WO2022224893A1 - Ink composition and method for producing same - Google Patents
Ink composition and method for producing same Download PDFInfo
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- WO2022224893A1 WO2022224893A1 PCT/JP2022/017718 JP2022017718W WO2022224893A1 WO 2022224893 A1 WO2022224893 A1 WO 2022224893A1 JP 2022017718 W JP2022017718 W JP 2022017718W WO 2022224893 A1 WO2022224893 A1 WO 2022224893A1
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- WIPO (PCT)
- Prior art keywords
- group
- ink composition
- type semiconductor
- photoelectric conversion
- semiconductor material
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 160
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 201
- 238000006243 chemical reaction Methods 0.000 claims abstract description 150
- 239000004065 semiconductor Substances 0.000 claims abstract description 142
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- 229910003472 fullerene Inorganic materials 0.000 claims description 17
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
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- 230000002687 intercalation Effects 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
- 150000002537 isoquinolines Chemical class 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 150000004658 ketimines Chemical class 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
- 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
- 238000000691 measurement method Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- ZLEFBGVPYZUUGI-UHFFFAOYSA-N methyl benzoate;2-methylbenzoic acid Chemical class COC(=O)C1=CC=CC=C1.CC1=CC=CC=C1C(O)=O ZLEFBGVPYZUUGI-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 125000001421 myristyl 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])[H] 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
- 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
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000006609 n-nonyloxy group Chemical group 0.000 description 1
- 125000006608 n-octyloxy group Chemical group 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002791 naphthoquinones Chemical class 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 125000002971 oxazolyl group Chemical group 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
- 229960003540 oxyquinoline Drugs 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
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 1
- 125000005582 pentacene group Chemical group 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 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
- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical compound C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 description 1
- 150000002987 phenanthrenes Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical class C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 125000005581 pyrene group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 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
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000007764 slot die coating Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 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
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 125000004426 substituted alkynyl group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 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
- 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
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- 125000005579 tetracene group Chemical group 0.000 description 1
- 125000004853 tetrahydropyridinyl group Chemical group N1(CCCC=C1)* 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-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
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to an ink composition for forming a functional layer of a photoelectric conversion element and a method for producing the same.
- Photoelectric conversion elements are attracting attention as they are extremely useful devices, for example, from the viewpoint of energy saving and reduction of carbon dioxide emissions.
- Non-Patent Document 1 In the production of a photoelectric conversion element, for example, a photodetector (OPD), the functions of an active layer, an electron transport layer, a hole transport layer, etc. are obtained by a coating method of applying an ink composition for manufacturing a photoelectric conversion element to an object to be coated. It is known that a manufacturing method for forming layers is applied (see Non-Patent Document 1).
- OPD photodetector
- the ink composition for forming the active layer usually contains a p-type semiconductor. Materials and n-type semiconductor materials and solvents are included. Such an ink composition may cause electrical defects such as insulation and short circuits in the active layer formed using the ink composition if foreign matter is mixed therein. Therefore, during the production of the ink composition, it is common to dissolve the p-type semiconductor material and the n-type semiconductor material in a solvent, and then filter the solution through a filter having a predetermined pore size.
- the filter may be clogged during filtration, making it impossible to perform filtration in the first place. In some cases, it became impossible to manufacture
- the inventors of the present invention conducted extensive research to solve the above problems, and discovered that the component in the ink composition that clogs the filter contains an ultra-high molecular weight component of a p-type semiconductor material.
- the ultra-high molecular weight component is contained in the ink composition in only a very small amount, and is extremely difficult to remove from the prepared ink composition. Therefore, the present inventors managed the content of the ultra-high molecular weight component in the p-type semiconductor material used as a raw material to be below a certain level, and kept the z-average molecular weight of the p-type semiconductor material contained in the ink composition within a predetermined range. In other words, the inventors have found that the above problems can be solved, and have completed the present invention.
- the present invention provides the following [1] to [9].
- An ink composition comprising a p-type semiconductor material, an n-type semiconductor material, and a solvent, wherein the p-type semiconductor material is a polymer compound having a z-average molecular weight of less than 5.0 ⁇ 10 5 .
- An ink composition for producing a photoelectric conversion element comprising: [2] The ink composition for producing a photoelectric conversion element according to [1], wherein the p-type semiconductor material contains a polymer compound having a weight average molecular weight of more than 6.0 ⁇ 10 4 .
- a photoelectric conversion element including a step of filtering the ink composition through a filter having a pore size of 0.5 ⁇ m or less.
- a method for producing an ink composition for producing a photoelectric conversion element comprising:
- the ink composition can be filtered more reliably without clogging the filter in the manufacturing process without trial and error, and is less likely to cause electrical defects such as insulation and short circuits. Furthermore, a method for producing an ink composition is provided that can further improve the production efficiency of the ink composition and, in turn, the production efficiency of the photoelectric conversion element.
- 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 a fingerprint detection unit.
- FIG. 4 is a diagram schematically showing a configuration example of an image detection unit for an X-ray imaging apparatus.
- FIG. 5 is a diagram schematically showing a configuration example of a vein detection unit for the vein authentication device.
- FIG. 6 is a diagram schematically showing a configuration example of an image detection unit for an indirect TOF rangefinder.
- polymer compound means a polymer having a molecular weight distribution and a polystyrene-equivalent number average molecular weight of 1 ⁇ 10 3 or more and 1 ⁇ 10 8 or less.
- the constituent units contained in the polymer compound are 100 mol % in total.
- the term "constituent unit” means a unit that exists at least one in a polymer compound and is derived from a monomer compound (monomer).
- the "hydrogen atom” may be either a hydrogen atom or a deuterium atom.
- halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.
- substituents include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, cycloalkynyl groups, alkyloxy groups, cycloalkyloxy groups, alkylthio groups, cycloalkylthio groups, aryl groups, aryloxy groups, arylthio groups, monovalent heterocyclic groups, substituted amino groups, acyl groups, imine residues, amide groups, acid imide groups, substituted oxycarbonyl groups, cyano groups, alkylsulfonyl groups, and nitro groups. .
- alkyl group may have a substituent.
- An “alkyl group” may be linear, branched, or cyclic, unless otherwise specified.
- the number of carbon atoms in the linear alkyl group is generally 1-50, preferably 1-30, more preferably 1-20, not including the number of carbon atoms in the substituents.
- the number of carbon atoms in the branched or cyclic alkyl group is usually 3 to 50, preferably 3 to 30, more preferably 4 to 20, not including the number of carbon atoms in substituents.
- alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isoamyl, 2-ethylbutyl, n- hexyl group, cyclohexyl group, n-heptyl group, cyclohexylmethyl group, cyclohexylethyl group, n-octyl group, 2-ethylhexyl group, 3-n-propylheptyl group, adamantyl group, n-decyl group, 3,7-dimethyl Unsubstituted alkyl groups such as octyl group, 2-ethyloctyl group, 2-n-hexyl-decyl group, n-dodecyl group, tetradecyl group, hexadecyl group,
- a “cycloalkyl group” may be a monocyclic group or a polycyclic group.
- a cycloalkyl group may have a substituent.
- the number of carbon atoms in the cycloalkyl group is usually 3-30, preferably 3-20, not including the number of carbon atoms in the substituents.
- cycloalkyl groups include unsubstituted alkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and adamantyl groups, and hydrogen atoms in these groups are alkyl groups, alkyloxy groups, and aryl groups. , 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 in the alkenyl group is usually 2-30, preferably 2-20, not including the number of carbon atoms in the substituents.
- alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 5-hexenyl, Alkenyl groups having no substituents such as 7-octenyl groups, and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyloxy groups, aryl groups and fluorine atoms are included.
- a "cycloalkenyl group” may be a monocyclic group or a polycyclic group.
- a cycloalkenyl group may have a substituent.
- the number of carbon atoms in the cycloalkenyl group is usually 3-30, preferably 3-20, not including the number of carbon atoms in the substituents.
- cycloalkenyl groups include unsubstituted cycloalkenyl groups such as cyclohexenyl groups, and hydrogen atoms in these groups are substituted groups such as alkyl groups, alkyloxy groups, aryl groups, and fluorine atoms. Substituted groups are included.
- substituted cycloalkenyl groups 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 in the alkynyl group is usually 2-30, preferably 2-20, not including the number of carbon atoms in the substituents.
- alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, 3-butynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl and 5-hexynyl groups. and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyloxy groups, aryl groups and fluorine atoms.
- a “cycloalkynyl group” may be a monocyclic group or a polycyclic group.
- a cycloalkynyl group may have a substituent.
- the number of carbon atoms in the cycloalkynyl group is usually 4-30, preferably 4-20, not including the number of carbon atoms in the substituents.
- cycloalkynyl groups include unsubstituted cycloalkynyl groups such as cyclohexynyl groups, and hydrogen atoms in these groups substituted with substituents such as alkyl groups, alkyloxy groups, aryl groups and fluorine atoms. groups.
- substituted cycloalkynyl groups 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 in the alkyloxy group is generally 1-30, preferably 1-20, not including the number of carbon atoms in the substituent.
- alkyloxy groups include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tert-butyloxy, n-pentyloxy, n-hexyloxy, 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.
- Alkyloxy groups having no substituents, and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyloxy groups, aryl groups and fluorine atoms are included.
- the cycloalkyl group possessed by the "cycloalkyloxy group” may be a monocyclic group or a polycyclic group.
- a cycloalkyloxy group may have a substituent.
- the number of carbon atoms in the cycloalkyloxy group is usually 3-30, preferably 3-20, not including the number of carbon atoms in the substituent.
- cycloalkyloxy groups include unsubstituted cycloalkyloxy groups such as cyclopentyloxy, cyclohexyloxy, and cycloheptyloxy, and hydrogen atoms in these groups are fluorine atoms, alkyl groups, and the like.
- a group substituted with a substituent can be mentioned.
- alkylthio group may be linear or branched.
- the alkylthio group may have a substituent.
- the number of carbon atoms in the alkylthio group is generally 1-30, preferably 1-20, not including the number of carbon atoms in the substituent.
- optionally substituted alkylthio groups include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, tert-butylthio, n-pentylthio, 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 possessed by the "cycloalkylthio group” may be a monocyclic group or a polycyclic group.
- a cycloalkylthio group may have a substituent.
- the number of carbon atoms in the cycloalkylthio group is usually 3-30, preferably 3-20, not including the number of carbon atoms in the substituent.
- a cyclohexylthio group is mentioned as an example of the cycloalkylthio group which may have a substituent.
- P-valent aromatic carbocyclic group means the remaining atomic group excluding p hydrogen atoms directly bonded to the carbon atoms constituting the ring from an aromatic hydrocarbon optionally having 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 in the aryl group is usually 6-60, preferably 6-48, not including the number of carbon atoms in the substituents.
- aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, Aryl groups having no substituents such as 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group and 4-phenylphenyl group, and hydrogen atoms in these groups 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 in the aryloxy group is generally 6-60, preferably 6-48, not including the number of carbon atoms in the substituents.
- aryloxy groups include phenoxy groups, 1-naphthyloxy groups, 2-naphthyloxy groups, 1-anthracenyloxy groups, 9-anthracenyloxy groups, 1-pyrenyloxy groups, and the like.
- Examples include aryloxy groups and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkyloxy groups and fluorine atoms.
- the "arylthio group” may have a substituent.
- the number of carbon atoms in the arylthio group is usually 6-60, preferably 6-48, not including the number of carbon atoms in the substituents.
- optionally substituted arylthio groups include a phenylthio group, a C1-C12 alkyloxyphenylthio group, a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and pentafluorophenyl A thio group can be mentioned.
- C1-C12 means that the group immediately following it has 1-12 carbon atoms.
- Cm-Cn indicates that the number of carbon atoms in the group immediately following it is from m to n. The same applies hereinafter.
- p-valent heterocyclic group (p represents an integer of 1 or more.) is a hydrogen directly bonded to a carbon atom or heteroatom constituting a ring from a heterocyclic compound optionally having a substituent It means an atomic group remaining excluding p hydrogen atoms among atoms.
- a "p-valent heterocyclic group” includes a "p-valent aromatic heterocyclic group”.
- p-valent aromatic heterocyclic group from an optionally substituted aromatic heterocyclic compound, p It means the remaining atomic groups excluding hydrogen atoms.
- Aromatic heterocyclic compounds include not only compounds in which the heterocycle itself exhibits aromaticity, but also compounds in which an aromatic ring is fused to a heterocycle, even if the heterocycle itself does not exhibit aromaticity. be.
- aromatic heterocyclic compounds specific examples of compounds 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 dibenzophosphole.
- aromatic heterocyclic compounds specific examples of compounds in which the heterocyclic ring itself does not show aromaticity and the aromatic ring is fused to the heterocyclic ring include phenoxazine, phenothiazine, dibenzoborol, dibenzosilol, and benzopyrans.
- the p-valent heterocyclic group may have a substituent.
- the number of carbon atoms in the p-valent heterocyclic group is usually 2 to 60, preferably 2 to 20, not including the number of carbon atoms in the substituents.
- monovalent heterocyclic groups include monovalent aromatic heterocyclic groups (e.g., thienyl group, pyrrolyl group, furyl group, pyridyl group, quinolyl group, isoquinolyl group, pyrimidinyl group, triazinyl group), monovalent Examples include non-aromatic heterocyclic groups (eg, piperidyl group, piperazyl group), and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkyloxy groups, and fluorine atoms.
- monovalent aromatic heterocyclic groups e.g., thienyl group, pyrrolyl group, furyl group, pyridyl group, quinolyl group, isoquinolyl group, pyrimidinyl group, triazinyl group
- monovalent Examples include non-aromatic heterocyclic groups (eg, piperidyl group, piperazyl group), and groups in which hydrogen atoms in these groups are substitute
- Substituted amino group means an amino group having a substituent. Alkyl groups, aryl groups, and monovalent heterocyclic groups are preferred as the substituents possessed by the amino group. The number of carbon atoms in the substituted amino group is usually 2-30 not including the number of carbon atoms in 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 and bis(3,5-di-tert-butylphenyl)amino group).
- dialkylamino groups eg, dimethylamino group, diethylamino group
- diarylamino groups eg, diphenylamino group, bis(4-methylphenyl)amino group, bis(4-tert-butylphenyl ) amino group and bis(3,5-di-tert-butylphenyl)amino group).
- the "acyl group” may have a substituent.
- the number of carbon atoms in the acyl group is usually 2-20, preferably 2-18, not including the number of carbon atoms in the substituents.
- Specific examples of acyl groups include acetyl, propionyl, butyryl, isobutyryl, pivaloyl, benzoyl, trifluoroacetyl, and pentafluorobenzoyl groups.
- Imine residue means an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom or a nitrogen atom that constitutes a carbon atom-nitrogen atom double bond from an imine compound.
- An "imine compound” means an organic compound having a carbon atom-nitrogen atom double bond in the molecule.
- imine compounds include aldimines, ketimines, and compounds in which the hydrogen atoms bonded to the nitrogen atoms that constitute the carbon atom-nitrogen double bonds in aldimines are substituted with substituents such as alkyl groups. be done.
- the number of carbon atoms in the imine residue is usually 2-20, preferably 2-18.
- Examples of imine residues include groups represented by the following structural formulas.
- Amido group means an atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from amide.
- the amide group usually has about 1 to 20 carbon atoms, preferably 1 to 18 carbon atoms.
- 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. , a ditrifluoroacetamide group, and a dipentafluorobenzamide group.
- Acid imide group means an atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from an acid imide.
- the number of carbon atoms in the acid imide group is generally 4-20.
- Specific examples of acid imide groups include groups shown below.
- R' represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.
- the substituted oxycarbonyl group usually has 2 to 60 carbon atoms, preferably 2 to 48 carbon atoms.
- substituted oxycarbonyl groups 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 in the alkylsulfonyl group is usually 1-30, not including the number of carbon atoms in the substituents.
- Specific examples of alkylsulfonyl groups include methylsulfonyl, ethylsulfonyl, and dodecylsulfonyl groups.
- ⁇ -conjugated system means a system in which ⁇ electrons are delocalized over multiple bonds.
- (Meth)acrylic includes acrylic, methacrylic, and combinations thereof.
- the "ink composition” means a liquid composition used in the coating method, and is not limited to colored liquids.
- the “coating method” means a method of forming a film using a liquid substance represented by an ink composition.
- the "ink composition” may be a solution, or may be a dispersion liquid such as a dispersion liquid, an emulsion (emulsion), or a suspension (suspension).
- the ink composition of the present embodiment is an ink composition containing a p-type semiconductor material, an n-type semiconductor material, and a solvent, wherein the p-type semiconductor material has a z-average molecular weight of 5.0 ⁇
- the ink composition of the present embodiment is an ink composition for manufacturing a photoelectric conversion element, preferably an ink composition for forming an active layer.
- the p-type semiconductor material contains at least one electron-donating compound
- the n-type semiconductor material contains at least one electron-accepting compound. Whether the semiconductor material contained in the ink composition functions as a p-type semiconductor material or an n-type semiconductor material is relatively determined from the HOMO energy level value or the LUMO energy level value of the selected compound. I can.
- the relationship between the HOMO and LUMO energy level values of the p-type semiconductor material and the HOMO and LUMO energy level values of the n-type semiconductor material indicates that the (solidified) film formed from the ink composition has a photoelectric conversion function, It can be appropriately set within a range in which a predetermined function such as a light detection function is exhibited.
- the p-type semiconductor material may be a low-molecular compound or a high-molecular compound.
- Examples of p-type semiconductor materials that are low molecular weight compounds include phthalocyanine, metal phthalocyanine, porphyrin, metal porphyrin, oligothiophene, tetracene, pentacene, and rubrene.
- the p-type semiconductor material that the ink composition of the present embodiment may contain is a ⁇ -conjugated material having a donor-acceptor structure containing a donor structural unit (also referred to as a D structural unit) and an acceptor structural unit (also referred to as an A structural unit).
- system polymer compound also referred to as a DA type conjugated polymer compound.
- the donor structural unit is a structural unit with an excess of ⁇ electrons
- the acceptor structural unit is a structural unit with a ⁇ electron deficiency.
- the structural unit that can constitute the p-type semiconductor material may be a structural unit in which a donor structural unit and an acceptor structural unit are directly bonded, or a donor structural unit and an acceptor structural unit.
- Structural units linked via spacers are also included.
- Examples of p-type semiconductor materials that are polymer compounds include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives containing 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.
- As the p-type semiconductor material it is preferable to use a polymer compound containing a structural unit having a thiophene skeleton.
- the p-type semiconductor material contains a structural unit represented by the following formula (I) and/or A polymer compound containing a structural unit represented by formula (II) is preferred.
- Ar 1 and Ar 2 each independently represent a trivalent aromatic heterocyclic group which may have a substituent, and Z represents the following formulas (Z-1) to (Z -7) represents a group represented by any one.
- Ar 3 represents a divalent aromatic heterocyclic group.
- R is hydrogen atom, halogen atom, an optionally substituted alkyl group, a cycloalkyl group optionally having a substituent, an optionally substituted alkenyl group, a cycloalkenyl group optionally having a substituent, an optionally substituted alkynyl group, a cycloalkynyl group optionally having a substituent, an aryl group optionally having a substituent, an optionally substituted alkyloxy group, a cycloalkyloxy group optionally having a substituent, an optionally substituted aryloxy group, an optionally substituted alkylthio group, a cycloalkylthio group optionally having a substituent, an optionally substituted arylthio group, a monovalent heterocyclic group optionally having a substituent, a substituted amino group which may have a substituent, an imine residue optionally having a substituent, an amide group optionally
- R in formulas (Z-1) to (Z-7) is preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, still more preferably a hydrogen atom or 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, particularly preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. These groups may have a substituent. When there are multiple R's, the multiple R's may be the same or different.
- the structural unit represented by formula (I) is preferably a structural unit represented by formula (I-1) below.
- Examples of structural units represented by formula (I-1) include structural units represented by formulas (501) to (505) below.
- R has the same meaning as above.
- the two R's may be the same or different.
- the number of carbon atoms in the divalent aromatic heterocyclic group represented by Ar 3 is usually 2 to 60, preferably 4 to 60, more preferably 4 to 20. .
- the divalent aromatic heterocyclic group represented by Ar 3 may have a substituent.
- Examples of substituents that the divalent aromatic heterocyclic group represented by Ar 3 may have include halogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, monovalent heterocyclic groups, substituted amino groups, acyl groups, imine residues, amide groups, acid imide groups, substituted oxycarbonyl groups, alkenyl groups, alkynyl groups, cyano groups, and nitro groups.
- Examples of the divalent aromatic heterocyclic group represented by Ar 3 include groups represented by the following formulas (101) to (190).
- R has the same meaning as above.
- the multiple R's may be the same or different.
- structural units represented by the formula (II) structural units represented by the following formulas (II-1) to (II-6) are preferable.
- X 1 and X 2 each independently represent an oxygen atom or a sulfur atom, and R has the same meaning as above. When there are multiple R's, the multiple R's may be the same or different.
- both X 1 and X 2 in formulas (II-1) to (II-6) are preferably sulfur atoms.
- a polymer compound that is a p-type semiconductor material may contain two or more structural units of formula (I), and may contain two or more structural units of formula (II).
- the polymer compound that is the p-type semiconductor material may contain a structural unit represented by the following formula (III).
- Ar 4 represents an arylene group.
- the arylene group represented by Ar 4 means an atomic group remaining after removing two hydrogen atoms from an optionally substituted aromatic hydrocarbon.
- Aromatic hydrocarbons also include compounds having condensed rings, and compounds in which two or more selected from the group consisting of independent benzene rings and condensed rings are bonded directly or via a divalent group such as vinylene.
- Examples of the substituents that the aromatic hydrocarbon may have include the same substituents as those listed above as the substituents that the heterocyclic compound may have.
- the number of carbon atoms in the arylene group excluding substituents is usually 6-60, preferably 6-20.
- the number of carbon atoms in the arylene group including substituents is usually 6-100.
- arylene groups include phenylene groups (e.g. formulas 1 to 3 below), naphthalene-diyl groups (e.g. formulas 4 to 13 below), anthracene-diyl groups (e.g. formulas 14 to 19 below), Biphenyl-diyl group (eg, formulas 20 to 25 below), terphenyl-diyl group (eg, formulas 26 to 28 below), condensed ring compound group (eg, formulas 29 to 35 below), fluorene-diyl group (eg formulas 36 to 38 below) and benzofluorene-diyl groups (eg formulas 39 to 46 below).
- phenylene groups e.g. formulas 1 to 3 below
- naphthalene-diyl groups e.g. formulas 4 to 13 below
- anthracene-diyl groups e.g. formulas 14 to 19 below
- Biphenyl-diyl group e
- R has the same definition as above.
- the multiple R's may be the same or different.
- the polymer compound as the p-type semiconductor material contains the structural unit represented by formula (I) and/or the structural unit represented by formula (II), the structural unit represented by formula (I) and the formula
- the total amount of the structural units represented by (II) is usually 20 to 100 mol% when the amount of all the structural units contained in the polymer compound is 100 mol%, and the charge as a p-type semiconductor material It is preferably 40 to 100 mol %, more preferably 50 to 100 mol %, since it improves transportability.
- polymer compounds that are p-type semiconductor materials include polymer compounds represented by the following formulas P-1 to P-10.
- the p-type semiconductor material contains a polymer compound having a z-average molecular weight of less than 5.0 ⁇ 10 5 .
- the p-type semiconductor material has a weight of It preferably contains a polymer compound having an average molecular weight of more than 6.0 ⁇ 10 4 , and from the viewpoint of achieving both photoelectric conversion efficiency and filterability, the z-average molecular weight is less than 5.0 ⁇ 10 5 and weight More preferably, it contains a polymer compound with an average molecular weight greater than 6.0 ⁇ 10 4 .
- the z-average molecular weight (Mz) of the p-type semiconductor material is preferably larger than 1.5 ⁇ 10 5 from the viewpoint of achieving an external quantum efficiency of preferably 50% or more. .
- the polymer compound as the p-type semiconductor material has a weight-average molecular weight of usually 1 ⁇ 10 3 to 5 ⁇ 10 5 , from the viewpoint of improving the solubility in the solvent. Therefore, it is preferably 1 ⁇ 10 3 to 3 ⁇ 10 5 .
- the z-average molecular weight (Mz) and the weight-average molecular weight (Mw) are measured by gel permeation chromatography (GPC) performed using a conventionally known arbitrary suitable device. is the average molecular weight.
- the ink composition of the present embodiment may contain only one type of compound (polymer compound) that is a p-type semiconductor material, or may contain two or more types in any combination.
- the z-average molecular weight (Mz) is a weighted average molecular weight using the square of the molecular weight as a weight, and tends to be more susceptible to the presence of higher molecular weight molecules than the weight-average molecular weight (Mw). is a parameter.
- the z-average molecular weight (Mz) of the p-type semiconductor material which is a polymer compound
- Mz z-average molecular weight
- the charging composition (mixing ratio) of a plurality of types of monomers as raw materials is appropriately adjusted, the amount of the catalyst to be used is appropriately adjusted, and the reaction solution is
- the z-average molecular weight (Mz) can be adjusted within the preferred range by appropriately adjusting the concentration of . More specifically, for example, the z-average molecular weight (Mz) may be appropriately adjusted with reference to "Review of Network Polymer, 2009, 30, 261".
- the ink composition of the present embodiment which uses the p-type semiconductor material having the z-average molecular weight (Mz) as already described, trial and error is not required, and the filter is not clogged in the manufacturing process. Filtration can be carried out on a large scale, making it difficult for electrical defects such as insulation and short circuits to occur, and furthermore, the production efficiency of the ink composition and, in turn, the production efficiency of the photoelectric conversion element can be further improved.
- Mz z-average molecular weight
- n-type semiconductor material that the ink composition of the present embodiment may contain may be a low-molecular compound or a high-molecular compound.
- n-type semiconductor materials that are low molecular weight compounds
- n-type semiconductor materials include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyano Anthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, fullerenes such as C60 fullerene and fullerene derivatives thereof ( hereinafter referred to as fullerene compounds ), and phenanthrene derivatives such as bathocuproin.
- fullerene compounds such as C60 fullerene and fullerene derivatives thereof ( hereinafter referred to as fullerene compounds )
- phenanthrene derivatives such as bathocuproin.
- n-type semiconductor materials that are polymer compounds 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, polyquinoline and its derivatives, polyquinoxaline and its derivatives, and polyfluorene and its derivatives.
- the n-type semiconductor material is preferably one or more selected from fullerenes and fullerene derivatives, more preferably fullerene derivatives.
- fullerenes include C60 fullerene, C70 fullerene, C76 fullerene, C78 fullerene, and C84 fullerene .
- fullerene derivatives include derivatives of these fullerenes.
- a fullerene derivative means a compound in which at least a part of fullerene is modified.
- fullerene derivatives include compounds represented by the following formula.
- Ra represents an alkyl group, an aryl group, a monovalent heterocyclic group, or a group having an ester structure.
- a plurality of R a may be the same or different.
- Rb represents an alkyl group or an aryl group. A plurality of R b may be the same or different.
- Examples of groups having an ester structure represented by Ra include groups represented by the following formulae.
- u1 represents an integer of 1-6.
- u2 represents an integer from 0 to 6;
- R e represents an alkyl group, an aryl group, or a monovalent heterocyclic group.
- C60 fullerene derivatives include the following compounds.
- C70 fullerene derivatives include the following compounds.
- fullerene derivatives include [6,6]-phenyl-C61 butyric acid methyl ester (C60PCBM, [6,6]-phenyl C61 butyric acid methyl ester), [6,6]-phenyl-C71 butyric acid methyl ester ( C70PCBM, [6,6]-Phenyl C71 butyric acid methyl ester), [6,6]-phenyl-C85 butyric acid methyl ester (C84PCBM, [6,6]-Phenyl C85 butyric acid methyl ester), and [6,6 ]-Thienyl-C61 butyric acid methyl ester ([6,6]-Thienyl C61 butyric acid methyl ester).
- the n-type semiconductor material that can be contained in the ink composition of the present embodiment includes compounds other than fullerene compounds.
- n-type semiconductor materials that are not fullerene compounds are referred to as "non-fullerene compounds.”
- Various compounds are known as non-fullerene compounds, and any suitable conventionally known non-fullerene compound can be used as the n-type semiconductor material in this embodiment.
- the ink composition according to the present embodiment may contain only one type of compound that is an n-type semiconductor material, or may contain a plurality of types.
- the non-fullerene compound which is the n-type semiconductor material, is preferably a compound containing a perylenetetracarboxylic acid diimide structure.
- examples of compounds containing a perylenetetracarboxylic acid diimide structure, which are non-fullerene compounds include compounds represented by the following formulae.
- R is as defined above. Multiple R's may be the same or different.
- the n-type semiconductor material preferably contains a compound represented by the following formula (V).
- the compound represented by the following formula (V) is a non-fullerene compound containing a perylenetetracarboxylic acid diimide structure.
- R 1 is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted an alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryl group, or an optionally substituted monovalent aromatic heterocyclic group show. Multiple R 1 's may be the same or different.
- each of a plurality of R 1 is independently an optionally substituted alkyl group.
- R 2 is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkyloxy group, a substituent represents an optionally substituted cycloalkyloxy group, an optionally substituted aryl group, or an optionally substituted monovalent aromatic heterocyclic group.
- Multiple R 2 may be the same or different.
- Preferred examples of the compound represented by formula (V) include the compound represented by the following formula.
- the n-type semiconductor material preferably contains a compound represented by the following formula (VI).
- a 1 and A 2 each independently represent an electron-withdrawing group, and B 10 represents a group containing a ⁇ -conjugated system.
- Examples of electron-withdrawing groups A 1 and A 2 include groups represented by —CH ⁇ C(—CN) 2 and groups represented by the following formulas (a-1) to (a-9). and the group to be carried out.
- T represents an optionally substituted carbocyclic ring or an optionally substituted heterocyclic ring.
- Carbocyclic and heterocyclic rings may be monocyclic or condensed. When these rings have multiple substituents, the multiple substituents may be the same or different.
- optionally substituted carbocyclic rings for T include aromatic carbocyclic rings.
- the optionally substituted carbocyclic ring for T is preferably an aromatic carbocyclic ring.
- Specific examples of the optionally substituted carbocyclic ring for T include benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring and phenanthrene ring, preferably benzene ring, They are a naphthalene ring and a phenanthrene ring, more preferably a benzene ring and a naphthalene ring, and still more preferably a benzene ring. These rings may have a substituent.
