WO2023199670A1 - Capteur de lumière et dispositif d'affichage utilisant celui-ci - Google Patents

Capteur de lumière et dispositif d'affichage utilisant celui-ci Download PDF

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WO2023199670A1
WO2023199670A1 PCT/JP2023/009289 JP2023009289W WO2023199670A1 WO 2023199670 A1 WO2023199670 A1 WO 2023199670A1 JP 2023009289 W JP2023009289 W JP 2023009289W WO 2023199670 A1 WO2023199670 A1 WO 2023199670A1
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group
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optical sensor
photoelectric conversion
compound
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Japanese (ja)
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大輔 北澤
耕平 柴田
和真 長尾
大貴 野田
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東レ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • 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
    • H10K30/60—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation in which radiation controls flow of current through the devices, e.g. photoresistors
    • 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
    • H10K39/30—Devices controlled by radiation
    • H10K39/32—Organic image sensors
    • H10K39/34—Organic image sensors integrated with organic light-emitting diodes [OLED]
    • 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
    • H10K85/30—Coordination compounds
    • 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 optical sensor and a display device using the same.
  • Optical sensors generally include an independent photoelectric conversion element that converts light into electrical energy and a light emitting element, and the light from the light emitting element is irradiated onto an object, and the light transmitted or reflected from the object is used by the photoelectric conversion element. Receives and senses light.
  • Such an optical sensor can acquire biological information such as fingerprints, vein shapes, and blood oxygen concentration by using green light, red light, or near-infrared light, for example.
  • the substrate, the light emitting element, and the light receiving element mainly from organic materials, it is possible to construct a thin and flexible device (see, for example, Non-Patent Document 1).
  • Pyrromethene compounds have been studied as photoelectric conversion materials for use in such photoelectric conversion elements (see, for example, Patent Documents 1 to 5). Pyrromethene compounds generally have a high extinction coefficient, and have the advantage that the absorption wavelength region can be designed to a desired range by selecting substituents.
  • JP2020-72270A International Publication No. 2015/119039 Japanese Patent Application Publication No. 2008-109097 International Publication No. 2017/018351 JP2020-88360A
  • an object of the present invention is to provide an optical sensor that has high photoelectric conversion efficiency for red light, and as a more specific aspect, provides an optical sensor that is equipped with a photoelectric conversion element that has high photoelectric conversion efficiency for red light. With the goal.
  • the present invention is an optical sensor for acquiring biological information, which contains a compound having a structure represented by the following general formula (1).
  • R 1 and R 6 may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group.
  • R 2 and R 5 are hydrogen atoms.
  • R 3 and R 4 may be the same or different and represent an aryl group or a heteroaryl group.
  • R 7 represents an alkyl group, an alkoxy group or an aryloxy group.
  • R 8 to R 11 may be the same or different, and represent a condensation formed between a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an aryl group, a heteroaryl group, or an adjacent substituent.
  • X 1 and X 2 may be the same or different and represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, or a cyano group.
  • an optical sensor for acquiring biological information that has high photoelectric conversion efficiency for red light and is advantageous for acquiring biological information.
  • the optical sensor of the present invention contains a compound having a structure represented by the following general formula (1).
  • R 1 and R 6 may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group. Among these, aryl groups and heteroaryl groups are preferred from the viewpoint of further improving the photoelectric conversion efficiency of red light.
  • R 2 and R 5 are hydrogen atoms.
  • R 3 and R 4 may be the same or different and represent an aryl group or a heteroaryl group. By selecting these groups for R 3 and R 4 , the absorption peak wavelength of the photoelectric conversion layer can be easily adjusted to a range of 570 nm or more and 670 nm or less, allowing red light to be efficiently absorbed and increasing the photoelectric conversion efficiency of red light. can be improved.
  • R 3 and R 4 are an aryl group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group is preferred.
  • R 3 and R 4 are a heteroaryl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted thiophenyl group, Preferred are a pyrimidyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, and a substituted or unsubstituted indolyl group.
  • R 7 to R 11 may be the same or different, and represent a condensation formed between a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an aryl group, a heteroaryl group, or an adjacent substituent. represents a ring (provided that either or both of R 7 and R 11 is an alkyl group, an alkoxy group, or an aryloxy group).
