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WO2019082844A1 - Encre, film solidifié d'encre et élément de conversion photoélectrique - Google Patents

Encre, film solidifié d'encre et élément de conversion photoélectrique

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Publication number
WO2019082844A1
WO2019082844A1 PCT/JP2018/039195 JP2018039195W WO2019082844A1 WO 2019082844 A1 WO2019082844 A1 WO 2019082844A1 JP 2018039195 W JP2018039195 W JP 2018039195W WO 2019082844 A1 WO2019082844 A1 WO 2019082844A1
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WO
WIPO (PCT)
Prior art keywords
group
solvent
photoelectric conversion
ink
type semiconductor
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2018/039195
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English (en)
Japanese (ja)
Inventor
大輔 猪口
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
Original Assignee
Sumitomo Chemical Co Ltd
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Filing date
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Priority to CN201880068520.2A priority Critical patent/CN111263982A/zh
Priority to JP2019551121A priority patent/JP7129995B2/ja
Publication of WO2019082844A1 publication Critical patent/WO2019082844A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F30/00—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors
    • H10F30/20—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/88—Passivation; Containers; Encapsulations
    • 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 an ink, a solidified film of the ink, and a photoelectric conversion element.
  • Patent Document 1 a solar cell having an active layer containing a p-type semiconductor material and an n-type semiconductor material is known, and a technology for forming an active layer by an ink composition containing a combination of these semiconductor materials and a specific solvent is known.
  • a photoelectric conversion element can function as a light detection element when light is irradiated in a state where a reverse bias voltage is applied, and a photocurrent flows. In order to improve the detection sensitivity of the light detection element, it is required to improve the external quantum efficiency of the photoelectric conversion element.
  • the photoelectric conversion element can function as a solar cell. Solar cells that use natural energy do not consume resources such as fossil fuels during power generation and do not emit greenhouse gases. Therefore, a solar cell is expected as a power supply source using green energy, and its performance improvement is required. Therefore, also when making a photoelectric conversion element function as a solar cell, higher external quantum efficiency is calculated
  • the present inventor has found that the external quantum efficiency of a photoelectric conversion element in which an active layer is formed using an ink containing a specific solvent can be improved, and completes the present invention I did. That is, the present invention provides the following.
  • An ink comprising a p-type semiconductor material, an n-type semiconductor material, a first solvent which is a nitrogen-containing heterocyclic compound, and a second solvent which is an aromatic hydrocarbon.
  • the nitrogen-containing heterocyclic compound contains a six-membered ring structure, and the six-membered ring structure contains one or two hetero atoms, and the one or two hetero atoms are each a nitrogen atom, The ink according to [1] or [2].
  • the ink according to [3], wherein the 6-membered ring structure is a pyridine ring structure, a tetrahydropyridine ring structure, a piperidine ring structure, or a pyrazine ring structure.
  • the first solvent may have quinoline which may have a substituent, 1,2,3,4-tetrahydroquinoline which may have a substituent, and may have a substituent
  • the photoelectric conversion device according to [10] which is a light detection device.
  • An image sensor comprising the photoelectric conversion element according to [10] or [11].
  • a fingerprint authentication apparatus comprising the photoelectric conversion device according to [10] or [11].
  • a step (i) of applying the ink according to any one of [1] to [8] to a coating target to obtain a coated film, and a step of removing a solvent from the obtained coated film (ii) A method of producing a solidified film, comprising: [15] A method of manufacturing a photoelectric conversion element, comprising a first electrode, an active layer containing a p-type semiconductor material and an n-type semiconductor material, and a second electrode in this order, The process of forming the said active layer including the process of forming the said active layer, apply
  • the present invention can improve the external quantum efficiency of the photoelectric conversion element.
  • FIG. 1 is a schematic view showing an embodiment of the photoelectric conversion element of the present invention.
  • FIG. 2 is a view schematically showing a configuration example of an image detection unit for a solid-state imaging device.
  • FIG. 3 is a view schematically showing a configuration example of a fingerprint detection unit configured integrally with the display device.
