WO2021065374A1 - Élément de conversion photoélectrique - Google Patents

Élément de conversion photoélectrique Download PDF

Info

Publication number
WO2021065374A1
WO2021065374A1 PCT/JP2020/033894 JP2020033894W WO2021065374A1 WO 2021065374 A1 WO2021065374 A1 WO 2021065374A1 JP 2020033894 W JP2020033894 W JP 2020033894W WO 2021065374 A1 WO2021065374 A1 WO 2021065374A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
substituent
photoelectric conversion
conversion element
type semiconductor
Prior art date
Application number
PCT/JP2020/033894
Other languages
English (en)
Japanese (ja)
Inventor
美樹 西
貴史 荒木
ジョバンニ フェララ
Original Assignee
住友化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to CN202080067923.2A priority Critical patent/CN114514621A/zh
Publication of WO2021065374A1 publication Critical patent/WO2021065374A1/fr

Links

Images

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • 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
    • 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
    • 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
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a photoelectric conversion element, a method for producing the same, and a compound that can be used for these.
  • the photoelectric conversion element is attracting attention because it is an extremely useful device from the viewpoint of energy saving and reduction of carbon dioxide emissions, for example.
  • a photoelectric conversion element is an element having at least a pair of electrodes composed of an anode and a cathode and an active layer provided between the pair of electrodes.
  • at least one of the pair of electrodes is made of a transparent or translucent material, and light is incident on the active layer from the transparent or translucent electrode side.
  • the energy (h ⁇ ) of light incident on the active layer causes charges (holes and electrons) to be generated in the active layer, the generated holes move toward the anode, and the electrons move toward the cathode. Then, the electric charges that have reached the anode and the cathode are taken out of the device.
  • the active layer having a separated structure is also referred to as a bulk heterojunction type active layer.
  • Patent Document In a photoelectric conversion element provided with such a bulk heterojunction type active layer, an embodiment in which a fullerene derivative C60PCBM ([6,6] -phenyl-C61 butyric acid methyl ester) is used as an n-type semiconductor material is known (Patent Document). See 1 and Non-Patent Document 1).
  • C60PCBM [6,6] -phenyl-C61 butyric acid methyl ester
  • Non-Patent Document 1 Although the heat resistance is improved by further adding an additive as a material of the bulk heterojunction type active layer, it is used in the manufacturing process of the photoelectric conversion element and in the device. Considering the heating temperature at the time of assembling, it cannot be said that the heat resistance is still sufficient. Therefore, further improvement in heat resistance to heat treatment in the manufacturing process and heat resistance of the photoelectric conversion element itself is required.
  • the present inventor has found that heat resistance can be improved by using a predetermined semiconductor material as the material of the bulk heterojunction type active layer, and completed the present invention. I came to do it. That is, the present invention provides the following [1] to [19].
  • a photoelectric conversion element including an anode, a cathode, and an active layer provided between the anode and the cathode.
  • the active layer contains an n-type semiconductor material and a p-type semiconductor material.
  • the n-type semiconductor material is a compound represented by the following formula (I).
  • R 1 is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a monovalent aromatic hydrocarbon which may have a substituent.
  • a plurality of R 1s may be the same or different.
  • R 2 is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a monovalent aromatic hydrocarbon which may have a substituent.
  • a plurality of R 2s may be the same or different.
  • the p-type semiconductor material is a photoelectric conversion element which is a polymer compound containing a structural unit represented by the following formula (II).
  • Ar 1 and Ar 2 represent a trivalent aromatic heterocyclic group.
  • Z represents a group represented by the following formulas (Z-1) to (Z-7).
  • R is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, and an acid.
  • the two Rs may be the same or different from each other.
  • At least one of R 1 and R 2 is a fluorine atom, an alkyl group containing a fluorine atom as a substituent, an alkoxy group containing a fluorine atom as a substituent, and a monovalent aromatic containing a fluorine atom as a substituent.
  • R 1 is an alkyl group containing one or more fluorine atoms as a substituent.
  • R 1 is a group represented by -CH 2 (CF 2 ) 2 CF 3.
  • R 1 is an alkyl group which may have a substituent and
  • the photoelectric conversion element according to [7] is included.
  • the photoelectric conversion element according to [7] is included.
  • the steps of forming the active layer include the step (i) of applying an ink containing the n-type semiconductor material and the p-type semiconductor material to an application target to obtain a coating film, and removing the solvent from the obtained coating film.
  • a method for manufacturing a photoelectric conversion element which includes the step (ii).
  • the method for manufacturing a photoelectric conversion element according to [10] further comprising a step of heating at a heating temperature of 165 ° C. or higher.
  • the method for manufacturing a photoelectric conversion element according to [11] wherein the step of heating at a heating temperature of 165 ° C. or higher is carried out after the step (ii).
  • R 1 is an alkyl group containing one or more fluorine atoms as a substituent.
  • a plurality of R 1s may be the same or different.
  • R 2 is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a monovalent aromatic hydrocarbon which may have a substituent. Represents a monovalent aromatic heterocyclic group which may have a group or a substituent.
  • a plurality of R 2s may be the same or different.
  • R 1 is a group represented by -CH 2 (CF 2 ) 2 CF 3.
  • R 2 is a hydrogen atom A compound according to [13].
  • R 1 is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a monovalent aromatic hydrocarbon which may have a substituent.
  • a plurality of R 1s may be the same or different.
  • R 2 is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a monovalent aromatic hydrocarbon which may have a substituent.
  • R 1 is an alkyl group which may have a substituent and The compound according to [15], wherein two or more of the plurality of R 2 are alkyl groups containing one or more fluorine atoms as substituents.
  • N-4 The compound according to [15] or [16], which is represented by the following formula (N-4).
  • composition containing an n-type semiconductor material and a p-type semiconductor material, wherein the n-type semiconductor material is a compound according to any one of [13] to [17].
  • An ink containing the composition according to [18].
  • the photoelectric conversion element according to the present invention may have the following aspect [X].
  • [X] In a photoelectric conversion element including an anode, a cathode, and an active layer provided between the anode and the cathode.
  • the active layer contains an n-type semiconductor material and a p-type semiconductor material.
  • the n-type semiconductor material is a compound represented by the following formula (I).
  • R 1 is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a monovalent aromatic hydrocarbon which may have a substituent.
  • a plurality of R 1s may be the same or different.
  • R 2 is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a monovalent aromatic hydrocarbon which may have a substituent.
  • a plurality of R 2s may be the same or different.
  • the p-type semiconductor material is a photoelectric conversion element which is a polymer compound containing a structural unit represented by the following formula (II).
  • Ar 1 and Ar 2 represent a trivalent aromatic heterocyclic group.
  • Z represents a group represented by the following formulas (Z-1) to (Z-7).
  • R is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, and an acid.
  • the two Rs may be the same or different from each other.
  • the present invention it is possible to improve the heat resistance to heat treatment during the manufacturing process of the photoelectric conversion element or the incorporation into the device to which the photoelectric conversion element is applied.
  • FIG. 1 is a diagram schematically showing a configuration example of a photoelectric conversion element.
  • FIG. 2 is a diagram schematically showing a configuration example of an image detection unit.
  • FIG. 3 is a diagram schematically showing a configuration example of the fingerprint detection unit.
  • FIG. 4 is a graph showing the relationship between the heating temperature and EQE heat / EQE 100 ° C.
  • FIG. 5 is a graph showing the relationship between the heating temperature and the dark current heat / dark current 100 ° C.
  • FIG. 6 is a graph showing the relationship between the heating temperature of the sealed body and EQE heat / EQE un heat.
  • the “polymer compound” means a polymer having a molecular weight distribution and having a polystyrene-equivalent number average molecular weight of 1 ⁇ 10 3 or more and 1 ⁇ 108 or less.
  • the structural units contained in the polymer compound are 100 mol% in total.
  • the "constituent unit” means a residue derived from a raw material monomer, which is present at least one in the polymer compound.
  • the "hydrogen atom” may be a light hydrogen atom or a deuterium atom.
  • halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.
  • the "alkyl group” may be linear, branched, or cyclic.
  • the number of carbon atoms of the linear alkyl group is usually 1 to 50, preferably 1 to 30, and more preferably 1 to 20 without including the number of carbon atoms of the substituent.
  • the number of carbon atoms of the branched or cyclic alkyl group is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20, not including the number of carbon atoms of the substituent.
  • the alkyl group may have a substituent.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, 2-ethylbutyl group and n-.
  • Examples thereof include an alkyl group further having a substituent such as a ru group, a 3- (4-methylphenyl) propyl group, a 3- (3,5-di-n-hexylphenyl) propyl group, and a 6-ethyloxyhexyl group.
  • a substituent such as a ru group, a 3- (4-methylphenyl) propyl group, a 3- (3,5-di-n-hexylphenyl) propyl group, and a 6-ethyloxyhexyl group.
  • Aromatic hydrocarbon group (aryl group) means the remaining atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon which may have a substituent. To do.
  • the aromatic hydrocarbon group may have a substituent.
  • aromatic hydrocarbon group examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-pyrenyl group, a 2-pyrenyl group, and 4 -Pyrenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group, 4-phenylphenyl group, and alkyl group, alkoxy group, aryl group, fluorine atom, etc. Examples thereof include a group further having a substituent of.
  • the "alkoxy group” may be linear, branched, or cyclic.
  • the number of carbon atoms of the linear alkoxy group is usually 1 to 40, preferably 1 to 10, not including the number of carbon atoms of the substituent.
  • the number of carbon atoms of the branched or cyclic alkoxy group is usually 3 to 40, preferably 4 to 10, not including the number of carbon atoms of the substituent.
  • the alkoxy group may have a substituent.
  • alkoxy group examples include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a tert-butyloxy group, an n-pentyloxy group and an n-hexyloxy group.