  • hydrogen atoms and alkyl groups are preferred from the viewpoint of chemical stability and reduction of deposition temperature.
  • R 7 and R 11 is an alkyl group, an alkoxy group, or an aryloxy group, so that the benzene ring to which R 7 or R 11 is bonded is substituted with the benzene ring.
  • Either or both of R 7 and R 11 is preferably an alkyl group or an alkoxy group from the viewpoint of reducing the deposition temperature.
  • X 1 and X 2 may be the same or different and represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, or a cyano group.
  • fluorine atoms are preferred from the viewpoints of ease of synthesis, chemical stability, electrochemical stability, and photostability.
  • the alkyl group refers to a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group; It may or may not have.
  • substituents include an alkoxy group, an alkoxycarbonyl group, a halogen, an aryl group, and a heteroaryl group.
  • the number of carbon atoms in the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and even more preferably 1 or more and 6 or less.
  • the carbon number of the alkyl group does not include the carbon number of the substituent, and this point is also common to the following description.
  • a cycloalkyl group refers to a saturated alicyclic hydrocarbon group such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, or an adamantyl group, and may or may not have a substituent. Good too. Examples of the substituent include the groups exemplified as substituents for alkyl groups and alkyl groups.
  • the number of ring carbon atoms in the cycloalkyl group is preferably in the range of 3 or more and 20 or less. Further, the number of carbon atoms in the cycloalkyl group is preferably 5 or more and 10 or less.
  • Aryl groups include, for example, phenyl group, biphenyl group, terphenyl group, naphthyl group, fluorenyl group, benzofluorenyl group, dibenzofluorenyl group, phenanthryl group, anthracenyl group, benzophenanthryl group, and benzanthracetyl group.
  • Indicates aromatic hydrocarbon groups such as nyl group, chrysenyl group, pyrenyl group, fluoranthenyl group, triphenylenyl group, benzofluoranthenyl group, dibenzaanthracenyl group, perylenyl group, and helicenyl group.
  • phenyl group biphenyl group, terphenyl group, naphthyl group, fluorenyl group, phenanthryl group, anthracenyl group, pyrenyl group, fluoranthenyl group, and triphenylenyl group are preferable.
  • the aryl group may or may not have a substituent.
  • substituents include an alkyl group, an alkoxy group, an aryloxy group, an amino group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, a diarylamino group, a cyano group, an alkoxycarbonyl group, a halogen, a hydroxy group, Examples include a thiol group, a thioalkyl group, a nitro group, and a heteroaryl group.
  • the number of ring carbon atoms in the aryl group is preferably 6 or more and 40 or less, more preferably 6 or more and 30 or less.
  • the phenyl group when there are substituents on two adjacent carbon atoms in the phenyl group, these substituents may form a ring structure together. Further, the number of carbon atoms in the aryl group is preferably 6 or more and 40 or less.
  • heteroaryl groups include pyridyl group, pyrrolyl group, furanyl group, thiophenyl group, quinolinyl group, isoquinolinyl group, pyrazinyl group, pyrimidyl group, pyridazinyl group, triazinyl group, naphthyridinyl group, cinnolinyl group, phthalazinyl group, quinoxalinyl group, Quinazolinyl group, benzofuranyl group, benzothiophenyl group, indolyl group, dibenzofuranyl group, dibenzothiophenyl group, carbazolyl group, benzocarbazolyl group, carbolinyl group, indolocarbazolyl group, benzofurocarbazolyl group, benzothienocarbazolyl group, dihydroindenocarbazolyl group, benzoquinolinyl group, acridinyl group, dibenzaacri
  • the naphthyridinyl group refers to any of the following: 1,5-naphthyridinyl group, 1,6-naphthyridinyl group, 1,7-naphthyridinyl group, 1,8-naphthyridinyl group, 2,6-naphthyridinyl group, 2,7-naphthyridinyl group. Show that.
  • a heteroaryl group may or may not have a substituent.
  • substituents include alkyl groups, alkoxy groups, aryloxy groups, amino groups, monoalkylamino groups, dialkylamino groups, monoarylamino groups, diarylamino groups, cyano groups, ester groups, halogens, hydroxy groups, and thiols. group, thioalkyl group, nitro group, and aryl group.