- Examples of the optionally substituted heterocyclic ring for T include aromatic heterocyclic rings, preferably aromatic heterocyclic rings.
- Specific examples of the optionally substituted heterocyclic ring for T include pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, and a thienothiophene ring, preferably a thiophene ring, a pyridine ring, a pyrazine ring, a thiazole ring, and a thienothiophene ring, more preferably a thiophene ring. These rings may have a substituent.
- substituents that the carbocyclic or heterocyclic ring for T may have include halogen atoms, alkyl groups, alkyloxy groups, aryl groups, and monovalent heterocyclic groups, preferably fluorine atoms and/or or an alkyl group having 1 to 6 carbon atoms.
- X 7 is a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkyl group, an optionally substituted alkyloxy group, an optionally substituted aryl group, or represents a monovalent heterocyclic group.
- R a1 , R a2 , R a3 , R a4 , and R a5 each independently represent a hydrogen atom, an optionally substituted alkyl group, a halogen atom, an optionally substituted alkyl represents an oxy group, an optionally substituted aryl group or a monovalent heterocyclic group, preferably an optionally substituted alkyl group or an optionally substituted aryl group is.
- R a6 and R a7 each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, or a substituent optionally substituted cycloalkyl group, optionally substituted alkyloxy group, optionally substituted cycloalkyloxy group, optionally substituted monovalent aromatic carbon It represents a cyclic group or an optionally substituted monovalent aromatic heterocyclic group, and a plurality of R a6 and R a7 may be the same or different.
- the electron-withdrawing groups A 1 and A 2 include the following formulas (a-1-1) to (a-1-4), formulas (a-6-1) and formulas (a-7 -1) is preferable, and a group represented by formula (a-1-1) is more preferable.
- multiple R a10 each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group.
- R a3 , R a4 and R a5 are each independently the same as defined above, preferably each independently an optionally substituted alkyl group or an optionally substituted aryl represents a group.
- An example of the group containing a ⁇ -conjugated system as B 10 is a group represented by -(S 1 ) n1 -B 11 -(S 2 ) n2 - in the compound represented by formula (VII) described later. mentioned.
- the n-type semiconductor material is preferably a compound represented by the following formula (VII).
- a 1 and A 2 each independently represent an electron-withdrawing group. Examples and preferred examples of A 1 and A 2 are the same as the examples and preferred examples described for A 1 and A 2 in formula (VI) above.
- the divalent carbocyclic group optionally having substituent(s) and the divalent heterocyclic group optionally having substituent(s) represented by S 1 and S 2 may be a condensed ring. .
- the divalent carbocyclic group or divalent heterocyclic group has multiple substituents, the multiple substituents may be the same or different.
- n1 and n2 each independently represent an integer of 0 or greater, preferably each independently represent 0 or 1, more preferably both represent 0 or 1.
- divalent carbocyclic groups examples include divalent aromatic carbocyclic groups.
- divalent heterocyclic groups examples include divalent aromatic heterocyclic groups.
- the divalent aromatic carbocyclic group or divalent aromatic heterocyclic group is a condensed ring
- all of the rings constituting the condensed ring may be condensed rings having aromaticity, only a part It may be a condensed ring having aromaticity.
- S 1 and S 2 are groups represented by any of the formulas (101) to (190) given as examples of the divalent aromatic heterocyclic group represented by Ar 3 already explained, and groups in which hydrogen atoms in these groups are substituted with substituents.
- S 1 and S 2 preferably each independently represent a group represented by formula (s-1) or (s-2) below.
- X3 represents an oxygen atom or a sulfur atom.
- R a10 is as defined above.
- S 1 and S 2 are preferably each independently a group represented by formula (142), formula (148), or formula (184), or a group in which a hydrogen atom in these groups is substituted with a substituent and more preferably a group represented by the formula (142) or (184), or a group in which one hydrogen atom in the group represented by the formula (184) is substituted with an alkyloxy group. .
- B 11 is a condensed ring group having two or more structures selected from the group consisting of a carbocyclic structure and a heterocyclic ring structure, a condensed ring group containing no ortho-peri condensed structure, and having a substituent; represents an optional condensed ring group.
- the condensed ring group represented by B11 may contain a structure in which two or more identical structures are condensed.
- the multiple substituents may be the same or different.
- Examples of the carbocyclic structure that can constitute the condensed ring group represented by B 11 include a ring structure represented by the following formula (Cy1) or (Cy2).
- heterocyclic structures that can constitute the condensed ring group represented by B 11 include ring structures represented by any of the following formulas (Cy3) to (Cy10).
- B 11 is preferably a condensed ring group having two or more structures selected from the group consisting of structures represented by formulas (Cy1) to (Cy10), It is a condensed ring group which does not contain a condensed structure and which may have a substituent.
- B 11 may include a structure in which two or more identical structures among the structures represented by formulas (Cy1) to (Cy10) are condensed.
- B 11 is more preferably a condensed ring group having two or more structures selected from the group consisting of structures represented by formulas (Cy1) to (Cy6) and (Cy8), wherein the ortho-pericondensed It is a condensed ring group having no structure and optionally having a substituent.
- the substituent that the condensed ring group B 11 may have is preferably an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted and an optionally substituted monovalent heterocyclic group.
- the aryl group that the condensed ring group represented by B 11 may have may be substituted with, for example, an alkyl group.
- Examples of the condensed ring group for B 11 include groups represented by the following formulas (b-1) to (b-14), and hydrogen atoms in these groups are substituents (preferably, substituents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, or an optionally substituted monovalent heterocyclic group ) substituted with.
- the condensed ring group for B 11 is a group represented by the following formula (b-2) or (b-3), or a hydrogen atom in these groups has a substituent (preferably, a substituent optionally substituted alkyl group, optionally substituted aryl group, optionally substituted alkyloxy group, or optionally substituted monovalent heterocyclic group) is preferred, and a group represented by the following formula (b-2) or (b-3) is more preferred.
- R a10 is as defined above.
- a plurality of R a10 are each independently preferably an optionally substituted alkyl group or optionally substituted It is an aryl group.
- Examples of compounds represented by formula (VI) or formula (VII) include compounds represented by the following formula.
- R is as defined above, and X represents a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group.
- R is preferably a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted alkyloxy group.
- Examples of compounds represented by formula (VI) or (VII) include compounds represented by the following formulas.
- the n-type semiconductor material may contain, in addition to the non-fullerene compound, a combination of the fullerene and the fullerene derivative (fullerene compound) already described.
- n-type semiconductor material in the present embodiment include compounds represented by the following formulas.
- the ink composition of the present embodiment may contain an aromatic hydrocarbon as a solvent.
- the aromatic hydrocarbon may have a substituent.
- the aromatic hydrocarbon is preferably a compound capable of dissolving the p-type semiconductor material already described.
- aromatic hydrocarbons examples include toluene, xylene (eg, o-xylene, m-xylene, p-xylene), trimethylbenzene (eg, mesitylene, 1,2,4-trimethylbenzene (pseudocumene), )), butylbenzene (e.g. n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (e.g.
- the solvent may be composed of only one aromatic hydrocarbon, or may be composed of two or more aromatic hydrocarbons.
- Aromatic hydrocarbons that can constitute the solvent are preferably toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert.
- -butylbenzene methylnaphthalene, tetralin, 1-chloronaphthalene, chlorobenzene and dichlorobenzene (1,2-dichlorobenzene), more preferably toluene, o-xylene, m- xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, tetralin, indane, 1-chloronaphthalene, chlorobenzene or dichlorobenzene (o -dichlorobenzene).
- the ink composition of this embodiment may contain an alkyl halide as a solvent.
- Alkyl halides that can be used as solvents include, for example, chloroform.
- the ink composition of the present embodiment preferably includes toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, One or more selected from the group consisting of tert-butylbenzene, methylnaphthalene, tetralin, indane, 1-chloronaphthalene, chlorobenzene or dichlorobenzene (1,2-dichlorobenzene) and chloroform.
- a further solvent may be used in combination.
- examples of additional solvents include aromatic carbonyl compounds, aromatic ester compounds and nitrogen-containing heterocyclic compounds.
- aromatic carbonyl compound examples include acetophenone optionally having substituent(s), propiophenone optionally having substituent(s), butyrophenone optionally having substituent(s), cyclohexylphenone which may be substituted, and benzophenone which may have a substituent.
- aromatic ester compound examples include optionally substituted methyl benzoate (methyl benzoate), optionally substituted ethyl benzoate, and optionally substituted benzoic acid.
- propyl, optionally substituted butyl benzoate, optionally substituted isopropyl benzoate, optionally substituted benzyl benzoate, optionally substituted Cyclohexyl benzoate and phenyl benzoate which may have a substituent may be mentioned.
- nitrogen-containing heterocyclic compounds include optionally substituted pyridine, optionally substituted quinoline, optionally substituted quinoxaline, and optionally substituted optionally substituted pyrimidine, optionally substituted pyrazine, and optionally substituted quinazoline .
- the nitrogen-containing heterocyclic compound may have a substituent directly bonded to the ring structure.
- substituents that the ring structure of the nitrogen-containing heterocyclic compound may have include: Examples include alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, halogen groups, and alkylthio groups.
- nitrogen-containing heterocyclic compounds containing a pyridine ring structure examples include optionally substituted pyridine, optionally substituted quinoline, and optionally substituted isoquinoline. mentioned.
- nitrogen-containing cyclic compounds containing a pyrazine ring structure include optionally substituted pyrazine and optionally substituted quinoxaline.
- Nitrogen-containing cyclic compounds containing a tetrahydropyridine ring structure include, for example, optionally substituted 1,2,3,4-tetrahydroquinoline and optionally substituted 1,2, 3,4-tetrahydroisoquinolines can be mentioned.
- nitrogen-containing cyclic compounds containing a pyrimidine ring structure examples include optionally substituted pyrimidine and optionally substituted quinazoline.
- the solvent further contains an aromatic carbonyl compound, an aromatic ester compound, or a nitrogen-containing heterocyclic compound as a further solvent, or further contains two or more selected from these. You can stay.
- the weight ratio of the solvent to the additional solvent (solvent/additional solvent)
- the range is preferably from 80/20 to 99.9/0.1.
- the total weight of the solvent contained in the ink composition is preferably 90 mass 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 ink composition is 100 mass%. % or more, more preferably 92% by mass or more, and still more preferably 95% by mass or more, and the concentration of the p-type semiconductor material and the n-type semiconductor material in the ink composition is increased to achieve a constant thickness From the viewpoint of facilitating the formation of the above layers, the content is preferably 99.9% by mass or less.
- the ink composition may further contain any solvent in addition to the solvents and additional solvents already described.
- the content of any solvent is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by weight or less.
- the optional solvent it is preferred to use a solvent with a higher boiling point than the further solvent.
- the total concentration of the p-type semiconductor material and the n-type semiconductor material in the ink composition may be any suitable concentration depending on the thickness of the required functional layer (active layer), desired properties, etc. can.
- the total concentration of the p-type semiconductor material and the n-type semiconductor material is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, preferably 10% by mass or less, and more preferably 5% by mass or less, more preferably 0.01% by mass or more and 20% by mass or less, particularly preferably 0.01% by mass or more and 10% by mass or less, and even more preferably 0.01% by mass or more and 5 % by mass or less, particularly preferably 0.1% by mass or more and 5% by mass or less.
- the p-type semiconductor material and the n-type semiconductor material may be dissolved or dispersed in the ink composition.
- the p-type semiconductor material and the n-type semiconductor material are preferably at least partially dissolved, more preferably completely dissolved.
- 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 ink composition is preferably 1/9 or more, more preferably 1/5 or more, and further It is preferably 1/3 or more, preferably 9/1 or less, more preferably 5/1 or less, still more preferably 3/1 or less.
- the ink composition prepared by selecting the p-type semiconductor material, the n-type semiconductor material, and the solvent has a pore size of 0.5 ⁇ m or less. including the process of being filtered through a filter of
- the method for producing an ink composition includes a preparatory step of preparing a plurality of types of polymer compounds that are p-type semiconductor materials; A selection step of selecting a polymer compound of less than 0 ⁇ 10 5 as a p-type semiconductor material, and mixing the p-type semiconductor material and n-type semiconductor material selected in the selection step with a solvent to produce an ink composition. It may be a method for producing an ink composition for producing a photoelectric conversion element, comprising the step of
- the z-average molecular weight of the polymer compound prepared in the preparation step is determined by, for example, the already described measurement method. It can be a sorting step that measures and sorts based on the measured z-average molecular weight.
- the ink composition can be produced by any suitable conventionally known method.
- the mixed solvent is added with a p-type semiconductor material and an n-type semiconductor material.
- a (first) composition is prepared by adding a p-type semiconductor material to a solvent, and separately from this, a (second) composition is prepared by adding an n-type semiconductor material to an additional solvent.
- a method of preparing (manufacturing) by mixing two or more compositions obtained in other words, a step of preparing a composition includes a step of preparing two or more compositions, and a step of preparing an ink composition However, it can be produced by a production method including a step of mixing two or more compositions.
- the solvent (and further solvent), the p-type semiconductor material and the n-type semiconductor material may be heated to a temperature below the boiling point of the solvent and mixed.
- the step of preparing the ink composition is preferably carried out under conditions of 0°C or higher and 200°C or lower, and preferably carried out under conditions of 0°C or higher and 100°C or lower.
- the step of filtering the prepared ink composition is specifically performed by mixing the solvent (and further solvent), the p-type semiconductor material and the n-type semiconductor material in preparing (manufacturing) the ink composition. are mixed, the resulting mixture (ink composition) may be filtered by a conventional method using a filter having a predetermined pore size.
- filters that can be used for filtration include, for example, filters made of fluororesins such as cellulose acetate, glass fiber, polyvinylidene fluoride (PVdF), and polytetrafluoroethylene (PTFE).
- fluororesins such as cellulose acetate, glass fiber, polyvinylidene fluoride (PVdF), and polytetrafluoroethylene (PTFE).
- the pore size of the filter that can be used is preferably 1 ⁇ m or less, more preferably 1 ⁇ m or less, from the viewpoint of filter availability, filtration efficiency, and suppression of defects in the formed functional layer (active layer).
- the ink composition of the present embodiment is generally used to form a film containing a p-type semiconductor material and an n-type semiconductor material.
- the ink composition of this embodiment is suitably used for forming an active layer included in a photoelectric conversion element.
- the ink composition of the present embodiment can be used particularly suitably for forming an active layer included in a photodetector to which a reverse bias voltage is applied during use.
- the solidified film of the ink composition can be formed by removing the solvent from the film and solidifying the film.
- a solidified film of the ink composition can be suitably used to form a functional layer, particularly an active layer, included in the photodetector.
- the solidified film of the ink composition can be produced by any suitable production method.
- the method for producing a solidified film of an ink composition includes a step (i) of applying the ink composition to an object to be coated to obtain a coating film, and a step (ii) of removing the solvent from the obtained coating film. including. Steps (i) and (ii) are described below.
- the coating method is preferably a slit coating method, a knife coating method, a spin coating method, a micro gravure coating method, a gravure coating method, a bar coating method, an inkjet coating method, a nozzle coating method, or a capillary coating method.
- a slit coating method, a spin coating method, a capillary coating method, or a bar coating method is more preferable, and a slit coating method or a spin coating method is even more preferable.
- the ink composition is applied to any application target.
- the ink composition can be applied to a functional layer that can be included in the photoelectric conversion element, such as an electrode (anode or cathode), an electron transport layer, or a hole transport layer, during the manufacturing process of the photoelectric conversion element.
- any suitable method can be used as a method for removing the solvent from the coating film of the ink composition formed in step (i).
- methods for removing the solvent include drying methods such as hot air drying, infrared heating drying, flash lamp annealing drying, and vacuum drying.
- Photoelectric conversion element (1) Structure of photoelectric conversion element
- the photoelectric conversion element according to the present embodiment includes a first electrode, a second electrode, and an active layer provided between the first electrode and the second electrode. and wherein the active layer is the solidified film already described.
- FIG. 1 is a diagram schematically showing a configuration example of a photoelectric conversion element.
- the photoelectric conversion element 10 is provided on a support substrate 11.
- the photoelectric conversion element 10 includes a first electrode 12 provided in contact with a support substrate 11 , an electron transport layer 13 provided in contact with the first electrode 12 , and an electron transport layer 13 provided in contact with the electron transport layer 13 . , a hole transport layer 15 provided in contact with the active layer 14, and a second electrode 16 provided in contact with the hole transport layer 15. there is In this configuration example, a sealing member 17 is further provided so as to be in contact with the first electrode 16 .
- a photoelectric conversion element is usually formed on a substrate (support substrate). Further, it may be further sealed with a substrate (sealing substrate).
- a substrate substrate
- One of a pair of electrodes consisting of a first electrode and a second electrode is usually 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 the layer containing the organic compound is formed.
- the electrode opposite to the electrode provided on the opaque substrate is preferably a transparent or translucent electrode.
- a photoelectric conversion element includes a pair of electrodes, a first electrode and a second electrode. At least one of the first electrode and the second electrode is preferably a transparent or translucent electrode in order to allow light to enter.
- Examples of materials for transparent or semi-transparent electrodes include conductive metal oxide films and semi-transparent metal thin films. Specifically, indium oxide, zinc oxide, tin oxide, and their composites indium tin oxide (ITO), indium zinc oxide (IZO), conductive materials such as NESA, gold, platinum, silver, copper. ITO, IZO, and tin oxide are preferable as materials for transparent or translucent electrodes. Moreover, as the electrode, a transparent conductive film using an organic compound such as polyaniline and its derivatives, polythiophene and its derivatives 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 with low light transmittance.
- materials for electrodes with low light transmittance include metals and conductive polymers.
- Specific examples of low light transmissive electrode materials include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, Metals such as terbium, ytterbium, and alloys of two or more thereof, or one or more of these metals together with gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin alloys with one or more metals selected from the group consisting of graphite, graphite intercalation compounds, polyaniline and its derivatives, polythiophene and its derivatives.
- Alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, and calcium-aluminum alloys.
- the photoelectric conversion element of this embodiment includes the solidified film of the ink composition already described as an active layer.
- the active layer of this embodiment has a bulk heterojunction structure.
- the thickness of the active layer is not particularly limited.
- the thickness of the active layer can be any suitable thickness, for example, considering the balance between suppression of dark current and extraction of the generated photocurrent.
- the thickness of the active layer is preferably 100 nm or more, more preferably 100 nm or more, and even more preferably 200 nm or more, particularly from the viewpoint of further reducing dark current.
- the thickness of the active layer is preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less, and still more preferably 600 nm or less.
- the photoelectric conversion device of the present embodiment includes, for example, a charge transport layer (electron transport layer, hole transport layer, electron injection layer, An intermediate layer (buffer layer) such as a hole injection layer is preferably provided.
- 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( 4-styrenesulfonate)) (PEDOT:PSS).
- metals such as calcium, inorganic oxide semiconductors such as molybdenum oxide and zinc oxide
- PEDOT poly(3,4-ethylenedioxythiophene)
- PSS poly( 4-styrenesulfonate)
- the intermediate layer can be formed by any suitable conventionally known forming method.
- the intermediate layer can be formed by a vacuum deposition method or a coating method similar to the method for forming the active layer.
- the photoelectric conversion element of this embodiment preferably has an electron transport layer between the first electrode and the active layer.
- the electron transport layer has a function of transporting electrons from the active layer to the electrode.
- the photoelectric conversion element may not have an electron transport layer.
- the electron transport layer provided in contact with the first electrode is sometimes called an electron injection layer.
- An electron transport layer (electron injection layer) provided in contact with the first electrode has a function of promoting injection of electrons into the first electrode.
- the electron transport layer (electron injection layer) may be in contact with the active layer.
- the electron-transporting layer contains an electron-transporting material.
- electron-transporting materials include polyalkyleneimine and derivatives thereof, high-molecular compounds having a fluorene structure, metals such as calcium, and metal oxides.
- polyalkyleneimines and derivatives thereof include alkyleneimine having 2 to 8 carbon atoms, especially alkyleneimine having 2 to 8 carbon atoms, such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, octyleneimine.
- alkyleneimine having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, octyleneimine.
- Polymers obtained by conventionally polymerizing one or more of 2 to 4 alkyleneimines, and polymers chemically modified by reacting them with various compounds can be mentioned.
- Preferred polyalkyleneimines and derivatives thereof are polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE).
- 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 perylene diimide.
- the intermediate layer is the electron transport layer
- the substrate supporting substrate
- the first electrode the electron transport layer
- the active layer the hole transport layer
- the second electrode are arranged in this order. It is preferred to have a configuration that is stacked against each other.
- the photoelectric conversion device of the present embodiment preferably has a hole transport layer as an intermediate layer between the second electrode and the active layer.
- the hole transport layer has a function of transporting holes from the active layer to the second electrode.
- the hole transport layer may be in contact with the second electrode.
- the hole transport layer may be in contact with the active layer.
- the photoelectric conversion element may not have a hole transport layer.
- the hole-transporting layer provided in contact with the second electrode is sometimes called a hole-injecting layer.
- a hole transport layer (hole injection layer) provided in contact with the second electrode has a function of promoting injection of holes generated in the active layer into the second electrode.
- the hole-transporting layer contains a hole-transporting material.
- hole-transporting materials include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing constitutional units having aromatic amine residues, CuSCN, CuI, NiO, tungsten oxide (WO 3 ) and molybdenum oxide. (MoO 3 ).
- the photoelectric conversion element of the present embodiment further includes a sealing member, and is a sealed body sealed with the sealing member.
- sealing member Any suitable conventionally known member can be used as the sealing member.
- the sealing member include a combination of a glass substrate as 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.
- layers constituting the sealing layer include gas barrier layers and gas barrier films.
- the sealing layer is preferably made of a material that has a property of blocking moisture (water vapor barrier property) or a property of blocking oxygen (oxygen barrier property).
- suitable materials for the sealing layer include polyethylene trifluoride, polytrifluoroethylene chloride (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, ethylene-vinyl alcohol copolymer, and the like.
- Examples include organic materials, inorganic materials such as silicon oxide, silicon nitride, aluminum oxide, and diamond-like carbon.
- the sealing member is usually made of a material that can withstand a heat treatment to which the photoelectric conversion element is applied, for example, when it is incorporated into a device of the application example described later.
- the photoelectric conversion element of the present embodiment can be manufactured by any suitable conventionally known manufacturing method.
- the photoelectric conversion element of the present embodiment may be manufactured by combining processes suitable for materials selected for forming constituent elements.
- a method for manufacturing a photoelectric conversion element having a configuration in which a substrate (supporting substrate), a first electrode, a hole transport layer, an active layer, an electron transport layer, and a second electrode are in contact with each other in this order. explain.
- a support substrate provided with a first electrode is prepared.
- a substrate provided with a conductive thin film formed of the electrode material already described is obtained from the market, and if necessary, the conductive thin film is patterned to form a first electrode, A support substrate provided with a first electrode can be prepared.
- the method for forming the first electrode is not particularly limited when the first electrode is formed on the support substrate.
- the first electrode is a structure in which the first electrode is formed by any suitable conventionally known method such as a vacuum deposition method, a sputtering method, an ion plating method, a plating method, a coating method, etc., using the material already described ( (e.g., supporting substrate, active layer, 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.
- a method for forming the hole transport layer is not particularly limited. From the viewpoint of simplifying the process of forming the hole transport layer, it is preferable to form the hole transport layer by any suitable conventionally known coating method.
- the hole transport layer can be formed, for example, by a coating method or a vacuum deposition method using a coating liquid containing a material capable of forming the hole transport layer and a solvent.
- the active layer is formed on the hole transport layer.
- the active layer can be formed by any suitable conventionally known formation process.
- the active layer can be produced by a coating method using the ink composition already described.
- the active layer can be formed in the same manner as the "solidified film" already described.
- An active layer can be formed by a process including a process.
- the method for manufacturing the photoelectric conversion element of this embodiment can include a step of forming an electron transport layer (electron injection layer) provided so as to be in contact with the active layer.
- an electron transport layer electron injection layer
- the method for forming the electron transport layer is not particularly limited. From the viewpoint of making the step of forming the electron transport layer simpler, it is preferable to form the electron transport layer by any suitable conventionally known vacuum vapor deposition method.
- a method for forming the second electrode is not particularly limited.
- the second electrode can be formed, for example, from the materials of the electrodes exemplified above by any suitable conventionally known method such as a coating method, a vacuum deposition method, a sputtering method, an ion plating method, and a plating method. Through the above steps, the photoelectric conversion element of this embodiment is manufactured.
- Step of forming sealing body In forming the sealing body, in the present embodiment, a conventionally known and suitable sealing material (adhesive) and substrate (sealing substrate) are used. Specifically, a sealing material such as a UV curable resin is applied to the support substrate so as to surround the manufactured photoelectric conversion element, and the sealing material is used to bond the substrate without any gaps.
- a photoelectric conversion element sealed body can be obtained by sealing the photoelectric conversion element in the gap between the support substrate and the sealing substrate using a method such as irradiation of UV light, which is suitable for the sealing material. can.
- Applications of Photoelectric Conversion Element include photodetection elements and solar cells.
- the photoelectric conversion element of the present embodiment allows a photocurrent to flow by irradiating light from the transparent or translucent electrode side while a voltage (reverse bias voltage) is applied between the electrodes. and can be operated as a photodetector (optical sensor). Also, it can be used as an image sensor by integrating a plurality of photodetectors.
- the photoelectric conversion element of this embodiment can be suitably used particularly as a photodetector.
- the photoelectric conversion element of the present embodiment can generate a photovoltaic force between 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 can be used as a photodetector in various electronic devices such as workstations, personal computers, personal digital assistants, entrance/exit management systems, digital cameras, and medical equipment. It can be suitably applied to the detection unit provided in the device.
- the photoelectric conversion element of the present embodiment is provided in the above-exemplified electronic device, for example, an image detection unit for a solid-state imaging device such as an X-ray imaging device and a CMOS image sensor (e.g., an image sensor such as an X-ray sensor), a fingerprint Detection units of biometric information authentication devices that detect predetermined features of a part of a living body, such as detection units, face detection units, vein detection units, and iris detection units (e.g., near-infrared sensors), and optical biosensors such as pulse oximeters. It can be suitably applied to a detection unit or the like.
- a CMOS image sensor e.g., an image sensor such as an X-ray sensor
- a fingerprint Detection units of biometric information authentication devices that detect predetermined features of a part of a living body, such as detection units, face detection units, vein detection units, and iris detection units (e.g., near-infrared sensors), and optical biosensor
- the photoelectric conversion element of this 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 measurement device (TOF type distance measurement device).
- TOF time-of-flight
- the TOF rangefinder measures the distance by causing the photoelectric conversion element to receive the light emitted from the light source and reflected by the object to be measured. Specifically, the distance to the object to be measured is obtained by detecting the time of flight until the irradiation light emitted from the light source is reflected by the object to be measured and returns as reflected light.
- the TOF type includes a direct TOF method and an indirect TOF method.
- the direct TOF method directly measures the difference between the time when the light is irradiated from the light source and the time when the reflected light is received by the photoelectric conversion element. to measure the distance.
- the distance measurement principle used in the indirect TOF method to obtain the time of flight by charge accumulation includes a continuous wave (especially sine wave) modulation method in which the time of flight is obtained from the phases of the light emitted from the light source and the reflected light reflected by the measurement target. and pulse modulation method.
- an image detection unit for a solid-state imaging device an image detection unit for an X-ray imaging device, a biometric authentication device (for example, a fingerprint authentication device, a vein Configuration examples of a fingerprint detection unit and a vein detection unit for an authentication device, etc., and an image detection unit of a TOF rangefinder (indirect TOF method) will be described with reference to the drawings.
- a biometric authentication device for example, a fingerprint authentication device, a vein Configuration examples of a fingerprint detection unit and a vein detection unit for an authentication device, etc.
- an image detection unit of a TOF rangefinder indirect TOF method
- FIG. 2 is a diagram schematically showing a configuration example of an image detection unit for a solid-state imaging device.
- the image detection unit 1 includes a CMOS transistor substrate 20, an interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20, and a photoelectric conversion element provided on the interlayer insulating film 30 according to the embodiment of the present invention. It is provided so as to penetrate the element 10 and the interlayer insulating film 30 , and is provided so as to cover the photoelectric conversion element 10 and the interlayer wiring part 32 electrically connecting the CMOS transistor substrate 20 and the photoelectric conversion element 10 . and a color filter 50 provided on the sealing layer 40 .
- the CMOS transistor substrate 20 has a conventionally well-known arbitrary and suitable configuration in accordance with the design.
- the CMOS transistor substrate 20 includes functional elements such as CMOS transistor circuits (MOS transistor circuits) for realizing various functions, including transistors and capacitors formed within the thickness of the substrate.
- MOS transistor circuits CMOS transistor circuits
- Functional elements include, for example, floating diffusions, reset transistors, output transistors, and selection transistors.
- a signal readout circuit and the like are built into the CMOS transistor substrate 20 with such functional elements, wiring, and the like.
- the interlayer insulating film 30 can be made of any suitable conventionally known insulating material such as silicon oxide and insulating resin.
- the interlayer wiring section 32 can be made of any suitable conventionally known conductive material (wiring material) such as copper and tungsten.
- the interlayer wiring portion 32 may be, for example, an in-hole wiring formed simultaneously with the formation of the wiring layer, or an embedded plug formed separately from the wiring layer.
- the sealing layer 40 may be made of any suitable conventionally known material on the condition that it can prevent or suppress permeation of harmful substances such as oxygen and water that may functionally deteriorate the photoelectric conversion element 10. can be done.
- the sealing layer 40 can have the same configuration as the sealing member 17 already described.
- the color filter 50 for example, a primary color filter made of any conventionally known suitable material and corresponding 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 be used. As complementary color filters, for example, three types of (yellow, cyan, magenta), three types of (yellow, cyan, transparent), three types of (yellow, transparent, magenta), and three types of (transparent, cyan, magenta) A combination of types of color filters can be used. These can be arranged in any suitable arrangement corresponding to the design of the photoelectric conversion element 10 and the CMOS transistor substrate 20 on the condition that color image data can be generated.
- the light received by the photoelectric conversion element 10 through the color filter 50 is converted by the photoelectric conversion element 10 into an electric signal corresponding to the amount of light received, and is output as a light reception signal, that is, the object to be imaged, to the outside of the photoelectric conversion element 10 through the electrodes. is output as an electrical signal corresponding to
- the received light signal output from the photoelectric conversion element 10 is input to the CMOS transistor substrate 20 via the interlayer wiring portion 32, read by a signal readout circuit built into the CMOS transistor substrate 20, and further Image information based on the object to be imaged is generated by performing signal processing by an arbitrary 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. 200.