  • alkoxy group examples include cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, 3,7-dimethyloctyloxy group and lauryloxy group.
  • the number of carbon atoms of the "aryloxy group” is usually 6 to 60, preferably 6 to 48, not including the number of carbon atoms of the substituent.
  • the aryloxy group may have a substituent.
  • aryloxy group examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthryloxy group, a 9-anthryloxy group, a 1-pyrenyloxy group, and an alkyl group and an alkoxy group.
  • substituent such as a fluorine atom.
  • alkylthio group may be linear, branched, or cyclic.
  • the number of carbon atoms of the linear alkylthio group is usually 1 to 40, preferably 1 to 10, not including the number of carbon atoms of the substituent.
  • the number of carbon atoms of the branched and cyclic alkylthio groups is usually 3 to 40, preferably 4 to 10, not including the number of carbon atoms of the substituent.
  • the alkylthio group may have a substituent.
  • alkylthio group examples include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, tert-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2 Included are ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, and trifluoromethylthio group.
  • the number of carbon atoms of the "arylthio group” is usually 6 to 60, preferably 6 to 48, not including the number of carbon atoms of the substituent.
  • the arylthio group may have a substituent.
  • arylthio group examples include a phenylthio group and a C1 to C12 alkyloxyphenylthio group (here, "C1 to C12" indicates that the group described immediately after that has 1 to 12 carbon atoms. The same applies to the above.), C1-C12 alkylphenylthio groups, 1-naphthylthio groups, 2-naphthylthio groups, and pentafluorophenylthio groups.
  • a "p-valent heterocyclic group” (p represents an integer of 1 or more) is a heterocyclic compound which may have a substituent and is directly bonded to a carbon atom or a hetero atom constituting a ring. It means the remaining atomic group excluding p hydrogen atoms among the hydrogen atoms.
  • the "p-valent heterocyclic group” includes a "p-valent aromatic heterocyclic group”.
  • the "p-valent aromatic heterocyclic group” is a p of a hydrogen atom directly bonded to a carbon atom or a hetero atom constituting a ring from an aromatic heterocyclic compound which may have a substituent. It means the remaining atomic group excluding one hydrogen atom.
  • heterocyclic compound may have include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic group and a substituted amino group.
  • substituents that the heterocyclic compound may have include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic group and a substituted amino group.
  • Aromatic heterocyclic compounds include, in addition to compounds in which the heterocycle itself exhibits aromaticity, compounds in which the heterocycle itself has an aromatic ring condensed into the heterocycle even if the heterocycle itself does not exhibit aromaticity.
  • aromatic heterocyclic compounds specific examples of the compound in which the heterocycle itself exhibits aromaticity include oxadiazole, thiadiazole, thiazole, oxazol, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, and triazine. , Pyridazine, quinoline, isoquinolin, carbazole, and dibenzophosphol.
  • aromatic heterocyclic compounds specific examples of compounds in which the aromatic heterocycle itself does not exhibit aromaticity and the aromatic ring is fused to the heterocycle include phenoxazine, phenothiazine, dibenzoborol, and dibenzo. Examples include silol and benzopyran.
  • the number of carbon atoms of the monovalent heterocyclic group is usually 2 to 60, preferably 4 to 20, excluding the number of carbon atoms of the substituent.
  • the monovalent heterocyclic group may have a substituent, and specific examples of the monovalent heterocyclic group include, for example, a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a piperidyl group and a quinolyl group. Examples thereof include an isoquinolyl group, a pyrimidinyl group, a triazinyl group, and a group further having a substituent such as an alkyl group and an alkoxy group.
  • Substituent amino group means an amino group having a substituent.
  • substituent contained in the amino group an alkyl group, an aryl group and a monovalent heterocyclic group are preferable.
  • the number of carbon atoms of the substituted amino group is usually 2 to 30.
  • Examples of the substituted amino group include a dialkylamino group such as a dimethylamino group and a diethylamino group, a diphenylamino group, a bis (4-methylphenyl) amino group, a bis (4-tert-butylphenyl) amino group, and a bis (3, Examples thereof include a diarylamino group such as a 5-di-tert-butylphenyl) amino group.
  • the number of carbon atoms of the "acyl group” is usually 2 to 20, preferably 2 to 18.
  • Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.
  • Imine residue means the remaining atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom or a nitrogen atom forming a carbon atom-nitrogen atom double bond from imine.
  • the "imine compound” means an organic compound having a carbon atom-nitrogen atom double bond in the molecule.
  • imine compounds include compounds in which the hydrogen atom bonded to the nitrogen atom constituting the carbon atom-nitrogen atom double bond in aldimine, ketimine, and aldimine is replaced with an alkyl group or the like.
  • the number of carbon atoms of the imine residue is usually 2 to 20, preferably 2 to 18.
  • Examples of imine residues include groups represented by the following structural formulas.
  • the "amide group” means the remaining atomic group obtained by removing one hydrogen atom bonded to a nitrogen atom from the amide.
  • the number of carbon atoms of the amide group is usually 1 to 20, preferably 1 to 18.
  • Specific examples of the amide group include a formamide group, an acetamido group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group and a dibenzamide group. , Ditrifluoroacetamide group, and dipentafluorobenzamide group.
  • the "acid imide group” means the remaining atomic group obtained by removing one hydrogen atom bonded to a nitrogen atom from the acid imide.
  • the number of carbon atoms of the acidimide group is usually 4 to 20.
  • Specific examples of the acidimide group include a group represented by the following structural formula.
  • R' represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.
  • the number of carbon atoms of the substituted oxycarbonyl group is usually 2 to 60, preferably 2 to 48.
  • substituted oxycarbonyl group examples include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group, and a hexyloxycarbonyl group.
  • alkenyl group may be linear, branched, or cyclic.
  • the number of carbon atoms of the linear alkenyl group is usually 2 to 30, preferably 3 to 20, not including the number of carbon atoms of the substituent.
  • the number of carbon atoms of the branched or cyclic alkenyl group is usually 3 to 30, preferably 4 to 20, not including the number of carbon atoms of the substituent.
  • the alkenyl group may have a substituent.
  • alkenyl group examples include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group and a 5-hexenyl group. , 7-octenyl group, and a group further having a substituent such as an alkyl group or an alkoxy group can be mentioned.
  • the "alkynyl group” may be linear, branched, or cyclic.
  • the number of carbon atoms of the linear alkenyl group is usually 2 to 20, preferably 3 to 20, not including the number of carbon atoms of the substituent.
  • the number of carbon atoms of the branched or cyclic alkenyl group is usually 4 to 30, preferably 4 to 20, not including the number of carbon atoms of the substituent.
  • the alkynyl group may have a substituent.
  • alkynyl group examples include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-hexynyl group and a 5-hexynyl group.
  • a group further having a substituent such as an alkyl group or an alkoxy group.
  • EQE means external quantum efficiency, and among the electrons generated with respect to the number of photons irradiated to the photoelectric conversion element, the electrons that can be taken out to the outside of the photoelectric conversion element.
  • the value of the number of is expressed as a ratio (%).
  • the photoelectric conversion element according to the present embodiment is a photoelectric conversion element including an anode, a cathode, and an active layer provided between the anode and the cathode.
  • the active layer contains an n-type semiconductor material and a p-type semiconductor material.
  • the n-type semiconductor material is a compound represented by the following formula (I).
  • R 1 is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a monovalent aromatic hydrocarbon which may have a substituent.
  • a plurality of R 1s may be the same or different.
  • R 2 is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a monovalent aromatic hydrocarbon which may have a substituent.
  • a plurality of R 2s may be the same or different.
  • the p-type semiconductor material is a photoelectric conversion element which is a polymer compound containing a structural unit represented by the following formula (II).
  • Ar 1 and Ar 2 represent a trivalent aromatic heterocyclic group.
  • Z represents a group represented by the following formulas (Z-1) to (Z-7).
  • R is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, and an acid.
  • the two Rs may be the same or different from each other.
  • the heat resistance to heat treatment in the manufacturing process of the photoelectric conversion element or when the photoelectric conversion element is incorporated into the device to which the photoelectric conversion element is applied is effectively improved. Can be improved.
  • FIG. 1 is a diagram schematically showing a configuration of a photoelectric conversion element of the present embodiment.
  • the photoelectric conversion element 10 is provided on the support substrate 11.
  • the photoelectric conversion element 10 is provided so as to be in contact with the anode 12 provided in contact with the support substrate 11, the hole transport layer 13 provided in contact with the anode 12, and the hole transport layer 13.
  • the active layer 14 is provided, an electron transporting layer 15 is provided so as to be in contact with the active layer 14, and a cathode 16 is provided so as to be in contact with the electron transporting layer 15.
  • the sealing member 17 is further provided so as to be in contact with the cathode 16.
  • the photoelectric conversion element is usually formed on a substrate (support substrate). Further, it may be further sealed by a substrate (sealing substrate).
  • the substrate is usually formed with one of a pair of electrodes consisting of an anode and a cathode.
  • the material of the substrate is not particularly limited as long as it is a material that does not chemically change when forming a layer containing an organic compound.
  • the substrate material examples include glass, plastic, polymer film, and silicon.
  • the electrode on the side opposite to the electrode provided on the opaque substrate side is a transparent or translucent electrode. ..
  • the photoelectric conversion element includes a pair of electrodes, an anode and a cathode. At least one of the anode and the cathode is preferably a transparent or translucent electrode in order to allow light to enter.
  • transparent or translucent electrode materials include conductive metal oxide films and translucent metal thin films. Specifically, indium oxide, zinc oxide, tin oxide, and conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), and NESA, which are composites thereof, gold, platinum, silver, and the like. Copper is mentioned. As a transparent or translucent electrode material, ITO, IZO, and tin oxide are preferable. Further, as the electrode, a transparent conductive film using an organic compound such as polyaniline and its derivative, polythiophene and its derivative as a material may be used. The transparent or translucent electrode may be an anode or a cathode.