  • the number of ring carbon atoms in the heteroaryl group is preferably 2 or more and 40 or less, more preferably 2 or more and 30 or less. Further, the number of carbon atoms in the heteroaryl group is preferably 2 or more and 40 or less.
  • An alkoxy group refers to a functional group to which an aliphatic hydrocarbon group is bonded via an ether bond, such as a methoxy group, an ethoxy group, or a propoxy group, and this aliphatic hydrocarbon group may have a substituent. It is not necessary to have it.
  • substituents include the groups exemplified as substituents for alkyl groups.
  • the number of carbon atoms in the alkoxy group is preferably in the range of 1 or more and 20 or less.
  • An aryloxy group refers to a functional group such as a phenoxy group to which an aromatic hydrocarbon group is bonded via an oxygen atom, and this aromatic hydrocarbon group may or may not have a substituent. Good too.
  • substituents include the groups exemplified as substituents for alkyl groups and alkyl groups.
  • the number of ring carbon atoms in the aryloxy group is preferably in the range of 6 or more and 40 or less.
  • Halogen atoms refer to fluorine, chlorine, bromine, and iodine.
  • a cyano group is a functional group whose structure is represented by -C ⁇ N.
  • the compound having the structure represented by general formula (1) is purified by organic synthesis methods such as recrystallization and column chromatography, and then further purified by heating under reduced pressure, which is generally called sublimation purification, to obtain low-boiling point components. It is preferable to remove and improve purity.
  • the heating temperature in sublimation purification is preferably 350°C or lower, more preferably 330°C or lower, from the viewpoint of preventing thermal decomposition.
  • the compound having the structure represented by general formula (1) preferably has a molecular weight of 600 or more in order to ensure thermal stability of the optical sensor.
  • a molecular weight of 600 or more there is no particular limit to the upper limit of the molecular weight, but it is desirable to set it to 1000 or less from the viewpoint of processability and handling.
  • the purity of the compound having the structure represented by general formula (1) is preferably 99% by weight or more from the viewpoint of stabilizing photoelectric conversion characteristics.
  • the compound having the structure represented by general formula (1) used in the present invention is a type of pyrromethene boron complex.
  • this compound is used as an optical sensor having a photoelectric conversion layer on two electrodes (referred to as an anode and a cathode for convenience), it is used as a material constituting the photoelectric conversion layer.
  • the optical sensor of the present invention is an optical sensor in which a photoelectric conversion layer that converts light into electrical energy is present between an anode and a cathode.
  • the photoelectric conversion layer preferably contains two or more types of photoelectric conversion materials, and for example, it is preferable to combine a compound having a structure represented by the general formula (1) of the present invention with another photoelectric conversion material.
  • the photoelectric conversion material to be combined is preferably an organic semiconductor exhibiting p-type or n-type semiconductor characteristics, and more preferably an organic semiconductor exhibiting n-type semiconductor characteristics.
  • the compound represented by the general formula (1) used in the present invention has the ability to highly efficiently and selectively absorb red light and the ability to transport holes among the charges (electrons and holes) generated after photoelectric conversion. Since it has a high value, it is particularly preferable to use it as a p-type organic semiconductor in the photoelectric conversion layer. In this case, the compound represented by general formula (1) absorbs light and generates excitons, then transfers electrons to the n-type organic semiconductor and becomes a radical cation, so it is an electron donor material. .
  • n-type organic semiconductors include 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA), 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), 3,4,9, 10-perylenetetracarboxylic bisbenzimidazole (PTCBI), N,N'-dioctyl-3,4,9,10-naphthyltetracarboxydiimide (PTCDI-C8H); 2-(4-biphenylyl)-5-(4 -t-butylphenyl)-1,3,4-oxadiazole (PBD), oxazole derivatives such as 2,5-di(1-naphthyl)-1,3,4-oxadiazole (BND), 3- Triazole derivatives such as (4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (
  • fullerene compounds are preferably used because they have the characteristics of high charge separation rate and high electron transfer rate.
  • fullerene compounds include unsubstituted ones including C60, C70, C76, C78, C82, C84, C90, and C94, [6,6]-phenyl C61 butyric acid methyl ester ([6,6]-PCBM ), [5,6]-phenyl C61 butyric acid methyl ester ([5,6]-PCBM), [6,6]-phenyl C61 butyric acid hexyl ester ([6,6]-PCBH), [6 ,6]-phenyl C61 butyric acid dodecyl ester ([6,6]-PCBD), phenyl C71 butyric acid methyl ester (PC70BM), phenyl C85 butyric acid methyl ester (PC84BM), and the like.
