reference to the method described in International Publication No. 2011/052709.
As the polymer compound (polymer) P-3, which is a p-type semiconductor material, PDTSTPD (trade name, manufactured by 1-material) was obtained from the market and used.
As the polymer compound (polymer) P-4, which is a p-type semiconductor material, PBDTTPD (trade name, manufactured by 1-material) was obtained from the market and used.
(n型半導体材料)
n型半導体材料として、下記の化合物N-1~N-2を用いた。 (N-type semiconductor material)
The following compounds N-1 to N-2 were used as the n-type semiconductor material.
n型半導体材料として、下記の化合物N-1~N-2を用いた。 (N-type semiconductor material)
The following compounds N-1 to N-2 were used as the n-type semiconductor material.
n型半導体材料である化合物N-1は、Coi8DFIC(商品名、1-material社製)を市場より入手して使用した。
n型半導体材料である化合物N-2は、E100(商品名、フロンティアカーボン社製)を市場より入手して使用した。 For compound N-1, which is an n-type semiconductor material, Coi8DFIC (trade name, manufactured by 1-material) was obtained from the market and used.
For compound N-2, which is an n-type semiconductor material, E100 (trade name, manufactured by Frontier Carbon Co., Ltd.) was obtained from the market and used.
n型半導体材料である化合物N-2は、E100(商品名、フロンティアカーボン社製)を市場より入手して使用した。 For compound N-1, which is an n-type semiconductor material, Coi8DFIC (trade name, manufactured by 1-material) was obtained from the market and used.
For compound N-2, which is an n-type semiconductor material, E100 (trade name, manufactured by Frontier Carbon Co., Ltd.) was obtained from the market and used.
(絶縁材料)
絶縁材料として、下記の重合体Z-1~Z-2を用いた。 (Insulating material)
The following polymers Z-1 to Z-2 were used as the insulating material.
絶縁材料として、下記の重合体Z-1~Z-2を用いた。 (Insulating material)
The following polymers Z-1 to Z-2 were used as the insulating material.
絶縁材料である化合物Z-1は、Polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene(重量平均分子量Mw 118000以下、Aldrich社製)を市場より入手して使用した。
絶縁材料である化合物Z-2は、Polystyrene-block-polyisoprene-block-polystyrene(数平均分子量Mn 1900、Aldrich社製)を市場より入手して使用した。 For compound Z-1, which is an insulating material, Polystyrene-block-poly (ethylene-ran-butyrene) -block-polystyrene (weight average molecular weight Mw 118000 or less, manufactured by Aldrich) was obtained from the market and used.
As the insulating material, the compound Z-2 was obtained from the market and used Polystyrene-block-polyisoprene-block-polystyrene (number average molecular weight Mn 1900, manufactured by Aldrich).
絶縁材料である化合物Z-2は、Polystyrene-block-polyisoprene-block-polystyrene(数平均分子量Mn 1900、Aldrich社製)を市場より入手して使用した。 For compound Z-1, which is an insulating material, Polystyrene-block-poly (ethylene-ran-butyrene) -block-polystyrene (weight average molecular weight Mw 118000 or less, manufactured by Aldrich) was obtained from the market and used.
As the insulating material, the compound Z-2 was obtained from the market and used Polystyrene-block-polyisoprene-block-polystyrene (number average molecular weight Mn 1900, manufactured by Aldrich).
[絶縁材料の溶媒への溶解性]
絶縁材料の溶媒への溶解性を、下記のとおり評価した。
第1溶媒としてテトラリン、第2溶媒として安息香酸ブチルを用い、第1溶媒と第2溶媒との重量比を97:3として混合溶媒を調製した。
前記混合溶媒が99重量部に、絶縁材料である化合物Z-1又はZ-2を1重量部添加し、60℃で1時間撹拌した。25℃に冷却後、撹拌後の混合物を目視で観察し、絶縁材料が溶け残っているか否かを確認した。絶縁材料の溶け残りがない場合を、混合溶媒への溶解性が「良」とした。
またテトラリンへの溶解性についても、前記混合溶媒をテトラリン単独溶媒へ変更した以外は混合溶媒への溶解性の評価と同様に評価した。
評価結果を下表に示す。絶縁材料Z-1~Z-2は、前記混合溶媒又はテトラリンに25℃で0.1重量%以上溶解する材料であることが分かった。 [Solubility of insulating material in solvent]
The solubility of the insulating material in the solvent was evaluated as follows.
Tetralin was used as the first solvent, butyl benzoate was used as the second solvent, and the weight ratio of the first solvent to the second solvent was 97: 3, and a mixed solvent was prepared.
To 99 parts by weight of the mixed solvent, 1 part by weight of the compound Z-1 or Z-2 as an insulating material was added, and the mixture was stirred at 60 ° C. for 1 hour. After cooling to 25 ° C., the mixture after stirring was visually observed to confirm whether or not the insulating material remained undissolved. When there was no undissolved residue of the insulating material, the solubility in the mixed solvent was regarded as "good".
The solubility in tetralin was also evaluated in the same manner as the evaluation of the solubility in the mixed solvent except that the mixed solvent was changed to the tetralin single solvent.
The evaluation results are shown in the table below. It was found that the insulating materials Z-1 to Z-2 are materials that are dissolved in the mixed solvent or tetralin at 25 ° C. in an amount of 0.1% by weight or more.
絶縁材料の溶媒への溶解性を、下記のとおり評価した。
第1溶媒としてテトラリン、第2溶媒として安息香酸ブチルを用い、第1溶媒と第2溶媒との重量比を97:3として混合溶媒を調製した。
前記混合溶媒が99重量部に、絶縁材料である化合物Z-1又はZ-2を1重量部添加し、60℃で1時間撹拌した。25℃に冷却後、撹拌後の混合物を目視で観察し、絶縁材料が溶け残っているか否かを確認した。絶縁材料の溶け残りがない場合を、混合溶媒への溶解性が「良」とした。
またテトラリンへの溶解性についても、前記混合溶媒をテトラリン単独溶媒へ変更した以外は混合溶媒への溶解性の評価と同様に評価した。
評価結果を下表に示す。絶縁材料Z-1~Z-2は、前記混合溶媒又はテトラリンに25℃で0.1重量%以上溶解する材料であることが分かった。 [Solubility of insulating material in solvent]
The solubility of the insulating material in the solvent was evaluated as follows.