  • the other electrode may be an electrode having low light transmission.
  • materials for electrodes having low light transmission include metals and conductive polymers.
  • Specific examples of materials for electrodes with low light transmission include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, and europium.
  • Metals such as terbium and itterbium, and two or more alloys of these, or one or more of these metals, and gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin.
  • Examples include alloys with one or more metals selected from the group consisting of, graphite, graphite interlayer compounds, polyaniline and its derivatives, polythiophene and its derivatives.
  • Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.
  • the active layer of the present embodiment includes an n-type semiconductor material (electron-accepting compound) and a p-type semiconductor material (electron-donating compound). Whether it is an n-type semiconductor material or a p-type semiconductor material can be relatively determined from the energy level of the HOMO (highest occupied orbital) or LUMO (lowest empty orbital) of the selected compound. ..
  • the thickness of the active layer is not particularly limited. Any suitable thickness may be used in consideration of the balance between the suppression of the dark current and the extraction of the generated photocurrent.
  • the active layer of the present embodiment is formed by a step including a treatment of heating at a heating temperature of 165 ° C. or higher (details will be described later).
  • n-type semiconductor material and a p-type semiconductor material suitable as materials for the active layer of the photoelectric conversion element according to the present embodiment will be described.
  • n-type semiconductor material The photoelectric conversion element of the present embodiment is characterized by an n-type semiconductor material used as an active layer.
  • the n-type semiconductor material is a compound represented by the following formula (I).
  • R 1 may have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent 1.
  • a plurality of R 1s may be the same or different.
  • R 1 is preferably an alkyl group which may have a substituent.
  • R 1 is one of a group represented by-(CH 2 ) n CH 3 , a group represented by -CH (C n H 2n + 1 ) 2 , or a group represented by-(CH 2 ) n CH 3.
  • the above hydrogen atom is preferably an alkyl group substituted with a fluorine atom, and more preferably a group represented by ⁇ (CH 2 ) (CF 2 ) n-1 CF 3.
  • n means an integer, and when R 1 is a group represented by ⁇ (CH 2 ) n CH 3 , the lower limit of n is preferably 1, more preferably 5, further preferably 7, of n.
  • the upper limit is preferably 30, more preferably 25, and even more preferably 15.
  • R 1 is a group represented by ⁇ (CH 2 ) (CF 2 ) n-1 CF 3
  • the lower limit of n is preferably 1, more preferably 3, and the upper limit of n is preferably 10.
  • 7 is more preferable, and 5 is even more preferable.
  • R 2 is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a monovalent aromatic hydrocarbon which may have a substituent. Represents a monovalent aromatic heterocyclic group which may have a group or a substituent.
  • R 2 is preferably an electron-withdrawing group from the viewpoint of energy level, and contains a halogen atom, an alkyl group containing one or more halogen atoms as a substituent, and one or more halogen atoms as a substituent.
  • it is a monovalent aromatic hydrocarbon group containing one or more halogen atoms as a substituent or a monovalent aromatic heterocyclic group containing one or more halogen atoms as a substituent, and bromine.
  • a monovalent aromatic heterocyclic group containing a hydrogen group or one or more fluorine atoms as a substituent is more preferable, and an alkyl group containing one or more fluorine atoms as a substituent is most preferable.
  • a plurality of R 2s may be the same or different.
  • R 1 and R 2 contains a fluorine atom, an alkyl group containing a fluorine atom as a substituent, an alkoxy group containing a fluorine atom as a substituent, and a monovalent containing a fluorine atom as a substituent. It is preferably a monovalent aromatic heterocyclic group containing an aromatic hydrocarbon group or a fluorine atom as a substituent, R 1 is an alkyl group containing one or more fluorine atoms as a substituent, and R 2 is. It is more preferably a hydrogen atom.
  • Examples of the n-type semiconductor material that can be suitably used in this embodiment include a compound in which R 1 is a group represented by ⁇ CH 2 (CF 2 ) 2 CF 3 and R 2 is a hydrogen atom. Be done.
  • R 1 is an alkyl group that may have a substituent, and two or more of a plurality of R 2 are 1 Examples thereof include compounds which are alkyl groups containing one or more fluorine atoms as substituents.
  • R 1 is a group represented by -CH (C 5 H 11 ) 2
  • R 2 is a hydrogen atom or a group represented by -CF 3
  • the heat resistance is improved, the decrease in EQE is suppressed or the EQE is further improved, and further, the increase in dark current is suppressed or the dark current is further reduced. Since these can be well balanced, it is preferable to use the compounds represented by the above formulas (N-1) to (N-3).
  • the p-type semiconductor material may be a low molecular weight compound or a high molecular weight compound.
  • Examples of the p-type semiconductor material which is a low molecular weight compound include phthalocyanine, metallic phthalocyanine, porphyrin, metallic porphyrin, oligothiophene, tetracene, pentacene, and rubrene.
  • the polymer compound has a predetermined polystyrene-equivalent weight average molecular weight.
  • the polystyrene-equivalent weight average molecular weight means the weight average molecular weight calculated using a standard polystyrene sample using gel permeation chromatography (GPC).
  • the polystyrene-equivalent weight average molecular weight of the p-type semiconductor material is preferably 20,000 or more and 200,000 or less, more preferably 30,000 or more and 180,000 or less, and 40,000 or more and 150,000 or less from the viewpoint of improving the solubility in a solvent. It is more preferable to have.
  • Examples of the p-type semiconductor material which is a polymer compound include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives, polythiophene and its derivatives. , Polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, polyfluorene and its derivatives.
  • the p-type semiconductor material which is a polymer compound, is preferably a polymer compound containing a structural unit containing a thiophene skeleton.
  • the p-type semiconductor material is preferably a polymer compound containing a structural unit represented by the following formula (II) and / or a structural unit represented by the following formula (III).
  • Ar 1 and Ar 2 represent a trivalent aromatic heterocyclic group, and Z represents a group represented by the following formulas (Z-1) to (Z-7).
  • R is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic group, or a substituent.
  • the two Rs may be the same or different from each other.
  • Ar 3 represents a divalent aromatic heterocyclic group.
  • the structural unit represented by the formula (II) is preferably the structural unit represented by the following formula (II-1).
  • Examples of the structural unit represented by the formula (II-1) include the structural units represented by the following formulas (501) to (505).
  • R has the same meaning as described above.
  • the two Rs may be the same or different.
  • the number of carbon atoms of the divalent aromatic heterocyclic group represented by Ar 3 is usually 2 to 60, preferably 4 to 60, and more preferably 4 to 20.
  • the divalent aromatic heterocyclic group represented by Ar 3 may have a substituent. Examples of substituents that the divalent aromatic heterocyclic group represented by Ar 3 may have include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group and an arylthio group.
  • Examples thereof include a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an acidimide group, a substituted oxycarbonyl group, an alkenyl group, an alkynyl group, a cyano group, and a nitro group.
  • Examples of the divalent aromatic heterocyclic group represented by Ar 3 include groups represented by the following formulas (101) to (185).
  • R has the same meaning as described above.
  • the plurality of R's may be the same as or different from each other.
  • the structural unit represented by the above formula (III) the structural unit represented by the following formulas (III-1) to (III-6) is preferable.
  • X 1 and X 2 independently represent an oxygen atom or a sulfur atom, and R has the same meaning as described above. When a plurality of R's are present, the plurality of R's may be the same as or different from each other.
  • both X 1 and X 2 in the formulas (III-1) to (III-6) are sulfur atoms.
  • the polymer compound which is a p-type semiconductor material may contain two or more kinds of structural units represented by the formula (II), and may contain two or more kinds of structural units represented by the formula (III). May be good.
  • the polymer compound which is a p-type semiconductor material may contain a structural unit represented by the following formula (IV).
  • Ar 4 represents an arylene group.
  • the arylene group represented by Ar 4 means the remaining atomic group obtained by removing two hydrogen atoms from the aromatic hydrocarbon which may have a substituent.
  • Aromatic hydrocarbons include compounds in which two or more selected from the group consisting of a compound having a condensed ring, an independent benzene ring and a condensed ring are bonded directly or via a divalent group such as a vinylene group. included.
  • Examples of the substituents that the aromatic hydrocarbon may have include the same substituents as those exemplified as the substituents that the heterocyclic compound may have.
  • the number of carbon atoms in the portion of the arylene group excluding the substituent is usually 6 to 60, preferably 6 to 20.
  • the number of carbon atoms of the arylene group including the substituent is usually about 6 to 100.
  • arylene group examples include a phenylene group (for example, the following formulas 1 to 3), a naphthalene-diyl group (for example, the following formulas 4 to 13), an anthracene-diyl group (for example, the following formulas 14 to 19), and the like.
  • Biphenyl-diyl group eg, formulas 20 to 25 below
  • terphenyl-diyl group eg, formulas 26 to 28 below
  • fused ring compound group eg, formulas 29 to 35 below
  • fluorene-diyl group for example, the following formulas 36 to 38
  • a benzofluorene-diyl group for example, the following formulas 39 to 46
  • the structural unit constituting the polymer compound which is a p-type semiconductor material is selected from the structural unit represented by the formula (II), the structural unit represented by the formula (III), and the structural unit represented by the formula (IV). It may be a structural unit in which two or more types of structural units to be formed are combined and connected.
  • the polymer compound as the p-type semiconductor material contains a structural unit represented by the formula (II) and / or a structural unit represented by the formula (III), the structural unit and the formula represented by the formula (II).
  • the total amount of the structural units represented by (III) is usually 20 to 100 mol% when the amount of all the structural units contained in the polymer compound is 100 mol%, and has a charge transport property as a p-type semiconductor material. It is preferably 40 to 100 mol%, and more preferably 50 to 100 mol%.
  • polymer compound as a p-type semiconductor material examples include polymer compounds represented by the following formulas (P-1) to (P-10).