  • the “polymer compound” means a polymer having a molecular weight distribution and having a polystyrene-equivalent number average molecular weight of 1 ⁇ 10 3 or more and 1 ⁇ 10 8 or less.
  • the structural units contained in the polymer compound are 100 mol% in total.
  • the "constituent unit” means a unit which is present in one or more in the polymer compound.
  • the "hydrogen atom” may be a light hydrogen atom or a deuterium atom.
  • halogen atom includes fluorine atom, chlorine atom, bromine atom and iodine atom.
  • 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, not including the number of carbon atoms of the substituent.
  • the carbon atom number 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 carbon atom number of the substituent.
  • the alkyl group may have a substituent.
  • Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isoamyl group, 2-ethylbutyl group, n- Hexyl, cyclohexyl, n-heptyl, cyclohexylmethyl, cyclohexylethyl, n-octyl, 2-ethylhexyl, 3-n-propylheptyl, adamantyl, n-decyl, 3,7-dimethyl Non-substituted alkyl group such as octyl group, 2-ethyloctyl group, 2-n-hexyl-decyl group, n-dodecyl group, tetrade
  • aryl group means an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon which may have a substituent.
  • the aryl group may have a substituent.
  • Specific examples of the aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group, 4-phenylphenyl group, and a hydrogen atom in these groups is an alkyl group, an alkoxy group, An aryl group, a group substituted with a fluorine atom and the like can be mentioned.
  • the "alkoxy group” may be linear, branched or cyclic.
  • the carbon atom number of the linear alkoxy group is usually 1 to 40, preferably 1 to 10, not including the carbon atom number of the substituent.
  • the carbon atom number of the branched or cyclic alkoxy group is usually 3 to 40, preferably 4 to 10, not including the carbon atom number of the substituent.
  • the alkoxy group may have a substituent.
  • Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, And cyclohexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, n-nonyloxy, n-decyloxy, 3,7-dimethyloctyloxy, and lauryloxy groups.
  • 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.
  • Specific examples of the aryloxy group include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 1-anthracenyloxy group, 9-anthracenyloxy group, 1-pyrenyloxy group, and these groups
  • the hydrogen atom in is substituted by an alkyl group, an alkoxy group, a fluorine atom and the like.
  • alkylthio group may be linear, branched or cyclic.
  • the carbon atom number of the linear alkylthio group is usually 1 to 40, preferably 1 to 10, not including the carbon atom number of the substituent.
  • the carbon atom number of the branched and cyclic alkylthio group is usually 3 to 40, preferably 4 to 10, not including the carbon atom number of the substituent.
  • the alkylthio group may have a substituent.
  • Specific examples of the alkylthio group are 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 And -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.
  • the arylthio group include phenylthio group and C1 to C12 alkyloxyphenylthio group (C1 to C12 indicate that the number of carbon atoms of the group described immediately thereafter is 1 to 12. The same applies to the following.
  • the “p-valent heterocyclic group” (p represents an integer of 1 or more) is a direct bond from a heterocyclic compound which may have a substituent to a carbon atom or a heteroatom constituting a ring. It means the remaining atomic groups excluding p hydrogen atoms among the hydrogen atoms. Among p-valent heterocyclic groups, “p-valent aromatic heterocyclic group” is preferable.
  • the “p-valent aromatic heterocyclic group” is a p-membered hydrogen atom directly bonded to a carbon atom or a hetero atom constituting a ring, from the aromatic heterocyclic compound which may have a substituent. Means the remaining atomic groups excluding the hydrogen atom of
  • Examples of the substituent which 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 an aromatic ring is fused to the heterocycle even if the heterocycle itself exhibits no aromaticity are included Ru.
  • aromatic heterocyclic compounds specific examples of compounds in which the heterocycle itself exhibits aromaticity include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine And pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphole.
  • aromatic heterocyclic compounds specific examples of compounds in which the aromatic heterocycle itself does not exhibit aromaticity and in which an aromatic ring is fused to the heterocycle include phenoxazine, phenothiazine, dibenzoborole, and dibenzo. And silole and benzopyran.
  • the carbon atom number of the monovalent heterocyclic group is usually 2 to 60, preferably 4 to 20, not including the carbon atom number of the substituent.