  • Examples of p-type organic semiconductors include oligothiophene compounds such as terthiophene, quarterthiophene, sexithiophene, and octithiophene, phenylene vinylene compounds, p-phenylene compounds, polyfluorene compounds, compound H2 phthalocyanine (H2Pc), Phthalocyanine derivatives such as copper phthalocyanine (CuPc) and zinc phthalocyanine (ZnPc), porphyrin derivatives, N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diphenyl-1,1' -diamine (TPD), triarylamine derivatives such as N,N'-dinaphthyl-N,N'-diphenyl-4,4'-diphenyl-1,1'-diamine (NPD), 4,4'-di( Examples include carbazole derivatives such as carbazol-9-yl)b
  • the photoelectric conversion layer contains two or more types of photoelectric conversion materials
  • these materials may be mixed in one layer, or layers containing each photoelectric conversion material may be laminated, but the rectification property From this point of view, it is preferable that they are laminated.
  • the layer containing the p-type organic semiconductor is located on the anode side, and the layer containing the n-type organic semiconductor is located on the cathode side.
  • a mixed layer may be provided at the laminated interface.
  • Such a structure is called a pin structure, where the i layer mainly takes charge of charge separation, and the p layer and n layer take charge of hole transport and electron transport, respectively, thereby increasing the photoelectric conversion efficiency. can be further increased.
  • the compound having the structure represented by general formula (1) and the material to be combined are compatible at the molecular level or phase-separated at the nano level.
  • the domain size of the phase-separated structure is preferably 1 nm or more and 50 nm or less.
  • the thickness of the photoelectric conversion layer is preferably 10 nm to 500 nm, more preferably 20 nm to 100 nm.
  • the thickness of the layer containing the photoelectric conversion material having the structure represented by general formula (1) and the thickness of the layer to be laminated out of the total thickness of the photoelectric conversion layer.
  • the thickness is preferably 5 nm to 495 nm, more preferably 10 nm to 50 nm.
  • the thickness of the i-layer is preferably 1 nm to 100 nm, more preferably 5 nm to 50 nm.
  • the optical sensor it is preferable that either or both of the anode and the cathode have optical transparency.
  • the light transmittance of the electrode is not particularly limited as long as incident light reaches the photoelectric conversion layer and an electromotive force is generated.
  • the light transmittance is a value determined by [transmitted light intensity (W/m 2 )/incident light intensity (W/m 2 )] ⁇ 100 (%).
  • the thickness of the light-transmitting electrode may be within a range that has both light transparency and conductivity, and although it varies depending on the electrode material, it is preferably 20 nm to 300 nm. Note that the electrode that does not have light transmittance only needs to have electrical conductivity, and its thickness is not particularly limited.
  • a conductive material with a high work function for one electrode it is preferable to use a conductive material with a low work function for the other electrode.
  • an electrode made of a conductive material with a high work function As the anode, it is preferable to use an electrode made of a conductive material with a high work function as the anode.
  • conductive materials with a high work function include metals such as gold, platinum, chromium, and nickel.
  • transparent metal oxides such as indium, tin, and molybdenum, and composite metal oxides such as indium tin oxide (ITO) and indium zinc oxide (IZO) are preferably used.
  • the conductive material used for the anode is preferably one that makes ohmic contact with the photoelectric conversion layer.
  • the conductive material used for the anode is preferably one that forms an ohmic contact with the hole transport layer.
  • An optimal method for forming the anode can be selected depending on the material used to form the anode, and examples thereof include sputtering, vapor deposition, and inkjet methods. For example, when forming the anode using a metal oxide, a sputtering method is preferably used, and when forming an anode using a metal, a vapor deposition method is preferably used.
  • an electrode made of a conductive material with a low work function As the cathode, it is preferable to use an electrode made of a conductive material with a low work function as the cathode.
  • the conductive material with a low work function include alkali metals such as lithium, magnesium, calcium, etc. Alkaline earth metals such as tin, silver, aluminum, and alloys thereof are preferably used. A laminate using two or more of these may also be used.