Tetralin was used as the first solvent, butyl benzoate was used as the second solvent, and the weight ratio of the first solvent to the second solvent was 97: 3, and a mixed solvent was prepared.
To 99 parts by weight of the mixed solvent, 1 part by weight of the compound Z-1 or Z-2 as an insulating material was added, and the mixture was stirred at 60 ° C. for 1 hour. After cooling to 25 ° C., the mixture after stirring was visually observed to confirm whether or not the insulating material remained undissolved. When there was no undissolved residue of the insulating material, the solubility in the mixed solvent was regarded as "good".
The solubility in tetralin was also evaluated in the same manner as the evaluation of the solubility in the mixed solvent except that the mixed solvent was changed to the tetralin single solvent.
The evaluation results are shown in the table below. It was found that the insulating materials Z-1 to Z-2 are materials that are dissolved in the mixed solvent or tetralin at 25 ° C. in an amount of 0.1% by weight or more.
絶縁材料として、化合物Z-1又はZ-2を用いて、インクである組成物を調製した。
A composition as an ink was prepared using compound Z-1 or Z-2 as an insulating material.
[インク(組成物)の調製]
[調製例1]インクI-1の調製
第1溶媒としてテトラリン、第2溶媒として安息香酸ブチルを用い、第1溶媒と第2溶媒との重量比を97:3として混合溶媒を調製した。 [Preparation of ink (composition)]
[Preparation Example 1] Preparation of Ink I-1 Using tetralin as the first solvent and butyl benzoate as the second solvent, a mixed solvent was prepared with a weight ratio of 97: 3 between the first solvent and the second solvent.
[調製例1]インクI-1の調製
第1溶媒としてテトラリン、第2溶媒として安息香酸ブチルを用い、第1溶媒と第2溶媒との重量比を97:3として混合溶媒を調製した。 [Preparation of ink (composition)]
[Preparation Example 1] Preparation of Ink I-1 Using tetralin as the first solvent and butyl benzoate as the second solvent, a mixed solvent was prepared with a weight ratio of 97: 3 between the first solvent and the second solvent.
得られた混合溶媒に、p型半導体材料である高分子化合物(重合体)P-1をインクの全重量に対し1重量%の濃度となるように、n型半導体材料である化合物N-1をインクの全重量に対して1重量%の濃度となるように、絶縁材料である化合物Z-1をインクの全重量に対して0.5重量%の濃度となるように、それぞれ添加し、60℃で8時間撹拌し、混合液を得た。得られた混合液をフィルターを用いてろ過し、インクI-1を得た。
In the obtained mixed solvent, the polymer compound (polymer) P-1 which is a p-type semiconductor material has a concentration of 1% by weight based on the total weight of the ink, and the compound N-1 which is an n-type semiconductor material. Was added so as to have a concentration of 1% by weight based on the total weight of the ink, and compound Z-1 as an insulating material was added so as to have a concentration of 0.5% by weight based on the total weight of the ink. The mixture was stirred at 60 ° C. for 8 hours to obtain a mixed solution. The obtained mixed solution was filtered using a filter to obtain ink I-1.
[調製例2]インクI-2の調製
・混合溶媒の代わりに、テトラリン溶媒を用いた。
・化合物N-1の代わりにn型半導体材料である化合物N-2を用い、テトラリン溶媒に、化合物N-2をインクの全重量に対して2重量%の濃度となるように添加した。
・化合物Z-1の代わりに絶縁材料である化合物Z-2を用い、テトラリン溶媒に、化合物Z-2をインクの全重量に対して1重量%の濃度となるように添加した。
以上の事項以外は、調製例1と同様に操作して、インクI-2を得た。 [Preparation Example 2] Preparation of Ink I-2 ・ A tetralin solvent was used instead of the mixed solvent.
-Compound N-2, which is an n-type semiconductor material, was used instead of compound N-1, and compound N-2 was added to the tetralin solvent so as to have a concentration of 2% by weight based on the total weight of the ink.
-Compound Z-2, which is an insulating material, was used instead of Compound Z-1, and Compound Z-2 was added to the tetralin solvent so as to have a concentration of 1% by weight based on the total weight of the ink.
Ink I-2 was obtained by operating in the same manner as in Preparation Example 1 except for the above items.
・混合溶媒の代わりに、テトラリン溶媒を用いた。
・化合物N-1の代わりにn型半導体材料である化合物N-2を用い、テトラリン溶媒に、化合物N-2をインクの全重量に対して2重量%の濃度となるように添加した。
・化合物Z-1の代わりに絶縁材料である化合物Z-2を用い、テトラリン溶媒に、化合物Z-2をインクの全重量に対して1重量%の濃度となるように添加した。
以上の事項以外は、調製例1と同様に操作して、インクI-2を得た。 [Preparation Example 2] Preparation of Ink I-2 ・ A tetralin solvent was used instead of the mixed solvent.
-Compound N-2, which is an n-type semiconductor material, was used instead of compound N-1, and compound N-2 was added to the tetralin solvent so as to have a concentration of 2% by weight based on the total weight of the ink.
-Compound Z-2, which is an insulating material, was used instead of Compound Z-1, and Compound Z-2 was added to the tetralin solvent so as to have a concentration of 1% by weight based on the total weight of the ink.
Ink I-2 was obtained by operating in the same manner as in Preparation Example 1 except for the above items.
[調製例3]インクI-3の調製
・混合溶媒の代わりに、テトラリン溶媒を用いた。
・重合体P-1の代わりにp型半導体材料である高分子化合物(重合体)P-2を用いた。
・化合物N-1の代わりにn型半導体材料である化合物N-2を用い、テトラリン溶媒に、化合物N-2をインクの全重量に対して2重量%の濃度となるように添加した。
・テトラリン溶媒に、化合物Z-2をインクの全重量に対して1重量%の濃度となるように添加した。
以上の事項以外は、調製例1と同様に操作して、インクI-3を得た。 [Preparation Example 3] Preparation of Ink I-3 ・ A tetralin solvent was used instead of the mixed solvent.
-A polymer compound (polymer) P-2, which is a p-type semiconductor material, was used instead of the polymer P-1.
-Compound N-2, which is an n-type semiconductor material, was used instead of compound N-1, and compound N-2 was added to the tetralin solvent so as to have a concentration of 2% by weight based on the total weight of the ink.
-Compound Z-2 was added to the tetralin solvent so as to have a concentration of 1% by weight based on the total weight of the ink.
Ink I-3 was obtained by operating in the same manner as in Preparation Example 1 except for the above items.