  • the monovalent heterocyclic group may have a substituent, and examples of the monovalent heterocyclic group include, for example, thienyl group, pyrrolyl group, furyl group, pyridyl group, piperidyl group, quinolyl group, and the like. Examples include an isoquinolyl group, a pyrimidinyl group, a triazinyl group, and a group in which a hydrogen atom in these groups is substituted with an alkyl group, an alkoxy group or the like.
  • the “substituted amino group” means an amino group having two substituents.
  • monohydric heterocyclic group are mentioned as an example of the substituent which an amino group has, An alkyl group, an aryl group, or a monovalent
  • the carbon atom number of the substituted amino group is usually 2-30.
  • substituted amino group examples include dialkylamino groups such as dimethylamino and diethylamino; diphenylamino, bis (4-methylphenyl) amino, bis (4-tert-butylphenyl) amino, bis (3, And diarylamino groups such as 5-di-tert-butylphenyl) amino group.
  • the "acyl group” usually has about 2 to 20 carbon atoms, and preferably 2 to 18 carbon atoms. Specific examples of the acyl group include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, benzoyl group, trifluoroacetyl group, and pentafluorobenzoyl group.
  • the “imine residue” refers to an atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom or a nitrogen atom constituting a carbon atom-nitrogen atom double bond from an imine compound.
  • the "imine compound” means an organic compound having a carbon atom-nitrogen atom double bond in the molecule.
  • the imine compound include aldimine, ketimine, and a compound in which a hydrogen atom bonded to a nitrogen atom constituting a carbon atom-nitrogen atom double bond in the aldimine is substituted with an alkyl group or the like.
  • the imine residue usually has about 2 to 20 carbon atoms, and preferably 2 to 18 carbon atoms.
  • Examples of imine residues include groups represented by the following structural formula.
  • the "amide group” means the remaining group except one hydrogen atom bonded to the nitrogen atom from the amide.
  • the carbon atom number of the amide group is usually about 1 to 20, preferably 1 to 18.
  • Specific examples of the amide group include formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group, pentafluorobenzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group , Ditrifluoroacetamide group, and dipentafluorobenzamide group.
  • the "acid imide group” refers to the remaining atomic group from acid imide except one hydrogen atom bonded to a nitrogen atom.
  • the number of carbon atoms of the acid imide group is usually about 4 to 20.
  • Specific examples of the acid imide group include the groups shown below.
  • R ′ represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.
  • the substituted oxycarbonyl group usually has about 2 to 60 carbon atoms, and preferably 2 to 48 carbon atoms.
  • substituted oxycarbonyl group examples include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group Group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3, 7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, tri Fluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl , Perfluorooctyl group,
  • alkenyl group may be linear, branched or cyclic.
  • the carbon atom number of the linear alkenyl group is usually 2 to 30, preferably 3 to 20, not including the carbon atom number of the substituent.
  • the carbon atom number of the branched or cyclic alkenyl group is usually 3 to 30, preferably 4 to 20, not including the carbon atom number of the substituent.
  • the alkenyl group may have a substituent.
  • Specific examples of the alkenyl group include vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, 3-butenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 5-hexenyl group And 7-octenyl groups, and groups in which a hydrogen atom in these groups is substituted with an alkyl group, an alkoxy group or the like.
  • the "alkynyl group” may be linear, branched or cyclic.
  • the carbon atom number of the linear alkenyl group is usually 2 to 20, preferably 3 to 20, not including the carbon atom number of the substituent.
  • the carbon atom number of the branched or cyclic alkenyl group is usually 4 to 30, preferably 4 to 20, not including the carbon atom number of the substituent.
  • the alkynyl group may have a substituent.
  • Specific examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4-pentynyl group, 4-pentynyl group, 1-hexynyl group, 5-hexynyl group And groups in which a hydrogen atom in these groups is substituted with an alkyl group, an alkoxy group or the like.
  • the term “ink” means a liquid used in a coating method and is not limited to colored liquids.