- the fingerprint detection section 100 is provided in an area that matches the display area 200a of the display panel section 200 .
- the display panel section 200 is integrally laminated above the fingerprint detection section 100 .
- the fingerprint detection section 100 may be provided so as to correspond only to the partial area.
- 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 essential functions.
- the fingerprint detection unit 100 includes any suitable conventionally known members such as a protection film (not shown), a support substrate, a sealing substrate, a sealing member, a barrier film, a bandpass filter, and an infrared cut film. It may be provided in a manner corresponding to the design to obtain the properties.
- the fingerprint detection unit 100 may adopt the configuration of the image detection unit already described.
- the photoelectric conversion element 10 can be included in any manner within the display area 200a.
- 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 electrodes or second electrodes), for example, in a matrix.
- the light received by the photoelectric conversion element 10 is converted by the photoelectric conversion element 10 into an electrical signal corresponding to the amount of received light, and the received light signal, that is, the electricity corresponding to the imaged fingerprint, is output outside the photoelectric conversion element 10 via the electrodes. output as a signal.
- the display panel section 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, a display panel having an arbitrary and suitable conventionally known configuration such as a liquid crystal display panel including a light source such as a backlight, instead of the organic EL display panel.
- the display panel section 200 is provided on the fingerprint detection section 100 already described.
- the display panel section 200 includes an organic electroluminescence element (organic EL element) 220 as a functional section that performs an essential function.
- the display panel unit 200 further includes an arbitrary and suitable substrate such as a conventionally known glass substrate (support substrate 210 or sealing substrate 240), a sealing member, a barrier film, a polarizing plate such as a circularly polarizing plate, and an arbitrary substrate such as a touch sensor panel 230.
- Suitable conventionally known members may be provided in a manner corresponding to the desired properties.
- the organic EL element 220 is used as a light source for the pixels in the display area 200a, and is also used as a light source for imaging the fingerprint in the fingerprint detection section 100.
- the fingerprint detection unit 100 detects the fingerprint using 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 the constituent elements existing between the organic EL element 220 and the photoelectric conversion element 10 of the fingerprint detection unit 100, and the display in the display area 200a is displayed. The light is reflected by the skin (finger surface) of the fingertip placed in contact with the surface of the panel section 200 . At least part of the light reflected by the finger surface is transmitted through intervening components and received by the photoelectric conversion element 10 , and converted into an electrical signal corresponding to the amount of light received by the photoelectric conversion element 10 . Image information about the fingerprint on the surface of the finger is constructed from the converted electric signal.
- the mobile information terminal equipped with the display device 2 performs fingerprint authentication by comparing the obtained image information with pre-recorded fingerprint data for fingerprint authentication by any suitable conventionally known step.
- FIG. 4 is a diagram schematically showing a configuration example of an image detection unit for an X-ray imaging apparatus.
- An image detection unit 1 for an X-ray imaging device includes a CMOS transistor substrate 20, an interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20, and an interlayer insulating film 30 provided on the interlayer insulating film 30.
- a photoelectric conversion element 10 according to the embodiment; , a scintillator 42 provided on the sealing layer 40, a reflective layer 44 provided to cover the scintillator 42, and a reflective layer 44 provided to cover the and a protective layer 46 having a
- the CMOS transistor substrate 20 has a conventionally well-known arbitrary and suitable configuration in accordance with the design.
- the CMOS transistor substrate 20 includes functional elements such as CMOS transistor circuits (MOS transistor circuits) for realizing various functions, including transistors and capacitors formed within the thickness of the substrate.
- MOS transistor circuits CMOS transistor circuits
- Functional elements include, for example, floating diffusions, reset transistors, output transistors, and selection transistors.
- a signal readout circuit and the like are built into the CMOS transistor substrate 20 with such functional elements, wiring, and the like.
- the interlayer insulating film 30 can be made of any suitable conventionally known insulating material such as silicon oxide and insulating resin.
- the interlayer wiring section 32 can be made of any suitable conventionally known conductive material (wiring material) such as copper and tungsten.
- the interlayer wiring portion 32 may be, for example, an in-hole wiring formed simultaneously with the formation of the wiring layer, or an embedded plug formed separately from the wiring layer.
- the sealing layer 40 may be made of any suitable conventionally known material on the condition that it can prevent or suppress permeation of harmful substances such as oxygen and water that may functionally deteriorate the photoelectric conversion element 10. can be done.
- the sealing layer 40 can have the same configuration as the sealing member 17 already described.
- the scintillator 42 can be made of any conventionally known suitable material that corresponds to the design of the image detection section 1 for the X-ray imaging apparatus.
- suitable materials for the scintillator 42 include inorganic crystals of inorganic materials such as CsI (cesium iodide), NaI (sodium iodide), ZnS (zinc sulfide), GOS (gadolinium oxysulfide), and GSO (gadolinium silicate).
- organic crystals of organic materials such as anthracene, naphthalene, and stilbene
- organic liquids obtained by dissolving organic materials such as diphenyloxazole (PPO) and terphenyl (TP) in organic solvents such as toluene, xylene, and dioxane
- organic materials such as xenon and helium. Gases, plastics, 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 scintillator 42 converts incident X-rays into light having a wavelength centered in the visible region to generate image data. Any suitable arrangement can be used.
- 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 detection sensitivity.
- the reflective layer 44 can also block light that is directly incident from the outside.
- the protective layer 46 can be made of any suitable conventionally known material on the condition that it can prevent or suppress permeation of harmful substances such as oxygen and water that may functionally deteriorate the scintillator 42.
- 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) with a wavelength in the infrared range from ultraviolet, centered on the visible range. 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 by the photoelectric conversion element 10 into an electric signal corresponding to the amount of light received, and the received light signal is output outside the photoelectric conversion element 10 via the electrodes. That is, it is output as an electrical signal corresponding to the object to be imaged.
- Radiation energy (X-rays) to be detected may be incident from either the scintillator 42 side or the photoelectric conversion element 10 side.
- the received light signal output from the photoelectric conversion element 10 is input to the CMOS transistor substrate 20 via the interlayer wiring portion 32, read by a signal readout circuit built into the CMOS transistor substrate 20, and further Image information based on the object to be imaged is generated by performing signal processing by an arbitrary suitable conventionally known functional unit.
- FIG. 5 is a diagram schematically showing a configuration example of a vein detection unit for the vein authentication device.
- the vein detection unit 300 for the vein authentication device includes a cover unit 306 defining an insertion unit 310 into which a finger to be measured (eg, one or more fingertips, fingers and palm) is inserted during measurement, and a cover unit 306 .
- a light source unit 304 provided in a unit 306 for irradiating light onto an object to be measured, a photoelectric conversion element 10 for receiving the light emitted from the light source unit 304 through the object to be measured, and a support for supporting the photoelectric conversion element 10 .
- the glass substrate 302 is arranged so as to face the substrate 11 and the support substrate 11 with the photoelectric conversion element 10 interposed therebetween, is separated from the cover portion 306 at a predetermined distance, and defines the insertion portion 306 together with the cover portion 306 .
- the light source unit 304 is configured integrally with the cover unit 306 so that the photoelectric conversion element 10 is separated from the photoelectric conversion element 10 while sandwiching the object to be measured during use.
- the light source unit 304 is not necessarily positioned on the cover unit 306 side.
- the object to be measured can be efficiently irradiated with the light from the light source unit 304, for example, a reflection imaging method in which the object to be measured is irradiated from the photoelectric conversion element 10 side may be employed.
- 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 essential functions.
- the vein detection unit 300 includes any suitable conventionally known member such as a protection film (not shown), a sealing member, a barrier film, a bandpass filter, a near-infrared transmission filter, a visible light cut film, and a finger placement guide. can be provided in a manner corresponding to the design to obtain the desired properties.
- the vein detection unit 300 may employ the configuration of the image detection unit 1 already described.
- the photoelectric conversion element 10 can be included 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 electrodes or second electrodes), for example, in a matrix.
- the light received by the photoelectric conversion element 10 is converted by the photoelectric conversion element 10 into an electrical signal corresponding to the amount of light received, and the received light signal, that is, the electricity corresponding to the imaged vein, is output outside the photoelectric conversion element 10 via the electrodes. output as a signal.
- the object to be measured 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 using light emitted from the light source unit 304 . Specifically, the light emitted from the light source unit 304 is transmitted through the measurement target and converted into an electrical signal corresponding to the amount of light received by the photoelectric conversion element 10 . Image information of the vein pattern to be measured is constructed from the converted electrical signal.
- vein authentication is performed by comparing the obtained image information with previously recorded vein data for vein authentication by any suitable conventionally known step.
- FIG. 6 is a diagram schematically showing a configuration example of an image detection unit for an indirect TOF rangefinder.
- the image detection unit 400 for the TOF type distance measuring device includes a CMOS transistor substrate 20, an interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20, and an interlayer insulating film 30 provided on the interlayer insulating film 30.
- the photoelectric conversion element 10 according to the embodiment, the two floating diffusion layers 402 spaced apart to sandwich the photoelectric conversion element 10, and the photoelectric conversion element 10 and the floating diffusion layer 402 are provided to cover the photoelectric conversion element 10. It comprises an insulating layer 40 and two photogates 404 provided on the insulating layer 40 and spaced apart from each other.
- a part of the insulating layer 40 is exposed from the gap between the two photogates 404 separated from each other, and the remaining area is shielded from light 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 .
- the interlayer insulating film 30 can be made of any suitable conventionally known insulating material such as silicon oxide and insulating resin.
- the interlayer wiring section 32 can be made of any suitable conventionally known conductive material (wiring material) such as copper and tungsten.
- the interlayer wiring portion 32 may be, for example, an in-hole wiring formed simultaneously with the formation of the wiring layer, or an embedded plug formed separately from the wiring layer.
- the insulating layer 40 in this configuration example may have any conventionally known and suitable configuration such as a field oxide film made of silicon oxide.
- the photogate 404 can be made of any suitable conventionally known material such as polysilicon.
- the image detection section 400 for the TOF type rangefinder includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional section that performs essential functions.
- the image detector 400 for the TOF-type rangefinder uses any suitable conventional film such as a protection film (not shown), a support substrate, a sealing substrate, a sealing member, a barrier film, a bandpass filter, an infrared cut film, and the like.
- Known components may be provided in a manner corresponding to the design to obtain the desired properties.
- Two photogates 404 are provided between the photoelectric conversion element 10 and the floating diffusion layer 402 , and by alternately applying pulses, signal charges generated by the photoelectric conversion element 10 are transferred to the two floating diffusion layers 402 . The charge is transferred to either one and accumulated in the floating diffusion layer 402 .
- the light pulse arrives so as to equally straddle the timing of opening the two photogates 404, the amount of charge accumulated in the two floating diffusion layers 402 becomes equal. If the light pulse arrives at the other photogate 404 with a delay with respect to the timing at which the light pulse arrives at the one photogate 404, the amount of charge accumulated in the two floating diffusion layers 402 will differ.
- the difference in the amount of charge accumulated in the floating diffusion layer 402 depends on the delay time of the light pulse.
- the amount of light received by the photoelectric conversion element 10 is converted into an electrical signal as the difference between the amounts of charge accumulated in the two floating diffusion layers 402, and the received light signal, that is, the electricity corresponding to the object to be measured, is output outside the photoelectric conversion element 10. output as a signal.
- the received light signal output from the floating diffusion layer 402 is input to the CMOS transistor substrate 20 via the interlayer wiring portion 32, read by a signal readout circuit built into the CMOS transistor substrate 20, and read out by a signal readout circuit (not shown).
- Distance information based on the measurement object is generated through signal processing by an arbitrary suitable conventionally known functional unit.
- the photoelectric conversion element of the present embodiment can have a photodetection function capable of converting irradiated light into an electric signal corresponding to the amount of received light and outputting the signal to an external circuit via an electrode. . Therefore, the photoelectric conversion element according to the embodiment of the present invention can be particularly suitably applied as a photodetector having a photodetection function.
- the photodetector element of this embodiment may be a photoelectric conversion element itself, or may further include a functional element for voltage control in addition to the photoelectric conversion element.
- PCE-10 1-material company's trade name: PCE-10 was obtained from the market and used.
- DiPDI 1-material company's trade name: DiPDI was obtained from the market and used.
- the z-average molecular weight (Mz) and weight-average molecular weight (Mw) of the p-type semiconductor material are determined by gel permeation chromatography (GPC) (manufactured by Shimadzu Corporation, LC-20AT) to determine the z-average molecular weight (Mz) and weight in terms of polystyrene. It was determined as an average molecular weight (Mw).
- GPC gel permeation chromatography
- o-Dichlorobenzene was used as the mobile phase for GPC, and flowed at a flow rate of 1.0 mL/min.
- Shodex KD-806M manufactured by Showa Denko KK was used, and as the guard column, Shodex KD-G manufactured by Showa Denko KK was used.
- UV-vis detector Shiadzu Corporation, SPD-M20A
- a differential refractive index detector Shiadzu Corporation, RID-10A
- the compound (polymer) to be measured was mixed with 1-chloronaphthalene as a solvent so as to have a concentration of 0.05% by mass, and stirred at 80°C for 2 hours to obtain a solution. .
- Example 1 [Preparation of ink composition] To 1,2,3,4-tetrahydronaphthalene, material P-1 as a p-type semiconductor material, material N as an n-type semiconductor material to be 0.8% by weight with respect to the total weight of the ink composition. -1 was mixed so as to be 1.6% by mass with respect to the mass of the ink composition, and the mixture was stirred at 60° C. for 6 hours to obtain an ink composition (I-1).
- Examples 2 to 6 and Comparative Example 1 An ink composition was prepared and filtered in the same manner as in Example 1, except that material P-1 having a z-average molecular weight (Mz) and a weight-average molecular weight (Mw) shown in Table 3 below was used as the p-type semiconductor material. A test was conducted. The results are also shown in Table 3 below.
- Mz z-average molecular weight
- Mw weight-average molecular weight
- Example 7 [Ink composition]
- the material P-1 is used as the p-type semiconductor material, the material P-1 is 2.0% by mass with respect to the total mass of the ink composition, and the material N-1 is used as the n-type semiconductor material in the ink composition.
- Ink composition (I-8) was prepared in the same manner as in Example 1, except that it was mixed so as to be 1.0% by mass with respect to the total mass of .
- Example 8 and Comparative Example 2 A material P-1 having a z-average molecular weight (Mz) and a weight-average molecular weight (Mw) shown in Table 3 below is used as a p-type semiconductor material, and the material P-1 is 1% by mass with respect to the total mass of the ink composition.
- Material N-2 is used as the n-type semiconductor material, and o-xylene (97% by mass) is used as a solvent so that the material N-2 is 0.3% by mass relative to the total mass of the ink composition.
- acetophenone 3% by mass were mixed in the same manner as in Example 1, except that ink compositions (I-9) and (I-10) were prepared and filtered. A test was conducted. The results are shown in Table 5 below.
- Example 9 and Comparative Example 3 A material P-1 having a z-average molecular weight (Mz) and a weight-average molecular weight (Mw) shown in Table 4 below is used as a p-type semiconductor material, and the material P-1 is 1.0 mass with respect to the total mass of the ink composition. %, using material N-3 as an n-type semiconductor material, and using o-dichlorobenzene as a solvent so that material N-3 is 1.0% by mass with respect to the total mass of the ink composition. Inks (I-11) and (I-12) were prepared in the same manner as in Example 1, except that they were mixed together, and a filterability test was conducted. The results are shown in Table 6 below.
- Example 10 and Comparative Example 4 A material P-2 having a z-average molecular weight (Mz) and a weight-average molecular weight (Mw) shown in Table 4 below is used as a p-type semiconductor material, and the material P-2 is 0.8 mass with respect to the total mass of the ink composition.
- Ink compositions (I-13) and (I-14) were prepared in the same manner as in Example 1, except that they were mixed so that the ratio was 1%, and a filterability test was conducted. The results are shown in Table 7 below.
- the filterability of the ink composition cannot be controlled by the weight average molecular weight (Mw), and the type of n-type semiconductor material used in the ink composition, the solvent
- Mw weight average molecular weight
- Mz z-average molecular weight
- the dried glass substrate is washed with water, the washed glass substrate is placed on a hot plate, and the coating film on the cathode is dried under the conditions of 100° C. for 10 minutes in the atmosphere to form the coating film as an electron transport layer.
- the ink composition (I-1) according to Example 1 was applied onto the electron transport layer by slot die coating to form a coating film, followed by vacuum drying (pressure 10 Pa, 70° C.) for 5 hours. minutes, and the coating film was used as an active layer.
- the glass substrate with the active layer formed thereon was placed on a hot plate, and the active layer was dried at 100° C. for 12 minutes.
- the thickness of the active layer after drying was 200 nm.
- Example 12 to 14> A photoelectric conversion device was produced in the same manner as in Example 11, except that ink composition I-2 was used as the material for the active layer, and EQE was determined. Table 8 shows the results.
- photoelectric conversion elements using ink compositions I-1 and I-2 as active layer materials functioned without problems.
- photoelectric conversion elements using ink compositions I-3 and I-4 in which the weight average molecular weight of the p-type semiconductor material is greater than 6.0 ⁇ 10 4 as the material for the active layer, can obtain a higher EQE. was confirmed.
- REFERENCE SIGNS LIST 1 image detection unit 2 display device 10 photoelectric conversion element 11, 210 support substrate 12 first electrode 13 electron transport layer 14 active layer 15 hole transport layer 16 second electrode 17 sealing member 20 CMOS transistor substrate 30 interlayer insulating film 32 Interlayer Wiring Section 40 Sealing Layer 42 Scintillator 44 Reflective Layer 46 Protective Layer 50 Color Filter 100 Fingerprint Detection Section 200 Display Panel Section 200a Display Area 220 Organic EL Element 230 Touch Sensor Panel 240 Sealing Substrate 300 Vein Detection Section 302 Glass Substrate 304 Light source unit 306 Cover unit 310 Insertion unit 400 Image detection unit for TOF rangefinder 402 Floating diffusion layer 404 Photogate 406 Light shielding unit
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Abstract
Provided is an ink composition which requires no trial and error to make it possible to more reliably carry out filtration without clogging a filter in a production step and which is unlikely to cause an electrical defect such as electrical insulation or a short circuit. Also provided is a method for producing an ink composition which makes it possible to more improve the efficiency of producing an ink composition and the efficiency of producing a photoelectric conversion element. An ink composition for producing a photoelectric conversion element comprises a p-type semiconductor material, an n-type semiconductor material, and a solvent, wherein the p-type semiconductor material contains a polymer compound which has a z average molecular weight of less than 5.0×105. The p-type semiconductor material preferably contains a polymer compound which has a weight-average molecular weight of more than 6.0×104.
Description
本発明は、光電変換素子の機能層を形成するためのインク組成物及びその製造方法に関する。
The present invention relates to an ink composition for forming a functional layer of a photoelectric conversion element and a method for producing the same.
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デバイスであり、注目されている。
Photoelectric conversion elements are attracting attention as they are extremely useful devices, for example, from the viewpoint of energy saving and reduction of carbon dioxide emissions.
光電変換素子、例えば光検出素子(OPD)の製造にあたっては、光電変換素子製造用のインク組成物を塗布対象に塗工する塗布法により、活性層、電子輸送層、正孔輸送層などの機能層を形成する製造方法が適用されることが知られている(非特許文献1参照。)。
In the production of a photoelectric conversion element, for example, a photodetector (OPD), the functions of an active layer, an electron transport layer, a hole transport layer, etc. are obtained by a coating method of applying an ink composition for manufacturing a photoelectric conversion element to an object to be coated. It is known that a manufacturing method for forming layers is applied (see Non-Patent Document 1).
インク組成物を用いて塗布法により機能層が形成される光電変換素子において、例えばバルクヘテロ接合型の活性層を形成する場合には、活性層形成用のインク組成物には、通常、p型半導体材料とn型半導体材料と溶媒が含まれる。このようなインク組成物は、異物が混入してしまうと当該インク組成物を用いて形成された活性層において絶縁、短絡といった電気的な欠陥の原因となってしまうおそれがある。よって、インク組成物の製造時において、p型半導体材料とn型半導体材料を溶媒へ溶解させた後、所定の孔径を有するフィルターによりろ過する処理を行うのが通常である。
In a photoelectric conversion element in which a functional layer is formed by a coating method using an ink composition, for example, when a bulk heterojunction active layer is formed, the ink composition for forming the active layer usually contains a p-type semiconductor. Materials and n-type semiconductor materials and solvents are included. Such an ink composition may cause electrical defects such as insulation and short circuits in the active layer formed using the ink composition if foreign matter is mixed therein. Therefore, during the production of the ink composition, it is common to dissolve the p-type semiconductor material and the n-type semiconductor material in a solvent, and then filter the solution through a filter having a predetermined pore size.
しかしながら、上記従来のインク組成物においては、p型半導体材料及び/又はn型半導体材料の選択によっては、ろ過の際にフィルターが閉塞してしまい、そもそもろ過を行うことができず、光電変換素子を製造することができなくなってしまう場合もあった。
However, in the above-described conventional ink composition, depending on the selection of the p-type semiconductor material and/or the n-type semiconductor material, the filter may be clogged during filtration, making it impossible to perform filtration in the first place. In some cases, it became impossible to manufacture
本発明者らは、上記課題を解決すべく鋭意研究を進めたところ、フィルターを閉塞させるインク組成物中の成分にp型半導体材料の超高分子量成分が含まれていることを見出した。しかしながら、当該超高分子量成分は、インク組成物中に極少量しか含まれておらず、調製されたインク組成物から取り除くことは極めて難しい。そこで、本発明者らは、原料として用いるp型半導体材料の超高分子量成分の含有量を一定以下に管理し、インク組成物に含まれるp型半導体材料のz平均分子量を所定の範囲とすれば、上記課題を解決できることを見出し、本発明を完成するに至った。
The inventors of the present invention conducted extensive research to solve the above problems, and discovered that the component in the ink composition that clogs the filter contains an ultra-high molecular weight component of a p-type semiconductor material. However, the ultra-high molecular weight component is contained in the ink composition in only a very small amount, and is extremely difficult to remove from the prepared ink composition. Therefore, the present inventors managed the content of the ultra-high molecular weight component in the p-type semiconductor material used as a raw material to be below a certain level, and kept the z-average molecular weight of the p-type semiconductor material contained in the ink composition within a predetermined range. In other words, the inventors have found that the above problems can be solved, and have completed the present invention.
よって、本発明は、下記[1]~[9]を提供する。
[1] p型半導体材料と、n型半導体材料と、溶媒とを含むインク組成物であって、該p型半導体材料が、z平均分子量が5.0×105未満である高分子化合物を含む、光電変換素子製造用のインク組成物。
[2] 前記p型半導体材料が、重量平均分子量が6.0×104よりも大きい高分子化合物を含む、[1]に記載の光電変換素子製造用のインク組成物。
[3] 前記p型半導体材料が、チオフェン骨格を有する構成単位を含む高分子化合物を含む、[1]又は[2]に記載の光電変換素子製造用のインク組成物。
[4] 前記p型半導体材料が、ドナー・アクセプター構造を有する高分子化合物を含む、[3]に記載の光電変換素子製造用のインク組成物。
[5] 前記溶媒が、芳香族炭化水素を含む、[1]~[4]のいずれか1つに記載の光電変換素子製造用のインク組成物。
[6] 前記n型半導体材料が、フラーレン誘導体を含む、[1]~[5]のいずれか1つに記載の光電変換素子製造用のインク組成物。
[7] 前記n型半導体材料が、非フラーレン化合物を含む、[1]~[5]のいずれか1つに記載の光電変換素子製造用のインク組成物。
[8] [1]~[7]のいずれか1つに記載のインク組成物の製造方法において、該インク組成物が、孔径0.5μm以下のフィルターでろ過される工程を含む、光電変換素子製造用のインク組成物の製造方法。
[9] p型半導体材料である複数種類の高分子化合物を準備する準備工程と、
前記準備工程で準備した前記高分子化合物のうち、z平均分子量が5.0×105未満である高分子化合物をp型半導体材料として選別する選別工程と、
前記選別工程で選別されたp型半導体材料とn型半導体材料と溶媒とを混合して、インク組成物を製造する工程と、
を含む、光電変換素子製造用のインク組成物の製造方法。 Accordingly, the present invention provides the following [1] to [9].
[1] An ink composition comprising a p-type semiconductor material, an n-type semiconductor material, and a solvent, wherein the p-type semiconductor material is a polymer compound having a z-average molecular weight of less than 5.0×10 5 . An ink composition for producing a photoelectric conversion element, comprising:
[2] The ink composition for producing a photoelectric conversion element according to [1], wherein the p-type semiconductor material contains a polymer compound having a weight average molecular weight of more than 6.0×10 4 .
[3] The ink composition for producing a photoelectric conversion element according to [1] or [2], wherein the p-type semiconductor material contains a polymer compound containing a structural unit having a thiophene skeleton.
[4] The ink composition for producing a photoelectric conversion element according to [3], wherein the p-type semiconductor material contains a polymer compound having a donor-acceptor structure.
[5] The ink composition for producing a photoelectric conversion element according to any one of [1] to [4], wherein the solvent contains an aromatic hydrocarbon.
[6] The ink composition for producing a photoelectric conversion element according to any one of [1] to [5], wherein the n-type semiconductor material contains a fullerene derivative.
[7] The ink composition for producing a photoelectric conversion element according to any one of [1] to [5], wherein the n-type semiconductor material contains a non-fullerene compound.
[8] In the method for producing the ink composition according to any one of [1] to [7], a photoelectric conversion element including a step of filtering the ink composition through a filter having a pore size of 0.5 μm or less. A method of making an ink composition for manufacturing.
[9] a preparatory step of preparing a plurality of types of polymer compounds that are p-type semiconductor materials;
a selecting step of selecting polymer compounds having a z-average molecular weight of less than 5.0×10 5 among the polymer compounds prepared in the preparing step as p-type semiconductor materials;
mixing the p-type semiconductor material, the n-type semiconductor material, and the solvent selected in the selecting step to produce an ink composition;
A method for producing an ink composition for producing a photoelectric conversion element, comprising:
[1] p型半導体材料と、n型半導体材料と、溶媒とを含むインク組成物であって、該p型半導体材料が、z平均分子量が5.0×105未満である高分子化合物を含む、光電変換素子製造用のインク組成物。
[2] 前記p型半導体材料が、重量平均分子量が6.0×104よりも大きい高分子化合物を含む、[1]に記載の光電変換素子製造用のインク組成物。
[3] 前記p型半導体材料が、チオフェン骨格を有する構成単位を含む高分子化合物を含む、[1]又は[2]に記載の光電変換素子製造用のインク組成物。
[4] 前記p型半導体材料が、ドナー・アクセプター構造を有する高分子化合物を含む、[3]に記載の光電変換素子製造用のインク組成物。
[5] 前記溶媒が、芳香族炭化水素を含む、[1]~[4]のいずれか1つに記載の光電変換素子製造用のインク組成物。
[6] 前記n型半導体材料が、フラーレン誘導体を含む、[1]~[5]のいずれか1つに記載の光電変換素子製造用のインク組成物。
[7] 前記n型半導体材料が、非フラーレン化合物を含む、[1]~[5]のいずれか1つに記載の光電変換素子製造用のインク組成物。
[8] [1]~[7]のいずれか1つに記載のインク組成物の製造方法において、該インク組成物が、孔径0.5μm以下のフィルターでろ過される工程を含む、光電変換素子製造用のインク組成物の製造方法。
[9] p型半導体材料である複数種類の高分子化合物を準備する準備工程と、
前記準備工程で準備した前記高分子化合物のうち、z平均分子量が5.0×105未満である高分子化合物をp型半導体材料として選別する選別工程と、
前記選別工程で選別されたp型半導体材料とn型半導体材料と溶媒とを混合して、インク組成物を製造する工程と、
を含む、光電変換素子製造用のインク組成物の製造方法。 Accordingly, the present invention provides the following [1] to [9].
[1] An ink composition comprising a p-type semiconductor material, an n-type semiconductor material, and a solvent, wherein the p-type semiconductor material is a polymer compound having a z-average molecular weight of less than 5.0×10 5 . An ink composition for producing a photoelectric conversion element, comprising:
[2] The ink composition for producing a photoelectric conversion element according to [1], wherein the p-type semiconductor material contains a polymer compound having a weight average molecular weight of more than 6.0×10 4 .
[3] The ink composition for producing a photoelectric conversion element according to [1] or [2], wherein the p-type semiconductor material contains a polymer compound containing a structural unit having a thiophene skeleton.
[4] The ink composition for producing a photoelectric conversion element according to [3], wherein the p-type semiconductor material contains a polymer compound having a donor-acceptor structure.
[5] The ink composition for producing a photoelectric conversion element according to any one of [1] to [4], wherein the solvent contains an aromatic hydrocarbon.
[6] The ink composition for producing a photoelectric conversion element according to any one of [1] to [5], wherein the n-type semiconductor material contains a fullerene derivative.
[7] The ink composition for producing a photoelectric conversion element according to any one of [1] to [5], wherein the n-type semiconductor material contains a non-fullerene compound.
[8] In the method for producing the ink composition according to any one of [1] to [7], a photoelectric conversion element including a step of filtering the ink composition through a filter having a pore size of 0.5 μm or less. A method of making an ink composition for manufacturing.
[9] a preparatory step of preparing a plurality of types of polymer compounds that are p-type semiconductor materials;
a selecting step of selecting polymer compounds having a z-average molecular weight of less than 5.0×10 5 among the polymer compounds prepared in the preparing step as p-type semiconductor materials;
mixing the p-type semiconductor material, the n-type semiconductor material, and the solvent selected in the selecting step to produce an ink composition;
A method for producing an ink composition for producing a photoelectric conversion element, comprising:
本発明によれば、試行錯誤を要せずに、製造工程においてフィルターを閉塞させることなく、より確実にろ過を行うことができ、絶縁、短絡といった電気的な欠陥を生じさせにくいインク組成物、さらにはインク組成物の製造効率、ひいては光電変換素子の製造効率をより向上させることができるインク組成物の製造方法が提供される。
According to the present invention, the ink composition can be filtered more reliably without clogging the filter in the manufacturing process without trial and error, and is less likely to cause electrical defects such as insulation and short circuits. Furthermore, a method for producing an ink composition is provided that can further improve the production efficiency of the ink composition and, in turn, the production efficiency of the photoelectric conversion element.