  • the heat resistance is improved, the decrease in EQE is suppressed, the EQE is further improved, and the increase in dark current is suppressed, or the dark current is reduced. It is preferable to use the polymer compound represented by the above formula P-1 because it can be further lowered to improve the balance between them.
  • the photoelectric conversion element of the present embodiment has, for example, a charge transport layer (electron transport layer, hole transport layer, electron injection layer, etc.) as a component for improving characteristics such as photoelectric conversion efficiency. It is preferable to have an intermediate layer (buffer layer) such as a hole injection layer).
  • a charge transport layer electron transport layer, hole transport layer, electron injection layer, etc.
  • an intermediate layer buffer layer such as a hole injection layer.
  • Examples of materials used for the intermediate layer include metals such as calcium, inorganic oxide semiconductors such as molybdenum oxide and zinc oxide, and PEDOT (poly (3,4-ethylenedioxythiophene)) and PSS (poly (poly (3,4-ethylenedioxythiophene)). 4-styrene sulfonate)) and a mixture (PEDOT: PSS) can be mentioned.
  • the photoelectric conversion element preferably includes a hole transport layer between the anode and the active layer.
  • the hole transport layer has a function of transporting holes from the active layer to the electrode.
  • the hole transport layer provided in contact with the anode may be particularly referred to as a hole injection layer.
  • the hole transport layer (hole injection layer) provided in contact with the anode has a function of promoting the injection of holes into the anode.
  • the hole transport layer (hole injection layer) may be in contact with the active layer.
  • the hole transport layer contains a hole transport material.
  • hole-transporting materials include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing structural units having aromatic amine residues, CuSCN, CuI, NiO, tungsten oxide (WO 3 ) and molybdenum oxide. (MoO 3 ) can be mentioned.
  • the intermediate layer can be formed by a conventionally known arbitrary suitable forming method.
  • the intermediate layer can be formed by a coating method similar to the vacuum deposition method or the active layer forming method.
  • the intermediate layer is an electron transport layer
  • the substrate support substrate
  • the anode, the hole transport layer, the active layer, the electron transport layer, and the cathode are laminated so as to be in contact with each other in this order. It is preferable to have a structure.
  • the photoelectric conversion element of the present embodiment preferably includes an electron transport layer as an intermediate layer between the cathode and the active layer.
  • the electron transport layer has a function of transporting electrons from the active layer to the cathode.
  • the electron transport layer may be in contact with the cathode.
  • the electron transport layer may be in contact with the active layer.
  • the electron transport layer provided in contact with the cathode may be particularly referred to as an electron injection layer.
  • the electron transport layer (electron injection layer) provided in contact with the cathode has a function of promoting the injection of electrons generated in the active layer into the cathode.
  • the electron transport layer contains an electron transport material.
  • the electron-transporting material include polyalkyleneimine and its derivatives, polymer compounds containing a fluorene structure, metals such as calcium, and metal oxides.
  • polyalkyleneimines and derivatives thereof include alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, and octyleneimine, particularly having 2 to 8 carbon atoms.
  • alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, and octyleneimine, particularly having 2 to 8 carbon atoms.
  • examples thereof include polymers obtained by polymerizing one or more of 2 to 4 alkyleneimines by a conventional method, and polymers obtained by reacting them with various compounds to chemically modify them.
  • polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE) are preferable.
  • polymer compounds containing a fluorene structure examples include poly [(9,9-bis (3'-(N, N-dimethylamino) propyl) -2,7-fluorene) -ortho-2,7- (9). , 9'-Dioctylfluorene)] (PFN) and PFN-P2.
  • metal oxides examples include zinc oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, titanium oxide and niobium oxide.
  • a metal oxide containing zinc is preferable, and zinc oxide is particularly preferable.
  • Examples of other electron-transporting materials include poly (4-vinylphenol) and perylene diimide.
  • the photoelectric conversion element of the present embodiment further includes a sealing member and is a sealed body sealed by such a sealing member.
  • a sealing member Any suitable conventionally known member can be used as the sealing member.
  • the sealing member include a combination of a glass substrate which is a substrate (sealing substrate) and a sealing material (adhesive) such as a UV curable resin.
  • the sealing member may be a sealing layer having a layer structure of one or more layers.
  • Examples of the layer constituting the sealing layer include a gas barrier layer and a gas barrier film.
  • the sealing layer is preferably formed of a material having a property of blocking water (water vapor barrier property) or a property of blocking oxygen (oxygen barrier property).
  • suitable materials for the sealing layer include polyethylene trifluoride, polychlorotrifluoroethylene (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, ethylene-vinyl alcohol copolymer and the like.
  • Examples include organic materials, silicon oxide, silicon nitride, aluminum oxide, and inorganic materials such as diamond-like carbon.
  • the sealing member is usually made of a material that can withstand the heat treatment performed when the photoelectric conversion element is applied, for example, when it is incorporated into the device of the following application example.
  • Photoelectric conversion element of this embodiment Applications of the photoelectric conversion element of this embodiment include a photodetector element and a solar cell. More specifically, in the photoelectric conversion element of the present embodiment, a light current is passed by irradiating light from the transparent or translucent electrode side in a state where a voltage (reverse bias voltage) is applied between the electrodes. It can be operated as an optical detection element (optical sensor). It can also be used as an image sensor by integrating a plurality of photodetector elements. As described above, the photoelectric conversion element of the present embodiment can be particularly preferably used as a photodetection element.
  • the photoelectric conversion element of the present embodiment can generate photovoltaic power between the electrodes by being irradiated with light, and can be operated as a solar cell.
  • a solar cell module can also be obtained by integrating a plurality of photoelectric conversion elements.
  • the photoelectric conversion element according to the present embodiment is suitably applied as a photodetector to a detection unit provided in various electronic devices such as workstations, personal computers, personal digital assistants, entry / exit management systems, digital cameras, and medical devices. can do.
  • the photoelectric conversion element of the present embodiment includes, for example, an image detection unit (image sensor), a fingerprint detection unit, a face detection unit, for a solid-state imaging device such as an X-ray imaging device and a CMOS image sensor, provided in the above-exemplified electronic device. It can be suitably applied to a detection unit that detects a predetermined feature of a part of a living body such as a vein detection unit and an iris detection unit, a detection unit of an optical biosensor such as a pulse oximeter, and the like.
  • FIG. 2 is a diagram schematically showing a configuration example of an image detection unit for a solid-state image sensor.
  • the image detection unit 1 comprises a CMOS transistor substrate 20, an interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20, and a photoelectric conversion according to an embodiment of the present invention provided on the interlayer insulating film 30. It is provided so as to penetrate the element 10 and the interlayer insulating film 30, and is provided so as to cover the interlayer wiring portion 32 that electrically connects the CMOS transistor substrate 20 and the photoelectric conversion element 10 and the photoelectric conversion element 10.
  • the sealing layer 40 and the color filter 50 provided on the sealing layer 40 are provided.
  • the CMOS transistor substrate 20 is provided with a conventionally known arbitrary suitable configuration in a mode according to the design.
  • the CMOS transistor substrate 20 includes transistors, capacitors, etc. formed within the thickness of the substrate, and includes functional elements such as a CMOS transistor circuit (MOS transistor circuit) for realizing various functions.
  • MOS transistor circuit CMOS transistor circuit
  • Examples of functional elements include floating diffusion, reset transistor, output transistor, and selection transistor.
  • a signal readout circuit and the like are built in the CMOS transistor substrate 20 by such functional elements and wiring.
  • the interlayer insulating film 30 can be made of any conventionally known suitable insulating material such as silicon oxide or an insulating resin.
  • the interlayer wiring portion 32 can be made of, for example, any conventionally known suitable conductive material (wiring material) such as copper or tungsten.
  • the interlayer wiring portion 32 may be, for example, an in-hole wiring formed at the same time as the formation of the wiring layer, or an embedded plug formed separately from the wiring layer.
  • the sealing layer 40 is made of any suitable material known conventionally, provided that the permeation of harmful substances such as oxygen and water that may functionally deteriorate the photoelectric conversion element 10 can be prevented or suppressed. Can be done.
  • the sealing layer 40 can have the same structure as the sealing member 17 described above.
  • a primary color filter that is made of a conventionally known arbitrary suitable material and that corresponds to the design of the image detection unit 1 can be used.
  • a complementary color filter that can be thinner than the primary color filter can also be used.
  • Complementary color filters include, for example, three types (yellow, cyan, magenta), three types (yellow, cyan, transparent), three types (yellow, transparent, magenta), and three types (transparent, cyan, magenta). Color filters that combine types can be used. These can be arranged in any suitable arrangement corresponding to the design of the photoelectric conversion element 10 and the CMOS transistor substrate 20, provided that color image data can be generated.
  • the light received by the photoelectric conversion element 10 via the color filter 50 is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10, and the light received signal outside the photoelectric conversion element 10 via the electrode, that is, an image pickup target. Is output as an electric signal corresponding to.
  • the light receiving signal output from the photoelectric conversion element 10 is input to the CMOS transistor substrate 20 via the interlayer wiring unit 32, and is read out by a signal readout circuit built in the CMOS transistor substrate 20, which is not shown.
  • Image information based on the imaging target is generated by signal processing by any suitable conventionally known functional unit.
  • FIG. 3 is a diagram schematically showing a configuration example of a fingerprint detection unit integrally configured with a display device.