  • the conductive material used for the cathode is preferably one that makes an ohmic contact with the photoelectric conversion layer.
  • the conductive material used for the cathode is preferably one that forms an ohmic contact with the electron transport layer. Furthermore, it is also possible to improve the extraction current by introducing a metal fluoride such as lithium fluoride or cesium fluoride into the interface between the cathode and the electron transport layer.
  • the optical sensor is preferably formed on a substrate in order to maintain the mechanical strength of the optical sensor, suppress thermal deformation, and provide barrier properties that suppress entry of water vapor and oxygen into the photoelectric conversion layer.
  • the substrate include a glass plate, a ceramic plate, a resin film, a thin resin film obtained by hardening varnish, and a thin metal plate.
  • glass substrates are preferably used because they are transparent and easy to process.
  • flexible displays and foldable displays are increasing mainly in mobile devices such as smartphones, and resin films and resin thin films are suitable for this use.
  • Examples of such a substrate include heat-resistant films such as polyimide films and polyethylene naphthalate films.
  • a hole transport layer may be provided between the anode and the photoelectric conversion layer.
  • Materials for forming the hole transport layer include the aforementioned oligothiophene compounds, phenylene vinylene compounds, p-phenylene compounds, polyfluorene compounds, H2 phthalocyanine (H2Pc), copper phthalocyanine (CuPc), and zinc phthalocyanine (ZnPc).
  • Phthalocyanine derivatives such as, porphyrin derivatives, N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diphenyl-1,1'-diamine (TPD), N,N'- Triarylamine derivatives such as dinaphthyl-N,N'-diphenyl-4,4'-diphenyl-1,1'-diamine (NPD), 4,4'-di(carbazol-9-yl)biphenyl (CBP), etc.
  • Examples include carbazole derivatives, and metal oxides exhibiting p-type semiconductor properties such as molybdenum oxide and tungsten oxide.
  • the thickness of the hole transport layer is preferably 1 nm to 200 nm, more preferably 5 nm to 100 nm.
  • a hole extraction layer may be provided between the anode and the hole transport layer.
  • the material forming the hole extraction layer include charge transfer complexes such as tris(4-bromophenyl)aminium hexachloroantimonate (TBPAH), 1,4,5,8,9,11-hexaazatriphenylene- Hexacarbonitrile (HAT-CN6), 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), tetracyanoquinodimethane derivative, radialene derivative, fluorine Examples include copper phthalocyanine.
  • TPAH tris(4-bromophenyl)aminium hexachloroantimonate
  • HAT-CN6 1,4,5,8,9,11-hexaazatriphenylene- Hexacarbonitrile
  • F4-TCNQ 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquino
  • an electron transport layer may be provided between the photoelectric conversion layer and the cathode.
  • materials for forming the electron transport layer include, in addition to the above-mentioned n-type organic semiconductors, polycyclic aromatic derivatives, styryl aromatic ring derivatives, quinone derivatives, phosphorus oxide derivatives, and tris(8-quinolinolato)aluminum(III).
  • metal complexes such as quinolinol complexes, benzoquinolinol complexes, hydroxyazole complexes, azomethine complexes, tropolone metal complexes, and flavonol metal complexes.
  • the electron-accepting nitrogen refers to a nitrogen atom forming multiple bonds with adjacent atoms. Since the heteroaryl group containing electron-accepting nitrogen has a large electron affinity, it becomes easier to transport electrons and contributes to further improving the photoelectric conversion efficiency.
  • Examples of compounds having a heteroaryl group structure containing electron-accepting nitrogen include pyridine derivatives, triazine derivatives, pyrazine derivatives, pyrimidine derivatives, quinoline derivatives, quinoxaline derivatives, quinazoline derivatives, naphthyridine derivatives, benzoquinoline derivatives, phenanthroline derivatives, and imidazole.
  • Examples include derivatives, oxazole derivatives, thiazole derivatives, triazole derivatives, oxadiazole derivatives, thiadiazole derivatives, benzimidazole derivatives, benzoxazole derivatives, benzthiazole derivatives, phenanthroimidazole derivatives, and oligopyridine derivatives such as bipyridine and terpyridine. Two or more types of these may be used.
  • the electron transport material has a condensed polycyclic aromatic skeleton because the glass transition temperature is improved and the electron mobility is large.