・混合溶媒の代わりに、テトラリン溶媒を用いた。
・重合体P-1の代わりにp型半導体材料である高分子化合物(重合体)P-2を用いた。
・化合物N-1の代わりにn型半導体材料である化合物N-2を用い、テトラリン溶媒に、化合物N-2をインクの全重量に対して2重量%の濃度となるように添加した。
・テトラリン溶媒に、化合物Z-2をインクの全重量に対して1重量%の濃度となるように添加した。
以上の事項以外は、調製例1と同様に操作して、インクI-3を得た。 [Preparation Example 3] Preparation of Ink I-3 ・ A tetralin solvent was used instead of the mixed solvent.
-A polymer compound (polymer) P-2, which is a p-type semiconductor material, was used instead of the polymer P-1.
-Compound N-2, which is an n-type semiconductor material, was used instead of compound N-1, and compound N-2 was added to the tetralin solvent so as to have a concentration of 2% by weight based on the total weight of the ink.
-Compound Z-2 was added to the tetralin solvent so as to have a concentration of 1% by weight based on the total weight of the ink.
Ink I-3 was obtained by operating in the same manner as in Preparation Example 1 except for the above items.
[比較調製例1]インクC-1の調製
・混合溶媒の代わりに、テトラリン溶媒を用いた。
・重合体P-1の代わりにp型半導体材料である高分子化合物(重合体)P-3を用いた。
・化合物N-1の代わりにn型半導体材料である化合物N-2を用い、テトラリン溶媒に、化合物N-2をインクの全重量に対して2重量%の濃度となるように添加した。
・テトラリン溶媒に、化合物Z-2をインクの全重量に対して1重量%の濃度となるように添加した。
以上の事項以外は、調製例1と同様に操作して、インクC-1を得た。 [Comparative Preparation Example 1] Preparation of Ink C-1 ・ A tetralin solvent was used instead of the mixed solvent.
-A polymer compound (polymer) P-3, which is a p-type semiconductor material, was used instead of the polymer P-1.
-Compound N-2, which is an n-type semiconductor material, was used instead of compound N-1, and compound N-2 was added to the tetralin solvent so as to have a concentration of 2% by weight based on the total weight of the ink.
-Compound Z-2 was added to the tetralin solvent so as to have a concentration of 1% by weight based on the total weight of the ink.
Ink C-1 was obtained by operating in the same manner as in Preparation Example 1 except for the above items.
・混合溶媒の代わりに、テトラリン溶媒を用いた。
・重合体P-1の代わりにp型半導体材料である高分子化合物(重合体)P-3を用いた。
・化合物N-1の代わりにn型半導体材料である化合物N-2を用い、テトラリン溶媒に、化合物N-2をインクの全重量に対して2重量%の濃度となるように添加した。
・テトラリン溶媒に、化合物Z-2をインクの全重量に対して1重量%の濃度となるように添加した。
以上の事項以外は、調製例1と同様に操作して、インクC-1を得た。 [Comparative Preparation Example 1] Preparation of Ink C-1 ・ A tetralin solvent was used instead of the mixed solvent.
-A polymer compound (polymer) P-3, which is a p-type semiconductor material, was used instead of the polymer P-1.
-Compound N-2, which is an n-type semiconductor material, was used instead of compound N-1, and compound N-2 was added to the tetralin solvent so as to have a concentration of 2% by weight based on the total weight of the ink.
-Compound Z-2 was added to the tetralin solvent so as to have a concentration of 1% by weight based on the total weight of the ink.
Ink C-1 was obtained by operating in the same manner as in Preparation Example 1 except for the above items.
[比較調製例2]インクC-2の調製
・混合溶媒の代わりに、テトラリン溶媒を用いた。
・重合体P-1の代わりにp型半導体材料である高分子化合物(重合体)P-4を用いた。
・化合物N-1の代わりにn型半導体材料である化合物N-2を用い、テトラリン溶媒に、化合物N-2をインクの全重量に対して2重量%の濃度となるように添加した。
・テトラリン溶媒に、化合物Z-2をインクの全重量に対して1重量%の濃度となるように添加した。
以上の事項以外は、調製例1と同様に操作して、インクC-2を得た。 [Comparative Preparation Example 2] Preparation of Ink C-2 ・ A tetralin solvent was used instead of the mixed solvent.
-A polymer compound (polymer) P-4, which is a p-type semiconductor material, was used instead of the polymer P-1.
-Compound N-2, which is an n-type semiconductor material, was used instead of compound N-1, and compound N-2 was added to the tetralin solvent so as to have a concentration of 2% by weight based on the total weight of the ink.
-Compound Z-2 was added to the tetralin solvent so as to have a concentration of 1% by weight based on the total weight of the ink.
Ink C-2 was obtained by operating in the same manner as in Preparation Example 1 except for the above items.
・混合溶媒の代わりに、テトラリン溶媒を用いた。
・重合体P-1の代わりにp型半導体材料である高分子化合物(重合体)P-4を用いた。
・化合物N-1の代わりにn型半導体材料である化合物N-2を用い、テトラリン溶媒に、化合物N-2をインクの全重量に対して2重量%の濃度となるように添加した。
・テトラリン溶媒に、化合物Z-2をインクの全重量に対して1重量%の濃度となるように添加した。
以上の事項以外は、調製例1と同様に操作して、インクC-2を得た。 [Comparative Preparation Example 2] Preparation of Ink C-2 ・ A tetralin solvent was used instead of the mixed solvent.
-A polymer compound (polymer) P-4, which is a p-type semiconductor material, was used instead of the polymer P-1.
-Compound N-2, which is an n-type semiconductor material, was used instead of compound N-1, and compound N-2 was added to the tetralin solvent so as to have a concentration of 2% by weight based on the total weight of the ink.
-Compound Z-2 was added to the tetralin solvent so as to have a concentration of 1% by weight based on the total weight of the ink.
Ink C-2 was obtained by operating in the same manner as in Preparation Example 1 except for the above items.
各調製例の配合を下表に示す。
The formulation of each preparation example is shown in the table below.
<光電変換素子の製造及び評価>
[実施例1]
(1)光電変換素子及びその封止体の製造
以下のとおり、光電変換素子及びその封止体を製造した。 <Manufacturing and evaluation of photoelectric conversion element>
[Example 1]
(1) Manufacture of photoelectric conversion element and its encapsulant The photoelectric conversion element and its encapsulant were manufactured as follows.