  • the display device 2 of the mobile information terminal includes a fingerprint detection unit 100 including the photoelectric conversion element 10 according to the embodiment of the present invention as a main component, and a display panel provided on the fingerprint detection unit 100 and displaying a predetermined image. It is provided with a unit 200.
  • the fingerprint detection unit 100 is provided in an area that substantially coincides with the display area 200a of the display panel unit 200.
  • the display panel unit 200 is integrally laminated above the fingerprint detection unit 100.
  • the fingerprint detection unit 100 may be provided corresponding to only the part of the display area 200a.
  • the fingerprint detection unit 100 includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs an essential function.
  • the fingerprint detection unit 100 desires any suitable conventionally known member such as a protective film (projection film), a support substrate, a sealing substrate, a sealing member, a barrier film, a bandpass filter, and an infrared cut film (not shown). It can be provided in a manner corresponding to the design so that the characteristics can be obtained.
  • the configuration of the image detection unit already described can also be adopted.
  • the photoelectric conversion element 10 can be included in any aspect 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 (anode or cathode) in a matrix, for example.
  • the light received by the photoelectric conversion element 10 is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10, and the light received signal outside the photoelectric conversion element 10 via the electrode, that is, the electricity corresponding to the captured fingerprint. It is output as a signal.
  • the display panel unit 200 is configured as an organic electroluminescence display panel (organic EL display panel) including a touch sensor panel.
  • the display panel unit 200 may be configured by, for example, instead of the organic EL display panel, a display panel having an arbitrary suitable conventionally known configuration such as a liquid crystal display panel including a light source such as a backlight.
  • the display panel unit 200 is provided on the fingerprint detection unit 100 already described.
  • the display panel unit 200 includes an organic electroluminescence element (organic EL element) 220 as a functional unit that performs an essential function.
  • the display panel unit 200 is further optionally suitable such as a substrate (support substrate 210 or sealing substrate 240) such as a conventionally known glass substrate, a sealing member, a barrier film, a polarizing plate such as a circular polarizing plate, and a touch sensor panel 230.
  • Suitable conventionally known members may be provided in a manner corresponding to the desired characteristics.
  • the organic EL element 220 is used as a light source for pixels in the display area 200a and also as a light source for fingerprint imaging in the fingerprint detection unit 100.
  • the fingerprint detection unit 100 detects a fingerprint using the light emitted from the organic EL element 220 of the display panel unit 200. Specifically, the light emitted from the organic EL element 220 passes through a component existing between the organic EL element 220 and the photoelectric conversion element 10 of the fingerprint detection unit 100, and is displayed within the display area 200a. It is reflected by the skin (finger surface) of the fingertips of the fingers placed so as to be in contact with the surface of the panel portion 200. At least a part of the light reflected by the finger surface passes through the components existing between them and is received by the photoelectric conversion element 10, and is converted into an electric signal according to the amount of light received by the photoelectric conversion element 10. Then, image information about the fingerprint on the finger surface is constructed from the converted electric signal.
  • the portable information terminal provided with the display device 2 performs fingerprint authentication by comparing the obtained image information with the fingerprint data for fingerprint authentication recorded in advance by an arbitrary suitable step known conventionally.
  • heat treatment such as a reflow process for mounting on a wiring board or the like may be performed.
  • a step including a process of heating the photoelectric conversion element at a heating temperature of 165 ° C. or higher may be performed.
  • the n-type semiconductor material already described is used as the material of the active layer.
  • the process of forming the active layer in the process of manufacturing the photoelectric conversion element after the formation of the active layer, or when incorporating the manufactured photoelectric conversion element into an image sensor or a biometric authentication device.
  • the treatment is performed at a heating temperature of 165 ° C. or higher, even if the treatment is performed at a heating temperature of 200 ° C. or higher, the product is further heated at a heating temperature of 220 ° C. or higher. Even if the treatment is performed, the heat resistance can be effectively improved.
  • the decrease in EQE can be suppressed or the EQE can be further improved, and the increase in dark current can be suppressed or the dark current can be further reduced.
  • the heating temperature of the post-baking step is based on the EQE value of the photoelectric conversion element in which the heating temperature of the post-baking step in the active layer forming step of the method for manufacturing a photoelectric conversion element is 100 ° C.
  • the value (hereinafter referred to as "EQE heat / EQE 100 ° C. ") obtained by dividing by the EQE value of the photoelectric conversion element changed to a higher temperature (for example, 165 ° C. or higher) is 0.9 or higher. It is preferably 1.0 or more, and more preferably 1.0 or more.
  • EQE heat / EQE 100 ° C. is preferably 0.9 or more, more preferably 1.0 or more, for example, when the temperature of the post-baking step is 165 ° C. and the heating time is 1 hour. ..
  • the EQE of the encapsulant of the photoelectric conversion element is 165 ° C. or higher based on the EQE value of the encapsulant that has not been subjected to additional heat treatment at the time of incorporation into the encapsulant of the photoelectric conversion element. 1.
  • the value obtained by standardizing by dividing by the EQE value of the heat-treated sealed body (hereinafter referred to as "EQE heat / EQE unheat ”) is preferably 0.9 or more. It is more preferably 0 or more.
  • EQE heat / EQE unheat for example, the additional heating temperature 165 ° C. processing, when the heating time is 1 hour, preferably at least 0.9, more preferably 1.0 or more ..
  • the photoelectric conversion element in which the heating temperature in the post-baking process is changed to a higher temperature for example, 165 ° C. or higher
  • a higher temperature for example, 165 ° C. or higher
  • the value obtained by standardizing by dividing by the value of the dark current in (hereinafter referred to as "dark current heat / dark current 100 ° C. ") is preferably 1.10 or less.
  • the dark current heat / dark current 100 ° C. is preferably 1.10 or less, for example, when the temperature of the post-baking step is 165 ° C. and the heating time is 1 hour.
  • the dark current of the encapsulant of the photoelectric conversion element is 165 ° C., based on the value of the dark current in the encapsulant that has not been subjected to additional heat treatment at the time of incorporation into the encapsulant of the photoelectric conversion element.
  • the value obtained by standardizing by dividing by the value of the dark current in the sealed body subjected to the above heat treatment shall be 1.10 or less. Is preferable.
  • the dark current heat / dark current unheat is more preferably 1.10, for example, when the temperature of the additional heat treatment is 165 ° C. and the heating time is 1 hour.
  • the manufacturing method of the photoelectric conversion element of the present embodiment is not particularly limited.
  • the photoelectric conversion element of the present embodiment can be manufactured by combining a suitable forming method with the material selected for forming the constituent elements.
  • the method for manufacturing a photoelectric conversion element of the present embodiment includes a step including a process of heating at a heating temperature of 165 ° C. or higher. More specifically, the active layer is formed by a step including a treatment of heating at a heating temperature of 165 ° C. or higher, 200 ° C. or higher, or 220 ° C. or higher, and / or after the step of forming the active layer. , 165 ° C. or higher, 200 ° C. or higher, or 220 ° C. or higher may include a step of heating.
  • a method for manufacturing a photoelectric conversion element having a structure in which a substrate (support substrate), an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are in contact with each other in this order will be described.
  • a support substrate provided with an anode is prepared. Further, a substrate provided with a conductive thin film formed of the electrode material already described is obtained from the market, and an anode is provided by patterning the conductive thin film to form an anode, if necessary.
  • a support substrate can be prepared.
  • the method for forming the anode when forming the anode on the support substrate is not particularly limited.
  • the anode has a structure (eg, support substrate, activity) in which the material already described is to be formed by any conventionally known suitable method such as a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and a coating method. It can be formed on a layer (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 anode.
  • the method of forming the hole transport layer is not particularly limited. From the viewpoint of simplifying the step of forming the hole transport layer, it is preferable to form the hole transport layer by an arbitrary suitable coating method known in the past.
  • the hole transport layer can be formed, for example, by a coating method using a coating liquid containing the material and solvent of the hole transport layer and a vacuum vapor deposition method already described.
  • an active layer is formed on the hole transport layer.
  • the active layer which is the main component, can be formed by any suitable conventionally known forming step.
  • the active layer is preferably produced by a coating method using an ink (coating liquid).
  • step (i) and the step (ii) included in the step of forming the active layer which is the main component of the photoelectric conversion element of the present invention, will be described.
  • any suitable coating method can be used.
  • the coating method the slit coating method, the knife coating method, the spin coating method, the micro gravure coating method, the gravure coating method, the bar coating method, the inkjet printing method, the nozzle coating method, or the capillary coating method is preferable, and the slit coating method and the spin coating method are used.
  • the coating method, the capillary coating method, or the bar coating method is more preferable, and the slit coating method or the spin coating method is further preferable.
  • the ink for forming the active layer may be a solution, or may be a dispersion liquid such as a dispersion liquid, an emulsion (emulsion liquid), or a suspension (suspension).
  • a dispersion liquid such as a dispersion liquid, an emulsion (emulsion liquid), or a suspension (suspension).
  • the ink for forming the active layer will be described.
  • An ink for forming a bulk heterojunction type active layer will be described as an example. Therefore, the ink for forming the active layer contains a composition containing an n-type semiconductor material and a p-type semiconductor material, and further contains at least one type or two or more types of solvents.
  • the ink for forming the active layer may contain only one type of each of the n-type semiconductor material and the p-type semiconductor material, or may contain two or more types in an arbitrary ratio combination.