  • a condensed polycyclic aromatic skeleton a quinolinol complex, a triazine derivative, a fluoranthene skeleton, an anthracene skeleton, a pyrene skeleton, or a phenanthroline skeleton is preferable.
  • the electron transport layer may contain an electron donor material.
  • the electron donor material is a compound that improves the electrical conductivity of the electron transport layer.
  • Preferred examples of electron donor materials include alkali metals such as Li, inorganic salts containing alkali metals such as LiF, complexes of alkali metals and organic substances such as lithium quinolinol, alkaline earth metals, and alkaline earth metals.
  • examples include inorganic salts containing alkaline earth metals and organic substances, rare earth metals such as Eu and Yb, inorganic salts containing rare earth metals, and complexes of rare earth metals and organic substances. Two or more types of these may be used. Among these, metallic lithium, rare earth metals, and lithium quinolinol (Liq) are preferred.
  • the thickness of the electron transport layer is preferably 1 nm to 200 nm, more preferably 3 nm to 100 nm.
  • each of the above layers constituting the optical sensor may be either a dry process or a wet process, and examples thereof include resistance heating evaporation, electron beam evaporation, sputtering, molecular lamination method, coating method, inkjet method, printing method, etc. .
  • resistance heating vapor deposition is preferred from the viewpoint of device characteristics.
  • the optical sensor of the present invention has a function of converting light into electrical energy.
  • the absorption peak wavelength is 570 nm or more and 670 nm or less, and the absorption peak wavelength is 580 nm or more. More preferably, it is 660 nm or less.
  • the optical sensor of the present invention can be applied to various electronic devices and optical sensing devices that utilize the function of selectively and highly efficiently photoelectrically converting red light.
  • it can be used as an optical switch or an image sensor, and biological information such as fingerprints, veins, pulse waves, and blood oxygen concentration can be acquired with high sensitivity.
  • the biological information referred to in the present invention is not particularly limited as long as it is information obtained from a living body, but information obtained from irradiating a living body with synchrotron radiation and obtaining reflected light or transmitted light, or information from a living body. Information obtained as luminescence can be cited.
  • the objects to be measured include, for example, the iris, the shape of the face, the degree of dryness of the skin, and the blood sugar level.
  • a fingerprint authentication device of an apparatus is a display device that is used in combination with the optical sensor of the present invention and an organic light emitting element, and is equipped with a function of performing fingerprint authentication with the optical sensor using the light of the organic light emitting element.
  • the organic EL display can be provided with a fingerprint authentication function or a biosensing function.
  • the optical sensor of the present invention since the optical sensor of the present invention has excellent photoelectric conversion characteristics for red light, it is possible to perform sensing with high precision and sensitivity by using it in combination with a red light source. For example, fingerprint information can be obtained with high precision by receiving and photoelectrically converting red light emitted from an organic light emitting element of an organic EL display and reflected and scattered by a finger touching the display using the optical sensor of the present invention. can do.
  • the red light emitted from the organic light emitting element of the organic EL display by the finger touching the display the light is received and photoelectrically converted by the optical sensor of the present invention.
  • the optical sensor of the present invention Compared to short-wavelength green light, it has the property of penetrating inside the living body more, so it can obtain biological information such as veins, pulse waves, and blood oxygen concentration with higher precision than when using green light. can do.
  • Example 1 A 46 mm x 38 mm transparent glass substrate having an ITO electrode layer with a thickness of 125 nm was prepared as an anode. This substrate was immersed in a diluted solution of an alkaline cleaning solution ("Semico Clean” (registered trademark) EL56, manufactured by Furuuchi Chemical Co., Ltd.) diluted 10 times with pure water, subjected to ultrasonic cleaning for 10 minutes, and then soaked in pure water for 5 minutes. It was subjected to ultrasonic cleaning twice and thoroughly dried. Thereafter, UV ozone cleaning was performed for 30 minutes.
  • an alkaline cleaning solution (“Semico Clean” (registered trademark) EL56, manufactured by Furuuchi Chemical Co., Ltd.)
  • PEDOT:PSS poly-3,4-ethylenedioxythiophene
  • poly-4-styrene sulfonic acid and isopropyl alcohol mixed at a volume ratio of 6:4 was poured onto the ITO electrode layer of the substrate. ,000 rpm for 30 seconds, and heat-treated on a 150° C. hot plate for 10 minutes to form a hole extraction layer with a thickness of 55 nm.