[実施例1]
(1)光電変換素子及びその封止体の製造
以下のとおり、光電変換素子及びその封止体を製造した。 <Manufacturing and evaluation of photoelectric conversion element>
[Example 1]
(1) Manufacture of photoelectric conversion element and its encapsulant The photoelectric conversion element and its encapsulant were manufactured as follows.
スパッタ法により50nmの厚さでITOの薄膜(第一の電極)が、互いに平行に離間するように配置された複数の線状(以下、ストライプ状)に形成されたガラス基板を用意し、このガラス基板に対し、表面処理としてオゾンUV処理を行った。
By the sputtering method, a glass substrate having a thickness of 50 nm and formed into a plurality of linear shapes (hereinafter referred to as stripes) in which a thin film of ITO (first electrode) is arranged so as to be separated from each other in parallel is prepared. The glass substrate was subjected to ozone UV treatment as a surface treatment.
次に、ITOの薄膜上にスピンコート法によりインクI-1の塗膜を形成した後、窒素ガス雰囲気下で100℃に加熱したホットプレートを用いて10分間加熱処理して乾燥させ、活性層1を形成した。形成された活性層の厚さは約500nmであった。
Next, a coating film of Ink I-1 was formed on an ITO thin film by a spin coating method, and then heat-treated for 10 minutes using a hot plate heated to 100 ° C. under a nitrogen gas atmosphere to dry the active layer. 1 was formed. The thickness of the formed active layer was about 500 nm.
次に、抵抗加熱蒸着装置内にて、形成された活性層1の上にカルシウム(Ca)層を約5nmの厚さで形成し、電子輸送層とした。ストライプ状に形成されたITOの薄膜と、Ca層とが交差するように、Ca層の形成時は金属マスクを使用した。
Next, in the resistance heating vapor deposition apparatus, a calcium (Ca) layer was formed on the formed active layer 1 with a thickness of about 5 nm to form an electron transport layer. A metal mask was used when forming the Ca layer so that the striped ITO thin film intersects with the Ca layer.
次いで、形成された電子輸送層上に、銀(Ag)層を約60nmの厚さで形成し、第二の電極とした。ストライプ状に形成されたITOの薄膜と、Ag層とが交差するように、Ag層の形成時は金属マスクを使用した。ITOの薄膜とCa層及びAg層とが厚さ方向から見て重なる部分の単位がピクセルであり、一枚の基板上に6ピクセルが形成された。
ピクセルの有効面積は、ITOの薄膜とCa層及びAg層とが厚さ方向から見て重なる部分の面積である。 Next, a silver (Ag) layer was formed on the formed electron transport layer to a thickness of about 60 nm to form a second electrode. A metal mask was used when forming the Ag layer so that the striped ITO thin film intersects with the Ag layer. The unit of the portion where the thin film of ITO and the Ca layer and the Ag layer overlap when viewed from the thickness direction is a pixel, and 6 pixels are formed on one substrate.
The effective area of the pixel is the area of the portion where the ITO thin film and the Ca layer and the Ag layer overlap each other when viewed from the thickness direction.
ピクセルの有効面積は、ITOの薄膜とCa層及びAg層とが厚さ方向から見て重なる部分の面積である。 Next, a silver (Ag) layer was formed on the formed electron transport layer to a thickness of about 60 nm to form a second electrode. A metal mask was used when forming the Ag layer so that the striped ITO thin film intersects with the Ag layer. The unit of the portion where the thin film of ITO and the Ca layer and the Ag layer overlap when viewed from the thickness direction is a pixel, and 6 pixels are formed on one substrate.
The effective area of the pixel is the area of the portion where the ITO thin film and the Ca layer and the Ag layer overlap each other when viewed from the thickness direction.
以上の工程により光電変換素子が、ガラス基板上に製造された。得られた構造体をサンプル1とした。
The photoelectric conversion element was manufactured on a glass substrate by the above steps. The obtained structure was used as sample 1.
次に、製造された光電変換素子の周辺を囲むように、支持基板であるガラス基板上に封止材であるUV硬化性封止剤を塗布し、封止基板であるガラス基板を貼り合わせた。次いで、これにUV光を照射して、光電変換素子を、支持基板と封止基板との間隙に封止した。これにより、光電変換素子の封止体を得た。支持基板と封止基板との間隙に封止された光電変換素子を厚さ方向から見たときの平面的な形状は2mm×2mmの正方形であった。
Next, a UV curable sealant as a sealing material was applied onto a glass substrate as a support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and the glass substrate as a sealing substrate was bonded. .. Next, this was irradiated with UV light, and the photoelectric conversion element was sealed in the gap between the support substrate and the sealing substrate. As a result, a sealed body of the photoelectric conversion element was obtained. The planar shape of the photoelectric conversion element sealed in the gap between the support substrate and the sealing substrate when viewed from the thickness direction was a square of 2 mm × 2 mm.
(2)光電変換素子の暗電流の評価
光が照射されない暗状態において、製造された光電変換素子の封止体に対し、-8Vから2Vの電圧を印加して評価した。その暗電流をソースメータ(KEITHLEY 2450 Source Meter、ケースレーインスツルメンツ社製)を用いて測定して評価した。公知の手法を用いて測定された-8Vの電圧印加時の電流値を暗電流の値として得て、一枚の基板内の6ピクセルの暗電流のばらつきを評価した。 (2) Evaluation of dark current of photoelectric conversion element In a dark state where no light was irradiated, a voltage of -8V to 2V was applied to the sealed body of the manufactured photoelectric conversion element for evaluation. The dark current was measured and evaluated using a source meter (KEITHLEY 2450 Source Meter, manufactured by Keithley Instruments). The current value at the time of applying a voltage of -8V measured by a known method was obtained as a dark current value, and the variation of the dark current of 6 pixels in one substrate was evaluated.
光が照射されない暗状態において、製造された光電変換素子の封止体に対し、-8Vから2Vの電圧を印加して評価した。その暗電流をソースメータ(KEITHLEY 2450 Source Meter、ケースレーインスツルメンツ社製)を用いて測定して評価した。公知の手法を用いて測定された-8Vの電圧印加時の電流値を暗電流の値として得て、一枚の基板内の6ピクセルの暗電流のばらつきを評価した。 (2) Evaluation of dark current of photoelectric conversion element In a dark state where no light was irradiated, a voltage of -8V to 2V was applied to the sealed body of the manufactured photoelectric conversion element for evaluation. The dark current was measured and evaluated using a source meter (KEITHLEY 2450 Source Meter, manufactured by Keithley Instruments). The current value at the time of applying a voltage of -8V measured by a known method was obtained as a dark current value, and the variation of the dark current of 6 pixels in one substrate was evaluated.