  • the term “coating method” includes a method of forming a film using a liquid substance, for example, slit coating method, knife coating method, spin coating method, casting method, microgravure coating method, gravure coating method, bar Coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, gravure printing method, flexographic printing method, offset printing method, ink jet coating method, dispenser printing method, nozzle coating method, capillary The coat method is mentioned.
  • the “ink” may be a solution, or may be a dispersion, such as a dispersion, an emulsion (emulsion), a suspension (suspension) or the like.
  • the ink of the present invention comprises a p-type semiconductor material, an n-type semiconductor material, a first solvent, and a second solvent.
  • the first solvent is a nitrogen-containing heterocyclic compound.
  • the ink of the present invention contains a nitrogen-containing heterocyclic compound as the first solvent, the external quantum efficiency of the photoelectric conversion element can be improved. Although the reason is not to limit the present invention, the following mechanism is presumed.
  • the nitrogen-containing heterocyclic compound as the first solvent and the n-type semiconductor material such as the fullerene derivative strongly interact with each other due to a hydrogen bond, a dispersing force and the like.
  • the strong interaction between the nitrogen-containing heterocyclic compound and the n-type semiconductor material causes the n-type semiconductor material to be coated as well as removing the solvent. It is thought that it becomes possible to move (migration) easily in the middle.
  • a network of n-type semiconductor material functioning as a charge transfer path is sufficiently formed to improve the external quantum efficiency.
  • the nitrogen-containing heterocyclic compound includes, for example, pyridine which may have a substituent, quinoline which may have a substituent, quinoxaline which may have a substituent, and the like. And 1,2,3,4-tetrahydroquinoline, pyrimidine which may have a substituent, pyrazine which may have a substituent, and quinazoline which may have a substituent. .
  • the first solvent may be composed of one type of nitrogen-containing heterocyclic compound or may be composed of two or more types of nitrogen-containing heterocyclic compounds.
  • the first solvent is composed of one nitrogen-containing heterocyclic compound.
  • the nitrogen-containing heterocyclic compound may have a substituent on the ring structure.
  • a substituent which the ring structure (eg, quinoline ring structure, 1,2,3,4-tetrahydroquinoline ring structure, quinoxaline ring structure) of the nitrogen-containing heterocyclic compound may have, for example, the number of carbon atoms
  • an alkyl group of 1 to 5 an alkoxy group of 1 to 5 carbon atoms, a halogen group and an alkylthio group.
  • the nitrogen-containing heterocyclic compound as the first solvent contains a six-membered ring structure, and the six-membered ring structure contains one or two hetero atoms, and the one or two hetero atoms are respectively nitrogen atoms Is preferred.
  • the 6-membered ring structure containing one hetero atom and wherein one hetero atom is a nitrogen atom include a pyridine ring structure, a tetrahydropyridine ring structure, and a piperidine ring structure.
  • Examples of the 6-membered ring structure containing two hetero atoms, wherein the two hetero atoms are nitrogen atoms include a pyrazine ring structure and a pyrimidine ring structure.
  • nitrogen-containing heterocyclic compound containing a pyridine ring structure for example, pyridine which may have a substituent, quinoline which may have a substituent, and isoquinoline which may have a substituent are exemplified. It can be mentioned.
  • nitrogen-containing cyclic compound containing a tetrahydropyridine ring structure examples include optionally substituted 1,2,3,4-tetrahydroquinoline and optionally substituted 1,2,3 3,4- tetrahydroisoquinoline is mentioned.
  • nitrogen-containing cyclic compound containing a pyrazine ring structure examples include pyrazine which may have a substituent and quinoxaline which may have a substituent.
  • nitrogen-containing cyclic compound containing a pyrimidine ring structure examples include pyrimidine which may have a substituent, and quinazoline which may have a substituent.
  • the first solvent is a nitrogen-containing heterocyclic compound containing a pyridine ring structure, a tetrahydropyridine ring structure, a piperidine ring structure or a pyrazine ring structure, and more preferably a nitrogen-containing heterocyclic compound containing a pyridine ring structure, a tetrahydropyridine ring or a pyrazine ring structure
  • a heterocyclic compound More preferably, it is selected from the group consisting of quinoline which may have a substituent, 1,2,3,4-tetrahydroquinoline which may have a substituent, and quinoxaline which may have a substituent.