以下、図面を参照して、本発明の実施形態について説明する。なお、図面は、発明が理解できる程度に、構成要素の形状、大きさ及び配置が概略的に示されているに過ぎない。
本発明は以下の記述によって限定されるものではなく、各構成要素は本発明の要旨を逸脱しない範囲において適宜変更可能である。以下の説明に用いる図面において、同様の構成要素については同一の符号を付して示し、重複する説明については省略する場合がある。
また、本発明の実施形態にかかる構成は、必ずしも図示例の配置で使用されるとは限らない。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. It should be noted that the drawings only schematically show the shape, size and arrangement of the constituent elements to the extent that the invention can be understood.
The present invention is not limited by the following description, and each component can be changed as appropriate without departing from the gist of the present invention. In the drawings used for the following description, the same components are denoted by the same reference numerals, and redundant description may be omitted.
Also, the configuration according to the embodiment of the present invention is not necessarily used in the illustrated arrangement.
本発明は以下の記述によって限定されるものではなく、各構成要素は本発明の要旨を逸脱しない範囲において適宜変更可能である。以下の説明に用いる図面において、同様の構成要素については同一の符号を付して示し、重複する説明については省略する場合がある。
また、本発明の実施形態にかかる構成は、必ずしも図示例の配置で使用されるとは限らない。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. It should be noted that the drawings only schematically show the shape, size and arrangement of the constituent elements to the extent that the invention can be understood.
The present invention is not limited by the following description, and each component can be changed as appropriate without departing from the gist of the present invention. In the drawings used for the following description, the same components are denoted by the same reference numerals, and redundant description may be omitted.
Also, the configuration according to the embodiment of the present invention is not necessarily used in the illustrated arrangement.
1.共通する用語の説明
本明細書において、「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。高分子化合物に含まれる構成単位は、合計100モル%である。 1. Explanation of Common Terms As used herein, the term “polymer compound” means a polymer having a molecular weight distribution and a polystyrene-equivalent number average molecular weight of 1×10 3 or more and 1×10 8 or less. The constituent units contained in the polymer compound are 100 mol % in total.
本明細書において、「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。高分子化合物に含まれる構成単位は、合計100モル%である。 1. Explanation of Common Terms As used herein, the term “polymer compound” means a polymer having a molecular weight distribution and a polystyrene-equivalent number average molecular weight of 1×10 3 or more and 1×10 8 or less. The constituent units contained in the polymer compound are 100 mol % in total.
本明細書において、「構成単位」とは、高分子化合物中に1個以上存在する単位であって単量体化合物(モノマー)に由来する単位を意味する。
As used herein, the term "constituent unit" means a unit that exists at least one in a polymer compound and is derived from a monomer compound (monomer).
本明細書において、「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。
As used herein, the "hydrogen atom" may be either a hydrogen atom or a deuterium atom.
本明細書において、「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。
As used herein, 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 "optionally substituted" aspect, when all hydrogen atoms constituting the compound or group are unsubstituted, and when one or more hydrogen atoms are partially or entirely substituted by a substituent Both aspects 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 atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, cycloalkynyl groups, alkyloxy groups, cycloalkyloxy groups, alkylthio groups, cycloalkylthio groups, aryl groups, aryloxy groups, arylthio groups, monovalent heterocyclic groups, substituted amino groups, acyl groups, imine residues, amide groups, acid imide groups, substituted oxycarbonyl groups, cyano groups, alkylsulfonyl groups, and nitro groups. .
本明細書において、「アルキル基」は置換基を有していてもよい。「アルキル基」は、特に断らない限り、直鎖状、分岐状、及び環状のいずれであってもよい。直鎖状のアルキ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1~50であり、好ましくは1~30であり、より好ましくは1~20である。分岐状又は環状であるアルキ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3~50であり、好ましくは3~30であり、より好ましくは4~20である。
In this specification, the "alkyl group" may have a substituent. An "alkyl group" may be linear, branched, or cyclic, unless otherwise specified. The number of carbon atoms in the linear alkyl group is generally 1-50, preferably 1-30, more preferably 1-20, not including the number of carbon atoms in the substituents. The number of carbon atoms in the branched or cyclic alkyl group is usually 3 to 50, preferably 3 to 30, more preferably 4 to 20, not including the number of carbon atoms in substituents.
アルキル基の具体例としては、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、イソアミル基、2-エチルブチル基、n-ヘキシル基、シクロヘキシル基、n-ヘプチル基、シクロヘキシルメチル基、シクロヘキシルエチル基、n-オクチル基、2-エチルヘキシル基、3-n-プロピルヘプチル基、アダマンチル基、n-デシル基、3,7-ジメチルオクチル基、2-エチルオクチル基、2-n-ヘキシル-デシル基、n-ドデシル基、テトラデシル基、ヘキサデシル墓、オクタデシル基、エイコシル基等の非置換アルキル基;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-n-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等の置換アルキル基が挙げられる。
Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isoamyl, 2-ethylbutyl, n- hexyl group, cyclohexyl group, n-heptyl group, cyclohexylmethyl group, cyclohexylethyl group, n-octyl group, 2-ethylhexyl group, 3-n-propylheptyl group, adamantyl group, n-decyl group, 3,7-dimethyl Unsubstituted alkyl groups such as octyl group, 2-ethyloctyl group, 2-n-hexyl-decyl group, n-dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group; trifluoromethyl group, pentafluoroethyl group , perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, 3-phenylpropyl group, 3-(4-methylphenyl)propyl group, 3-(3,5-di-n-hexylphenyl)propyl group, Substituted alkyl groups such as 6-ethyloxyhexyl group are included.
「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めないで、通常3~30であり、好ましくは3~20である。
A "cycloalkyl group" may be a monocyclic group or a polycyclic group. A cycloalkyl group may have a substituent. The number of carbon atoms in the cycloalkyl group is usually 3-30, preferably 3-20, not including the number of carbon atoms in the substituents.
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 unsubstituted alkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and adamantyl groups, and hydrogen atoms in these groups are alkyl groups, alkyloxy groups, and aryl groups. , 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めないで、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 in the alkenyl group is usually 2-30, preferably 2-20, not including the number of carbon atoms in the substituents.
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、置換基を有しないアルケニル基、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, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 5-hexenyl, Alkenyl groups having no substituents such as 7-octenyl groups, and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyloxy groups, aryl groups and fluorine atoms are included.
「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めないで、通常3~30であり、好ましくは3~20である。
A "cycloalkenyl group" may be a monocyclic group or a polycyclic group. A cycloalkenyl group may have a substituent. The number of carbon atoms in the cycloalkenyl group is usually 3-30, preferably 3-20, not including the number of carbon atoms in the substituents.
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 include unsubstituted cycloalkenyl groups such as cyclohexenyl groups, and hydrogen atoms in these groups are substituted groups such as alkyl groups, alkyloxy groups, aryl groups, and fluorine atoms. Substituted groups are included.
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 substituted cycloalkenyl groups 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めないで、通常2~30であり、好ましくは2~20である。
"Alkynyl group" may be linear or branched. The alkynyl group may have a substituent. The number of carbon atoms in the alkynyl group is usually 2-30, preferably 2-20, not including the number of carbon atoms in the substituents.
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、置換基を有しないアルキニル基、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, 1-propynyl, 2-propynyl, 2-butynyl, 3-butynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl and 5-hexynyl groups. and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyloxy groups, aryl groups and fluorine atoms.
「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めないで、通常4~30であり、好ましくは4~20である。
A "cycloalkynyl group" may be a monocyclic group or a polycyclic group. A cycloalkynyl group may have a substituent. The number of carbon atoms in the cycloalkynyl group is usually 4-30, preferably 4-20, not including the number of carbon atoms in the substituents.
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し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 unsubstituted cycloalkynyl groups such as cyclohexynyl groups, and hydrogen atoms in these groups substituted with substituents such as alkyl groups, alkyloxy groups, aryl groups and fluorine atoms. groups.
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 substituted cycloalkynyl groups 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めないで、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 in the alkyloxy group is generally 1-30, preferably 1-20, not including the number of carbon atoms in the substituent.
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、置換基を有し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, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tert-butyloxy, n-pentyloxy, n-hexyloxy, 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. Alkyloxy groups having no substituents, and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyloxy groups, aryl groups and fluorine atoms are included.
「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めないで、通常3~30であり、好ましくは3~20である。
The cycloalkyl group possessed by the "cycloalkyloxy group" may be a monocyclic group or a polycyclic group. A cycloalkyloxy group may have a substituent. The number of carbon atoms in the cycloalkyloxy group is usually 3-30, preferably 3-20, not including the number of carbon atoms in the substituent.
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、置換基を有し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 cycloalkyloxy groups include unsubstituted cycloalkyloxy groups such as cyclopentyloxy, cyclohexyloxy, and cycloheptyloxy, and hydrogen atoms in these groups are fluorine atoms, alkyl groups, and the like. A group substituted with a substituent can be mentioned.
「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めないで、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 in the alkylthio group is generally 1-30, preferably 1-20, not including the number of carbon atoms in the substituent.
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 optionally substituted alkylthio groups include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, tert-butylthio, n-pentylthio, 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めないで、通常3~30であり、好ましくは3~20である。
The cycloalkyl group possessed by the "cycloalkylthio group" may be a monocyclic group or a polycyclic group. A cycloalkylthio group may have a substituent. The number of carbon atoms in the cycloalkylthio group is usually 3-30, preferably 3-20, not including the number of carbon atoms in the substituent.
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。
A cyclohexylthio group is mentioned as an example of the cycloalkylthio group which may have a substituent.
「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、置換基をさらに有していてもよい。
"P-valent aromatic carbocyclic group" means the remaining atomic group excluding p hydrogen atoms directly bonded to the carbon atoms constituting the ring from an aromatic hydrocarbon optionally having 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 in the aryl group is usually 6-60, preferably 6-48, not including the number of carbon atoms in the substituents.
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、置換基を有しないアリール基、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, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, Aryl groups having no substituents such as 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group and 4-phenylphenyl group, and hydrogen atoms in these groups 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めないで、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 in the aryloxy group is generally 6-60, preferably 6-48, not including the number of carbon atoms in the substituents.
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し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 aryloxy groups include phenoxy groups, 1-naphthyloxy groups, 2-naphthyloxy groups, 1-anthracenyloxy groups, 9-anthracenyloxy groups, 1-pyrenyloxy groups, and the like. Examples include aryloxy groups and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkyloxy groups and fluorine atoms.
「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めないで、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 in the arylthio group is usually 6-60, preferably 6-48, not including the number of carbon atoms in the substituents.
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であることを表す。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であることを表す。以下同様である。
Examples of optionally substituted arylthio groups include a phenylthio group, a C1-C12 alkyloxyphenylthio group, a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and pentafluorophenyl A thio group can be mentioned. "C1-C12" means that the group immediately following it has 1-12 carbon atoms. Furthermore, "Cm-Cn" indicates that the number of carbon atoms in the group immediately following it is from m to n. The same applies hereinafter.
「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。
"p-valent heterocyclic group" (p represents an integer of 1 or more.) is a hydrogen directly bonded to a carbon atom or heteroatom constituting a ring from a heterocyclic compound optionally having a substituent It means an atomic group remaining excluding p hydrogen atoms among atoms. A "p-valent heterocyclic group" includes a "p-valent aromatic heterocyclic group". "p-valent aromatic heterocyclic group", from an optionally substituted aromatic heterocyclic compound, p It means the remaining atomic groups excluding hydrogen atoms.
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 not only compounds in which the heterocycle itself exhibits aromaticity, but also compounds in which an aromatic ring is fused to a heterocycle, even if the heterocycle itself does not exhibit aromaticity. be.
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 aromatic heterocyclic compounds, specific examples of compounds 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 dibenzophosphole.
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 heterocyclic ring itself does not show aromaticity and the aromatic ring is fused to the heterocyclic ring include phenoxazine, phenothiazine, dibenzoborol, dibenzosilol, and benzopyrans.
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めないで、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 in the p-valent heterocyclic group is usually 2 to 60, preferably 2 to 20, not including the number of carbon atoms in the substituents.
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 (e.g., thienyl group, pyrrolyl group, furyl group, pyridyl group, quinolyl group, isoquinolyl group, pyrimidinyl group, triazinyl group), monovalent Examples include non-aromatic heterocyclic groups (eg, piperidyl group, piperazyl group), and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkyloxy groups, and fluorine atoms.
「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. Alkyl groups, aryl groups, and monovalent heterocyclic groups are preferred as the substituents possessed by the amino group. The number of carbon atoms in the substituted amino group is usually 2-30 not including the number of carbon atoms in 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 and 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 in the acyl group is usually 2-20, preferably 2-18, not including the number of carbon atoms in the substituents. Specific examples of acyl groups include acetyl, propionyl, butyryl, isobutyryl, pivaloyl, benzoyl, trifluoroacetyl, and pentafluorobenzoyl groups.
「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、アルキル基などの置換基で置換された化合物が挙げられる。
"Imine residue" means an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom or a nitrogen atom that constitutes a carbon atom-nitrogen atom double bond from an imine compound. An "imine compound" means an organic compound having a carbon atom-nitrogen atom double bond in the molecule. Examples of imine compounds include aldimines, ketimines, and compounds in which the hydrogen atoms bonded to the nitrogen atoms that constitute the carbon atom-nitrogen double bonds in aldimines are substituted with substituents such as alkyl groups. be done.
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 in the imine residue is usually 2-20, preferably 2-18. 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1つを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程度であり、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。
"Amido group" means an atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from amide. The amide group usually has about 1 to 20 carbon atoms, preferably 1 to 18 carbon atoms. 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. , a ditrifluoroacetamide group, and a 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1つを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、以下に示す基が挙げられる。
"Acid imide group" means an atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from an acid imide. The number of carbon atoms in the acid imide group is generally 4-20. Specific examples of acid imide groups include groups shown below.
「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、アリール基、アリールアルキル基、又は1価の複素環基を表す。 "Substituted oxycarbonyl group" means a group represented by R'-O-(C=O)-.
Here, R' represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.
ここで、R’は、アルキル基、アリール基、アリールアルキル基、又は1価の複素環基を表す。 "Substituted oxycarbonyl group" means a group represented by R'-O-(C=O)-.
Here, R' represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.
置換オキシカルボニル基は、炭素原子数が通常2~60であり、好ましくは炭素原子数が2~48である。
The substituted oxycarbonyl group usually has 2 to 60 carbon atoms, preferably 2 to 48 carbon atoms.
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 substituted oxycarbonyl groups 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 fluoromethoxycarbonyl, pentafluoroethoxycarbonyl, perfluorobutoxycarbonyl, perfluorohexyloxycarbonyl, perfluorooctyloxycarbonyl, phenoxycarbonyl, naphthoxycarbonyl, and pyridyloxycarbonyl groups.
「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 in the alkylsulfonyl group is usually 1-30, not including the number of carbon atoms in the substituents. Specific examples of alkylsulfonyl groups include methylsulfonyl, ethylsulfonyl, and dodecylsulfonyl groups.
化学式に付される「*」は、結合手を表す。
"*" attached to the chemical formula represents a bond.
「π共役系」とは、π電子が複数の結合にわたって非局在化している系を意味する。
"π-conjugated system" means a system in which π electrons are delocalized over multiple bonds.
「(メタ)アクリル」には、アクリル、メタクリル、及びこれらの組み合わせが含まれる。
"(Meth)acrylic" includes acrylic, methacrylic, and combinations thereof.
本明細書において、「インク組成物」は、塗布法に用いられる液状の組成物を意味し、着色した液に限定されない。また、「塗布法」は、インク組成物に代表される液状物質を用いて膜を形成する方法を意味している。
As used herein, the "ink composition" means a liquid composition used in the coating method, and is not limited to colored liquids. Also, the “coating method” means a method of forming a film using a liquid substance represented by an ink composition.
「インク組成物」は、溶液であってもよく、分散液、エマルション(乳濁液)、サスペンション(懸濁液)等の分散液であってもよい。
The "ink composition" may be a solution, or may be a dispersion liquid such as a dispersion liquid, an emulsion (emulsion), or a suspension (suspension).
2.インク組成物
本実施形態のインク組成物は、p型半導体材料と、n型半導体材料と、溶媒とを含有するインク組成物であって、p型半導体材料が、z平均分子量が5.0×105未満である高分子化合物を含む、光電変換素子製造用のインク組成物である。 2. Ink Composition The ink composition of the present embodiment is an ink composition containing a p-type semiconductor material, an n-type semiconductor material, and a solvent, wherein the p-type semiconductor material has a z-average molecular weight of 5.0× An ink composition for manufacturing a photoelectric conversion device, containing a polymer compound having a molecular weight of less than 10 5 .
本実施形態のインク組成物は、p型半導体材料と、n型半導体材料と、溶媒とを含有するインク組成物であって、p型半導体材料が、z平均分子量が5.0×105未満である高分子化合物を含む、光電変換素子製造用のインク組成物である。 2. Ink Composition The ink composition of the present embodiment is an ink composition containing a p-type semiconductor material, an n-type semiconductor material, and a solvent, wherein the p-type semiconductor material has a z-average molecular weight of 5.0× An ink composition for manufacturing a photoelectric conversion device, containing a polymer compound having a molecular weight of less than 10 5 .
本実施形態のインク組成物は、上記のとおり、光電変換素子製造用のインク組成物であって、好ましくは活性層形成用のインク組成物である。
As described above, the ink composition of the present embodiment is an ink composition for manufacturing a photoelectric conversion element, preferably an ink composition for forming an active layer.
以下、本実施形態のインク組成物に含まれうる成分について具体的に説明する。
Components that can be contained in the ink composition of the present embodiment are specifically described below.
ここで、p型半導体材料は、少なくとも1種の電子供与性化合物を含み、n型半導体材料は、少なくとも1種の電子受容性化合物を含む。インク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エネルギーレベルの値から相対的に決定しうる。
Here, the p-type semiconductor material contains at least one electron-donating compound, and the n-type semiconductor material contains at least one electron-accepting compound. Whether the semiconductor material contained in the ink composition functions as a p-type semiconductor material or an n-type semiconductor material is relatively determined from the HOMO energy level value or the LUMO energy level value of the selected compound. I can.
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、インク組成物から形成される(固化)膜が、光電変換機能、光検出機能といった所定の機能を発揮する範囲に適宜設定することができる
The relationship between the HOMO and LUMO energy level values of the p-type semiconductor material and the HOMO and LUMO energy level values of the n-type semiconductor material indicates that the (solidified) film formed from the ink composition has a photoelectric conversion function, It can be appropriately set within a range in which a predetermined function such as a light detection function is exhibited.
(1)p型半導体材料
本実施形態において、p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。 (1) p-type semiconductor material In the present embodiment, the p-type semiconductor material may be a low-molecular compound or a high-molecular compound.
本実施形態において、p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。 (1) p-type semiconductor material In the present embodiment, the p-type semiconductor material may be a low-molecular compound or a high-molecular compound.
低分子化合物であるp型半導体材料としては、例えば、フタロシアニン、金属フタロシアニン、ポルフィリン、金属ポルフィリン、オリゴチオフェン、テトラセン、ペンタセン、及びルブレンが挙げられる。
Examples of p-type semiconductor materials that are low molecular weight compounds include phthalocyanine, metal phthalocyanine, porphyrin, metal porphyrin, oligothiophene, tetracene, pentacene, and rubrene.
本実施形態のインク組成物が含みうるp型半導体材料は、ドナー構成単位(D構成単位ともいう。)とアクセプター構成単位(A構成単位ともいう。)とを含むドナー・アクセプター構造を有するπ共役系の高分子化合物(D-A型共役高分子化合物ともいう。)を含むことが好ましい。
The p-type semiconductor material that the ink composition of the present embodiment may contain is a π-conjugated material having a donor-acceptor structure containing a donor structural unit (also referred to as a D structural unit) and an acceptor structural unit (also referred to as an A structural unit). system polymer compound (also referred to as a DA type conjugated polymer compound).
ここで、ドナー構成単位はπ電子が過剰である構成単位であり、アクセプター構成単位はπ電子が欠乏している構成単位である。
Here, the donor structural unit is a structural unit with an excess of π electrons, and the acceptor structural unit is a structural unit with a π electron deficiency.
本実施形態において、p型半導体材料を構成し得る構成単位には、ドナー構成単位とアクセプター構成単位とが直接的に結合した構成単位、さらにはドナー構成単位とアクセプター構成単位とが、任意好適なスペーサー(基又は構成単位)を介して結合した構成単位も含まれる。
In the present embodiment, the structural unit that can constitute the p-type semiconductor material may be a structural unit in which a donor structural unit and an acceptor structural unit are directly bonded, or a donor structural unit and an acceptor structural unit. Structural units linked via spacers (groups or structural units) are also included.
高分子化合物であるp型半導体材料としては、例えば、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。p型半導体材料としては、チオフェン骨格を有する構成単位を含む高分子化合物を用いることが好ましい。
Examples of p-type semiconductor materials that are polymer compounds include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives containing 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. As the p-type semiconductor material, it is preferable to use a polymer compound containing a structural unit having a thiophene skeleton.
p型半導体材料は、インク組成物の安定性をより向上させる観点から、さらには光電変換素子の外部量子効率をより向上させる観点から、下記式(I)で表される構成単位及び/又は下記式(II)で表される構成単位を含む高分子化合物であることが好ましい。
From the viewpoint of further improving the stability of the ink composition and further improving the external quantum efficiency of the photoelectric conversion device, the p-type semiconductor material contains a structural unit represented by the following formula (I) and/or A polymer compound containing a structural unit represented by formula (II) is preferred.
式(I)中、Ar1及びAr2は、それぞれ独立して、置換基を有していもよい3価の芳香族複素環基を表し、Zは下記式(Z-1)~式(Z-7)のいずれか1つ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, and Z represents the following formulas (Z-1) to (Z -7) represents a group represented by any one.
式(II)中、Ar3は2価の芳香族複素環基を表す。
In formula (II), Ar 3 represents a divalent aromatic heterocyclic group.
式(Z-1)~(Z-7)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)-Rcで表される基、又は
-SO2-Rdで表される基を表し、
Rc及びRd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。 In formulas (Z-1) to (Z-7), R is
hydrogen atom,
halogen atom,
an optionally substituted alkyl group,
a cycloalkyl group optionally having a substituent,
an optionally substituted alkenyl group,
a cycloalkenyl group optionally having a substituent,
an optionally substituted alkynyl group,
a cycloalkynyl group optionally having a substituent,
an aryl group optionally having a substituent,
an optionally substituted alkyloxy group,
a cycloalkyloxy group optionally having a substituent,
an optionally substituted aryloxy group,
an optionally substituted alkylthio group,
a cycloalkylthio group optionally having a substituent,
an optionally substituted arylthio group,
a monovalent heterocyclic group optionally having a substituent,
a substituted amino group which may have a substituent,
an imine residue optionally having a substituent,
an amide group optionally having a substituent,
an acid imide group optionally having a substituent,
a substituted oxycarbonyl group optionally having a substituent,
cyano group,
nitro group,
a group represented by —C(=O)—R c or a group represented by —SO 2 —R d ,
R c and R d are each independently
hydrogen atom,
an optionally substituted alkyl group,
a cycloalkyl group optionally having a substituent,
an aryl group optionally having a substituent,
an optionally substituted alkyloxy group,
a cycloalkyloxy group optionally having a substituent,
It represents an optionally substituted aryloxy group or an optionally substituted monovalent heterocyclic group.
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)-Rcで表される基、又は
-SO2-Rdで表される基を表し、
Rc及びRd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。 In formulas (Z-1) to (Z-7), R is
hydrogen atom,
halogen atom,
an optionally substituted alkyl group,
a cycloalkyl group optionally having a substituent,
an optionally substituted alkenyl group,
a cycloalkenyl group optionally having a substituent,
an optionally substituted alkynyl group,
a cycloalkynyl group optionally having a substituent,
an aryl group optionally having a substituent,
an optionally substituted alkyloxy group,
a cycloalkyloxy group optionally having a substituent,
an optionally substituted aryloxy group,
an optionally substituted alkylthio group,
a cycloalkylthio group optionally having a substituent,
an optionally substituted arylthio group,
a monovalent heterocyclic group optionally having a substituent,
a substituted amino group which may have a substituent,
an imine residue optionally having a substituent,
an amide group optionally having a substituent,
an acid imide group optionally having a substituent,
a substituted oxycarbonyl group optionally having a substituent,
cyano group,
nitro group,
a group represented by —C(=O)—R c or a group represented by —SO 2 —R d ,
R c and R d are each independently
hydrogen atom,
an optionally substituted alkyl group,
a cycloalkyl group optionally having a substituent,
an aryl group optionally having a substituent,
an optionally substituted alkyloxy group,
a cycloalkyloxy group optionally having a substituent,
It represents an optionally substituted aryloxy group or an optionally substituted monovalent heterocyclic group.
式(Z-1)~式(Z-7)中、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。
In formulas (Z-1) to (Z-7), when there are two Rs, the two Rs may be the same or different.
式(Z-1)~(Z-7)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、さらに好ましくは、水素原子又は炭素原子数1~40のアルキル基であり、より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、特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。Rが複数存在する場合、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。
R in formulas (Z-1) to (Z-7) is preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, still more preferably a hydrogen atom or 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, particularly preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. These groups may have a substituent. When there are multiple R's, the multiple R's may be the same or different.
式(I)で表される構成単位は、下記式(I-1)で表される構成単位であることが好ましい。
The structural unit represented by formula (I) is preferably a structural unit represented by formula (I-1) below.
式(I-1)中、Zは前記と同様の意味を表す。
In formula (I-1), Z has the same meaning as above.
式(I-1)で表される構成単位の例としては、下記式(501)~式(505)で表される構成単位が挙げられる。
Examples of structural units represented by formula (I-1) include structural units represented by formulas (501) to (505) below.
上記式(501)~式(505)中、Rは前記と同様の意味を表す。Rが2つ存在する場合、2つのRは互いに同一であっても異なっていてもよい。
In formulas (501) to (505) above, R has the same meaning as above. When there are two R's, the two R's may be the same or different.
前記式(II)中、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。Ar3で表される2価の芳香族複素環基が有していてもよい置換基の例としては、ハロゲン原子、アルキル基、アリール基、アルコキシ基、アリールオキシ基、アルキルチオ基、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、アルケニル基、アルキニル基、シアノ基、及びニトロ基が挙げられる。
In the above formula (II), the number of carbon atoms in the divalent aromatic heterocyclic group represented by Ar 3 is usually 2 to 60, preferably 4 to 60, more preferably 4 to 20. . The divalent aromatic heterocyclic group represented by Ar 3 may have a substituent. Examples of substituents that the divalent aromatic heterocyclic group represented by Ar 3 may have include halogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, monovalent heterocyclic groups, substituted amino groups, acyl groups, imine residues, amide groups, acid imide groups, substituted oxycarbonyl groups, alkenyl groups, alkynyl groups, cyano groups, and nitro groups.
Ar3で表される2価の芳香族複素環基の例としては、下記式(101)~式(190)で表される基が挙げられる。
Examples of the divalent aromatic heterocyclic group represented by Ar 3 include groups represented by the following formulas (101) to (190).
式(101)~式(190)中、Rは前記と同じ意味を表す。Rが複数存在する場合、複数のRは、互いに同一であっても異なっていてもよい。
In formulas (101) to (190), R has the same meaning as above. When there are multiple R's, the multiple R's may be the same or different.
前記式(II)で表される構成単位としては、下記式(II-1)~式(II-6)で表される構成単位が好ましい。
As the structural unit represented by the formula (II), structural units represented by the following formulas (II-1) to (II-6) are preferable.
式(II-1)~式(II-6)中、X1及びX2は、それぞれ独立に、酸素原子又は硫黄原子を表し、Rは上記と同じ意味を表す。Rが複数存在する場合、複数のRは、互いに同一でも異なっていてもよい。
In formulas (II-1) to (II-6), X 1 and X 2 each independently represent an oxygen atom or a sulfur atom, and R has the same meaning as above. When there are multiple R's, the multiple R's may be the same or different.
原料化合物の入手性の観点から、式(II-1)~式(II-6)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 starting compounds, both X 1 and X 2 in formulas (II-1) to (II-6) are preferably sulfur atoms.
p型半導体材料である高分子化合物は、2種以上の式(I)の構成単位を含んでいてもよく、2種以上の式(II)の構成単位を含んでいてもよい。
A polymer compound that is a p-type semiconductor material may contain two or more structural units of formula (I), and may contain two or more structural units of formula (II).
溶媒に対する溶解性を向上させる観点から、p型半導体材料である高分子化合物は、下記式(III)で表される構成単位を含んでいてもよい。
From the viewpoint of improving solubility in solvents, the polymer compound that is the p-type semiconductor material may contain a structural unit represented by the following formula (III).
式(III)中、Ar4はアリーレン基を表す。
In formula (III), Ar 4 represents an arylene group.
Ar4で表されるアリーレン基とは、置換基を有していてもよい芳香族炭化水素から、水素原子2つを除いた残りの原子団を意味する。芳香族炭化水素には、縮合環を有する化合物、独立したベンゼン環及び縮合環からなる群から選ばれる2つ以上が、直接又はビニレン等の2価の基を介して結合した化合物も含まれる。
The arylene group represented by Ar 4 means an atomic group remaining after removing two hydrogen atoms from an optionally substituted aromatic hydrocarbon. Aromatic hydrocarbons also include compounds having condensed rings, and compounds in which two or more selected from the group consisting of independent benzene rings and condensed rings are bonded directly or via a divalent group such as vinylene.
芳香族炭化水素が有していてもよい置換基の例としては、複素環式化合物が有していてもよい置換基として挙げた上記例と同様の置換基が挙げられる。
Examples of the substituents that the aromatic hydrocarbon may have include the same substituents as those listed above as the substituents that the heterocyclic compound may have.
アリーレン基における、置換基を除いた部分の炭素原子数は、通常6~60であり、好ましくは6~20である。置換基を含めたアリーレン基の炭素原子数は、通常6~100である。
The number of carbon atoms in the arylene group excluding substituents is usually 6-60, preferably 6-20. The number of carbon atoms in the arylene group including substituents is usually 6-100.