一枚の基板内の6ピクセルの内、-8Vの電圧における暗電流の一番低い値を基準として、他の5ピクセルの暗電流の値がすべてその10倍以内に収まれば、暗電流のばらつき度合いが「良好(Good)」であると評価した。その反面、他の5ピクセルの内に、暗電流の値が一番低い値の10倍を超える場合があれば暗電流のばらつき度合いは「不良(Bad)」であると評価した。
If the dark current values of the other 5 pixels are all within 10 times the lowest value of the dark current at a voltage of -8V among the 6 pixels in one substrate, the dark current will vary. The degree was evaluated as "Good". On the other hand, if the dark current value exceeds 10 times the lowest value among the other 5 pixels, the degree of variation in the dark current is evaluated as "bad".
実施例1の暗電流のばらつきの評価結果を表3に示す。
Table 3 shows the evaluation results of the variation in dark current of Example 1.
[実施例2]
(1)光電変換素子及びその封止体の製造
以下のとおり、光電変換素子及びその封止体を製造した。 [Example 2]
(1) Manufacture of photoelectric conversion element and its encapsulant The photoelectric conversion element and its encapsulant were manufactured as follows.
(1)光電変換素子及びその封止体の製造
以下のとおり、光電変換素子及びその封止体を製造した。 [Example 2]
(1) Manufacture of photoelectric conversion element and its encapsulant The photoelectric conversion element and its encapsulant were manufactured as follows.
スパッタ法により50nmの厚さでITOの薄膜(第二の電極)がストライプ状に形成されたガラス基板を用意し、このガラス基板に対し、表面処理としてオゾンUV処理を行った。
A glass substrate having an ITO thin film (second electrode) formed in stripes with a thickness of 50 nm was prepared by a sputtering method, and the glass substrate was subjected to ozone UV treatment as a surface treatment.
次に、ポリエチレンイミンエトキシレート(PEIE)水溶液(アルドリッチ社製、商品名ポリエチレンイミン、80%エトキシ化溶液、重量平均分子量110000)を超純水で1000倍に希釈した溶液を電子輸送層形成用塗布液として用い、スピンコート法により、オゾンUV処理を行ったガラス基板のITO薄膜上に塗布し、塗布膜を形成した。
塗布膜が形成されたガラス基板を、ホットプレートを用いて、100℃で10分間加熱処理して、形成された塗布膜を硬化することにより、第二の電極であるITO薄膜上に電子輸送層を形成した。 Next, a solution obtained by diluting an aqueous solution of polyethyleneimine ethoxylate (PEIE) (manufactured by Aldrich, trade name polyethyleneimine, 80% ethoxylated solution, weight average molecular weight 110,000) with ultrapure water 1000 times was applied for forming an electron transport layer. It was used as a liquid and was applied onto an ITO thin film of a glass substrate treated with ozone UV by a spin coating method to form a coating film.
The glass substrate on which the coating film was formed was heat-treated at 100 ° C. for 10 minutes using a hot plate to cure the formed coating film, whereby an electron transport layer was placed on the ITO thin film, which is the second electrode. Was formed.
塗布膜が形成されたガラス基板を、ホットプレートを用いて、100℃で10分間加熱処理して、形成された塗布膜を硬化することにより、第二の電極であるITO薄膜上に電子輸送層を形成した。 Next, a solution obtained by diluting an aqueous solution of polyethyleneimine ethoxylate (PEIE) (manufactured by Aldrich, trade name polyethyleneimine, 80% ethoxylated solution, weight average molecular weight 110,000) with ultrapure water 1000 times was applied for forming an electron transport layer. It was used as a liquid and was applied onto an ITO thin film of a glass substrate treated with ozone UV by a spin coating method to form a coating film.
The glass substrate on which the coating film was formed was heat-treated at 100 ° C. for 10 minutes using a hot plate to cure the formed coating film, whereby an electron transport layer was placed on the ITO thin film, which is the second electrode. Was formed.
次に、インク(I-2)を、ITOの薄膜上にスピンコート法により塗膜を形成した後、窒素ガス雰囲気下で100℃に加熱したホットプレートを用いて10分間加熱処理して乾燥させ、活性層2を形成した。形成された活性層の厚さは約500nmであった。
Next, the ink (I-2) was formed into a coating film on an ITO thin film by a spin coating method, and then heat-treated for 10 minutes using a hot plate heated to 100 ° C. in a nitrogen gas atmosphere to dry it. , The active layer 2 was formed. The thickness of the formed active layer was about 500 nm.
次に、抵抗加熱蒸着装置内にて、形成された活性層2の上に酸化モリブデン(MoO3)を約15nmの厚さで蒸着することにより、MoO3層である正孔輸送層を形成した。
ストライプ状に形成されたITOの薄膜と、MoO3層とが交差するように、MoO3層の形成時は金属マスクを使用した。 Next, in the resistance heating vapor deposition apparatus, molybdenum oxide (MoO 3 ) was vapor-deposited on the formedactive layer 2 to a thickness of about 15 nm to form a hole transport layer which is a MoO 3 layer. ..
A metal mask was used when forming the MoO 3 layer so that the striped ITO thin film intersects with the MoO 3 layer.
ストライプ状に形成されたITOの薄膜と、MoO3層とが交差するように、MoO3層の形成時は金属マスクを使用した。 Next, in the resistance heating vapor deposition apparatus, molybdenum oxide (MoO 3 ) was vapor-deposited on the formed
A metal mask was used when forming the MoO 3 layer so that the striped ITO thin film intersects with the MoO 3 layer.
次いで、形成された正孔輸送層上に、銀(Ag)層を約60nmの厚さで形成し、第一の電極とした。ストライプ状に形成されたITOの薄膜と、Ag層とが交差するように、Ag層の形成時は金属マスクを使用した。
Next, a silver (Ag) layer was formed with a thickness of about 60 nm on the formed hole transport layer to serve as the first electrode. A metal mask was used when forming the Ag layer so that the striped ITO thin film intersects with the Ag layer.