  • the ink for forming an active layer of the present embodiment can improve heat resistance, suppress a decrease in EQE, or improve EQE, suppress an increase in dark current, or reduce dark current, and further.
  • the ink for forming the active layer it is preferable to use as a solvent a mixed solvent in which a first solvent and a second solvent described later are combined.
  • a mixed solvent in which a first solvent and a second solvent described later are combined.
  • the main solvent which is the main component and other additive solvents added for improving the solubility (first solvent)
  • It is preferable to contain a second solvent when the ink for forming the active layer contains two or more kinds of solvents, the main solvent (first solvent) which is the main component and other additive solvents added for improving the solubility (first solvent) ( It is preferable to contain a second solvent).
  • the first solvent a solvent in which a p-type semiconductor material can be dissolved is preferable.
  • the first solvent of this embodiment is an aromatic hydrocarbon.
  • aromatic hydrocarbon as the first solvent examples include toluene, xylene (eg, o-xylene, m-xylene, p-xylene), trimethylbenzene (eg, mesitylene, 1,2,4-trimethylbenzene). )), Butylbenzene (eg, n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (eg, 1-methylnaphthalene), tetralin and indane.
  • xylene eg, o-xylene, m-xylene, p-xylene
  • trimethylbenzene eg, mesitylene, 1,2,4-trimethylbenzene.
  • Butylbenzene eg, n-butylbenzene, sec-butylbenzene, tert-butylbenzene
  • methylnaphthalene eg, 1-methylna
  • the first solvent may be composed of one kind of aromatic hydrocarbons or may be composed of two or more kinds of aromatic hydrocarbons.
  • the first solvent is preferably composed of one type of aromatic hydrocarbon.
  • the first solvent is preferably toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, etc.
  • the second solvent is a solvent selected from the viewpoint of facilitating the implementation of the manufacturing process and further improving the characteristics of the photoelectric conversion element.
  • the second solvent include ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, acetophenone, and propiophenone, ethyl acetate, butyl acetate, phenyl acetate, ethyl cell solution acetate, methyl benzoate, butyl benzoate, and benzyl benzoate.
  • the second solvent is preferably acetophenone, propiophenone or butyl benzoate from the viewpoint of reducing dark current.
  • first solvent and the second solvent examples include a combination of tetralin and ethyl benzoate, tetralin and propyl benzoate, and tetralin and butyl benzoate.
  • a combination of tetralin and butyl benzoate is preferred.
  • the weight ratio of the first solvent, which is the main solvent, to the second solvent, which is the additive solvent (first solvent: second solvent), is an n-type semiconductor material and a p-type semiconductor. From the viewpoint of further improving the solubility of the material, the range is preferably in the range of 85:15 to 99: 1.
  • the solvent may contain any other solvent other than the first solvent and the second solvent.
  • the content of any other solvent is preferably 5% by weight or less, more preferably 3% by weight or less, still more preferably. It is 1% by weight or less.
  • a solvent having a boiling point higher than that of the second solvent is preferable.
  • Arbitrary component Ink includes a first solvent, a second solvent, an n-type semiconductor material and a p-type semiconductor material, as well as a surfactant and an ultraviolet absorber as long as the object and effect of the present invention are not impaired.
  • the total concentration of the n-type semiconductor material and the p-type semiconductor material in the ink is preferably 0.01% by weight or more and 20% by weight or less. It is more preferably 01% by weight or more and 10% by weight or less, further preferably 0.01% by weight or more and 5% by weight or less, and particularly preferably 0.1% by weight or more and 5% by weight or less.
  • the n-type semiconductor material and the p-type semiconductor material may be dissolved or dispersed. It is preferable that at least a part of the n-type semiconductor material and the p-type semiconductor material is dissolved, and more preferably all of them are dissolved.
  • a material having high heat resistance is used as the n-type semiconductor material
  • a solvent having a higher boiling point can also be used as the solvent. Therefore, since the range of choices of raw materials in the manufacturing process of the photoelectric conversion element is widened, the production of the photoelectric conversion element can be made more easily and easily.
  • Preparation of Ink can be prepared by a known method. For example, a method of preparing a mixed solvent by mixing a first solvent and a second solvent and adding an n-type semiconductor material and a p-type semiconductor material to the obtained mixed solvent, and adding a p-type semiconductor material to the first solvent. , The n-type semiconductor material is added to the second solvent, and then the first solvent and the second solvent to which each material is added are mixed, or the like.
  • the first solvent and the second solvent, the n-type semiconductor material, and the p-type semiconductor material may be heated to a temperature equal to or lower than the boiling point of the solvent and mixed.
  • the obtained mixture may be filtered using a filter, and the obtained filtrate may be used as the filtrate.
  • a filter for example, a filter formed of a fluororesin such as polytetrafluoroethylene (PTFE) can be used.
  • the ink for forming the active layer is applied to the coating target selected according to the photoelectric conversion element and the manufacturing method thereof.
  • the ink for forming the active layer can be applied to the functional layer of the photoelectric conversion element in the manufacturing process of the photoelectric conversion element, in which the active layer can exist. Therefore, the target of applying the ink for forming the active layer differs depending on the layer structure and the order of layer formation of the manufactured photoelectric conversion element. For example, when the photoelectric conversion element has a layer structure in which a substrate, an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are laminated, and the layer described on the left side is formed first.
  • the target of application of the ink for forming the active layer is the hole transport layer.
  • the photoelectric conversion element has a layer structure in which a substrate, a cathode, an electron transport layer, an active layer, a hole transport layer, and an anode are laminated, and the layer described on the left side is formed first.
  • the target of application of the ink for forming the active layer is the electron transport layer.
  • Any suitable method can be used as a method for removing the solvent from the coating film of the ink, that is, a method for removing the solvent from the coating film and solidifying it.
  • the method for removing the solvent include a method of directly heating with a hot plate in an atmosphere of an inert gas such as nitrogen gas, a hot air drying method, an infrared heating drying method, a flash lamp annealing drying method, and a vacuum drying method. Such a drying method can be mentioned.
  • the step (ii) is a step for volatilizing and removing the solvent, and is also referred to as a prebaking step (first heat treatment step).
  • a post-baking step (second heat-treating step) is performed following the pre-baking step to form a solidified film by heat treatment. Is preferable.
  • the conditions for carrying out the pre-baking step and the post-baking step can be arbitrarily set in consideration of the composition of the ink used, the boiling point of the solvent, and the like.
  • a pre-baking step and a post-baking step can be carried out using a hot plate in a nitrogen gas atmosphere.
  • the heating temperature in the pre-baking step and the post-baking step is usually about 100 ° C.
  • the heating temperature in the prebaking step and / or the postbaking step can be further increased.
  • the heating temperature in the pre-baking step and / or the post-baking step can be preferably 165 ° C. or higher, more preferably 200 ° C. or higher, still more preferably 220 ° C. or higher.
  • the upper limit of the heating temperature is 250 ° C., more preferably 300 ° C. or lower.
  • the total heat treatment time in the pre-baking step and the post-baking step can be, for example, 1 hour.
  • the heating temperature in the pre-baking step and the heating temperature in the post-baking step may be the same or different.
  • the heat treatment time can be, for example, 10 minutes or more.
  • the upper limit of the heat treatment time is not particularly limited, but may be, for example, 4 hours in consideration of the tact time and the like.
  • the thickness of the active layer can be set to a desired thickness by appropriately adjusting the solid content concentration in the coating liquid and the conditions of the above steps (i) and / or step (ii).
  • the step of forming the active layer may include other steps in addition to the steps (i) and (ii), provided that the object and effect of the present invention are not impaired.
  • the method for manufacturing a photoelectric conversion element of the present embodiment may be a method for manufacturing a photoelectric conversion element including a plurality of active layers, or a method in which steps (i) and (ii) are repeated a plurality of times. Good.
  • the method for manufacturing a photoelectric conversion element of the present embodiment includes a step of forming an electron transport layer (electron injection layer) provided on the active layer.
  • the method of forming the electron transport layer is not particularly limited. From the viewpoint of simplifying the process of forming the electron transport layer, it is preferable to form the electron transport layer by a conventionally known arbitrary suitable vacuum vapor deposition method.
  • the method of forming the cathode is not particularly limited.
  • the cathode can be formed on the electron transport layer by, for example, any conventionally known suitable method such as a coating method, a vacuum vapor deposition method, a sputtering method, an ion plating method, or a plating method. ..
  • the photoelectric conversion element of the present embodiment is manufactured by the above steps.
  • a conventionally known arbitrary suitable encapsulant (adhesive) and substrate (encapsulating substrate) are used.
  • a sealing material such as a UV curable resin is applied onto the support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and then bonded with the sealing material without gaps, and then UV.
  • a encapsulated body of the photoelectric conversion element can be obtained by sealing the photoelectric conversion element in the gap between the support substrate and the sealing substrate by using a method suitable for the selected sealing material such as light irradiation. ..
  • the photodetector element which is the photoelectric conversion element of the present embodiment, can function by being incorporated in the image sensor and the biometric authentication device as described above.
  • Such an image sensor and a biometric authentication device can be manufactured by a manufacturing method including a step of heating a photoelectric conversion element (encapsulating body of the photoelectric conversion element) at a heating temperature of 165 ° C. or higher.
  • a photoelectric conversion element when incorporating a photoelectric conversion element into an image sensor or a biometric authentication device, for example, a reflow process performed when mounting the photoelectric conversion element on a wiring board is performed, so that the temperature is 165 ° C. or higher, 200 ° C. or higher, and further 220. A process of heating at a heating temperature of ° C. or higher can be performed.