アリーレン基の例としては、フェニレン基(例えば、下記式1~式3)、ナフタレン-ジイル基(例えば、下記式4~式13)、アントラセン-ジイル基(例えば、下記式14~式19)、ビフェニル-ジイル基(例えば、下記式20~式25)、ターフェニル-ジイル基(例えば、下記式26~式28)、縮合環化合物基(例えば、下記式29~式35)、フルオレン-ジイル基(例えば、下記式36~式38)、及びベンゾフルオレン-ジイル基(例えば、下記式39~式46)が挙げられる。
Examples of arylene groups include phenylene groups (e.g. formulas 1 to 3 below), naphthalene-diyl groups (e.g. formulas 4 to 13 below), anthracene-diyl groups (e.g. formulas 14 to 19 below), Biphenyl-diyl group (eg, formulas 20 to 25 below), terphenyl-diyl group (eg, formulas 26 to 28 below), condensed ring compound group (eg, formulas 29 to 35 below), fluorene-diyl group (eg formulas 36 to 38 below) and benzofluorene-diyl groups (eg formulas 39 to 46 below).
式1~式46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 Formulas 1 to 46, R has the same definition as above. When there are multiple R's, the multiple R's may be the same or different.
p型半導体材料としての高分子化合物が、式(I)で表される構成単位及び/又は式(II)で表される構成単位を含む場合、式(I)で表される構成単位及び式(II)で表される構成単位の合計量は、高分子化合物が含むすべての構成単位の量を100モル%としたときに、通常20~100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ので、好ましくは40~100モル%であり、より好ましくは50~100モル%である。
When the polymer compound as the p-type semiconductor material contains the structural unit represented by formula (I) and/or the structural unit represented by formula (II), the structural unit represented by formula (I) and the formula The total amount of the structural units represented by (II) is usually 20 to 100 mol% when the amount of all the structural units contained in the polymer compound is 100 mol%, and the charge as a p-type semiconductor material It is preferably 40 to 100 mol %, more preferably 50 to 100 mol %, since it improves transportability.
p型半導体材料である高分子化合物の好適な具体例としては、下記式P-1~P-10で表される高分子化合物が挙げられる。
Preferable specific examples of polymer compounds that are p-type semiconductor materials include polymer compounds represented by the following formulas P-1 to P-10.
本実施形態にかかるインク組成物おいては、p型半導体材料は、z平均分子量が5.0×105未満である高分子化合物を含む。
In the ink composition according to this embodiment, the p-type semiconductor material contains a polymer compound having a z-average molecular weight of less than 5.0×10 5 .
本実施形態にかかるインク組成物においては、p型半導体材料は、光電変換効率を向上させる観点、より具体的には、例えば外部量子効率(EQE)を好ましくは50%以上とする観点から、重量平均分子量が6.0×104よりも大きい高分子化合物を含むことが好ましく、光電変換効率とろ過性とを両立させる観点から、z平均分子量が5.0×105未満であり、かつ重量平均分子量が6.0×104よりも大きい高分子化合物を含むことがより好ましい。
In the ink composition according to the present embodiment, the p-type semiconductor material has a weight of It preferably contains a polymer compound having an average molecular weight of more than 6.0×10 4 , and from the viewpoint of achieving both photoelectric conversion efficiency and filterability, the z-average molecular weight is less than 5.0×10 5 and weight More preferably, it contains a polymer compound with an average molecular weight greater than 6.0×10 4 .
本実施形態にかかるインク組成物においては、p型半導体材料のz平均分子量(Mz)は、外部量子効率を好ましくは50%以上とする観点から、1.5×105よりも大きいことが好ましい。
In the ink composition according to the present embodiment, the z-average molecular weight (Mz) of the p-type semiconductor material is preferably larger than 1.5×10 5 from the viewpoint of achieving an external quantum efficiency of preferably 50% or more. .
また、本実施形態にかかるインク組成物において、p型半導体材料としての高分子化合物は、重量平均分子量が、通常1×103~5×105であり、溶媒への溶解性を向上させる観点から、好ましくは1×103~3×105である。
Further, in the ink composition according to the present embodiment, the polymer compound as the p-type semiconductor material has a weight-average molecular weight of usually 1×10 3 to 5×10 5 , from the viewpoint of improving the solubility in the solvent. Therefore, it is preferably 1×10 3 to 3×10 5 .
本実施形態において、z平均分子量(Mz)及び重量平均分子量(Mw)は、従来公知の任意好適な装置を用いて実施されるゲルパーミテーションクロマトグラフィー(GPC)により測定することができるポリスチレン換算の平均分子量である。
In the present embodiment, the z-average molecular weight (Mz) and the weight-average molecular weight (Mw) are measured by gel permeation chromatography (GPC) performed using a conventionally known arbitrary suitable device. is the average molecular weight.
本実施形態のインク組成物は、p型半導体材料である化合物(高分子化合物)を1種のみ含んでいてもよく、2種以上を任意の組合せとして含んでいてもよい。
The ink composition of the present embodiment may contain only one type of compound (polymer compound) that is a p-type semiconductor material, or may contain two or more types in any combination.
ここで、z平均分子量(Mz)は、分子量の2乗を重みとして用いた加重平均分子量であって、重量平均分子量(Mw)と比較すると、より高分子量の分子の存在の影響を受け易い傾向があるパラメータである。
Here, the z-average molecular weight (Mz) is a weighted average molecular weight using the square of the molecular weight as a weight, and tends to be more susceptible to the presence of higher molecular weight molecules than the weight-average molecular weight (Mw). is a parameter.
本実施形態において、高分子化合物であるp型半導体材料のz平均分子量(Mz)は、当該高分子化合物の合成工程における条件を所定の条件とすることにより、上記好適範囲内に調節することができる。
In the present embodiment, the z-average molecular weight (Mz) of the p-type semiconductor material, which is a polymer compound, can be adjusted within the preferred range by setting the conditions in the synthesis process of the polymer compound to predetermined conditions. can.
具体的には、例えば、上記例示の高分子化合物の合成工程において、原料となる複数種類のモノマーの仕込み組成(混合比)を適宜調整すること、使用する触媒量を適宜調整すること、反応溶液の濃度を適宜調整することなどにより、z平均分子量(Mz)を上記好適範囲内に調節することができる。より具体的には、例えば、「ネットワークポリマー、2009、30、261記載の総説」などを参考にz平均分子量(Mz)を適宜調節すればよい。
Specifically, for example, in the step of synthesizing the polymer compound exemplified above, the charging composition (mixing ratio) of a plurality of types of monomers as raw materials is appropriately adjusted, the amount of the catalyst to be used is appropriately adjusted, and the reaction solution is The z-average molecular weight (Mz) can be adjusted within the preferred range by appropriately adjusting the concentration of . More specifically, for example, the z-average molecular weight (Mz) may be appropriately adjusted with reference to "Review of Network Polymer, 2009, 30, 261".
z平均分子量(Mz)が既に説明したとおりであるp型半導体材料を用いる本実施形態のインク組成物によれば、試行錯誤を要せずに、製造工程においてフィルターを閉塞させることなく、より確実にろ過を行うことができ、絶縁、短絡といった電気的な欠陥を生じさせにくくすることができ、さらにはインク組成物の製造効率、ひいては光電変換素子の製造効率をより向上させることができる。
According to the ink composition of the present embodiment, which uses the p-type semiconductor material having the z-average molecular weight (Mz) as already described, trial and error is not required, and the filter is not clogged in the manufacturing process. Filtration can be carried out on a large scale, making it difficult for electrical defects such as insulation and short circuits to occur, and furthermore, the production efficiency of the ink composition and, in turn, the production efficiency of the photoelectric conversion element can be further improved.
(2)n型半導体材料
本実施形態のインク組成物が含みうる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。 (2) n-type semiconductor material The n-type semiconductor material that the ink composition of the present embodiment may contain may be a low-molecular compound or a high-molecular compound.
本実施形態のインク組成物が含みうる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。 (2) n-type semiconductor material The n-type semiconductor material that the ink composition of the present embodiment may contain may be a low-molecular compound or a high-molecular compound.
低分子化合物であるn型半導体材料(電子受容性化合物)の例としては、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、C60フラーレン等のフラーレン及びその誘導体であるフラーレン誘導体(以下、フラーレン化合物という場合がある。)、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。
Examples of n-type semiconductor materials (electron-accepting compounds) that are low molecular weight compounds include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyano Anthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, fullerenes such as C60 fullerene and fullerene derivatives thereof ( hereinafter referred to as fullerene compounds ), and phenanthrene derivatives such as bathocuproin.
高分子化合物であるn型半導体材料の例としては、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有する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、ポリキノリン及びその誘導体、ポリキノキサリン及びその誘導体、並びに、ポリフルオレン及びその誘導体が挙げられる。
Examples of n-type semiconductor materials that are polymer compounds 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, polyquinoline and its derivatives, polyquinoxaline and its derivatives, and polyfluorene and its derivatives.
n型半導体材料としては、フラーレン及びフラーレン誘導体から選ばれる1種以上が好ましく、フラーレン誘導体がより好ましい。
The n-type semiconductor material is preferably one or more selected from fullerenes and fullerene derivatives, more preferably fullerene derivatives.
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。フラーレン誘導体の例としては、これらのフラーレンの誘導体が挙げられる。フラーレン誘導体とは、フラーレンの少なくとも一部が修飾された化合物を意味する。
Examples of fullerenes include C60 fullerene, C70 fullerene, C76 fullerene, C78 fullerene, and C84 fullerene . Examples of fullerene derivatives include derivatives of these fullerenes. A fullerene derivative means a compound in which at least a part of fullerene is modified.
フラーレン誘導体の例としては、下記式で表される化合物が挙げられる。
Examples of fullerene derivatives include compounds represented by the following formula.
式中、
Ra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Raは、互いに同一であっても異なっていてもよい。 During the ceremony,
Ra represents an alkyl group, an aryl group, a monovalent heterocyclic group, or a group having an ester structure. A plurality of R a may be the same or different.
Ra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Raは、互いに同一であっても異なっていてもよい。 During the ceremony,
Ra represents an alkyl group, an aryl group, a monovalent heterocyclic group, or a group having an ester structure. A plurality of R a may be the same or different.
Rbは、アルキル基、又はアリール基を表す。複数あるRbは、互いに同一であっても異なっていてもよい。
Rb represents an alkyl group or an aryl group. A plurality of R b may be the same or different.
Raで表されるエステル構造を有する基の例としては、下記式で表される基が挙げられる。
Examples of groups having an ester structure represented by Ra include groups represented by the following formulae.
式中、u1は、1~6の整数を表す。u2は、0~6の整数を表す。Re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 1-6. u2 represents an integer from 0 to 6; R e 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。
Examples of C60 fullerene derivatives include the following compounds.
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 C70 fullerene derivatives 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 fullerene derivatives include [6,6]-phenyl-C61 butyric acid methyl ester (C60PCBM, [6,6]-phenyl C61 butyric acid methyl ester), [6,6]-phenyl-C71 butyric acid methyl ester ( C70PCBM, [6,6]-Phenyl C71 butyric acid methyl ester), [6,6]-phenyl-C85 butyric acid methyl ester (C84PCBM, [6,6]-Phenyl C85 butyric acid methyl ester), and [6,6 ]-Thienyl-C61 butyric acid methyl ester ([6,6]-Thienyl C61 butyric acid methyl ester).
本実施形態のインク組成物に含まれうるn型半導体材料には、フラーレン化合物ではない化合物が含まれる。本明細書において、フラーレン化合物ではないn型半導体材料を、「非フラーレン化合物」という。非フラーレン化合物としては、多種の化合物が公知であり、従来公知の任意好適な非フラーレン化合物を本実施形態においてn型半導体材料として用いることができる。
The n-type semiconductor material that can be contained in the ink composition of the present embodiment includes compounds other than fullerene compounds. In this specification, n-type semiconductor materials that are not fullerene compounds are referred to as "non-fullerene compounds." Various compounds are known as non-fullerene compounds, and any suitable conventionally known non-fullerene compound can be used as the n-type semiconductor material in this embodiment.
本実施形態にかかるインク組成物は、n型半導体材料である化合物を、1種のみ含んでいてもよく、複数種類含んでいてもよい。
The ink composition according to the present embodiment may contain only one type of compound that is an n-type semiconductor material, or may contain a plurality of types.
本実施形態において、n型半導体材料である非フラーレン化合物は、ペリレンテトラカルボン酸ジイミド構造を含む化合物であることが好ましい。非フラーレン化合物である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 the present embodiment, the non-fullerene compound, which is the n-type semiconductor material, is preferably a compound containing a perylenetetracarboxylic acid diimide structure. Examples of compounds containing a perylenetetracarboxylic acid diimide structure, which are non-fullerene compounds, include compounds represented by the following formulae.
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. Multiple R's may be the same or different.
本実施形態において、n型半導体材料は、好ましくは、下記式(V)で表される化合物を含む。下記式(V)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 this embodiment, the n-type semiconductor material preferably contains a compound represented by the following formula (V). The compound represented by the following formula (V) is a non-fullerene compound containing a perylenetetracarboxylic acid diimide structure.
前記式(V)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 (V), R 1 is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted an alkyloxy group, an optionally substituted cycloalkyloxy group, an optionally substituted aryl group, or an optionally substituted monovalent aromatic heterocyclic group show. Multiple R 1 's may be the same or different.
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 a plurality of R 1 is independently an optionally substituted alkyl group.
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 optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkyloxy group, a substituent represents an optionally substituted cycloalkyloxy group, an optionally substituted aryl group, or an optionally substituted monovalent aromatic heterocyclic group. Multiple R 2 may be the same or different.
式(V)で表される化合物の好ましい例としては、下記式で表される化合物が挙げられる。
Preferred examples of the compound represented by formula (V) include the compound represented by the following formula.
本実施形態において、n型半導体材料は、下記式(VI)で表される化合物を含むことが好ましい。
In this embodiment, the n-type semiconductor material preferably contains a compound represented by the following formula (VI).
In this embodiment, the n-type semiconductor material preferably contains a compound represented by the following formula (VI).
A1-B10-A2 (VI)
A 1 -B 10 -A 2 (VI)
A 1 -B 10 -A 2 (VI)
式(VI)中、
A1及びA2は、それぞれ独立に、電子求引性の基を表し、B10は、π共役系を含む基を表す。 In formula (VI),
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、それぞれ独立に、電子求引性の基を表し、B10は、π共役系を含む基を表す。 In formula (VI),
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 A 1 and A 2 include groups represented by —CH═C(—CN) 2 and groups represented by the following formulas (a-1) to (a-9). and the group to be carried out.
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 formulas (a-1) to (a-7),
T represents an optionally substituted carbocyclic ring or an optionally substituted heterocyclic ring. Carbocyclic and heterocyclic rings may be monocyclic or condensed. When these rings have multiple substituents, the multiple 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 formulas (a-1) to (a-7),
T represents an optionally substituted carbocyclic ring or an optionally substituted heterocyclic ring. Carbocyclic and heterocyclic rings may be monocyclic or condensed. When these rings have multiple substituents, the multiple 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る。
Tである置換基を有していてもよい炭素環は、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。 Examples of optionally substituted carbocyclic rings for T include aromatic carbocyclic rings.
The optionally substituted carbocyclic ring for T is preferably an aromatic carbocyclic ring. Specific examples of the optionally substituted carbocyclic ring for T include benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring and phenanthrene ring, preferably benzene ring, They are a naphthalene ring and a phenanthrene ring, more preferably a benzene ring and a naphthalene ring, and still more preferably a benzene ring. These rings may have a substituent.
Tである置換基を有していてもよい炭素環は、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。 Examples of optionally substituted carbocyclic rings for T include aromatic carbocyclic rings.
The optionally substituted carbocyclic ring for T is preferably an aromatic carbocyclic ring. Specific examples of the optionally substituted carbocyclic ring for T include benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring and phenanthrene ring, preferably benzene ring, They are a naphthalene ring and a phenanthrene ring, more preferably a benzene ring and a naphthalene ring, and still more preferably a benzene ring. These rings may have a substituent.
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。
Examples of the optionally substituted heterocyclic ring for T include aromatic heterocyclic rings, preferably aromatic heterocyclic rings. Specific examples of the optionally substituted heterocyclic ring for T include pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, and a thienothiophene ring, preferably a thiophene ring, a pyridine ring, a pyrazine ring, a thiazole ring, and a thienothiophene ring, more preferably a thiophene ring. These rings may have a substituent.
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 substituents that the carbocyclic or heterocyclic ring for T may have include halogen atoms, alkyl groups, alkyloxy groups, aryl groups, and monovalent heterocyclic groups, preferably fluorine atoms and/or or 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 each independently represents an oxygen atom, a sulfur atom, an alkylidene group or a group represented by =C(-CN) 2 , preferably an oxygen atom, a sulfur atom, or =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 optionally substituted alkyl group, an optionally substituted alkyloxy group, an optionally substituted aryl group, or 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 each independently represent a hydrogen atom, an optionally substituted alkyl group, a halogen atom, an optionally substituted alkyl represents an oxy group, an optionally substituted aryl group or a monovalent heterocyclic group, preferably an optionally substituted alkyl group or an optionally substituted aryl group 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 formulas (a-8) and (a-9), R a6 and R a7 each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, or a substituent optionally substituted cycloalkyl group, optionally substituted alkyloxy group, optionally substituted cycloalkyloxy group, optionally substituted monovalent aromatic carbon It represents a cyclic group or an optionally substituted monovalent aromatic heterocyclic group, and a plurality of R a6 and R a7 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 electron-withdrawing groups A 1 and A 2 include the following formulas (a-1-1) to (a-1-4), formulas (a-6-1) and formulas (a-7 -1) is preferable, and a group represented by formula (a-1-1) is more preferable. Here, multiple R a10 each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group. R a3 , R a4 and R a5 are each independently the same as defined above, preferably each independently an optionally substituted alkyl group or an optionally substituted aryl 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(VII)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。
An example of the group containing a π-conjugated system as B 10 is a group represented by -(S 1 ) n1 -B 11 -(S 2 ) n2 - in the compound represented by formula (VII) described later. mentioned.
本実施形態において、n型半導体材料は、下記式(VII)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 (VII)
In this embodiment, the n-type semiconductor material is preferably a compound represented by the following formula (VII).
A 1 -(S 1 ) n1 -B 11 -(S 2 ) n2 -A 2 (VII)
A1-(S1)n1-B11-(S2)n2-A2 (VII)
In this embodiment, the n-type semiconductor material is preferably a compound represented by the following formula (VII).
A 1 -(S 1 ) n1 -B 11 -(S 2 ) n2 -A 2 (VII)
式(VII)中、A1及びA2は、それぞれ独立に、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(VI)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 (VII), A 1 and A 2 each independently represent an electron-withdrawing group. Examples and preferred examples of A 1 and A 2 are the same as the examples and preferred examples described for A 1 and A 2 in formula (VI) above.
S1及びS2は、それぞれ独立に、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、それぞれ独立に、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 each independently represent an optionally substituted divalent carbocyclic group, an optionally substituted divalent heterocyclic group, —C(R s1 )= A group represented by C(R s2 )- (here, R s1 and R s2 are each independently a hydrogen atom or a substituent (preferably a hydrogen atom, a halogen atom, or a substituent a good alkyl group or a monovalent heterocyclic group which may have a substituent), or a group represented by -C≡C-.
S1及びS2で表される、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 optionally having substituent(s) and the divalent heterocyclic group optionally having substituent(s) represented by S 1 and S 2 may be a condensed ring. . When the divalent carbocyclic group or divalent heterocyclic group has multiple substituents, the multiple substituents may be the same or different.
式(VII)中、n1及びn2は、それぞれ独立に、0以上の整数を表し、好ましくはそれぞれ独立に、0又は1を表し、より好ましくは、いずれも0又は1を表す。
In formula (VII), n1 and n2 each independently represent an integer of 0 or greater, preferably each independently represent 0 or 1, more preferably both represent 0 or 1.
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。
Examples of divalent carbocyclic groups include divalent aromatic carbocyclic groups.
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。
Examples of divalent heterocyclic groups include divalent aromatic heterocyclic groups.
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。
When the divalent aromatic carbocyclic group or divalent aromatic heterocyclic group is a condensed ring, all of the rings constituting the condensed ring may be condensed rings having aromaticity, only a part It may be a condensed 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 are groups represented by any of the formulas (101) to (190) given as examples of the divalent aromatic heterocyclic group represented by Ar 3 already explained, and groups in which hydrogen atoms in these groups are substituted with substituents.
S1及びS2は、好ましくは、それぞれ独立に、下記式(s-1)又は(s-2)で表される基を表す。
S 1 and S 2 preferably each independently represent a group represented by formula (s-1) or (s-2) below.
式(s-1)及び(s-2)中、
X3は、酸素原子又は硫黄原子を表す。 In formulas (s-1) and (s-2),
X3 represents an oxygen atom or a sulfur atom.
X3は、酸素原子又は硫黄原子を表す。 In formulas (s-1) and (s-2),
X3 represents an oxygen atom or a sulfur atom.
Ra10は、前記定義のとおりである。
R a10 is as defined above.
S1及びS2は、好ましくは、それぞれ独立に、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 each independently a group represented by formula (142), formula (148), or formula (184), or a group in which a hydrogen atom in these groups is substituted with a substituent and more preferably a group represented by the formula (142) or (184), or a group in which one hydrogen atom in the group represented by the formula (184) is substituted with an alkyloxy group. .
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 condensed ring group having two or more structures selected from the group consisting of a carbocyclic structure and a heterocyclic ring structure, a condensed ring group containing no ortho-peri condensed structure, and having a substituent; represents an optional condensed ring group.
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 condensed ring group represented by B11 may contain a structure in which two or more identical structures are condensed.
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 multiple substituents, the multiple 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 carbocyclic structure that can constitute the condensed ring group represented by B 11 include a ring structure represented by the following formula (Cy1) or (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 heterocyclic structures that can constitute the condensed ring group represented by B 11 include ring structures represented by any of the following formulas (Cy3) to (Cy10).
式(VII)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 (VII), B 11 is preferably a condensed ring group having two or more structures selected from the group consisting of structures represented by formulas (Cy1) to (Cy10), It is a condensed ring group which does not contain a condensed structure and which may have a substituent. B 11 may include a structure in which two or more identical structures among the structures represented by formulas (Cy1) to (Cy10) are condensed.
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 condensed ring group having two or more structures selected from the group consisting of structures represented by formulas (Cy1) to (Cy6) and (Cy8), wherein the ortho-pericondensed It is a condensed ring group having no structure and optionally having 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 that the condensed ring group B 11 may have is preferably an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted and an optionally substituted monovalent heterocyclic group. The aryl group that the condensed 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-2)又は(b-3)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-2)又は(b-3)で表される基がより好ましい。
Examples of the condensed ring group for B 11 include groups represented by the following formulas (b-1) to (b-14), and hydrogen atoms in these groups are substituents (preferably, substituents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, or an optionally substituted monovalent heterocyclic group ) substituted with. The condensed ring group for B 11 is a group represented by the following formula (b-2) or (b-3), or a hydrogen atom in these groups has a substituent (preferably, a substituent optionally substituted alkyl group, optionally substituted aryl group, optionally substituted alkyloxy group, or optionally substituted monovalent heterocyclic group) is preferred, and a group represented by the following formula (b-2) or (b-3) is more preferred.
式(b-1)~式(b-14)中、
Ra10は、前記定義のとおりである。 In formulas (b-1) to (b-14),
R a10 is as defined above.
Ra10は、前記定義のとおりである。 In formulas (b-1) to (b-14),
R a10 is as defined above.
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 formulas (b-1) to (b-14), a plurality of R a10 are each independently preferably an optionally substituted alkyl group or optionally substituted It is an aryl group.
式(VI)又は式(VII)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 compounds represented by formula (VI) or formula (VII) include compounds 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。
In the above formula, R is as defined above, and X represents a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group.
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 preferably a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted alkyloxy group. .
式(VI)又は(VII)で表される化合物としては、下記式で表される化合物が挙げられる。
Examples of compounds represented by formula (VI) or (VII) include compounds represented by the following formulas.
本実施形態のインク組成物おいて、n型半導体材料は、上記非フラーレン化合物に加えて、さらに既に説明したフラーレン及びフラーレン誘導体(フラーレン化合物)を組み合わせて含んでいてもよい。
In the ink composition of the present embodiment, the n-type semiconductor material may contain, in addition to the non-fullerene compound, a combination of the fullerene and the fullerene derivative (fullerene compound) already described.
本実施形態におけるn型半導体材料の好適な具体例としては、下記式で表される化合物が挙げられる。
Suitable specific examples of the n-type semiconductor material in the present embodiment include compounds represented by the following formulas.
(3)溶媒
本実施形態のインク組成物は、溶媒として、芳香族炭化水素を含みうる。当該芳香族炭化水素は置換基を有していてもよい。芳香族炭化水素としては、特に既に説明したp型半導体材料を溶解させることができる化合物であることが好ましい。 (3) Solvent The ink composition of the present embodiment may contain an aromatic hydrocarbon as a solvent. The aromatic hydrocarbon may have a substituent. The aromatic hydrocarbon is preferably a compound capable of dissolving the p-type semiconductor material already described.
本実施形態のインク組成物は、溶媒として、芳香族炭化水素を含みうる。当該芳香族炭化水素は置換基を有していてもよい。芳香族炭化水素としては、特に既に説明したp型半導体材料を溶解させることができる化合物であることが好ましい。 (3) Solvent The ink composition of the present embodiment may contain an aromatic hydrocarbon as a solvent. The aromatic hydrocarbon may have a substituent. The aromatic hydrocarbon is preferably a compound capable of dissolving the p-type semiconductor material already described.
溶媒として用いられう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)、1,2,3,4-テトラヒドロナフタレン(テトラリン)、インダン、1-クロロナフタレン、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 aromatic hydrocarbons that can be used as solvents include toluene, xylene (eg, o-xylene, m-xylene, p-xylene), trimethylbenzene (eg, mesitylene, 1,2,4-trimethylbenzene (pseudocumene), )), butylbenzene (e.g. n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (e.g. 1-methylnaphthalene), 1,2,3,4-tetrahydronaphthalene (tetralin), indane , 1-chloronaphthalene, chlorobenzene and dichlorobenzene (1,2-dichlorobenzene).
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。
The solvent may be composed of only one aromatic hydrocarbon, or may be composed of two or more aromatic hydrocarbons.
溶媒を構成しうる芳香族炭化水素は、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、1,2,4-トリメチルベンゼン、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、1-クロロナフタレン、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)からなる群から選択される1種以上であり、より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、1,2,4-トリメチルベンゼン、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、1-クロロナフタレン、クロロベンゼン又はジクロロベンゼン(o-ジクロロベンゼン)である。
Aromatic hydrocarbons that can constitute the solvent are preferably toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert. -butylbenzene, methylnaphthalene, tetralin, 1-chloronaphthalene, chlorobenzene and dichlorobenzene (1,2-dichlorobenzene), more preferably toluene, o-xylene, m- xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, tetralin, indane, 1-chloronaphthalene, chlorobenzene or dichlorobenzene (o -dichlorobenzene).
本実施形態のインク組成物は、溶媒として、ハロゲン化アルキルを含みうる。溶媒として用いられうるハロゲン化アルキルとしては、例えば、クロロホルムが挙げられる。
The ink composition of this embodiment may contain an alkyl halide as a solvent. Alkyl halides that can be used as solvents include, for example, chloroform.
本実施形態のインク組成物は、溶媒として、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、1,2,4-トリメチルベンゼン、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、1-クロロナフタレン、クロロベンゼン又はジクロロベンゼン(1,2-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。
As a solvent, the ink composition of the present embodiment preferably includes toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, One or more selected from the group consisting of tert-butylbenzene, methylnaphthalene, tetralin, indane, 1-chloronaphthalene, chlorobenzene or dichlorobenzene (1,2-dichlorobenzene) and chloroform.
本実施形態のインク組成物においては、上記の溶媒に加えて、さらなる溶媒を組み合わせて用いてもよい。
In the ink composition of the present embodiment, in addition to the above solvent, a further solvent may be used in combination.
本実施形態において、さらなる溶媒の例としては、芳香族カルボニル化合物、芳香族エステル化合物及び含窒素複素環式化合物が挙げられる。
In the present embodiment, examples of additional solvents include aromatic carbonyl compounds, aromatic ester compounds and nitrogen-containing heterocyclic compounds.
芳香族カルボニル化合物としては、例えば、置換基を有していてもよいアセトフェノン、置換基を有していてもよいプロピオフェノン、置換基を有していてもよいブチロフェノン、置換基を有していてもよいシクロへキシルフェノン、置換基を有していてもよいベンゾフェノンが挙げられる。
Examples of the aromatic carbonyl compound include acetophenone optionally having substituent(s), propiophenone optionally having substituent(s), butyrophenone optionally having substituent(s), cyclohexylphenone which may be substituted, and benzophenone which may have a substituent.
芳香族エステル化合物としては、例えば、置換基を有していてもよいメチルベンゾエート(安息香酸メチル)、置換基を有していてもよい安息香酸エチル、置換基を有していてもよい安息香酸プロピル、置換基を有していてもよい安息香酸ブチル、置換基を有していてもよい安息香酸イソプロピル、置換基を有していてもよい安息香酸ベンジル、置換基を有していてもよい安息香酸シクロへキシル、置換基を有していてもよい安息香酸フェニルが挙げられる。
Examples of the aromatic ester compound include optionally substituted methyl benzoate (methyl benzoate), optionally substituted ethyl benzoate, and optionally substituted benzoic acid. propyl, optionally substituted butyl benzoate, optionally substituted isopropyl benzoate, optionally substituted benzyl benzoate, optionally substituted Cyclohexyl benzoate and phenyl benzoate which may have a substituent may be mentioned.
含窒素複素環式化合物としては、例えば、置換基を有していてもよいピリジン、置換基を有していてもよいキノリン、置換基を有していてもよいキノキサリン、置換基を有していてもよい1,2,3,4-テトラヒドロキノリン、置換基を有していてもよいピリミジン、置換基を有していてもよいピラジン、及び置換基を有していてもよいキナゾリンが挙げられる。
Examples of nitrogen-containing heterocyclic compounds include optionally substituted pyridine, optionally substituted quinoline, optionally substituted quinoxaline, and optionally substituted optionally substituted pyrimidine, optionally substituted pyrazine, and optionally substituted quinazoline .
含窒素複素環式化合物は、環構造に直接的に結合する置換基を有していてもよい。
The nitrogen-containing heterocyclic compound may have a substituent directly bonded to the ring structure.