  • the substrate on which the hole extraction layer was formed was placed in a vacuum evaporation device (manufactured by Eiko Engineering Co., Ltd.), and the pressure was reduced to about 3 ⁇ 10 ⁇ 3 Pa.
  • N-[1,1'-biphenyl]-4-yl-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazol-3-yl) is placed on the hole extraction layer as a hole transport layer.
  • phenyl]-9H-fluoren-2-amine 40 nm was deposited to form a hole transport layer.
  • A-1 (15 nm) synthesized according to Synthesis Example 3 described in Patent No. 4941471 as a p-type organic semiconductor and fullerene (15 nm) having the following structure as an n-type organic semiconductor were deposited to form a photoelectric conversion layer. did.
  • Lithium quinolinol (5 nm) and aluminum (80 nm) were sequentially deposited on the photoelectric conversion layer to form an electron transport layer and a cathode, respectively.
  • the obtained laminate was sealed in a glove box with a barrier film (manufactured by TESA) to obtain an optical sensor.
  • the obtained optical sensor was evaluated by the method described above, it showed sensitivity in the red light region, external quantum efficiency was 6.9%, and the spectral sensitivity peak wavelength at that time was 618 nm.
  • Example 2 An optical sensor was obtained in the same manner as in Example 1 except that the hole extraction layer was not formed.
  • the obtained optical sensor was evaluated by the method described above, it showed sensitivity in the red light region, external quantum efficiency was 6.7%, and the spectral sensitivity peak wavelength at that time was 618 nm.
  • reaction solution was quenched with saturated ammonium chloride aqueous solution (200 mL), extracted with ethyl acetate (200 mL x 2), and the extracts were combined and washed with water (400 mL). The extract was dried over magnesium sulfate and then concentrated under reduced pressure to obtain compound A-2A as a crude product.
  • Sublimation purification was performed to further increase purity.
  • a metal container containing Compound A-2 was placed in a glass tube, and heated at 230° C. using an oil diffusion pump under a pressure of 4.2 ⁇ 10 ⁇ 3 Pa to sublimate it.
  • the solid adhering to the glass tube wall was collected and analyzed by LC-MS, and the purity was 99%.
  • Example 4 An optical sensor was obtained in the same manner as in Example 1 except that compound A-2 was used instead of compound A-1.
  • the obtained optical sensor was evaluated by the method described above, it showed sensitivity in the red light region, external quantum efficiency was 16.5%, and the peak spectral sensitivity wavelength was 590 nm.
  • Example 5 A photoelectric conversion element was obtained in the same manner as in Example 1 except that compound A-2 was used instead of compound A-1 and a hole extraction layer was not formed.
  • the obtained optical sensor was evaluated by the method described above, it showed sensitivity in the red light region, external quantum efficiency was 20.0%, and the spectral sensitivity peak wavelength was 590 nm.
  • the obtained optical sensor was evaluated using the method described above, it showed no sensitivity in the red light region.
  • the obtained optical sensor was evaluated using the method described above, it showed no sensitivity in the red light region.
  • the obtained optical sensor was evaluated by the method described above, it showed sensitivity in the red light region, external quantum efficiency was 2.0%, and the spectral sensitivity peak wavelength at that time was 672 nm.
  • the obtained optical sensor was evaluated by the method described above, it showed sensitivity in the red light region, external quantum efficiency was 3.1%, and the peak spectral sensitivity wavelength was 635 nm.
  • the obtained optical sensor was evaluated by the method described above, it showed sensitivity in the red light region, external quantum efficiency was 4.1%, and the spectral sensitivity peak wavelength at that time was 880 nm.