  • the photoelectric conversion element of the present embodiment since the n-type semiconductor material already described is used as the material of the active layer, the heat resistance can be effectively improved. As a result, it is possible to suppress the decrease in EQE of the incorporated photoelectric conversion element or further improve the EQE, and further suppress the increase in dark current or further reduce the dark current. It is possible to improve characteristics such as detection accuracy in sensors and biometric authentication devices.
  • the heat treatment time can be, for example, 10 minutes or more.
  • the upper limit of the heat treatment time is not particularly limited, but may be, for example, 4 hours in consideration of the tact time and the like.
  • compound N-1 which is an n-type semiconductor material
  • diPDI (trade name, manufactured by 1-material)
  • Compound N-2 which is an n-type semiconductor material
  • Compound N-3 which is an n-type semiconductor material
  • Compound N-4 which is an n-type semiconductor material
  • compound N-14 which is an n-type semiconductor material
  • E100 (trade name, manufactured by Frontier Carbon Co., Ltd.) was obtained from the market and used.
  • the polymer compound P-1 which is a p-type semiconductor material, was synthesized and used with reference to the method described in International Publication No. 2011/052709.
  • the polymer compound P-2 which is a p-type semiconductor material, was synthesized and used with reference to the method described in International Publication No. 2013/051676.
  • As the polymer compound P-3 which is a p-type semiconductor material, PTB7-Th (trade name, manufactured by 1-material) was obtained from the market and used.
  • As the polymer compound P-4 which is a p-type semiconductor material, P3HT (trade name, manufactured by SIGMA-ALDRICH) was obtained from the market and used.
  • reaction solution was cooled to room temperature, poured into 300 mL of a saturated aqueous sodium sulfite solution, and the resulting solid was filtered.
  • reaction solution was cooled to room temperature, poured into 500 mL of 2.0 M hydrochloric acid, and the resulting solid was filtered to obtain a solid.
  • a crude product was obtained by adding anhydrous magnesium sulfate to a solution prepared by dissolving the obtained solid in chloroform, stirring the mixture, and filtering the mixture.
  • the obtained solution was heated and stirred at 100 ° C. for 6 hours to react to obtain a reaction solution.
  • the obtained reaction solution was cooled to room temperature, poured into 100 mL of water, and the resulting solid was filtered to obtain a crude product.
  • the obtained solution was reacted by heating and stirring at 80 ° C. (bath temperature) for 8 hours. After completion of the reaction, the obtained reaction solution was cooled to room temperature and washed separately with water and 10% acetic acid water.
  • the organic layer obtained by liquid separation washing was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain a crude product.
  • 228 mg (0.149 mmol, yield 78.4%) of the target compound 6 was obtained as a black-brown solid.
  • compound N-1 which is an n-type semiconductor material is added so as to have a concentration of 2% by weight based on the total weight of the ink
  • compound P-1 which is a p-type semiconductor material is added.
  • Mix the mixture so that the concentration is 2% by weight based on the total weight of the ink (n-type semiconductor material / p-type semiconductor material 1/1), stir at 60 ° C. for 8 hours, and filter the obtained mixed solution. It was filtered using the ink (I-1).
  • Example 1 Manufacturing and evaluation of photoelectric conversion element
  • the photoelectric conversion element and its encapsulant were manufactured as follows. For the evaluation described later, a plurality of photoelectric conversion elements and their encapsulants were manufactured for each example (and comparative example).
  • a glass substrate on which an ITO thin film (anode) was formed with a thickness of 50 nm was prepared by a sputtering method, and the glass substrate was subjected to ozone UV treatment as a surface treatment.
  • the ink (I-1) was applied onto a thin film of ITO by a spin coating method to form a coating film, and then heat-treated for 10 minutes using a hot plate heated to 100 ° C. in a nitrogen gas atmosphere. And dried (pre-baking process).
  • a structure in which the anode and the active layer are laminated in this order is heat-treated for 50 minutes on a glass substrate on a hot plate heated to 100 ° C. in a nitrogen gas atmosphere (post-baking step) to form an active layer.
  • the thickness of the formed active layer was about 250 nm.
  • a calcium (Ca) layer was formed on the formed active layer to a thickness of about 5 nm to form an electron transport layer.
  • a silver (Ag) layer was formed on the formed electron transport layer to a thickness of about 60 nm and used as a cathode.
  • the photoelectric conversion element was manufactured on a glass substrate by the above steps. The obtained structure was used as sample 1.
  • a UV curable sealant as a sealing material was applied onto a glass substrate as a support substrate so as to surround the periphery of the manufactured photoelectric conversion element, and the glass substrate as a sealing substrate was bonded.
  • the photodetector was sealed in the gap between the support substrate and the sealing substrate by irradiating with UV light to obtain a sealed body of the photoelectric conversion element.
  • the planar shape of the photoelectric conversion element sealed in the gap between the support substrate and the sealing substrate when viewed from the thickness direction was a square of 2 mm ⁇ 2 mm.
  • EQE first, with a reverse bias voltage of -2.5 V applied to the encapsulant of the photoelectric conversion element, a constant number of photons (1.0 ⁇ 10 16 ) is applied every 20 nm in the wavelength range of 300 nm to 1200 nm. The current value of the current generated when the light was irradiated was measured, and the EQE spectrum at a wavelength of 300 nm to 1200 nm was obtained by a known method.
  • the measured value at the wavelength ( ⁇ max) closest to the absorption peak wavelength was taken as the EQE value (%).
  • FIG. 4 is a graph showing the relationship between the heating temperature and EQE heat / EQE 100 ° C.
  • Examples 2 to 5 and Comparative Examples 1 to 3> Manufacturing and evaluation of photoelectric conversion element
  • inks (I-2) to (I-5) and inks (C-1) to (C-3) were used instead of the ink (I-1).
  • the heating temperature in the post-baking step was 100 ° C. in both Examples 2 to 5 and Comparative Examples 1 to 3, in Comparative Example 1, the heating temperature in the post-baking step was 120 ° C.
  • the evaluation of the heat resistance of "Sample 2" according to Comparative Examples 1 to 3 is a value of "EQE heat / EQE 100 ° C. " in a range of at least 165 ° C. and 180 ° C. or lower. Since the value was less than 0.9, it was found that the EQE value had decreased due to the heat treatment by the post-baking step. Therefore, the evaluation of heat resistance using EQE as an index according to Comparative Examples 1 to 3 is "defective (x)".
  • the dark current in a dark state where no light is irradiated, a voltage of -10V to 2V is applied to the encapsulant of the photoelectric conversion element, and the current at the time of applying a voltage of -2.5V measured by a known method. The value was obtained as the value of dark current.
  • the standardized value (dark current heat / dark current 100 ° C. ) was evaluated by dividing by the dark current value in (Sample 2).
  • the evaluation results of Examples 1 to 4 are shown in Table 6 and FIG. 5 below.
  • FIG. 5 is a graph showing the relationship between the heating temperature and the dark current heat / dark current 100 ° C.
  • Comparative Examples 1 to 3 were also evaluated for dark current in the same manner as in Examples 1 to 4 above. However, in all of Comparative Examples 1 to 3, in addition to Sample 1 in which the heating temperature in the post-baking step was 100 ° C., in Comparative Example 1, the heating temperatures in the post-baking step were 120 ° C. (Sample 2-1) and 130 ° C. (Sample 2-2), 140 ° C (Sample 2-3), and four "Sample 2" changed to 150 ° C (Sample 2-4) were further prepared, and Comparative Examples 2 and 3 were heated in the post-baking step. "Sample 2" whose temperature was changed to 150 ° C. was prepared and evaluated. The results are shown in Table 7 and FIG. 5 below.
  • Example 2 according to Comparative Examples 1 to 3 has a “dark current heat / dark current 100 ° C. ” in the range of 120 ° C. or higher (at least 120 ° C. or higher and 150 ° C. or lower). Since the value exceeds 1.10, it was found that the dark current value was increased by the heat treatment by the post-baking step. Therefore, the evaluation of heat resistance according to Comparative Examples 1 to 3 is "defective (x)" from the viewpoint of dark current.
  • Example 6> Manufacturing and evaluation of photoelectric conversion element (1) Manufacture of photoelectric conversion element A plurality of photoelectric conversion elements are manufactured in the same manner as in Example 1 except that the post-baking step is not carried out, and a sealing step is performed on the manufactured photoelectric conversion element. Was carried out to manufacture a plurality of encapsulants of photoelectric conversion elements.
  • the photoelectric conversion element becomes an image sensor by performing an additional heat treatment for 10 minutes using a hot plate in a nitrogen gas atmosphere on the sealed body of the photoelectric conversion element manufactured.
  • the encapsulant that was not subjected to the additional heat treatment was designated as sample 1
  • the encapsulant that was subjected to the additional heat treatment was designated as sample 2.
  • the measured value for EQE was obtained in the same manner as in Example 1, and the evaluation for EQE was performed.
  • Example 2 a plurality of encapsulants (sample 2) which were heat-treated and whose heating temperatures were changed based on the EQE value of the encapsulant (sample 1) which was not subjected to the additional heat treatment. ) was divided by the value of EQE to evaluate the standardized value (EQE heat / EQE unheat).
  • the heating temperature was changed to 170 ° C (Sample 2-1), 180 ° C (Sample 2-2), 190 ° C (Sample 2-3) and 200 ° C (Sample 2-4), respectively. 4 "Sample 2" was used.
  • Table 8 is a graph showing the relationship between the heating temperature of the sealed body and “EQE heat / EQE unheat”.
  • the lack of heat resistance to the heating temperature of the components added after the formation of the active layer, especially the sealing member, the interface between the anode and the active layer, and the electron transport between the active layer and the active layer is considered to be due to the lack of heat resistance to chemical changes occurring at the interface with the layer and / or the interface between the electron transport layer and the cathode.
  • Image detector 2 Display device 10 Photoelectric conversion element 11, 210 Support substrate 12 Anode 13 Hole transport layer 14 Active layer 15 Electron transport layer 16 Cathode 17 Sealing member 20 CMOS Transistor substrate 30 Interlayer insulating film 32 Interlayer wiring part 40 Seal Stop layer 50 Color filter 100 Fingerprint detection unit 200 Display panel unit 200a Display area 220 Organic EL element 230 Touch sensor panel 240 Encapsulating substrate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Electromagnetism (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Photovoltaic Devices (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Light Receiving Elements (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