含窒素複素環式化合物の環構造(例、キノリン環構造、1,2,3,4-テトラヒドロキノリン環構造、キノキサリン環構造)が有していてもよい置換基としては、例えば、炭素原子数1~5のアルキル基、炭素原子数1~5のアルコキシ基、ハロゲン基、及びアルキルチオ基が挙げられる。
Examples of substituents that the ring structure of the nitrogen-containing heterocyclic compound (e.g., quinoline ring structure, 1,2,3,4-tetrahydroquinoline ring structure, quinoxaline ring structure) may have include: Examples include alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, halogen groups, and alkylthio groups.
ピリジン環構造を含む含窒素複素環式化合物としては、例えば、置換基を有していてもよいピリジン、置換基を有していてもよいキノリン、及び置換基を有していてもよいイソキノリンが挙げられる。
Examples of nitrogen-containing heterocyclic compounds containing a pyridine ring structure include optionally substituted pyridine, optionally substituted quinoline, and optionally substituted isoquinoline. mentioned.
ピラジン環構造を含む含窒素環式化合物としては、例えば、置換基を有していてもよいピラジン、置換基を有していてもよいキノキサリンが挙げられる。
Examples of nitrogen-containing cyclic compounds containing a pyrazine ring structure include optionally substituted pyrazine and optionally substituted quinoxaline.
テトラヒドロピリジン環構造を含む含窒素環式化合物としては、例えば、置換基を有していてもよい1,2,3,4-テトラヒドロキノリン、及び置換基を有していてもよい1,2,3,4-テトラヒドロイソキノリンが挙げられる。
Nitrogen-containing cyclic compounds containing a tetrahydropyridine ring structure include, for example, optionally substituted 1,2,3,4-tetrahydroquinoline and optionally substituted 1,2, 3,4-tetrahydroisoquinolines can be mentioned.
ピリミジン環構造を含む含窒素環式化合物としては、例えば、置換基を有していてもよいピリミジン、及び置換基を有していてもよいキナゾリンが挙げられる。
Examples of nitrogen-containing cyclic compounds containing a pyrimidine ring structure include optionally substituted pyrimidine and optionally substituted quinazoline.
本実施形態において、溶媒は、さらなる溶媒として、芳香族カルボニル化合物、芳香族エステル化合物又は含窒素複素環式化合物をさらに1種のみを含んでいても、これらから選択される2種以上をさらに含んでいてもよい。
In the present embodiment, the solvent further contains an aromatic carbonyl compound, an aromatic ester compound, or a nitrogen-containing heterocyclic compound as a further solvent, or further contains two or more selected from these. You can stay.
本実施形態において、溶媒は、環境保全の観点からハロゲンを含まない溶媒を使用することが好ましい。
In this embodiment, it is preferable to use a halogen-free solvent from the viewpoint of environmental conservation.
(溶媒及びさらなる溶媒の重量比)
本実施形態のインク組成物が、上記溶媒及び上記さらなる溶媒を含む場合、溶媒のさらなる溶媒に対する重量比(溶媒/さらなる溶媒)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、80/20~99.9/0.1の範囲とすることが好ましい。 (weight ratio of solvent and further solvent)
When the ink composition of the present embodiment contains the solvent and the additional solvent, the weight ratio of the solvent to the additional solvent (solvent/additional solvent) further improves the solubility of the p-type semiconductor material and the n-type semiconductor material. From the point of view, the range is preferably from 80/20 to 99.9/0.1.
本実施形態のインク組成物が、上記溶媒及び上記さらなる溶媒を含む場合、溶媒のさらなる溶媒に対する重量比(溶媒/さらなる溶媒)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、80/20~99.9/0.1の範囲とすることが好ましい。 (weight ratio of solvent and further solvent)
When the ink composition of the present embodiment contains the solvent and the additional solvent, the weight ratio of the solvent to the additional solvent (solvent/additional solvent) further improves the solubility of the p-type semiconductor material and the n-type semiconductor material. From the point of view, the range is preferably from 80/20 to 99.9/0.1.
(インク組成物における溶媒の重量百分率)
インク組成物に含まれる溶媒の総重量は、インク組成物の全重量を100質量%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質量%以上であり、より好ましくは92質量%以上であり、さらに好ましくは95質量%以上であり、インク組成物中のp型半導体材料及びn型半導体材料の濃度をより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質量%以下である。 (Weight percentage of solvent in ink composition)
The total weight of the solvent contained in the ink composition is preferably 90 mass 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 ink composition is 100 mass%. % or more, more preferably 92% by mass or more, and still more preferably 95% by mass or more, and the concentration of the p-type semiconductor material and the n-type semiconductor material in the ink composition is increased to achieve a constant thickness From the viewpoint of facilitating the formation of the above layers, the content is preferably 99.9% by mass or less.
インク組成物に含まれる溶媒の総重量は、インク組成物の全重量を100質量%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質量%以上であり、より好ましくは92質量%以上であり、さらに好ましくは95質量%以上であり、インク組成物中のp型半導体材料及びn型半導体材料の濃度をより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質量%以下である。 (Weight percentage of solvent in ink composition)
The total weight of the solvent contained in the ink composition is preferably 90 mass 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 ink composition is 100 mass%. % or more, more preferably 92% by mass or more, and still more preferably 95% by mass or more, and the concentration of the p-type semiconductor material and the n-type semiconductor material in the ink composition is increased to achieve a constant thickness From the viewpoint of facilitating the formation of the above layers, the content is preferably 99.9% by mass or less.
インク組成物は、既に説明した溶媒及びさらなる溶媒に加えて、任意の溶媒をさらに含んでいてもよい。インク組成物に含まれる全溶媒の合計重量を100重量%とした場合に、任意の溶媒の含有率は、好ましくは10質量%以下であり、より好ましくは5質量%以下であり、さらに好ましくは3重量%以下である。任意の溶媒としては、さらなる溶媒より沸点が高い溶媒を用いることが好ましい。
The ink composition may further contain any solvent in addition to the solvents and additional solvents already described. When the total weight of all solvents contained in the ink composition is 100% by weight, the content of any solvent is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by weight or less. As the optional solvent, it is preferred to use a solvent with a higher boiling point than the further solvent.
(インク組成物におけるp型半導体材料及びn型半導体材料の濃度)
インク組成物における、p型半導体材料及びn型半導体材料の合計の濃度は、必要とされる機能層(活性層)の厚さ、所望の特性等に応じて、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質量%以上であり、より好ましくは0.1質量%以上であり、好ましくは10質量%以下であり、より好ましくは5質量%以下であり、さらに好ましくは0.01質量%以上20質量%以下であり、特に好ましくは0.01質量%以上10重量%以下であり、さらに特に好ましくは0.01質量%以上5質量%以下であり、とりわけ好ましくは0.1質量%以上5質量%以下である。 (Concentration of p-type semiconductor material and n-type semiconductor material in ink composition)
The total concentration of the p-type semiconductor material and the n-type semiconductor material in the ink composition may be any suitable concentration depending on the thickness of the required functional layer (active layer), desired properties, etc. can. The total concentration of the p-type semiconductor material and the n-type semiconductor material is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, preferably 10% by mass or less, and more preferably 5% by mass or less, more preferably 0.01% by mass or more and 20% by mass or less, particularly preferably 0.01% by mass or more and 10% by mass or less, and even more preferably 0.01% by mass or more and 5 % by mass or less, particularly preferably 0.1% by mass or more and 5% by mass or less.
インク組成物における、p型半導体材料及びn型半導体材料の合計の濃度は、必要とされる機能層(活性層)の厚さ、所望の特性等に応じて、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質量%以上であり、より好ましくは0.1質量%以上であり、好ましくは10質量%以下であり、より好ましくは5質量%以下であり、さらに好ましくは0.01質量%以上20質量%以下であり、特に好ましくは0.01質量%以上10重量%以下であり、さらに特に好ましくは0.01質量%以上5質量%以下であり、とりわけ好ましくは0.1質量%以上5質量%以下である。 (Concentration of p-type semiconductor material and n-type semiconductor material in ink composition)
The total concentration of the p-type semiconductor material and the n-type semiconductor material in the ink composition may be any suitable concentration depending on the thickness of the required functional layer (active layer), desired properties, etc. can. The total concentration of the p-type semiconductor material and the n-type semiconductor material is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, preferably 10% by mass or less, and more preferably 5% by mass or less, more preferably 0.01% by mass or more and 20% by mass or less, particularly preferably 0.01% by mass or more and 10% by mass or less, and even more preferably 0.01% by mass or more and 5 % by mass or less, particularly preferably 0.1% by mass or more and 5% by mass or less.
インク組成物中、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。インク組成物中、p型半導体材料及びn型半導体材料は、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。
The p-type semiconductor material and the n-type semiconductor material may be dissolved or dispersed in the ink composition. In the ink composition, the p-type semiconductor material and the n-type semiconductor material are preferably at least partially dissolved, more preferably completely dissolved.
(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))
インク組成物中の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以上であり、より好ましくは1/5以上であり、さらに好ましくは1/3以上であり、好ましくは9/1以下であり、より好ましくは5/1以下であり、さらに好ましく好ましくは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 ink composition is preferably 1/9 or more, more preferably 1/5 or more, and further It is preferably 1/3 or more, preferably 9/1 or less, more preferably 5/1 or less, still more preferably 3/1 or less.
インク組成物中の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以上であり、より好ましくは1/5以上であり、さらに好ましくは1/3以上であり、好ましくは9/1以下であり、より好ましくは5/1以下であり、さらに好ましく好ましくは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 ink composition is preferably 1/9 or more, more preferably 1/5 or more, and further It is preferably 1/3 or more, preferably 9/1 or less, more preferably 5/1 or less, still more preferably 3/1 or less.
3.インク組成物の製造方法
本実施形態のインク組成物の製造方法は、上記のとおり、p型半導体材料、n型半導体材料及び溶媒を選択して調製されたインク組成物が、孔径0.5μm以下のフィルターでろ過される工程を含む。 3. Method for Producing Ink Composition In the method for producing the ink composition of the present embodiment, as described above, the ink composition prepared by selecting the p-type semiconductor material, the n-type semiconductor material, and the solvent has a pore size of 0.5 μm or less. including the process of being filtered through a filter of
本実施形態のインク組成物の製造方法は、上記のとおり、p型半導体材料、n型半導体材料及び溶媒を選択して調製されたインク組成物が、孔径0.5μm以下のフィルターでろ過される工程を含む。 3. Method for Producing Ink Composition In the method for producing the ink composition of the present embodiment, as described above, the ink composition prepared by selecting the p-type semiconductor material, the n-type semiconductor material, and the solvent has a pore size of 0.5 μm or less. including the process of being filtered through a filter of
また、本実施形態のインク組成物の製造方法は、p型半導体材料である複数種類の高分子化合物を準備する準備工程と、準備工程で準備した高分子化合物のうち、z平均分子量が5.0×105未満である高分子化合物をp型半導体材料として選別する選別工程と、選別工程で選別されたp型半導体材料とn型半導体材料と溶媒とを混合して、インク組成物を製造する工程とを含む、光電変換素子製造用のインク組成物の製造方法であってもよい。
Further, the method for producing an ink composition according to the present embodiment includes a preparatory step of preparing a plurality of types of polymer compounds that are p-type semiconductor materials; A selection step of selecting a polymer compound of less than 0×10 5 as a p-type semiconductor material, and mixing the p-type semiconductor material and n-type semiconductor material selected in the selection step with a solvent to produce an ink composition. It may be a method for producing an ink composition for producing a photoelectric conversion element, comprising the step of
z平均分子量が5.0×105未満である高分子化合物をp型半導体材料として選別する選別工程は、準備工程で準備した高分子化合物について、例えば、既に説明した測定方法によりz平均分子量を測定し、測定されたz平均分子量に基づいて選別する選別工程とすることができる。
In the selection step of selecting a polymer compound having a z-average molecular weight of less than 5.0×10 5 as a p-type semiconductor material, the z-average molecular weight of the polymer compound prepared in the preparation step is determined by, for example, the already described measurement method. It can be a sorting step that measures and sorts based on the measured z-average molecular weight.
本実施形態において、インク組成物は、従来公知の任意好適な方法により製造することができる。特に2種以上の溶媒が用いられる場合には、例えば、既に説明した溶媒及びさらなる溶媒を混合して混合溶媒を調製した後、混合溶媒にp型半導体材料及びn型半導体材料を添加して製造する方法、さらには溶媒にp型半導体材料を添加した(第1)組成物を調製し、これとは別に、さらなる溶媒にn型半導体材料を添加した(第2)組成物を調製し、得られた2種以上の組成物を混合して調製(製造)する方法、換言すると、組成物を調製する工程が、2種以上の組成物を調製する工程を含み、インク組成物を調製する工程が、2種以上の組成物を混合する工程を含む製造方法などにより、製造することができる。
In the present embodiment, the ink composition can be produced by any suitable conventionally known method. In particular, when two or more solvents are used, for example, after preparing a mixed solvent by mixing the already described solvent and a further solvent, the mixed solvent is added with a p-type semiconductor material and an n-type semiconductor material. Further, a (first) composition is prepared by adding a p-type semiconductor material to a solvent, and separately from this, a (second) composition is prepared by adding an n-type semiconductor material to an additional solvent. A method of preparing (manufacturing) by mixing two or more compositions obtained, in other words, a step of preparing a composition includes a step of preparing two or more compositions, and a step of preparing an ink composition However, it can be produced by a production method including a step of mixing two or more compositions.
インク組成物を調製するにあたり、溶媒(及びさらなる溶媒)とp型半導体材料及びn型半導体材料とを、溶媒の沸点以下の温度まで加温して混合してもよい。
In preparing the ink composition, the solvent (and further solvent), the p-type semiconductor material and the n-type semiconductor material may be heated to a temperature below the boiling point of the solvent and mixed.
本実施形態において、インク組成物を調製する工程は、0℃以上200℃以下の条件下で行われることが好ましく、0℃以上100℃以下での条件下で行われることが好ましい。
In the present embodiment, the step of preparing the ink composition is preferably carried out under conditions of 0°C or higher and 200°C or lower, and preferably carried out under conditions of 0°C or higher and 100°C or lower.
本実施形態において、調製されたインク組成物をろ過する工程は、具体的には、インク組成物を調製(製造)するにあたり、溶媒(及びさらなる溶媒)とp型半導体材料及びn型半導体材料とを混合した後、得られた混合物(インク組成物)を、所定の孔径を有するフィルターを用いて常法に従ってろ過すればよい。
In the present embodiment, the step of filtering the prepared ink composition is specifically performed by mixing the solvent (and further solvent), the p-type semiconductor material and the n-type semiconductor material in preparing (manufacturing) the ink composition. are mixed, the resulting mixture (ink composition) may be filtered by a conventional method using a filter having a predetermined pore size.
本実施形態において、ろ過に用いられうるフィルターとしては、例えば、セルロースアセテート、ガラス繊維、ポリフッ化ビニリデン(PVdF)、ポリテトラフルオロエチレン(PTFE)といったフッ素樹脂で形成されたフィルターが挙げられる。
In this embodiment, filters that can be used for filtration include, for example, filters made of fluororesins such as cellulose acetate, glass fiber, polyvinylidene fluoride (PVdF), and polytetrafluoroethylene (PTFE).
本実施形態において、用いられうるフィルターの孔径は、フィルターの入手性、ろ過の効率、形成される機能層(活性層)における欠陥発生を抑制する観点から、好ましくは1μm以下であり、より好ましくは0.5μm以下であり、さらに好ましくは0.45μm以下であり、好ましくは0.1μm以上であり、より好ましくは0.4μm以上であり、好ましくは0.1μm~0.5μmであり、より好ましくは0.1μm~0.5μmである。
In the present embodiment, the pore size of the filter that can be used is preferably 1 μm or less, more preferably 1 μm or less, from the viewpoint of filter availability, filtration efficiency, and suppression of defects in the formed functional layer (active layer). 0.5 μm or less, more preferably 0.45 μm or less, preferably 0.1 μm or more, more preferably 0.4 μm or more, preferably 0.1 μm to 0.5 μm, more preferably is 0.1 μm to 0.5 μm.
4.インク組成物の用途
本実施形態のインク組成物は、通常、p型半導体材料及びn型半導体材料を含む膜を形成するために用いられる。 4. Application of Ink Composition The ink composition of the present embodiment is generally used to form a film containing a p-type semiconductor material and an n-type semiconductor material.
本実施形態のインク組成物は、通常、p型半導体材料及びn型半導体材料を含む膜を形成するために用いられる。 4. Application of Ink Composition The ink composition of the present embodiment is generally used to form a film containing a p-type semiconductor material and an n-type semiconductor material.
本実施形態のインク組成物は、光電変換素子に含まれる活性層を形成するために好適に用いられる。特に、本実施形態のインク組成物は、使用時において逆バイアス電圧が印加される光検出素子に含まれる活性層を形成するために特に好適に用いることができる。
The ink composition of this embodiment is suitably used for forming an active layer included in a photoelectric conversion element. In particular, the ink composition of the present embodiment can be used particularly suitably for forming an active layer included in a photodetector to which a reverse bias voltage is applied during use.
5.インク組成物の固化膜
本実施形態のインク組成物を用いて膜を形成した後、膜から溶媒を除去して膜を固化させることによりインク組成物の固化膜を形成することができる。インク組成物の固化膜は光検出素子に含まれる機能層、特に活性層を形成するために好適に用いることができる。
インク組成物の固化膜は、任意好適な製造方法により製造することができる。 5. Solidified Film of Ink Composition After forming a film using the ink composition of the present embodiment, the solidified film of the ink composition can be formed by removing the solvent from the film and solidifying the film. A solidified film of the ink composition can be suitably used to form a functional layer, particularly an active layer, included in the photodetector.
The solidified film of the ink composition can be produced by any suitable production method.
本実施形態のインク組成物を用いて膜を形成した後、膜から溶媒を除去して膜を固化させることによりインク組成物の固化膜を形成することができる。インク組成物の固化膜は光検出素子に含まれる機能層、特に活性層を形成するために好適に用いることができる。
インク組成物の固化膜は、任意好適な製造方法により製造することができる。 5. Solidified Film of Ink Composition After forming a film using the ink composition of the present embodiment, the solidified film of the ink composition can be formed by removing the solvent from the film and solidifying the film. A solidified film of the ink composition can be suitably used to form a functional layer, particularly an active layer, included in the photodetector.
The solidified film of the ink composition can be produced by any suitable production method.
本実施形態において、インク組成物の固化膜の製造方法は、インク組成物を塗布対象に塗布して塗膜を得る工程(i)、及び得られた塗膜から溶媒を除去する工程(ii)を含む。以下、工程(i)及び工程(ii)について説明する。
In the present embodiment, the method for producing a solidified film of an ink composition includes a step (i) of applying the ink composition to an object to be coated to obtain a coating film, and a step (ii) of removing the solvent from the obtained coating film. including. Steps (i) and (ii) are described below.
[工程(i)]
工程(i)において、インク組成物を塗布対象に塗布する方法としては、既に説明した従来公知の任意の塗布法を用いることができる。本実施形態において、塗布法としては、スリットコート法、ナイフコート法、スピンコート法、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、インクジェットコート法、ノズルコート法、又はキャピラリーコート法が好ましく、スリットコート法、スピンコート法、キャピラリーコート法、又はバーコート法がより好ましく、スリットコート法又はスピンコート法がさらに好ましい。 [Step (i)]
In the step (i), as a method of applying the ink composition to the object to be applied, any conventionally known application method that has already been described can be used. In the present embodiment, the coating method is preferably a slit coating method, a knife coating method, a spin coating method, a micro gravure coating method, a gravure coating method, a bar coating method, an inkjet coating method, a nozzle coating method, or a capillary coating method. A slit coating method, a spin coating method, a capillary coating method, or a bar coating method is more preferable, and a slit coating method or a spin coating method is even more preferable.
工程(i)において、インク組成物を塗布対象に塗布する方法としては、既に説明した従来公知の任意の塗布法を用いることができる。本実施形態において、塗布法としては、スリットコート法、ナイフコート法、スピンコート法、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、インクジェットコート法、ノズルコート法、又はキャピラリーコート法が好ましく、スリットコート法、スピンコート法、キャピラリーコート法、又はバーコート法がより好ましく、スリットコート法又はスピンコート法がさらに好ましい。 [Step (i)]
In the step (i), as a method of applying the ink composition to the object to be applied, any conventionally known application method that has already been described can be used. In the present embodiment, the coating method is preferably a slit coating method, a knife coating method, a spin coating method, a micro gravure coating method, a gravure coating method, a bar coating method, an inkjet coating method, a nozzle coating method, or a capillary coating method. A slit coating method, a spin coating method, a capillary coating method, or a bar coating method is more preferable, and a slit coating method or a spin coating method is even more preferable.
工程(i)において、インク組成物は、任意の塗布対象に塗布される。インク組成物は、光電変換素子の製造工程において、例えば、電極(陽極又は陰極)、電子輸送層、又は正孔輸送層などの光電変換素子が含みうる機能層に塗布されうる。
In step (i), the ink composition is applied to any application target. The ink composition can be applied to a functional layer that can be included in the photoelectric conversion element, such as an electrode (anode or cathode), an electron transport layer, or a hole transport layer, during the manufacturing process of the photoelectric conversion element.
[工程(ii)]
工程(ii)において、工程(i)により形成されたインク組成物の塗膜から、溶媒を除去する方法としては、任意好適な方法を用いることができる。溶媒を除去する方法の例としては、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が挙げられる。 [Step (ii)]
In step (ii), any suitable method can be used as a method for removing the solvent from the coating film of the ink composition formed in step (i). Examples of methods for removing the solvent include drying methods such as hot air drying, infrared heating drying, flash lamp annealing drying, and vacuum drying.
工程(ii)において、工程(i)により形成されたインク組成物の塗膜から、溶媒を除去する方法としては、任意好適な方法を用いることができる。溶媒を除去する方法の例としては、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が挙げられる。 [Step (ii)]
In step (ii), any suitable method can be used as a method for removing the solvent from the coating film of the ink composition formed in step (i). Examples of methods for removing the solvent include drying methods such as hot air drying, infrared heating drying, flash lamp annealing drying, and vacuum drying.
6.光電変換素子
(1)光電変換素子の構成
本実施形態にかかる光電変換素子は、第1電極と、第2の電極と、該第1電極及び第2の電極の間に設けられている活性層とを含み、該活性層が既に説明した固化膜である。 6. Photoelectric conversion element (1) Structure of photoelectric conversion element The photoelectric conversion element according to the present embodiment includes a first electrode, a second electrode, and an active layer provided between the first electrode and the second electrode. and wherein the active layer is the solidified film already described.
(1)光電変換素子の構成
本実施形態にかかる光電変換素子は、第1電極と、第2の電極と、該第1電極及び第2の電極の間に設けられている活性層とを含み、該活性層が既に説明した固化膜である。 6. Photoelectric conversion element (1) Structure of photoelectric conversion element The photoelectric conversion element according to the present embodiment includes a first electrode, a second electrode, and an active layer provided between the first electrode and the second electrode. and wherein the active layer is the solidified film already described.
以下、図面を参照して本実施形態の光電変換素子の構成例について具体的に説明する。
A configuration example of the photoelectric conversion element of the present embodiment will be specifically described below 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1の電極12と、第1の電極12に接するように設けられている電子輸送層13と、電子輸送層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正孔輸送層15と、正孔輸送層15に接するように設けられている第2の電極16とを備えている。この構成例では、第1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。
As shown in FIG. 1, the photoelectric conversion element 10 is provided on a support substrate 11. As shown in FIG. The photoelectric conversion element 10 includes a first electrode 12 provided in contact with a support substrate 11 , an electron transport layer 13 provided in contact with the first electrode 12 , and an electron transport layer 13 provided in contact with the electron transport layer 13 . , a hole transport layer 15 provided in contact with the active layer 14, and a second electrode 16 provided in contact with the hole transport layer 15. there is In this configuration example, a sealing member 17 is further provided so as to be in contact with the first electrode 16 .
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。
Constituent elements that can be included in the photoelectric conversion element of the present embodiment will be specifically described below.
(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1の電極及び第2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)
A photoelectric conversion element is usually formed on a substrate (support substrate). Further, it may be further sealed with a substrate (sealing substrate). One of a pair of electrodes consisting of a first electrode and a second electrode is usually 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 the layer containing the organic compound is formed.
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1の電極及び第2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)
A photoelectric conversion element is usually formed on a substrate (support substrate). Further, it may be further sealed with a substrate (sealing substrate). One of a pair of electrodes consisting of a first electrode and a second electrode is usually 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 the layer containing the organic compound is formed.
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 substrate materials include glass, plastic, polymer film, and silicon. When an opaque substrate is used, the electrode opposite to the electrode provided on the opaque substrate (in other words, the electrode on the far side from the opaque substrate) is preferably a transparent or translucent electrode. .
(電極)
光電変換素子は、一対の電極である第1の電極及び第2の電極を含んでいる。第1の電極及び第2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)
A photoelectric conversion element includes a pair of electrodes, a first electrode and a second electrode. At least one of the first electrode and the second electrode is preferably 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1の電極及び第2の電極を含んでいる。第1の電極及び第2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)
A photoelectric conversion element includes a pair of electrodes, a first electrode and a second electrode. At least one of the first electrode and the second electrode is preferably 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1の電極であっても第2の電極であってもよい。
Examples of materials for transparent or semi-transparent electrodes include conductive metal oxide films and semi-transparent metal thin films. Specifically, indium oxide, zinc oxide, tin oxide, and their composites indium tin oxide (ITO), indium zinc oxide (IZO), conductive materials such as NESA, gold, platinum, silver, copper. ITO, IZO, and tin oxide are preferable as materials for transparent or translucent electrodes. Moreover, as the electrode, a transparent conductive film using an organic compound such as polyaniline and its derivatives, polythiophene and its derivatives 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 electrode of the pair of electrodes is transparent or translucent, the other electrode may be an electrode with low light transmittance. Examples of materials for electrodes with low light transmittance include metals and conductive polymers. Specific examples of low light transmissive electrode materials include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, Metals such as terbium, ytterbium, and alloys of two or more thereof, or one or more of these metals together with gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin alloys with one or more metals selected from the group consisting of graphite, graphite intercalation compounds, polyaniline and its derivatives, polythiophene and its derivatives. Alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, and calcium-aluminum alloys.
(活性層)
本実施形態の光電変換素子は、活性層として、既に説明したインク組成物の固化膜を含む。本実施形態の活性層は、バルクヘテロジャンクション型の構造を有している。 (active layer)
The photoelectric conversion element of this embodiment includes the solidified film of the ink composition already described as an active layer. The active layer of this embodiment has a bulk heterojunction structure.
本実施形態の光電変換素子は、活性層として、既に説明したインク組成物の固化膜を含む。本実施形態の活性層は、バルクヘテロジャンクション型の構造を有している。 (active layer)
The photoelectric conversion element of this embodiment includes the solidified film of the ink composition already described as an active layer. The active layer of this embodiment has a bulk heterojunction structure.
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、例えば、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100nm以上であり、さらに好ましくは200nm以上である。また、活性層の厚さは、好ましくは5μm以下であり、より好ましくは1μm以下であり、さらに好ましくは600nm以下である。
In this embodiment, the thickness of the active layer is not particularly limited. The thickness of the active layer can be any suitable thickness, for example, considering the balance between suppression of dark current and extraction of the generated photocurrent. The thickness of the active layer is preferably 100 nm or more, more preferably 100 nm or more, and even more preferably 200 nm or more, particularly from the viewpoint of further reducing dark current. Also, the thickness of the active layer is preferably 5 μm or less, more preferably 1 μm or less, and still more preferably 600 nm 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 device of the present embodiment includes, for example, a charge transport layer (electron transport layer, hole transport layer, electron injection layer, An intermediate layer (buffer layer) such as a hole injection layer is preferably provided.
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 device of the present embodiment includes, for example, a charge transport layer (electron transport layer, hole transport layer, electron injection layer, An intermediate layer (buffer layer) such as a hole injection layer is preferably provided.
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( 4-styrenesulfonate)) (PEDOT:PSS).
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 any suitable conventionally known forming method. The intermediate layer can be formed by a vacuum deposition method or a coating method similar to the method for forming the active layer.
図1に示されるように、本実施形態の光電変換素子は、第1の電極と活性層との間に、電子輸送層を備えることが好ましい。電子輸送層は、活性層から電極へと電子を輸送する機能を有する。
As shown in FIG. 1, the photoelectric conversion element of this embodiment preferably has an electron transport layer between the first electrode and the active layer. The electron transport layer has a function of transporting electrons from the active layer to the electrode.
別の実施形態では、光電変換素子は、電子輸送層を備えていなくてもよい。
In another embodiment, the photoelectric conversion element may not have an electron transport layer.
第1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1の電極に接して設けられる電子輸送層(電子注入層)は、第1の電極への電子の注入を促進する機能を有する。電子輸送層(電子注入層)は、活性層に接していてもよい。
The electron transport layer provided in contact with the first electrode is sometimes called an electron injection layer. An electron transport layer (electron injection layer) provided in contact with the first electrode has a function of promoting injection of electrons into the first electrode. The electron transport layer (electron injection layer) may be in contact with the active layer.
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-transporting layer contains an electron-transporting material. Examples of electron-transporting materials include polyalkyleneimine and derivatives thereof, high-molecular compounds having 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 alkyleneimine having 2 to 8 carbon atoms, especially alkyleneimine having 2 to 8 carbon atoms, such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, octyleneimine. Polymers obtained by conventionally polymerizing one or more of 2 to 4 alkyleneimines, and polymers chemically modified by reacting them with various compounds can be mentioned. Preferred polyalkyleneimines and derivatives thereof are polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE).
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 perylene diimide.
本実施形態にかかる光電変換素子は、中間層が電子輸送層であって、基板(支持基板)、第1の電極、電子輸送層、活性層、正孔輸送層、第2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 this embodiment, the intermediate layer is the electron transport layer, and the substrate (supporting substrate), the first electrode, the electron transport layer, the active layer, the hole transport layer, and the second electrode are arranged in this order. It is preferred to have a configuration that is stacked against each other.
図1に示されるように、本実施形態の光電変換素子は、第2の電極と活性層との間に、中間層として正孔輸送層を備えていることが好ましい。正孔輸送層は、活性層から第2の電極へと正孔を輸送する機能を有する。正孔輸送層は、第2の電極に接していてもよい。
正孔輸送層は活性層に接していてもよい。 As shown in FIG. 1, the photoelectric conversion device of the present embodiment preferably has a hole transport layer as an intermediate layer between the second electrode and the active layer. The hole transport layer has a function of transporting holes from the active layer to the second electrode. The hole transport layer may be in contact with the second electrode.