ITOの薄膜とMoO3層及びAg層とが厚さ方向から見て重なる部分の単位がピクセルであり、一枚の基板上に6ピクセルが形成された。ピクセルの有効面積は、ITOの薄膜とMoO3層及びAg層とが厚さ方向から見て重なる部分の面積である。
The unit of the portion where the ITO thin film and the MoO 3 layer and the Ag layer overlap when viewed from the thickness direction is a pixel, and 6 pixels are formed on one substrate. The effective area of the pixel is the area of the portion where the ITO thin film, the MoO 3 layer, and the Ag layer overlap each other when viewed from the thickness direction.
以上の工程により光電変換素子が、ガラス基板上に製造された。得られた構造体をサンプル2とした。
The photoelectric conversion element was manufactured on a glass substrate by the above steps. The obtained structure was used as sample 2.
次に、製造された光電変換素子の周辺を囲むように、支持基板であるガラス基板上に封止材であるUV硬化性封止剤を塗布し、封止基板であるガラス基板を貼り合わせた。次いで、これにUV光を照射して、光電変換素子を、支持基板と封止基板との間隙に封止した。これにより、光電変換素子の封止体を得た。支持基板と封止基板との間隙に封止された光電変換素子を厚さ方向から見たときの平面的な形状は2mm×2mmの正方形であった。
Next, a UV curable sealant as a sealing material was applied onto a glass substrate as a support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and the glass substrate as a sealing substrate was bonded. .. Next, this was irradiated with UV light, and the photoelectric conversion element was sealed in the gap between the support substrate and the sealing substrate. As a result, a sealed body of the photoelectric conversion element was obtained. The planar shape of the photoelectric conversion element sealed in the gap between the support substrate and the sealing substrate when viewed from the thickness direction was a square of 2 mm × 2 mm.
(2)光電変換素子の暗電流の評価
実施例1と同様の方法で、一枚の基板内の6ピクセルについて暗電流のばらつきを評価した。
評価結果を表3に示す。 (2) Evaluation of dark current of photoelectric conversion element The variation of dark current was evaluated for 6 pixels in one substrate by the same method as in Example 1.
The evaluation results are shown in Table 3.
実施例1と同様の方法で、一枚の基板内の6ピクセルについて暗電流のばらつきを評価した。
評価結果を表3に示す。 (2) Evaluation of dark current of photoelectric conversion element The variation of dark current was evaluated for 6 pixels in one substrate by the same method as in Example 1.
The evaluation results are shown in Table 3.
[実施例3]
インク(I-2)の代わりにインク(I-3)を用いて、500nmの膜厚が得られるようにスピンコート法における回転数を調整して活性層3を得た。それ以外は、既に説明した実施例2と同様にして、光電変換素子の封止体を製造し、暗電流のばらつきを評価した。評価結果を表3に示す。 [Example 3]
An ink (I-3) was used instead of the ink (I-2), and the rotation speed in the spin coating method was adjusted so that a film thickness of 500 nm could be obtained to obtain the active layer 3. Except for this, a sealed body of the photoelectric conversion element was manufactured in the same manner as in Example 2 described above, and the variation in dark current was evaluated. The evaluation results are shown in Table 3.
インク(I-2)の代わりにインク(I-3)を用いて、500nmの膜厚が得られるようにスピンコート法における回転数を調整して活性層3を得た。それ以外は、既に説明した実施例2と同様にして、光電変換素子の封止体を製造し、暗電流のばらつきを評価した。評価結果を表3に示す。 [Example 3]
An ink (I-3) was used instead of the ink (I-2), and the rotation speed in the spin coating method was adjusted so that a film thickness of 500 nm could be obtained to obtain the active layer 3. Except for this, a sealed body of the photoelectric conversion element was manufactured in the same manner as in Example 2 described above, and the variation in dark current was evaluated. The evaluation results are shown in Table 3.
[比較例1、2]
インク(I-2)の代わりにインク(C-1)、(C-2)を用いて、500nmの膜厚が得られるようにスピンコート法における回転数を調整して活性層4、活性層5をそれぞれ得た。それ以外は、既に説明した実施例2と同様にして、光電変換素子の封止体を製造し、暗電流のばらつきを評価した。評価結果を表3に示す。 [Comparative Examples 1 and 2]
Using inks (C-1) and (C-2) instead of inks (I-2), the number of rotations in the spin coating method was adjusted so that a film thickness of 500 nm could be obtained. 5 were obtained respectively. Except for this, a sealed body of the photoelectric conversion element was manufactured in the same manner as in Example 2 described above, and the variation in dark current was evaluated. The evaluation results are shown in Table 3.
インク(I-2)の代わりにインク(C-1)、(C-2)を用いて、500nmの膜厚が得られるようにスピンコート法における回転数を調整して活性層4、活性層5をそれぞれ得た。それ以外は、既に説明した実施例2と同様にして、光電変換素子の封止体を製造し、暗電流のばらつきを評価した。評価結果を表3に示す。 [Comparative Examples 1 and 2]
Using inks (C-1) and (C-2) instead of inks (I-2), the number of rotations in the spin coating method was adjusted so that a film thickness of 500 nm could be obtained. 5 were obtained respectively. Except for this, a sealed body of the photoelectric conversion element was manufactured in the same manner as in Example 2 described above, and the variation in dark current was evaluated. The evaluation results are shown in Table 3.
表3から明らかなとおり、p型半導体材料として式(I)で表される重合体と、n型半導体材料と、絶縁材料と、溶媒とを含む組成物(インク(I-1)~(I-3))から活性層が形成された、実施例1~3に係る素子(サンプル1~3)は、暗電流のばらつきの評価結果が良好である。
他方、p型半導体材料として式(I)で表される重合体を含まない組成物(インク(C-1)~(C-2))から活性層が形成された、比較例1、2にかかる素子(サンプル4~5)は、暗電流のばらつきの評価結果が不良であった。
比較例1、2に係るインク(C-1)及び(C-2)は、実施例2、3に係るインク(I-2)、及び(I-3)と同様に、絶縁材料Z-2を含む。しかし、比較例1、2は、暗電流のばらつきの評価結果が不良であることから、p型半導体材料としての式(I)で表される重合体と、絶縁材料との間に、何らかの相互作用が生じていることが推察される。かかる相互作用が、各成分の溶解状態、活性層乾燥の過程などに影響を与え、ひいては活性層の膜厚分布に影響を与えていることが推察される。しかし、以上の推察は、本発明を限定するものではない。 As is clear from Table 3, the compositions containing the polymer represented by the formula (I) as the p-type semiconductor material, the n-type semiconductor material, the insulating material, and the solvent (inks (I-1) to (I)). The elements (samples 1 to 3) according to Examples 1 to 3 in which the active layer was formed from -3)) have good evaluation results of variations in dark current.