La présente invention améliore la résistance à la chaleur.　L'invention concerne un élément de conversion photoélectrique 10 qui comprend une électrode positive 12, une électrode négative et une couche active 14 disposée entre lesdites électrodes positive et négative, la couche active contenant un matériau semi-conducteur de type n et un matériau semi-conducteur de type p, le matériau semi-conducteur de type n étant un composé représenté par la formule (I), et le matériau semi-conducteur de type p étant un composé polymère contenant une unité structurale représentée par la formule (II). (Dans la formule (I), R1 et R2 sont tels que définis dans la description.) (Dans la formule (II), Ar1, Ar2 et Z sont tels que définis dans la description.)
PCT/JP2020/033894 2019-10-01 2020-09-08 Élément de conversion photoélectrique WO2021065374A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202080067923.2A CN114514621A (zh) 2019-10-01 2020-09-08 光电转换元件

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2019-181462 2019-10-01
JP2019181462 2019-10-01
JP2020123176A JP2021057573A (ja) 2019-10-01 2020-07-17 光電変換素子
JP2020-123176 2020-07-17

Publications (1)

Publication Number Publication Date
WO2021065374A1 true WO2021065374A1 (fr) 2021-04-08

Family

ID=75271155

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/033894 WO2021065374A1 (fr) 2019-10-01 2020-09-08 Élément de conversion photoélectrique

Country Status (4)

Country Link
JP (1) JP2021057573A (fr)
CN (1) CN114514621A (fr)
TW (1) TW202115063A (fr)
WO (1) WO2021065374A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022004812A1 (fr) * 2020-07-03 2022-01-06 国立大学法人静岡大学 Composé de dimère de pérylène, son procédé de production, polymère de composé de dimère de pérylène et son procédé de production, batterie solaire à couches minces organiques, matériau d'électrode et batterie secondaire à ions alcalins

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023107154A (ja) * 2022-01-21 2023-08-02 住友化学株式会社 インク組成物及び当該インク組成物を用いた光電変換素子

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160233448A1 (en) * 2013-09-23 2016-08-11 The Regents Of The University Of California Multiple donor/acceptor bulk heterojunction solar cells
WO2017191468A1 (fr) * 2016-05-06 2017-11-09 Imperial Innovations Limited Accepteurs d'électrons sans fullerène
WO2019082852A1 (fr) * 2017-10-23 2019-05-02 住友化学株式会社 Élément de conversion photoélectrique et procédé de fabrication correspondant

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160233448A1 (en) * 2013-09-23 2016-08-11 The Regents Of The University Of California Multiple donor/acceptor bulk heterojunction solar cells
WO2017191468A1 (fr) * 2016-05-06 2017-11-09 Imperial Innovations Limited Accepteurs d'électrons sans fullerène
WO2019082852A1 (fr) * 2017-10-23 2019-05-02 住友化学株式会社 Élément de conversion photoélectrique et procédé de fabrication correspondant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YE, LONG ET AL.: "Enhanced Efficiency in Fullerene-Free Polymer Solar Cell by Incorporating Fine-designed Donor and Acceptor Materials", APPLIED MATERIALS & INTERFACES, vol. 7, 28 April 2015 (2015-04-28), pages 9274 - 9280, XP055637101, DOI: 10.1021/acsami.5b02012 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022004812A1 (fr) * 2020-07-03 2022-01-06 国立大学法人静岡大学 Composé de dimère de pérylène, son procédé de production, polymère de composé de dimère de pérylène et son procédé de production, batterie solaire à couches minces organiques, matériau d'électrode et batterie secondaire à ions alcalins

Also Published As

Publication number Publication date
CN114514621A (zh) 2022-05-17
TW202115063A (zh) 2021-04-16
JP2021057573A (ja) 2021-04-08

Similar Documents

Publication Publication Date Title
WO2022014482A1 (fr) Élément de conversion photoélectrique et son procédé de fabrication
WO2021065374A1 (fr) Élément de conversion photoélectrique
WO2022014483A1 (fr) Élément de conversion photoélectrique et son procédé de fabrication
WO2022019300A1 (fr) Composé et élément de conversion photoélectrique l'utilisant
JPWO2019182142A1 (ja) 光電変換素子
CN115336021A (zh) 光检测元件、包含其的传感器和生物体认证装置、以及组合物和油墨
JP7315531B2 (ja) 光検出素子
JP6697833B2 (ja) 光電変換素子およびその製造方法
WO2022224893A1 (fr) Composition d'encre, et procédé de fabrication de celle-ci
KR102545540B1 (ko) 잉크 조성물의 제조 방법
JP2023057054A (ja) 組成物及びインク組成物
JPWO2019082844A1 (ja) インク、インクの固化膜、及び光電変換素子
WO2020071223A1 (fr) Élément de conversion photoélectrique et son procédé de fabrication
WO2020026974A1 (fr) Élément photodétecteur
WO2023100844A1 (fr) Composé et élément de conversion photoélectrique faisant appel à celui-ci
WO2023008376A1 (fr) Composé, composition et élément de conversion photoélectrique
WO2023120359A1 (fr) Composé et élément de conversion photoélectrique l'utilisant
WO2023058725A1 (fr) Composition et composition d'encre
JP2023020911A (ja) 化合物、組成物及び光電変換素子
CN117769897A (zh) 化合物、组合物和光电转换元件
JP2020088170A (ja) 有機光電変換素子

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20871767

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20871767

Country of ref document: EP

Kind code of ref document: A1