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Abstract

La présente invention aborde le problème de la fourniture d'un capteur de lumière permettant d'acquérir des informations biométriques avec une efficacité de conversion photoélectrique élevée pour la lumière rouge, et pour résoudre ce problème, la présente invention concerne un capteur de lumière permettant d'acquérir des informations biométriques comprenant un composé ayant une structure représentée par la formule générale suivante (1). (Dans la formule générale (1) ci-dessus, R1 et R6 peuvent être identiques ou différents, et représentent des atomes d'hydrogène, des groupes alkyle, des groupes cycloalkyle, des groupes aryle ou des groupes hétéroaryle. R2 et R5 représentent des atomes d'hydrogène. R3 et R4 peuvent être identiques ou différents, et représentent des groupes aryle ou des groupes hétéroaryle. R7 représente un groupe alkyle, un groupe alcoxy ou un groupe aryloxy. R8 à R11 peuvent être identiques ou différents, et représentent des atomes d'hydrogène, des groupes alkyle, des groupes cycloalkyle, des groupes alcoxy, des groupes aryloxy, des groupes aryle, des groupes hétéroaryle ou des cycles condensés formés entre des substituants adjacents. X1 et X2 peuvent être identiques ou différents, et représentent des groupes alkyle, des groupes aryle, des groupes alcoxy, des groupes aryloxy, des atomes d'halogène ou des groupes cyano).
PCT/JP2023/009289 2022-04-11 2023-03-10 Capteur de lumière et dispositif d'affichage utilisant celui-ci WO2023199670A1 (fr)

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Publication number Priority date Publication date Assignee Title
JP2005221688A (ja) * 2004-02-05 2005-08-18 Sony Corp 表示装置および表示装置の駆動方法
JP2005539247A (ja) * 2001-12-31 2005-12-22 インテル コーポレイション エネルギをセンスする発光ダイオード・ディスプレイ
US20150303378A1 (en) * 2014-04-17 2015-10-22 Samsung Electronics Co., Ltd. Compound and organic photoelectronic device and image sensor
WO2017002707A1 (fr) * 2015-06-29 2017-01-05 東レ株式会社 Composition de conversion de couleur, film de conversion de couleur et dispositif électroluminescent le comprenant, appareil d'affichage à cristaux liquides, et appareil d'éclairage
WO2017018351A1 (fr) * 2015-07-30 2017-02-02 富士フイルム株式会社 Élément de conversion photoélectrique, élément d'imagerie, capteur de lumière, et composé
JP2019165102A (ja) * 2018-03-19 2019-09-26 出光興産株式会社 有機エレクトロルミネッセンス素子、及び電子機器
WO2020045242A1 (fr) * 2018-08-27 2020-03-05 東レ株式会社 Complexe pyrrométhène-bore, élément électroluminescent l'utilisant, dispositif d'affichage, dispositif d'éclairage, composition de conversion de couleur, film de conversion de couleur, substrat de conversion de couleur, unité de source lumineuse et dispositif d'éclairage
WO2021085460A1 (fr) * 2019-10-28 2021-05-06 東レ株式会社 Matériau d'élément luminescent contenant un complexe pyrrométhène bore, élément luminescent, dispositif d'affichage et dispositif d'éclairage

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005539247A (ja) * 2001-12-31 2005-12-22 インテル コーポレイション エネルギをセンスする発光ダイオード・ディスプレイ
JP2005221688A (ja) * 2004-02-05 2005-08-18 Sony Corp 表示装置および表示装置の駆動方法
US20150303378A1 (en) * 2014-04-17 2015-10-22 Samsung Electronics Co., Ltd. Compound and organic photoelectronic device and image sensor
WO2017002707A1 (fr) * 2015-06-29 2017-01-05 東レ株式会社 Composition de conversion de couleur, film de conversion de couleur et dispositif électroluminescent le comprenant, appareil d'affichage à cristaux liquides, et appareil d'éclairage
WO2017018351A1 (fr) * 2015-07-30 2017-02-02 富士フイルム株式会社 Élément de conversion photoélectrique, élément d'imagerie, capteur de lumière, et composé
JP2019165102A (ja) * 2018-03-19 2019-09-26 出光興産株式会社 有機エレクトロルミネッセンス素子、及び電子機器
WO2020045242A1 (fr) * 2018-08-27 2020-03-05 東レ株式会社 Complexe pyrrométhène-bore, élément électroluminescent l'utilisant, dispositif d'affichage, dispositif d'éclairage, composition de conversion de couleur, film de conversion de couleur, substrat de conversion de couleur, unité de source lumineuse et dispositif d'éclairage
WO2021085460A1 (fr) * 2019-10-28 2021-05-06 東レ株式会社 Matériau d'élément luminescent contenant un complexe pyrrométhène bore, élément luminescent, dispositif d'affichage et dispositif d'éclairage

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