  • the first solvent is Preferably, quinoline which may have a substituent, 1,2,3,4-tetrahydroquinoline which may have a substituent, or quinoxaline which may have a substituent is preferable. More preferably, quinoline having an alkyl group, 1,2,3,4-tetrahydroquinoline having an alkyl group, or quinoxaline having an alkyl group, More preferably, 2-methylquinoline, 3-methylquinoline, 6-methylquinoline, 8-methylquinoline, 1,2,3,4-tetrahydroquinaldine, or 2-methylquinoxaline.
  • the second solvent is an aromatic hydrocarbon.
  • a solvent capable of dissolving the p-type semiconductor material is preferable.
  • aromatic hydrocarbon for example, toluene, xylene (eg, o-xylene, m-xylene, p-xylene), trimethylbenzene (eg, mesitylene, 1,2,4-trimethylbenzene (pseudocumene)), butylbenzene
  • xylene eg, o-xylene, m-xylene, p-xylene
  • trimethylbenzene eg, mesitylene, 1,2,4-trimethylbenzene (pseudocumene)
  • butylbenzene examples are (for example, n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (eg 1-methylnaphthalene), tetralin and indane.
  • the second solvent may be composed of one aromatic hydrocarbon or may be composed of two or more aromatic hydrocarbons.
  • the second solvent is composed of one aromatic hydrocarbon.
  • the second solvent is preferably toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methyl At least one selected from the group consisting of naphthalene, tetralin and indane, More preferably, toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methyl naphthalene, tetralin or indane It is.
  • the weight ratio of the first solvent to the second solvent is preferably 1/99 from the viewpoint of improving the solubility of the p-type semiconductor material and the n-type semiconductor material. Or more, more preferably 3/97 or more, still more preferably 5/95 or more, preferably 20/80 or less, more preferably 15/85 or less, more preferably 10/90 or less, preferably 1/99 20/80 or less, more preferably 3/97 or more and 15/85 or less, still more preferably 5/95 or more and 10/90 or less.
  • the total weight of the first solvent and the second solvent contained in the ink is preferably from the viewpoint of making the solubility of the p-type semiconductor material and the n-type semiconductor material better with respect to 100% by weight of the total weight of the ink. Is 90% by weight or more, more preferably 92% by weight or more, still more preferably 95% by weight, and from the viewpoint of facilitating formation of a film having a certain thickness or more, preferably 99% by weight or less, more preferably 98% by weight % Or less, more preferably 97.5% by weight or less.
  • the ink may comprise any solvent other than the first solvent and the second solvent.
  • the content of the optional solvent is preferably 5% by weight or less, more preferably 3% by weight or less, still more preferably 1% by weight or less, based on 100% by weight of the total weight of all the solvents contained in the ink. Particularly preferably, it is 0% by weight.
  • the p-type semiconductor material may be a low molecular weight compound or a high molecular weight compound.
  • Examples of p-type semiconductor materials which are low molecular weight compounds include phthalocyanines, metal phthalocyanines, porphyrins, metal porphyrins, oligothiophenes, tetracenes, pentacenes, and rubrenes.
  • the p-type semiconductor material which is a polymer compound, for example, polyvinylcarbazole and its derivative, polysilane and its derivative, polysiloxane derivative having aromatic amine structure in side chain or main chain, polyaniline and its derivative, polythiophene and its derivative And polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, polyfluorene and derivatives thereof and the like.
  • the p-type semiconductor material is preferably a polymer compound from the viewpoint of making the stability of the ink excellent, and from the viewpoint of making the external quantum efficiency of the photoelectric conversion device excellent, the following formula (I) It is preferable that it is a high molecular compound containing the structural unit represented by the structural unit represented by, and / or following formula (II).
  • Ar 1 and Ar 2 each represent a trivalent aromatic heterocyclic group
  • Z is a group represented by any one of the following formulas (Z-1) to (Z-7) Represents
  • Ar 3 represents a divalent aromatic heterocyclic group.