On the other hand, in Comparative Examples 1 and 2 in which the active layer was formed from the composition (inks (C-1) to (C-2)) containing no polymer represented by the formula (I) as the p-type semiconductor material. Such elements (samples 4 to 5) had poor evaluation results of variations in dark current.
The inks (C-1) and (C-2) according to Comparative Examples 1 and 2 are the insulating material Z-2, similarly to the inks (I-2) and (I-3) according to Examples 2 and 3. including. However, in Comparative Examples 1 and 2, since the evaluation result of the variation in dark current is poor, some kind of mutual interaction between the polymer represented by the formula (I) as the p-type semiconductor material and the insulating material. It is inferred that the action is occurring. It is presumed that such an interaction affects the dissolution state of each component, the process of drying the active layer, and the like, which in turn affects the film thickness distribution of the active layer. However, the above inference does not limit the present invention.
他方、p型半導体材料として式(I)で表される重合体を含まない組成物(インク(C-1)~(C-2))から活性層が形成された、比較例1、2にかかる素子(サンプル4~5)は、暗電流のばらつきの評価結果が不良であった。
比較例1、2に係るインク(C-1)及び(C-2)は、実施例2、3に係るインク(I-2)、及び(I-3)と同様に、絶縁材料Z-2を含む。しかし、比較例1、2は、暗電流のばらつきの評価結果が不良であることから、p型半導体材料としての式(I)で表される重合体と、絶縁材料との間に、何らかの相互作用が生じていることが推察される。かかる相互作用が、各成分の溶解状態、活性層乾燥の過程などに影響を与え、ひいては活性層の膜厚分布に影響を与えていることが推察される。しかし、以上の推察は、本発明を限定するものではない。 As is clear from Table 3, the compositions containing the polymer represented by the formula (I) as the p-type semiconductor material, the n-type semiconductor material, the insulating material, and the solvent (inks (I-1) to (I)). The elements (
On the other hand, in Comparative Examples 1 and 2 in which the active layer was formed from the composition (inks (C-1) to (C-2)) containing no polymer represented by the formula (I) as the p-type semiconductor material. Such elements (samples 4 to 5) had poor evaluation results of variations in dark current.
The inks (C-1) and (C-2) according to Comparative Examples 1 and 2 are the insulating material Z-2, similarly to the inks (I-2) and (I-3) according to Examples 2 and 3. including. However, in Comparative Examples 1 and 2, since the evaluation result of the variation in dark current is poor, some kind of mutual interaction between the polymer represented by the formula (I) as the p-type semiconductor material and the insulating material. It is inferred that the action is occurring. It is presumed that such an interaction affects the dissolution state of each component, the process of drying the active layer, and the like, which in turn affects the film thickness distribution of the active layer. However, the above inference does not limit the present invention.
1 イメージ検出部
2 表示装置
10 光電変換素子
11、210 支持基板
12 第一の電極
13 正孔輸送層
14 活性層
15 電子輸送層
16 第二の電極
17 封止部材
20 CMOSトランジスタ基板
30 層間絶縁膜
32 層間配線部
40 封止層
42 シンチレータ
44 反射層
46 保護層
50 カラーフィルター
100 指紋検出部
200 表示パネル部
200a 表示領域
220 有機EL素子
230 タッチセンサーパネル
240 封止基板
300 静脈検出部
302 ガラス基板
304 光源部
306 カバー部
310 挿入部
400 TOF型測距装置用イメージ検出部
402 浮遊拡散層
404 フォトゲート
406 遮光部 1Image detector 2 Display device 10 Photoelectric conversion element 11, 210 Support substrate 12 First electrode 13 Hole transport layer 14 Active layer 15 Electron transport layer 16 Second electrode 17 Sealing member 20 CMOS transistor substrate 30 Interlayer insulating film 32 Interlayer wiring part 40 Sealing layer 42 Scintillator 44 Reflecting layer 46 Protective layer 50 Color filter 100 Fingerprint detection part 200 Display panel part 200a Display area 220 Organic EL element 230 Touch sensor panel 240 Sealing board 300 Vein detection part 302 Glass board 304 Light source part 306 Cover part 310 Insertion part 400 Image detection part for TOF type ranging device 402 Floating diffusion layer 404 Photogate 406 Shading part
2 表示装置
10 光電変換素子
11、210 支持基板
12 第一の電極
13 正孔輸送層
14 活性層
15 電子輸送層
16 第二の電極
17 封止部材
20 CMOSトランジスタ基板
30 層間絶縁膜
32 層間配線部
40 封止層
42 シンチレータ
44 反射層
46 保護層
50 カラーフィルター
100 指紋検出部
200 表示パネル部
200a 表示領域
220 有機EL素子
230 タッチセンサーパネル
240 封止基板
300 静脈検出部
302 ガラス基板
304 光源部
306 カバー部
310 挿入部
400 TOF型測距装置用イメージ検出部
402 浮遊拡散層
404 フォトゲート
406 遮光部 1
Claims (6)
- p型半導体材料と、n型半導体材料と、絶縁材料と、溶媒とを含む組成物であって、
前記p型半導体材料が、下記式(I)で表される構成単位を含む重合体を含む、組成物。
Ar1及びAr2は、それぞれ独立して、置換基を有していてもよい3価の芳香族複素環基を表す。
Zは、下記式(Z-1)~式(Z-4)で表される基を表す。
Rは、
水素原子、
ハロゲン原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアルケニル基、
置換基を有していてもよいシクロアルケニル基、
置換基を有していてもよいアルキニル基、
置換基を有していてもよいシクロアルキニル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいシクロアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、
置換基を有していてもよいアルキルチオ基、
置換基を有していてもよいシクロアルキルチオ基、
置換基を有していてもよいアリールチオ基、
置換基を有していてもよい1価の複素環基、
置換基を有していてもよい置換アミノ基、
置換基を有していてもよいイミン残基、
置換基を有していてもよいアミド基、
置換基を有していてもよい酸イミド基、
置換基を有していてもよい置換オキシカルボニル基、
シアノ基、
ニトロ基、
-C(=O)-Raで表される基、又は
-SO2-Rbで表される基を表し、
Ra及びRbは、それぞれ独立して、
水素原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいシクロアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、又は
置換基を有していてもよい1価の複素環基を表す。
式(Z-1)~式(Z-4)中、2つあるRは同一であっても異なっていてもよい。)) A composition containing a p-type semiconductor material, an n-type semiconductor material, an insulating material, and a solvent.