The hole transport layer may be in contact with the active layer.
正孔輸送層は活性層に接していてもよい。 As shown in FIG. 1, the photoelectric conversion device of the present embodiment preferably has a hole transport layer as an intermediate layer between the second electrode and the active layer. The hole transport layer has a function of transporting holes from the active layer to the second electrode. The hole transport layer may be in contact with the second electrode.
The hole transport layer may be in contact with the active 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 another embodiment, the photoelectric conversion element may not have a hole transport layer.
第2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2の電極に接して設けられる正孔輸送層(正孔注入層)は、活性層で発生した正孔の第2の電極への注入を促進する機能を有する。
The hole-transporting layer provided in contact with the second electrode is sometimes called a hole-injecting layer. A hole transport layer (hole injection layer) provided in contact with the second electrode has a function of promoting injection of holes generated in the active layer into the second electrode.
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-transporting layer contains a hole-transporting material. Examples of hole-transporting materials include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing constitutional units having aromatic amine residues, CuSCN, CuI, NiO, tungsten oxide (WO 3 ) and molybdenum oxide. (MoO 3 ).
(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。 (sealing member)
Preferably, the photoelectric conversion element of the present embodiment further includes a sealing member, and is a sealed body sealed with the sealing member.
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。 (sealing member)
Preferably, the photoelectric conversion element of the present embodiment further includes a sealing member, and is a sealed body sealed with the sealing member.
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。
Any suitable conventionally known member can be used as the sealing member. Examples of the sealing member include a combination of a glass substrate as 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 layers constituting the sealing layer include gas barrier layers and gas barrier films.
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 made of a material that has a property of blocking moisture (water vapor barrier property) or a property of blocking oxygen (oxygen barrier property). Examples of suitable materials for the sealing layer include polyethylene trifluoride, polytrifluoroethylene chloride (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, ethylene-vinyl alcohol copolymer, and the like. Examples include organic materials, inorganic materials such as silicon oxide, silicon nitride, aluminum oxide, and 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うる材料により構成される。
The sealing member is usually made of a material that can withstand a heat treatment to which the photoelectric conversion element is applied, for example, when it is incorporated into a device of the application example described later.
(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、従来公知の任意好適な製造方法により製造しうる。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工程を組み合わせて製造すればよい。 (2) Manufacturing Method of Photoelectric Conversion Element The photoelectric conversion element of the present embodiment can be manufactured by any suitable conventionally known manufacturing method. The photoelectric conversion element of the present embodiment may be manufactured by combining processes suitable for materials selected for forming constituent elements.
本実施形態の光電変換素子は、従来公知の任意好適な製造方法により製造しうる。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工程を組み合わせて製造すればよい。 (2) Manufacturing Method of Photoelectric Conversion Element The photoelectric conversion element of the present embodiment can be manufactured by any suitable conventionally known manufacturing method. The photoelectric conversion element of the present embodiment may be manufactured by combining processes suitable for materials selected for forming constituent elements.
以下、本発明の実施形態として、基板(支持基板)、第1の電極、正孔輸送層、活性層、電子輸送層、第2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を説明する。
Hereinafter, as an embodiment of the present invention, a method for manufacturing a photoelectric conversion element having a configuration in which a substrate (supporting substrate), a first electrode, a hole transport layer, an active layer, an electron transport layer, and a second electrode are in contact with each other in this order. explain.
(基板を用意する工程)
本工程では、例えば第1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1の電極を形成することにより、第1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 of preparing substrate)
In this step, for example, a support substrate provided with a first electrode is prepared. Alternatively, a substrate provided with a conductive thin film formed of the electrode material already described is obtained from the market, and if necessary, the conductive thin film is patterned to form a first electrode, A support substrate provided with a first electrode can be prepared.
本工程では、例えば第1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1の電極を形成することにより、第1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 of preparing substrate)
In this step, for example, a support substrate provided with a first electrode is prepared. Alternatively, a substrate provided with a conductive thin film formed of the electrode material already described is obtained from the market, and if necessary, the conductive thin film is patterned to form a first electrode, A support substrate provided with a 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1の電極を形成する場合の第1の電極の形成方法は特に限定されない。第1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1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 the photoelectric conversion element according to this embodiment, the method for forming the first electrode is not particularly limited when the first electrode is formed on the support substrate. The first electrode is a structure in which the first electrode is formed by any suitable conventionally known method such as a vacuum deposition method, a sputtering method, an ion plating method, a plating method, a coating method, etc., using the material already described ( (e.g., supporting substrate, active layer, 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1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。 (Step 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1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。 (Step 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を構成しうる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。 A method for forming the hole transport layer is not particularly limited. From the viewpoint of simplifying the process of forming the hole transport layer, it is preferable to form the hole transport layer by any suitable conventionally known coating method.
The hole transport layer can be formed, for example, by a coating method or a vacuum deposition method using a coating liquid containing a material capable of forming the hole transport layer and a solvent.
正孔輸送層は、例えば、既に説明した正孔輸送層を構成しうる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。 A method for forming the hole transport layer is not particularly limited. From the viewpoint of simplifying the process of forming the hole transport layer, it is preferable to form the hole transport layer by any suitable conventionally known coating method.
The hole transport layer can be formed, for example, by a coating method or a vacuum deposition method using a coating liquid containing a material capable of forming the hole transport layer and a solvent.
(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が形成される。活性層は、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、活性層は、既に説明したインク組成物を用いる塗布法により製造することができる。 (Step of forming active layer)
In the method for manufacturing the photoelectric conversion element of this embodiment, the active layer is formed on the hole transport layer. The active layer can be formed by any suitable conventionally known formation process. In this embodiment, the active layer can be produced by a coating method using the ink composition already described.
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が形成される。活性層は、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、活性層は、既に説明したインク組成物を用いる塗布法により製造することができる。 (Step of forming active layer)
In the method for manufacturing the photoelectric conversion element of this embodiment, the active layer is formed on the hole transport layer. The active layer can be formed by any suitable conventionally known formation process. In this embodiment, the active layer can be produced by a coating method using the ink composition already described.
活性層は、既に説明した「固化膜」と同様にして形成することができる。本実施形態では、p型半導体材料と、n型半導体材料と、溶媒とを含むインク組成物を、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、活性層を形成することができる。
The active layer can be formed in the same manner as the "solidified film" already described. In this embodiment, a step of applying an ink composition containing a p-type semiconductor material, an n-type semiconductor material, and a solvent onto a hole transport layer to form a coating film, and then drying the coating film. An active layer can be formed by a process including a process.
(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、活性層に接するよう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みうる。 (Step of forming electron transport layer)
The method for manufacturing the photoelectric conversion element of this embodiment can include a step of forming an electron transport layer (electron injection layer) provided so as to be in contact with the active layer.
本実施形態の光電変換素子の製造方法は、活性層に接するよう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みうる。 (Step of forming electron transport layer)
The method for manufacturing the photoelectric conversion element of this embodiment can include a step of forming an electron transport layer (electron injection layer) provided so as to be in contact with 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 for forming the electron transport layer is not particularly limited. From the viewpoint of making the step of forming the electron transport layer simpler, it is preferable to form the electron transport layer by any suitable conventionally known vacuum vapor deposition method.
(第2の電極の形成工程)
第2の電極の形成方法は特に限定されない。第2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 second electrode)
A method for forming the second electrode is not particularly limited. The second electrode can be formed, for example, from the materials of the electrodes exemplified above by any suitable conventionally known method such as a coating method, a vacuum deposition method, a sputtering method, an ion plating method, and a plating method. Through the above steps, the photoelectric conversion element of this embodiment is manufactured.
第2の電極の形成方法は特に限定されない。第2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 second electrode)
A method for forming the second electrode is not particularly limited. The second electrode can be formed, for example, from the materials of the electrodes exemplified above by any suitable conventionally known method such as a coating method, a vacuum deposition method, a sputtering method, an ion plating method, and a plating method. Through the above steps, the photoelectric conversion element of this 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。 (Step of forming sealing body)
In forming the sealing body, in the present embodiment, a conventionally known and suitable sealing material (adhesive) and substrate (sealing substrate) are used. Specifically, a sealing material such as a UV curable resin is applied to the support substrate so as to surround the manufactured photoelectric conversion element, and the sealing material is used to bond the substrate without any gaps. A photoelectric conversion element sealed body can be obtained by sealing the photoelectric conversion element in the gap between the support substrate and the sealing substrate using a method such as irradiation of UV light, which is suitable for the sealing material. 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。 (Step of forming sealing body)
In forming the sealing body, in the present embodiment, a conventionally known and suitable sealing material (adhesive) and substrate (sealing substrate) are used. Specifically, a sealing material such as a UV curable resin is applied to the support substrate so as to surround the manufactured photoelectric conversion element, and the sealing material is used to bond the substrate without any gaps. A photoelectric conversion element sealed body can be obtained by sealing the photoelectric conversion element in the gap between the support substrate and the sealing substrate using a method such as irradiation of UV light, which is suitable for the sealing material. can.
(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。 (3) Applications of Photoelectric Conversion Element Applications of the photoelectric conversion element of the present embodiment include photodetection elements and solar cells.
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。 (3) Applications of Photoelectric Conversion Element Applications of the photoelectric conversion element of the present embodiment include photodetection elements and solar cells.
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。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。
More specifically, the photoelectric conversion element of the present embodiment allows a photocurrent to flow by irradiating light from the transparent or translucent electrode side while a voltage (reverse bias voltage) is applied between the electrodes. and can be operated as a photodetector (optical sensor). Also, it can be used as an image sensor by integrating a plurality of photodetectors. The photoelectric conversion element of this embodiment can be suitably used particularly as a photodetector.
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。
In addition, the photoelectric conversion element of the present embodiment can generate a photovoltaic force between 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.
(4)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。 (4) Application Examples of Photoelectric Conversion Element The photoelectric conversion element according to the present embodiment can be used as a photodetector in various electronic devices such as workstations, personal computers, personal digital assistants, entrance/exit management systems, digital cameras, and medical equipment. It can be suitably applied to the detection unit provided in the device.
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。 (4) Application Examples of Photoelectric Conversion Element The photoelectric conversion element according to the present embodiment can be used as a photodetector in various electronic devices such as workstations, personal computers, personal digital assistants, entrance/exit management systems, digital cameras, and medical equipment. It can be suitably applied to the detection unit provided in the device.
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 is provided in the above-exemplified electronic device, for example, an image detection unit for a solid-state imaging device such as an X-ray imaging device and a CMOS image sensor (e.g., an image sensor such as an X-ray sensor), a fingerprint Detection units of biometric information authentication devices that detect predetermined features of a part of a living body, such as detection units, face detection units, vein detection units, and iris detection units (e.g., near-infrared sensors), and optical biosensors such as pulse oximeters. 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 this 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 measurement device (TOF type distance measurement 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。
The TOF rangefinder measures the distance by causing the photoelectric conversion element to receive the light emitted from the light source and reflected by the object to be measured. Specifically, the distance to the object to be measured is obtained by detecting the time of flight until the irradiation light emitted from the light source is reflected by the object to be measured and returns as reflected light. The TOF type includes a direct TOF method and an indirect TOF method. The direct TOF method directly measures the difference between the time when the light is irradiated from the light source and the time when the reflected light is received by the photoelectric conversion element. to measure the distance. The distance measurement principle used in the indirect TOF method to obtain the time of flight by charge accumulation includes a continuous wave (especially sine wave) modulation method in which the time of flight is obtained from the phases of the light emitted from the light source and the reflected light reflected by the measurement target. and 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 detection units to which the photoelectric conversion element according to the present embodiment can be preferably applied, an image detection unit for a solid-state imaging device, an image detection unit for an X-ray imaging device, a biometric authentication device (for example, a fingerprint authentication device, a vein Configuration examples of a fingerprint detection unit and a vein detection unit for an authentication device, etc., and an image detection unit of a TOF rangefinder (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 imaging device)
FIG. 2 is a diagram schematically showing a configuration example of an image detection unit for a solid-state imaging device.
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 imaging device)
FIG. 2 is a diagram schematically showing a configuration example of an image detection unit for a solid-state imaging device.
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 includes a CMOS transistor substrate 20, an interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20, and a photoelectric conversion element provided on the interlayer insulating film 30 according to the embodiment of the present invention. It is provided so as to penetrate the element 10 and the interlayer insulating film 30 , and is provided so as to cover the photoelectric conversion element 10 and the interlayer wiring part 32 electrically connecting the CMOS transistor substrate 20 and the photoelectric conversion element 10 . and a color filter 50 provided on the sealing layer 40 .
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 has a conventionally well-known arbitrary and suitable configuration in accordance with 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 functional elements such as CMOS transistor circuits (MOS transistor circuits) for realizing various functions, including transistors and capacitors formed within the thickness of the substrate.
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。
Functional elements include, for example, floating diffusions, reset transistors, output transistors, and selection transistors.
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。
A signal readout circuit and the like are built into the CMOS transistor substrate 20 with such functional elements, wiring, and the like.
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 suitable conventionally known insulating material such as silicon oxide and insulating resin. The interlayer wiring section 32 can be made of any suitable conventionally known conductive material (wiring material) such as copper and tungsten. The interlayer wiring portion 32 may be, for example, an in-hole wiring formed simultaneously with 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 may be made of any suitable conventionally known material on the condition that it can prevent or suppress permeation of harmful substances such as oxygen and water that may functionally deteriorate the photoelectric conversion element 10. can be done. The sealing layer 40 can have the same configuration as the sealing member 17 already described.
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 made of any conventionally known suitable material and corresponding 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 be used. As complementary color filters, for example, three types of (yellow, cyan, magenta), three types of (yellow, cyan, transparent), three types of (yellow, transparent, magenta), and three types of (transparent, cyan, magenta) A combination of types of color filters can be used. These can be arranged in any suitable arrangement corresponding to the design of the photoelectric conversion element 10 and the CMOS transistor substrate 20 on the condition 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 through the color filter 50 is converted by the photoelectric conversion element 10 into an electric signal corresponding to the amount of light received, and is output as a light reception signal, that is, the object to be imaged, to the outside of the photoelectric conversion element 10 through the electrodes. is output as an electrical 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 received light signal output from the photoelectric conversion element 10 is input to the CMOS transistor substrate 20 via the interlayer wiring portion 32, read by a signal readout circuit built into the CMOS transistor substrate 20, and further Image information based on the object to be imaged is generated by performing signal processing by an arbitrary 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. 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 section 100 is provided in an area that matches the display area 200a of the display panel section 200 . In other words, the display panel section 200 is integrally laminated above the fingerprint detection section 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。
In the case where fingerprint detection is performed only in a partial area of the display area 200a, the fingerprint detection section 100 may be provided so as to correspond only to the partial area.
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 essential functions. The fingerprint detection unit 100 includes any suitable conventionally known members such as a protection film (not shown), a support substrate, a sealing substrate, a sealing member, a barrier film, a bandpass filter, and an infrared cut film. It may be provided in a manner corresponding to the design to obtain the properties. The fingerprint detection unit 100 may adopt the configuration of the image detection unit already described.
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 can be included in any manner within the display area 200a. 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 already described, the photoelectric conversion element 10 is provided on the support substrate 11, and the support substrate 11 is provided with electrodes (first electrodes or second electrodes), for example, in a matrix.
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 by the photoelectric conversion element 10 into an electrical signal corresponding to the amount of received light, and the received light signal, that is, the electricity corresponding to the imaged fingerprint, is output outside the photoelectric conversion element 10 via the electrodes. 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 section 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, a display panel having an arbitrary and suitable conventionally known configuration such as a liquid crystal display panel including a light source such as a backlight, instead of the organic EL display panel.
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 section 200 is provided on the fingerprint detection section 100 already described. The display panel section 200 includes an organic electroluminescence element (organic EL element) 220 as a functional section that performs an essential function. The display panel unit 200 further includes an arbitrary and suitable substrate such as a conventionally known glass substrate (support substrate 210 or sealing substrate 240), a sealing member, a barrier film, a polarizing plate such as a circularly polarizing plate, and an arbitrary substrate such as a touch sensor panel 230. Suitable conventionally known members may be provided in a manner corresponding to the desired properties.
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 the pixels in the display area 200a, and is also used as a light source for imaging the fingerprint in the fingerprint detection section 100.
ここで、指紋検出部100の動作について簡単に説明する。
Here, the operation of the fingerprint detection unit 100 will be briefly described.
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。
When fingerprint authentication is performed, the fingerprint detection unit 100 detects the fingerprint using 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 the constituent elements existing between the organic EL element 220 and the photoelectric conversion element 10 of the fingerprint detection unit 100, and the display in the display area 200a is displayed. The light is reflected by the skin (finger surface) of the fingertip placed in contact with the surface of the panel section 200 . At least part of the light reflected by the finger surface is transmitted through intervening components and received by the photoelectric conversion element 10 , and converted into an electrical signal corresponding to the amount of light received by the photoelectric conversion element 10 . Image information about the fingerprint on the surface of the finger is constructed from the converted electric signal.
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 mobile information terminal equipped with the display device 2 performs fingerprint authentication by comparing the obtained image information with pre-recorded fingerprint data for fingerprint authentication by any suitable conventionally known step.
(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 imaging device)
FIG. 4 is a diagram schematically showing a configuration example of an image detection unit for an X-ray imaging 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 imaging device)
FIG. 4 is a diagram schematically showing a configuration example of an image detection unit for an X-ray imaging 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。
An image detection unit 1 for an X-ray imaging device includes a CMOS transistor substrate 20, an interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20, and an interlayer insulating film 30 provided on the interlayer insulating film 30. a photoelectric conversion element 10 according to the embodiment; , a scintillator 42 provided on the sealing layer 40, a reflective layer 44 provided to cover the scintillator 42, and a reflective layer 44 provided to cover the and a protective layer 46 having a
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 has a conventionally well-known arbitrary and suitable configuration in accordance with 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 functional elements such as CMOS transistor circuits (MOS transistor circuits) for realizing various functions, including transistors and capacitors formed within the thickness of the substrate.
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。
Functional elements include, for example, floating diffusions, reset transistors, output transistors, and selection transistors.
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。
A signal readout circuit and the like are built into the CMOS transistor substrate 20 with such functional elements, wiring, and the like.
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 suitable conventionally known insulating material such as silicon oxide and insulating resin. The interlayer wiring section 32 can be made of any suitable conventionally known conductive material (wiring material) such as copper and tungsten. The interlayer wiring portion 32 may be, for example, an in-hole wiring formed simultaneously with 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 may be made of any suitable conventionally known material on the condition that it can prevent or suppress permeation of harmful substances such as oxygen and water that may functionally deteriorate the photoelectric conversion element 10. can be done. The sealing layer 40 can have the same configuration as the sealing member 17 already described.
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 suitable material that corresponds to the design of the image detection section 1 for the X-ray imaging apparatus. Examples of suitable materials for the scintillator 42 include inorganic crystals of inorganic materials such as CsI (cesium iodide), NaI (sodium iodide), ZnS (zinc sulfide), GOS (gadolinium oxysulfide), and GSO (gadolinium silicate). , organic crystals of organic materials such as anthracene, naphthalene, and stilbene; organic liquids obtained by dissolving organic materials such as diphenyloxazole (PPO) and terphenyl (TP) in organic solvents such as toluene, xylene, and dioxane; and organic materials such as xenon and helium. Gases, plastics, 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 scintillator 42 converts incident X-rays into light having a wavelength centered in the visible region to generate image data. Any suitable arrangement can be used.
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 detection sensitivity. In addition, the reflective layer 44 can also block light that is 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 conventionally known material on the condition that it can prevent or suppress permeation of harmful substances such as oxygen and water that may functionally deteriorate the scintillator 42.
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 imaging 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) with a wavelength in the infrared range from ultraviolet, centered on the visible range. 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 by the photoelectric conversion element 10 into an electric signal corresponding to the amount of light received, and the received light signal is output outside the photoelectric conversion element 10 via the electrodes. That is, it is output as an electrical signal corresponding to the object to be imaged. Radiation energy (X-rays) 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 received light signal output from the photoelectric conversion element 10 is input to the CMOS transistor substrate 20 via the interlayer wiring portion 32, read by a signal readout circuit built into the CMOS transistor substrate 20, and further Image information based on the object to be imaged is generated by performing signal processing by an arbitrary 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。 (Vein detector)
FIG. 5 is a diagram schematically showing a configuration example of a vein detection unit for the vein authentication device.
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。 (Vein detector)
FIG. 5 is a diagram schematically showing a configuration example of a vein detection unit for the vein authentication device.
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。
The vein detection unit 300 for the vein authentication device includes a cover unit 306 defining an insertion unit 310 into which a finger to be measured (eg, one or more fingertips, fingers and palm) is inserted during measurement, and a cover unit 306 . A light source unit 304 provided in a unit 306 for irradiating light onto an object to be measured, a photoelectric conversion element 10 for receiving the light emitted from the light source unit 304 through the object to be measured, and a support for supporting the photoelectric conversion element 10 . The glass substrate 302 is arranged so as to face the substrate 11 and the support substrate 11 with the photoelectric conversion element 10 interposed therebetween, is separated from the cover portion 306 at a predetermined distance, and defines the insertion portion 306 together with the cover portion 306 . consists of
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 is configured integrally with the cover unit 306 so that the photoelectric conversion element 10 is separated from the photoelectric conversion element 10 while sandwiching the object to be measured during use. , the light source unit 304 is not necessarily positioned 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 object to be measured can be efficiently irradiated with the light from the light source unit 304, for example, a reflection imaging method in which the object to be measured is irradiated from the photoelectric conversion element 10 side may be employed.
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 essential functions. The vein detection unit 300 includes any suitable conventionally known member such as a protection film (not shown), a sealing member, a barrier film, a bandpass filter, a near-infrared transmission filter, a visible light cut film, and a finger placement guide. can be provided in a manner corresponding to the design to obtain the desired properties. The vein detection unit 300 may employ the configuration of the image detection unit 1 already described.
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 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 already described, the photoelectric conversion element 10 is provided on the support substrate 11, and the support substrate 11 is provided with electrodes (first electrodes or second electrodes), for example, in a matrix.
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 by the photoelectric conversion element 10 into an electrical signal corresponding to the amount of light received, and the received light signal, that is, the electricity corresponding to the imaged vein, is output outside the photoelectric conversion element 10 via the electrodes. 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 object to be measured 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。
Here, the operation of the vein detection unit 300 will be briefly described.
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。
During vein detection, the vein detection unit 300 detects the vein pattern to be measured using light emitted from the light source unit 304 . Specifically, the light emitted from the light source unit 304 is transmitted through the measurement target and converted into an electrical signal corresponding to the amount of light received by the photoelectric conversion element 10 . Image information of the vein pattern to be measured is constructed from the converted electrical signal.
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 authentication device, vein authentication is performed by comparing the obtained image information with previously recorded vein data for vein authentication by any suitable conventionally known step.
(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 rangefinder)
FIG. 6 is a diagram schematically showing a configuration example of an image detection unit for an indirect TOF rangefinder.
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 rangefinder)
FIG. 6 is a diagram schematically showing a configuration example of an image detection unit for an indirect TOF rangefinder.
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 the TOF type distance measuring device includes a CMOS transistor substrate 20, an interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20, and an interlayer insulating film 30 provided on the interlayer insulating film 30. The photoelectric conversion element 10 according to the embodiment, the two floating diffusion layers 402 spaced apart to sandwich the photoelectric conversion element 10, and the photoelectric conversion element 10 and the floating diffusion layer 402 are provided to cover the photoelectric conversion element 10. It comprises an insulating layer 40 and two photogates 404 provided on the insulating layer 40 and spaced 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 photogates 404 separated from each other, and the remaining area is shielded from light 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 suitable conventionally known insulating material such as silicon oxide and insulating resin. The interlayer wiring section 32 can be made of any suitable conventionally known conductive material (wiring material) such as copper and tungsten. The interlayer wiring portion 32 may be, for example, an in-hole wiring formed simultaneously with 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。
The insulating layer 40 in this configuration example may have any conventionally known and suitable configuration such as a field oxide film made 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 suitable conventionally known 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 section 400 for the TOF type rangefinder includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional section that performs essential functions. The image detector 400 for the TOF-type rangefinder uses any suitable conventional film such as a protection film (not shown), a support substrate, a sealing substrate, a sealing member, a barrier film, a bandpass filter, an infrared cut film, and the like. Known components may be provided in a manner corresponding to the design to obtain the desired properties.
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 TOF rangefinder image detection unit 400 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 object to be measured, and the photoelectric conversion element 10 receives the reflected light. Two photogates 404 are provided between the photoelectric conversion element 10 and the floating diffusion layer 402 , and by alternately applying pulses, signal charges generated by the photoelectric conversion element 10 are transferred to the two floating diffusion layers 402 . The charge is transferred to either one and accumulated in the floating diffusion layer 402 . When the light pulse arrives so as to equally straddle the timing of opening the two photogates 404, the amount of charge accumulated in the two floating diffusion layers 402 becomes equal. If the light pulse arrives at the other photogate 404 with a delay with respect to the timing at which the light pulse arrives at the one photogate 404, the amount of charge accumulated in the two floating diffusion layers 402 will differ.
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 accumulated in the floating diffusion layer 402 depends on the delay time of the light pulse. The distance L to the object to be measured has a relationship of L=(1/2) ctd using the round trip time td of light and the speed of light c. 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 electrical signal as the difference between the amounts of charge accumulated in the two floating diffusion layers 402, and the received light signal, that is, the electricity corresponding to the object to be measured, is output outside the photoelectric conversion element 10. 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 received light signal output from the floating diffusion layer 402 is input to the CMOS transistor substrate 20 via the interlayer wiring portion 32, read by a signal readout circuit built into the CMOS transistor substrate 20, and read out by a signal readout circuit (not shown). Distance information based on the measurement object is generated through signal processing by an arbitrary suitable conventionally known functional unit.
7.光検出素子
前記のとおり、本実施形態の光電変換素子は、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。よって、本発明の実施形態にかか光電変換素子は、光検出機能を有する光検出素子として特に好適に適用されうる。ここで、本実施形態の光検出素子は、光電変換素子そのものであってもよく、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さらに含んでいてもよい。 7. Photodetection element As described above, the photoelectric conversion element of the present embodiment can have a photodetection function capable of converting irradiated light into an electric signal corresponding to the amount of received light and outputting the signal to an external circuit via an electrode. . Therefore, the photoelectric conversion element according to the embodiment of the present invention can be particularly suitably applied as a photodetector having a photodetection function. Here, the photodetector element of this embodiment may be a photoelectric conversion element itself, or may further include a functional element for voltage control in addition to the photoelectric conversion element.
前記のとおり、本実施形態の光電変換素子は、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。よって、本発明の実施形態にかか光電変換素子は、光検出機能を有する光検出素子として特に好適に適用されうる。ここで、本実施形態の光検出素子は、光電変換素子そのものであってもよく、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さらに含んでいてもよい。 7. Photodetection element As described above, the photoelectric conversion element of the present embodiment can have a photodetection function capable of converting irradiated light into an electric signal corresponding to the amount of received light and outputting the signal to an external circuit via an electrode. . Therefore, the photoelectric conversion element according to the embodiment of the present invention can be particularly suitably applied as a photodetector having a photodetection function. Here, the photodetector element of this embodiment may be a photoelectric conversion element itself, or may further include a functional element for voltage control in addition to the 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。本発明は下記の実施例に限定されない。
Examples are given below to describe the present invention in more detail. The invention is not limited to the following examples.
<半導体材料>
材料P-1として、WO2013/051676に記載の方法を参考にして合成された材料を使用した。 <Semiconductor material>
As material P-1, a material synthesized with reference to the method described in WO2013/051676 was used.
材料P-1として、WO2013/051676に記載の方法を参考にして合成された材料を使用した。 <Semiconductor material>
As material P-1, a material synthesized with reference to the method described in WO2013/051676 was used.
材料P-2として、1-material社製、商品名:PCE-10を市場より入手して使用した。
As material P-2, 1-material company's trade name: PCE-10 was obtained from the market and used.
材料N-1として、フロンティアカーボン社製、商品名:E100を市場より入手して使用した。
As material N-1, Frontier Carbon's product name: E100 was obtained from the market and used.
材料N-2として、1-material社製、商品名:DiPDIを市場より入手して使用した。
As material N-2, 1-material company's trade name: DiPDI was obtained from the market and used.
材料N-3として、1-material社製、商品名:ITICを市場より入手して使用した。
As the material N-3, ITIC manufactured by 1-material Co., Ltd. was obtained from the market and used.
本実施例で使用される上記p型半導体材料である材料P-1及びP-2、並びにn型半導体材料である材料N-1~N-3の具体的な構造を、下記表1及び表2に示す。
Specific structures of the materials P-1 and P-2, which are the p-type semiconductor materials, and the materials N-1 to N-3, which are the n-type semiconductor materials, used in this embodiment are shown in Table 1 and Table 2.
<分子量の測定>
p型半導体材料のz平均分子量(Mz)、重量平均分子量(Mw)は、ゲルパーミテーションクロマトグラフィー(GPC)(島津製作所社製、LC―20AT)によりポリスチレン換算のz平均分子量(Mz)、重量平均分子量(Mw)として求めた。以下、具体的に説明する。 <Measurement of molecular weight>
The z-average molecular weight (Mz) and weight-average molecular weight (Mw) of the p-type semiconductor material are determined by gel permeation chromatography (GPC) (manufactured by Shimadzu Corporation, LC-20AT) to determine the z-average molecular weight (Mz) and weight in terms of polystyrene. It was determined as an average molecular weight (Mw). A specific description will be given below.
p型半導体材料のz平均分子量(Mz)、重量平均分子量(Mw)は、ゲルパーミテーションクロマトグラフィー(GPC)(島津製作所社製、LC―20AT)によりポリスチレン換算のz平均分子量(Mz)、重量平均分子量(Mw)として求めた。以下、具体的に説明する。 <Measurement of molecular weight>
The z-average molecular weight (Mz) and weight-average molecular weight (Mw) of the p-type semiconductor material are determined by gel permeation chromatography (GPC) (manufactured by Shimadzu Corporation, LC-20AT) to determine the z-average molecular weight (Mz) and weight in terms of polystyrene. It was determined as an average molecular weight (Mw). A specific description will be given below.
GPCの移動相としてはo-ジクロロベンゼンを用い、1.0mL/minの流速で流した。カラムとしては、昭和電工社製、Shodex KD-806Mを用い、ガードカラムとしては、昭和電工社製、Shodex KD-Gを用いた。
o-Dichlorobenzene was used as the mobile phase for GPC, and flowed at a flow rate of 1.0 mL/min. As the column, Shodex KD-806M manufactured by Showa Denko KK was used, and as the guard column, Shodex KD-G manufactured by Showa Denko KK was used.
検出器としてはUV-vis検出器(島津製作所社製、SPD-M20A)及び示差屈折率検出器(島津製作所社製、RID-10A)を用いた。
As detectors, a UV-vis detector (Shimadzu Corporation, SPD-M20A) and a differential refractive index detector (Shimadzu Corporation, RID-10A) were used.
測定対象の化合物(重合体)は、溶媒である1-クロロナフタレンに、0.05質量%の濃度になるように混合して、80℃で2時間撹拌することで溶解させた溶解液とした。
The compound (polymer) to be measured was mixed with 1-chloronaphthalene as a solvent so as to have a concentration of 0.05% by mass, and stirred at 80°C for 2 hours to obtain a solution. .
得られた溶解液を、上記測定装置(GPC)にサンプルとして10μL注入することで、z平均分子量(Mz)、重量平均分子量(Mw)を測定した。
By injecting 10 μL of the obtained solution as a sample into the measuring device (GPC), the z-average molecular weight (Mz) and weight-average molecular weight (Mw) were measured.
<実施例1>
[インク組成物の調製]
1,2,3,4-テトラヒドロナフタレンに、p型半導体材料として材料P-1を、インク組成物の全質量に対し、0.8質量%となるように、及びn型半導体材料として材料N-1を、インク組成物の質量に対し、1.6質量%となるように混合し、60℃で6時間撹拌することで、インク組成物(I-1)を得た。 <Example 1>
[Preparation of ink composition]
To 1,2,3,4-tetrahydronaphthalene, material P-1 as a p-type semiconductor material, material N as an n-type semiconductor material to be 0.8% by weight with respect to the total weight of the ink composition. -1 was mixed so as to be 1.6% by mass with respect to the mass of the ink composition, and the mixture was stirred at 60° C. for 6 hours to obtain an ink composition (I-1).
[インク組成物の調製]
1,2,3,4-テトラヒドロナフタレンに、p型半導体材料として材料P-1を、インク組成物の全質量に対し、0.8質量%となるように、及びn型半導体材料として材料N-1を、インク組成物の質量に対し、1.6質量%となるように混合し、60℃で6時間撹拌することで、インク組成物(I-1)を得た。 <Example 1>
[Preparation of ink composition]
To 1,2,3,4-tetrahydronaphthalene, material P-1 as a p-type semiconductor material, material N as an n-type semiconductor material to be 0.8% by weight with respect to the total weight of the ink composition. -1 was mixed so as to be 1.6% by mass with respect to the mass of the ink composition, and the mixture was stirred at 60° C. for 6 hours to obtain an ink composition (I-1).
[インク組成物のろ過性試験]
上記のとおり調製されたインク組成物を用いて、インク組成物のろ過性試験を行った。
具体的には、所定の孔径を有するフィルターを用いて、インク組成物が当該フィルターを透過できるか否かを評価した。すなわち、インク組成物がフィルターを透過でき、ろ過が行えた場合にはろ過性が良好である(○)と評価し、インク組成物がフィルターを透過できず、フィルターが閉塞してしまいろ過ができなかった場合をろ過性が不良である(×)と評価した。 [Filterability test of ink composition]
An ink composition filterability test was performed using the ink composition prepared as described above.
Specifically, a filter having a predetermined pore size was used to evaluate whether or not the ink composition could pass through the filter. That is, when the ink composition can pass through the filter and can be filtered, the filterability is evaluated as good (○), and the ink composition cannot pass through the filter and the filter is clogged, making it impossible to filter. The filterability was evaluated to be poor (x) when there was no such case.
上記のとおり調製されたインク組成物を用いて、インク組成物のろ過性試験を行った。
具体的には、所定の孔径を有するフィルターを用いて、インク組成物が当該フィルターを透過できるか否かを評価した。すなわち、インク組成物がフィルターを透過でき、ろ過が行えた場合にはろ過性が良好である(○)と評価し、インク組成物がフィルターを透過できず、フィルターが閉塞してしまいろ過ができなかった場合をろ過性が不良である(×)と評価した。 [Filterability test of ink composition]
An ink composition filterability test was performed using the ink composition prepared as described above.
Specifically, a filter having a predetermined pore size was used to evaluate whether or not the ink composition could pass through the filter. That is, when the ink composition can pass through the filter and can be filtered, the filterability is evaluated as good (○), and the ink composition cannot pass through the filter and the filter is clogged, making it impossible to filter. The filterability was evaluated to be poor (x) when there was no such case.
より具体的には、上記のとおり調製されたインク組成物(I-1)10gを、孔径0.5μmのPTFEフィルターを設置したステンレスホルダー(アドバンテック東洋社製、KS047)に加えて、ろ過試験を行った。
More specifically, 10 g of the ink composition (I-1) prepared as described above was added to a stainless steel holder (KS047, manufactured by Advantech Toyo Co., Ltd.) equipped with a PTFE filter having a pore size of 0.5 μm, and a filtration test was performed. gone.
結果として、インク組成物I-1はPTFEフィルターを閉塞させることなく、透過してろ過が終了した。よって、ろ過性は良好である(○)と評価された。結果を表1にも示した。
As a result, the ink composition I-1 passed through the PTFE filter without clogging it, and the filtration was completed. Therefore, the filterability was evaluated as good (◯). The results are also shown in Table 1.
<実施例2~6及び比較例1>
p型半導体材料として下記表3に示すz平均分子量(Mz)及び重量平均分子量(Mw)を有する材料P-1を使用した以外は、実施例1と同様にして、インク組成物の調製及びろ過試験を実施した。結果を下記表3にも示した。 <Examples 2 to 6 and Comparative Example 1>
An ink composition was prepared and filtered in the same manner as in Example 1, except that material P-1 having a z-average molecular weight (Mz) and a weight-average molecular weight (Mw) shown in Table 3 below was used as the p-type semiconductor material. A test was conducted. The results are also shown in Table 3 below.
p型半導体材料として下記表3に示すz平均分子量(Mz)及び重量平均分子量(Mw)を有する材料P-1を使用した以外は、実施例1と同様にして、インク組成物の調製及びろ過試験を実施した。結果を下記表3にも示した。 <Examples 2 to 6 and Comparative Example 1>
An ink composition was prepared and filtered in the same manner as in Example 1, except that material P-1 having a z-average molecular weight (Mz) and a weight-average molecular weight (Mw) shown in Table 3 below was used as the p-type semiconductor material. A test was conducted. The results are also shown in Table 3 below.
<実施例7>
[インク組成物]
p型半導体材料として材料P-1を用い、材料P-1をインク組成物の全質量に対し、2.0質量%となるように、及びn型半導体材料として材料N-1をインク組成物の全質量に対し、1.0質量%となるように混合した以外は実施例1と同様にして、インク組成物(I-8)を調製した。 <Example 7>
[Ink composition]
The material P-1 is used as the p-type semiconductor material, the material P-1 is 2.0% by mass with respect to the total mass of the ink composition, and the material N-1 is used as the n-type semiconductor material in the ink composition. Ink composition (I-8) was prepared in the same manner as in Example 1, except that it was mixed so as to be 1.0% by mass with respect to the total mass of .
[インク組成物]
p型半導体材料として材料P-1を用い、材料P-1をインク組成物の全質量に対し、2.0質量%となるように、及びn型半導体材料として材料N-1をインク組成物の全質量に対し、1.0質量%となるように混合した以外は実施例1と同様にして、インク組成物(I-8)を調製した。 <Example 7>
[Ink composition]
The material P-1 is used as the p-type semiconductor material, the material P-1 is 2.0% by mass with respect to the total mass of the ink composition, and the material N-1 is used as the n-type semiconductor material in the ink composition. Ink composition (I-8) was prepared in the same manner as in Example 1, except that it was mixed so as to be 1.0% by mass with respect to the total mass of .
[インク組成物のろ過性試験]
実施例1と同様にしてろ過性試験を行った。 [Filterability test of ink composition]
A filterability test was performed in the same manner as in Example 1.
実施例1と同様にしてろ過性試験を行った。 [Filterability test of ink composition]
A filterability test was performed in the same manner as in Example 1.
結果として、インク組成物I-8は、PTFEフィルターを閉塞させることなく、透過してろ過が終了した。よって、ろ過性は良好である(○)と評価された。結果を下記表4にも示した。
As a result, the ink composition I-8 passed through the PTFE filter without clogging, and the filtration was completed. Therefore, the filterability was evaluated as good (◯). The results are also shown in Table 4 below.
<実施例8及び比較例2>
p型半導体材料として下記表3に示すz平均分子量(Mz)及び重量平均分子量(Mw)を有する材料P-1を用い、材料P-1をインク組成物の全質量に対し、1質量%となるように、、n型半導体材料として材料N-2を用い、材料N-2をインク組成物の全質量に対し、0.3質量%となるように、溶媒としてo-キシレン(97質量%)とアセトフェノン(3質量%)とを混合した混合溶媒を使用して混合した以外は実施例1と同様にして、インク組成物(I-9)及び(I-10)を調製し、ろ過性試験を実施した。結果を下記表5に示した。 <Example 8 and Comparative Example 2>
A material P-1 having a z-average molecular weight (Mz) and a weight-average molecular weight (Mw) shown in Table 3 below is used as a p-type semiconductor material, and the material P-1 is 1% by mass with respect to the total mass of the ink composition. Material N-2 is used as the n-type semiconductor material, and o-xylene (97% by mass) is used as a solvent so that the material N-2 is 0.3% by mass relative to the total mass of the ink composition. ) and acetophenone (3% by mass) were mixed in the same manner as in Example 1, except that ink compositions (I-9) and (I-10) were prepared and filtered. A test was conducted. The results are shown in Table 5 below.
p型半導体材料として下記表3に示すz平均分子量(Mz)及び重量平均分子量(Mw)を有する材料P-1を用い、材料P-1をインク組成物の全質量に対し、1質量%となるように、、n型半導体材料として材料N-2を用い、材料N-2をインク組成物の全質量に対し、0.3質量%となるように、溶媒としてo-キシレン(97質量%)とアセトフェノン(3質量%)とを混合した混合溶媒を使用して混合した以外は実施例1と同様にして、インク組成物(I-9)及び(I-10)を調製し、ろ過性試験を実施した。結果を下記表5に示した。 <Example 8 and Comparative Example 2>
A material P-1 having a z-average molecular weight (Mz) and a weight-average molecular weight (Mw) shown in Table 3 below is used as a p-type semiconductor material, and the material P-1 is 1% by mass with respect to the total mass of the ink composition. Material N-2 is used as the n-type semiconductor material, and o-xylene (97% by mass) is used as a solvent so that the material N-2 is 0.3% by mass relative to the total mass of the ink composition. ) and acetophenone (3% by mass) were mixed in the same manner as in Example 1, except that ink compositions (I-9) and (I-10) were prepared and filtered. A test was conducted. The results are shown in Table 5 below.
<実施例9及び比較例3>
p型半導体材料として下記表4に示すz平均分子量(Mz)及び重量平均分子量(Mw)を有する材料P-1を用い、材料P-1をインク組成物の全質量に対し、1.0質量%となるように、n型半導体材料として材料N-3を用い、材料N-3をインク組成物の全質量に対し、1.0質量%となるように、溶媒としてo-ジクロロベンゼンを使用して混合した以外は実施例1と同様にして、インク(I-11)及び(I-12)を調製し、ろ過性試験を実施した。結果を下記表6に示した。 <Example 9 and Comparative Example 3>
A material P-1 having a z-average molecular weight (Mz) and a weight-average molecular weight (Mw) shown in Table 4 below is used as a p-type semiconductor material, and the material P-1 is 1.0 mass with respect to the total mass of the ink composition. %, using material N-3 as an n-type semiconductor material, and using o-dichlorobenzene as a solvent so that material N-3 is 1.0% by mass with respect to the total mass of the ink composition. Inks (I-11) and (I-12) were prepared in the same manner as in Example 1, except that they were mixed together, and a filterability test was conducted. The results are shown in Table 6 below.
p型半導体材料として下記表4に示すz平均分子量(Mz)及び重量平均分子量(Mw)を有する材料P-1を用い、材料P-1をインク組成物の全質量に対し、1.0質量%となるように、n型半導体材料として材料N-3を用い、材料N-3をインク組成物の全質量に対し、1.0質量%となるように、溶媒としてo-ジクロロベンゼンを使用して混合した以外は実施例1と同様にして、インク(I-11)及び(I-12)を調製し、ろ過性試験を実施した。結果を下記表6に示した。 <Example 9 and Comparative Example 3>
A material P-1 having a z-average molecular weight (Mz) and a weight-average molecular weight (Mw) shown in Table 4 below is used as a p-type semiconductor material, and the material P-1 is 1.0 mass with respect to the total mass of the ink composition. %, using material N-3 as an n-type semiconductor material, and using o-dichlorobenzene as a solvent so that material N-3 is 1.0% by mass with respect to the total mass of the ink composition. Inks (I-11) and (I-12) were prepared in the same manner as in Example 1, except that they were mixed together, and a filterability test was conducted. The results are shown in Table 6 below.
<実施例10及び比較例4>
p型半導体材料として下記表4に示すz平均分子量(Mz)及び重量平均分子量(Mw)を有する材料P-2を用い、材料P-2をインク組成物の全質量に対し、0.8質量%となるように混合した以外は、実施例1と同様にして、インク組成物(I-13)及び(I-14)を調製し、ろ過性試験を実施した。結果を下記表7に示した。 <Example 10 and Comparative Example 4>
A material P-2 having a z-average molecular weight (Mz) and a weight-average molecular weight (Mw) shown in Table 4 below is used as a p-type semiconductor material, and the material P-2 is 0.8 mass with respect to the total mass of the ink composition. Ink compositions (I-13) and (I-14) were prepared in the same manner as in Example 1, except that they were mixed so that the ratio was 1%, and a filterability test was conducted. The results are shown in Table 7 below.
p型半導体材料として下記表4に示すz平均分子量(Mz)及び重量平均分子量(Mw)を有する材料P-2を用い、材料P-2をインク組成物の全質量に対し、0.8質量%となるように混合した以外は、実施例1と同様にして、インク組成物(I-13)及び(I-14)を調製し、ろ過性試験を実施した。結果を下記表7に示した。 <Example 10 and Comparative Example 4>
A material P-2 having a z-average molecular weight (Mz) and a weight-average molecular weight (Mw) shown in Table 4 below is used as a p-type semiconductor material, and the material P-2 is 0.8 mass with respect to the total mass of the ink composition. Ink compositions (I-13) and (I-14) were prepared in the same manner as in Example 1, except that they were mixed so that the ratio was 1%, and a filterability test was conducted. The results are shown in Table 7 below.
以上の実施例及び比較例より明らかなとおり、インク組成物のろ過性は、重量平均分子量(Mw)によっては制御することはできず、またインク組成物に用いられるn型半導体材料の種類、溶媒、また濃度との相関はみられないものの、p型半導体材料のz平均分子量(Mz)を上記所定の範囲内とすれば、試行錯誤を要せずに、フィルターを閉塞させることなく、向上させることができることがわかった。
As is clear from the above examples and comparative examples, the filterability of the ink composition cannot be controlled by the weight average molecular weight (Mw), and the type of n-type semiconductor material used in the ink composition, the solvent Although there is no correlation with the concentration, if the z-average molecular weight (Mz) of the p-type semiconductor material is within the above predetermined range, it can be improved without trial and error and without clogging the filter. I found that it can be done.
<実施例11>
[光電変換素子の製造及び評価]
(1)光電変換素子の製造
(陰極の形成)
スパッタ法により100nmの厚さでITO膜が形成されたガラス基板(以下、製造中途のガラス基板を含む積層体を、単にガラス基板という。)を用意した。当該ガラス基板に対してオゾンUV処理による清浄処理を行って陰極を形成した。 <Example 11>
[Manufacture and evaluation of photoelectric conversion element]
(1) Manufacture of photoelectric conversion element (formation of cathode)
A glass substrate on which an ITO film having a thickness of 100 nm was formed by a sputtering method (hereinafter, a laminated body including a glass substrate in the middle of production is simply referred to as a glass substrate) was prepared. The glass substrate was subjected to cleaning treatment by ozone UV treatment to form a cathode.
[光電変換素子の製造及び評価]
(1)光電変換素子の製造
(陰極の形成)
スパッタ法により100nmの厚さでITO膜が形成されたガラス基板(以下、製造中途のガラス基板を含む積層体を、単にガラス基板という。)を用意した。当該ガラス基板に対してオゾンUV処理による清浄処理を行って陰極を形成した。 <Example 11>
[Manufacture and evaluation of photoelectric conversion element]
(1) Manufacture of photoelectric conversion element (formation of cathode)
A glass substrate on which an ITO film having a thickness of 100 nm was formed by a sputtering method (hereinafter, a laminated body including a glass substrate in the middle of production is simply referred to as a glass substrate) was prepared. The glass substrate was subjected to cleaning treatment by ozone UV treatment to form a cathode.
(電子輸送層の形成)
次に、洗浄済みのガラス基板を、ポリエチレンイミン80%エトキシ化水溶液(シグマアルドリッチ社製、37質量%水溶液)を水に0.1質量%となるように溶解させた溶液に、5分間浸漬し、ガラス基板を引き上げた後にホットプレート上に載せ、大気中において100℃で10分間の条件で塗膜を乾燥させた。 (Formation of electron transport layer)
Next, the washed glass substrate was immersed for 5 minutes in a solution prepared by dissolving an 80% polyethyleneimine ethoxylated aqueous solution (manufactured by Sigma-Aldrich, 37% by mass aqueous solution) in water to a concentration of 0.1% by mass. After pulling up the glass substrate, it was placed on a hot plate and the coating film was dried at 100° C. for 10 minutes in the atmosphere.
次に、洗浄済みのガラス基板を、ポリエチレンイミン80%エトキシ化水溶液(シグマアルドリッチ社製、37質量%水溶液)を水に0.1質量%となるように溶解させた溶液に、5分間浸漬し、ガラス基板を引き上げた後にホットプレート上に載せ、大気中において100℃で10分間の条件で塗膜を乾燥させた。 (Formation of electron transport layer)
Next, the washed glass substrate was immersed for 5 minutes in a solution prepared by dissolving an 80% polyethyleneimine ethoxylated aqueous solution (manufactured by Sigma-Aldrich, 37% by mass aqueous solution) in water to a concentration of 0.1% by mass. After pulling up the glass substrate, it was placed on a hot plate and the coating film was dried at 100° C. for 10 minutes in the atmosphere.
乾燥させたガラス基板を水で洗浄し、洗浄後のガラス基板をホットプレート上に載せ、大気中において100℃で10分間の条件で陰極上の塗膜を乾燥させて、塗膜を電子輸送層とした。
The dried glass substrate is washed with water, the washed glass substrate is placed on a hot plate, and the coating film on the cathode is dried under the conditions of 100° C. for 10 minutes in the atmosphere to form the coating film as an electron transport layer. and
(活性層の形成)
次に、実施例1にかかるインク組成物(I-1)を、電子輸送層上に、スロットダイコート方により塗布して塗膜を形成した後、真空乾燥処理(圧力10Pa、70℃)を5分間行い、塗膜を活性層とした。活性層が形成されたガラス基板をホットプレート上に載せ、100℃で12分間の条件で活性層を乾燥させた。乾燥後の活性層の厚さは、200nmであった。 (Formation of active layer)
Next, the ink composition (I-1) according to Example 1 was applied onto the electron transport layer by slot die coating to form a coating film, followed by vacuum drying (pressure 10 Pa, 70° C.) for 5 hours. minutes, and the coating film was used as an active layer. The glass substrate with the active layer formed thereon was placed on a hot plate, and the active layer was dried at 100° C. for 12 minutes. The thickness of the active layer after drying was 200 nm.
次に、実施例1にかかるインク組成物(I-1)を、電子輸送層上に、スロットダイコート方により塗布して塗膜を形成した後、真空乾燥処理(圧力10Pa、70℃)を5分間行い、塗膜を活性層とした。活性層が形成されたガラス基板をホットプレート上に載せ、100℃で12分間の条件で活性層を乾燥させた。乾燥後の活性層の厚さは、200nmであった。 (Formation of active layer)
Next, the ink composition (I-1) according to Example 1 was applied onto the electron transport layer by slot die coating to form a coating film, followed by vacuum drying (
(陽極の形成)
次いで、ポリ(3,4-エチレンジオキシチオフェン)/ポリスチレンスルホン酸を水に溶解させた懸濁液(ヘレウス社製、Clevios F HC Solar)を、スピンコート法により活性層上に塗布し、塗膜を形成した。塗膜が形成されたガラス基板をオーブンに入れ、85℃で30分間の条件で塗膜を乾燥させて陽極とした。乾燥後の陽極の厚さは、約120nmであった。以上の工程により、実施例11にかかる光電変換素子が製造された。 (Formation of anode)
Next, a suspension of poly(3,4-ethylenedioxythiophene)/polystyrene sulfonic acid dissolved in water (Clevios FHC Solar, manufactured by Heraeus) was applied onto the active layer by spin coating. A film was formed. The glass substrate with the coating film formed thereon was placed in an oven, and the coating film was dried at 85° C. for 30 minutes to obtain an anode. The thickness of the anode after drying was about 120 nm. Through the above steps, the photoelectric conversion device according to Example 11 was manufactured.
次いで、ポリ(3,4-エチレンジオキシチオフェン)/ポリスチレンスルホン酸を水に溶解させた懸濁液(ヘレウス社製、Clevios F HC Solar)を、スピンコート法により活性層上に塗布し、塗膜を形成した。塗膜が形成されたガラス基板をオーブンに入れ、85℃で30分間の条件で塗膜を乾燥させて陽極とした。乾燥後の陽極の厚さは、約120nmであった。以上の工程により、実施例11にかかる光電変換素子が製造された。 (Formation of anode)
Next, a suspension of poly(3,4-ethylenedioxythiophene)/polystyrene sulfonic acid dissolved in water (Clevios FHC Solar, manufactured by Heraeus) was applied onto the active layer by spin coating. A film was formed. The glass substrate with the coating film formed thereon was placed in an oven, and the coating film was dried at 85° C. for 30 minutes to obtain an anode. The thickness of the anode after drying was about 120 nm. Through the above steps, the photoelectric conversion device according to Example 11 was manufactured.
[光電変換素子の評価]
(外部量子効率(EQE)の評価)
上記のとおり製造さえた光電変換素子に2Vの逆バイアス電圧を印加した状態で、分光感度測定装置(分光計器社製、商品名:CEP-2000型)を用いて、800nmの単色光(フォトン数:5×1014)を光電変換素子に照射し、発生する電流値を測定し、公知の手法によりEQEを求めた。結果を表8に示す。 [Evaluation of photoelectric conversion element]
(Evaluation of external quantum efficiency (EQE))
With a reverse bias voltage of 2 V applied to the photoelectric conversion element manufactured as described above, a spectral sensitivity measurement device (manufactured by Spectroscopy Instruments Co., Ltd., trade name: CEP-2000 type) is used to measure monochromatic light of 800 nm (the number of photons : 5×10 14 ) was irradiated to the photoelectric conversion element, the generated current value was measured, and the EQE was obtained by a known method. Table 8 shows the results.
(外部量子効率(EQE)の評価)
上記のとおり製造さえた光電変換素子に2Vの逆バイアス電圧を印加した状態で、分光感度測定装置(分光計器社製、商品名:CEP-2000型)を用いて、800nmの単色光(フォトン数:5×1014)を光電変換素子に照射し、発生する電流値を測定し、公知の手法によりEQEを求めた。結果を表8に示す。 [Evaluation of photoelectric conversion element]
(Evaluation of external quantum efficiency (EQE))
With a reverse bias voltage of 2 V applied to the photoelectric conversion element manufactured as described above, a spectral sensitivity measurement device (manufactured by Spectroscopy Instruments Co., Ltd., trade name: CEP-2000 type) is used to measure monochromatic light of 800 nm (the number of photons : 5×10 14 ) was irradiated to the photoelectric conversion element, the generated current value was measured, and the EQE was obtained by a known method. Table 8 shows the results.
<実施例12~14>
活性層の材料として、インク組成物I-2を用いた以外は、実施例11と同様にして、光電変換素子を製造し、EQEを求めた。結果を表8に示す。 <Examples 12 to 14>
A photoelectric conversion device was produced in the same manner as in Example 11, except that ink composition I-2 was used as the material for the active layer, and EQE was determined. Table 8 shows the results.
活性層の材料として、インク組成物I-2を用いた以外は、実施例11と同様にして、光電変換素子を製造し、EQEを求めた。結果を表8に示す。 <Examples 12 to 14>
A photoelectric conversion device was produced in the same manner as in Example 11, except that ink composition I-2 was used as the material for the active layer, and EQE was determined. Table 8 shows the results.
表8に示されるようにインク組成物I-1及びI-2を活性層の材料として用いた光電変換素子は問題なく機能することが確認できた。とりわけ、p型半導体材料の重量平均分子量が6.0×104よりも大きいインク組成物I-3及びI-4を活性層の材料として用いた光電変換素子は、より高いEQEが得られることが確認できた。
As shown in Table 8, it was confirmed that the photoelectric conversion elements using ink compositions I-1 and I-2 as active layer materials functioned without problems. In particular, photoelectric conversion elements using ink compositions I-3 and I-4, in which the weight average molecular weight of the p-type semiconductor material is greater than 6.0×10 4 as the material for the active layer, can obtain a higher EQE. was confirmed.
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1の電極
13 電子輸送層
14 活性層
15 正孔輸送層
16 第2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 REFERENCE SIGNSLIST 1 image detection unit 2 display device 10 photoelectric conversion element 11, 210 support substrate 12 first electrode 13 electron transport layer 14 active layer 15 hole transport layer 16 second electrode 17 sealing member 20 CMOS transistor substrate 30 interlayer insulating film 32 Interlayer Wiring Section 40 Sealing Layer 42 Scintillator 44 Reflective Layer 46 Protective Layer 50 Color Filter 100 Fingerprint Detection Section 200 Display Panel Section 200a Display Area 220 Organic EL Element 230 Touch Sensor Panel 240 Sealing Substrate 300 Vein Detection Section 302 Glass Substrate 304 Light source unit 306 Cover unit 310 Insertion unit 400 Image detection unit for TOF rangefinder 402 Floating diffusion layer 404 Photogate 406 Light shielding unit
2 表示装置
10 光電変換素子
11、210 支持基板
12 第1の電極
13 電子輸送層
14 活性層
15 正孔輸送層
16 第2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 REFERENCE SIGNS
Claims (9)
- p型半導体材料と、n型半導体材料と、溶媒とを含むインク組成物であって、該p型半導体材料が、z平均分子量が5.0×105未満である高分子化合物を含む、光電変換素子製造用のインク組成物。 An ink composition comprising a p-type semiconductor material, an n-type semiconductor material, and a solvent, wherein the p-type semiconductor material comprises a polymeric compound having a z-average molecular weight of less than 5.0×10 5 . An ink composition for manufacturing conversion elements.
- 前記p型半導体材料が、重量平均分子量が6.0×104よりも大きい高分子化合物を含む、請求項1に記載の光電変換素子製造用のインク組成物。 The ink composition for manufacturing a photoelectric conversion device according to claim 1, wherein the p-type semiconductor material contains a polymer compound having a weight average molecular weight of more than 6.0 x 104.
- 前記p型半導体材料が、チオフェン骨格を有する構成単位を含む高分子化合物を含む、請求項1又は2に記載の光電変換素子製造用のインク組成物。 The ink composition for producing a photoelectric conversion element according to claim 1 or 2, wherein the p-type semiconductor material contains a polymer compound containing a structural unit having a thiophene skeleton.
- 前記p型半導体材料が、ドナー・アクセプター構造を有する高分子化合物を含む、請求項3に記載の光電変換素子製造用のインク組成物。 The ink composition for manufacturing a photoelectric conversion element according to claim 3, wherein the p-type semiconductor material contains a polymer compound having a donor-acceptor structure.
- 前記溶媒が、芳香族炭化水素を含む、請求項1~4のいずれか1項に記載の光電変換素子製造用のインク組成物。 The ink composition for producing a photoelectric conversion element according to any one of claims 1 to 4, wherein the solvent contains an aromatic hydrocarbon.
- 前記n型半導体材料が、フラーレン誘導体を含む、請求項1~5のいずれか1項に記載の光電変換素子製造用のインク組成物。 The ink composition for manufacturing a photoelectric conversion element according to any one of claims 1 to 5, wherein the n-type semiconductor material contains a fullerene derivative.
- 前記n型半導体材料が、非フラーレン化合物を含む、請求項1~5のいずれか1項に記載の光電変換素子製造用のインク組成物。 The ink composition for manufacturing a photoelectric conversion element according to any one of claims 1 to 5, wherein the n-type semiconductor material contains a non-fullerene compound.
- 請求項1~7のいずれか1項に記載のインク組成物の製造方法において、該インク組成物が、孔径0.5μm以下のフィルターでろ過される工程を含む、光電変換素子製造用のインク組成物の製造方法。 8. The ink composition for producing a photoelectric conversion element according to claim 1, comprising a step of filtering the ink composition through a filter having a pore size of 0.5 μm or less. A method of making things.
- p型半導体材料である複数種類の高分子化合物を準備する準備工程と、
前記準備工程で準備した前記高分子化合物のうち、z平均分子量が5.0×105未満である高分子化合物をp型半導体材料として選別する選別工程と、
前記選別工程で選別されたp型半導体材料とn型半導体材料と溶媒とを混合して、インク組成物を製造する工程と、
を含む、光電変換素子製造用のインク組成物の製造方法。 A preparatory step of preparing a plurality of types of polymer compounds that are p-type semiconductor materials;
a selecting step of selecting polymer compounds having a z-average molecular weight of less than 5.0×10 5 among the polymer compounds prepared in the preparing step as p-type semiconductor materials;
mixing the p-type semiconductor material, the n-type semiconductor material, and the solvent selected in the selecting step to produce an ink composition;
A method for producing an ink composition for producing a photoelectric conversion element, comprising:
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WO2019059231A1 (en) * | 2017-09-21 | 2019-03-28 | 東レ株式会社 | Photovoltaic power device |
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JP2011119705A (en) * | 2009-10-30 | 2011-06-16 | Sumitomo Chemical Co Ltd | Organic photoelectric conversion element and production method therefor |
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