A composition in which the p-type semiconductor material contains a polymer containing a structural unit represented by the following formula (I).
Ar 1 and Ar 2 each independently represent a trivalent aromatic heterocyclic group which may have a substituent.
Z represents a group represented by the following formulas (Z-1) to (Z-4).
R is
Hydrogen atom,
Halogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
An alkenyl group which may have a substituent,
Cycloalkenyl groups, which may have substituents,
An alkynyl group, which may have a substituent,
A cycloalkynyl group which may have a substituent,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Aryloxy groups, which may have substituents,
Alkylthio groups, which may have substituents,
Cycloalkylthio groups, which may have substituents,
An arylthio group, which may have a substituent,
A monovalent heterocyclic group which may have a substituent,
Substituted amino groups, which may have substituents,
Imine residues, which may have substituents,
An amide group which may have a substituent,
An acidimide group, which may have a substituent,
Substituted oxycarbonyl group, which may have a substituent,
Cyano group,
Nitro group,
Represents a group represented by -C (= O) -R a or a group represented by -SO 2 -R b .
R a and R b are independent of each other.
Hydrogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Represents an aryloxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent.
In the formulas (Z-1) to (Z-4), the two Rs may be the same or different. ))) - 前記絶縁材料が、前記溶媒に25℃で0.1重量%以上溶解する材料である、請求項1に記載の組成物。 The composition according to claim 1, wherein the insulating material is a material that dissolves in the solvent at 25 ° C. in an amount of 0.1% by weight or more.
- 前記絶縁材料が、下記式(II)で表される構成単位を含む重合体を含む、請求項1又は2に記載の組成物。
Ri1は、水素原子、ハロゲン原子、又は炭素原子数1~20のアルキル基を表し、
Ri2は、水素原子、ハロゲン原子、炭素原子数1~20のアルキル基、下記式(III-1)で表される基、式(III-2)で表される基、又は式(III-3)で表される基を表す。
複数あるRi2aは、それぞれ独立して、水素原子、ハロゲン原子、又は炭素原子数1~20のアルキル基を表す。)
Ri2bは、水素原子又は炭素原子数1~20のアルキル基を表す。)
Ri2cは、炭素原子数1~20のアルキル基を表す。)) The composition according to claim 1 or 2, wherein the insulating material contains a polymer containing a structural unit represented by the following formula (II).
R i1 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms.
R i2 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a group represented by the following formula (III-1), a group represented by the formula (III-2), or a group represented by the formula (III-2). Represents the group represented by 3).
Each of the plurality of Ri2a independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms. )
R i2b represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. )
R i2c represents an alkyl group having 1 to 20 carbon atoms. ))) - p型半導体材料と、n型半導体材料と、絶縁材料とを含み、
前記p型半導体材料が、下記式(I)で表される構成単位を含む重合体を含む、膜。
Ar1及びAr2は、それぞれ独立して、置換基を有していてもよい3価の芳香族複素環基を表す。
Zは、下記式(Z-1)~式(Z-4)で表される基を表す。
Rは、
水素原子、
ハロゲン原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアルケニル基、
置換基を有していてもよいシクロアルケニル基、
置換基を有していてもよいアルキニル基、
置換基を有していてもよいシクロアルキニル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいシクロアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、
置換基を有していてもよいアルキルチオ基、
置換基を有していてもよいシクロアルキルチオ基、
置換基を有していてもよいアリールチオ基、
置換基を有していてもよい1価の複素環基、
置換基を有していてもよい置換アミノ基、
置換基を有していてもよいイミン残基、
置換基を有していてもよいアミド基、
置換基を有していてもよい酸イミド基、
置換基を有していてもよい置換オキシカルボニル基、
シアノ基、
ニトロ基、
-C(=O)-Raで表される基、又は
-SO2-Rbで表される基を表し、
Ra及びRbは、それぞれ独立して、
水素原子、
置換基を有していてもよいアルキル基、
置換基を有していてもよいシクロアルキル基、
置換基を有していてもよいアリール基、
置換基を有していてもよいアルキルオキシ基、
置換基を有していてもよいシクロアルキルオキシ基、
置換基を有していてもよいアリールオキシ基、又は
置換基を有していてもよい1価の複素環基を表す。
式(Z-1)~式(Z-4)中、2つあるRは同一であっても異なっていてもよい。)) Including a p-type semiconductor material, an n-type semiconductor material, and an insulating material,
A film in which the p-type semiconductor material contains a polymer containing a structural unit represented by the following formula (I).
Ar 1 and Ar 2 each independently represent a trivalent aromatic heterocyclic group which may have a substituent.
Z represents a group represented by the following formulas (Z-1) to (Z-4).
R is
Hydrogen atom,
Halogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
An alkenyl group which may have a substituent,
Cycloalkenyl groups, which may have substituents,
An alkynyl group, which may have a substituent,
A cycloalkynyl group which may have a substituent,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Aryloxy groups, which may have substituents,
Alkylthio groups, which may have substituents,
Cycloalkylthio groups, which may have substituents,
An arylthio group, which may have a substituent,
A monovalent heterocyclic group which may have a substituent,
Substituted amino groups, which may have substituents,
Imine residues, which may have substituents,
An amide group which may have a substituent,
An acidimide group, which may have a substituent,
Substituted oxycarbonyl group, which may have a substituent,
Cyano group,
Nitro group,
Represents a group represented by -C (= O) -R a or a group represented by -SO 2 -R b .
R a and R b are independent of each other.
Hydrogen atom,
Alkyl groups, which may have substituents,
Cycloalkyl groups, which may have substituents,
Aryl groups, which may have substituents,
Alkyloxy groups, which may have substituents,
Cycloalkyloxy groups, which may have substituents,
Represents an aryloxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent.
In the formulas (Z-1) to (Z-4), the two Rs may be the same or different. ))) - 第一の電極と、請求項4に記載の膜と、第二の電極とをこの順で含む、有機光電変換素子。 An organic photoelectric conversion element containing the first electrode, the film according to claim 4, and the second electrode in this order.
- 請求項5に記載の有機光電変換素子を含む、光検出素子。 A photodetection element including the organic photoelectric conversion element according to claim 5.
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