  • R represents 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 group It represents an amino group, an acyl group, an imine residue, an amido group, an acid imide group, a substituted oxycarbonyl group, an alkenyl group, an alkynyl group, a cyano group or a nitro group.
  • two R's may be the same as or different from each other.
  • the constitutional unit represented by the formula (I) is preferably a constitutional unit represented by the following formula (I-1).
  • Z represents the same meaning as described above.
  • Examples of the structural unit represented by the formula (I-1) include structural units represented by the following formulas (501) to (505).
  • R represents the same meaning as described above.
  • two R's may be the same or different.
  • the number of carbon atoms of the divalent aromatic heterocyclic group represented by Ar 3 is generally 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.
  • substituent which 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, an arylthio group, Examples thereof include monovalent heterocyclic groups, substituted amino groups, acyl groups, imine residues, amide groups, acid imide groups, substituted oxycarbonyl groups, alkenyl groups, alkynyl groups, cyano groups, and nitro groups.
  • Examples of the divalent aromatic heterocyclic group represented by Ar 3 include groups represented by the following formulas (101) to (185).
  • R represents the same meaning as described above.
  • the plurality of R's may be the same or different.
  • constitutional units represented by the formula (II) constitutional units represented by the following formulas (II-1) to (II-6) are preferable.
  • X 1 and X 2 each independently represent an oxygen atom or a sulfur atom, and R represents the same meaning as described above. When a plurality of R's are present, the plurality of R's may be the same or different.
  • each of X 1 and X 2 in the formulas (II-1) to (II-6) is a sulfur atom because the raw material compounds are easily available.
  • the polymer compound which is a p-type semiconductor material may contain two or more structural units of the formula (I), and may contain two or more structural units of the formula (II).
  • the polymer compound which is a p-type semiconductor material may contain a constitutional unit represented by the following formula (III).
  • Ar 4 represents an arylene group.
  • the arylene group represented by Ar 4 means an atomic group remaining after removing two hydrogen atoms from an aromatic hydrocarbon which may have a substituent.
  • the aromatic hydrocarbon also includes a compound having a condensed ring, and a compound in which two or more members selected from the group consisting of independent benzene rings and condensed rings are directly or linked via a divalent group such as vinylene.
  • Examples of the substituent which the aromatic hydrocarbon may have include the same substituents as the examples mentioned above as the substituent which the heterocyclic compound may have.
  • the carbon atom number of the arylene group excluding the substituent is usually 6 to 60, and preferably 6 to 20.
  • the number of carbon atoms of the arylene group including the substituent is usually about 6 to 100.
  • arylene groups include phenylene (for example, the following formulas 1 to 3), naphthalene-diyl (for example, the following formulas 4 to 13), anthracene-diyl (for example, the following formulas 14 to 19), Biphenyl-diyl group (for example, the following formulas 20 to 25), terphenyl-diyl group (for example, the following formulas 26 to 28), fused ring compound group (for example, the following formulas 29 to 35), fluorene-diyl group (For example, the following formulas 36 to 38), and a benzofluorene-diyl group (for example, the following formulas 39 to 46).
  • phenylene for example, the following formulas 1 to 3
  • naphthalene-diyl for example, the following formulas 4 to 13
  • anthracene-diyl for example, the following formulas 14 to 19
  • Biphenyl-diyl group for example,
  • the polymer compound as the p-type semiconductor material contains the constitutional unit represented by the formula (I) and / or the constitutional unit represented by the formula (II), the constitutional unit represented by the formula (I) and the formula
  • the total amount of the constituent units represented by (II) is usually 20 to 100 mol%, assuming that the amount of all constituent units contained in the polymer compound is 100 mol%, and the charge transportability as a p-type semiconductor material Preferably from 40 to 100 mol%, more preferably from 50 to 100 mol%.
  • polymer compound as the p-type semiconductor material examples include polymer compounds represented by the following formula
  • the polymer compound as a p-type semiconductor material has a polystyrene equivalent weight average molecular weight of usually 1 ⁇ 10 3 to 1 ⁇ 10 8 and is preferably 1 ⁇ 10 3 to 3 in view of improving the solubility in a solvent. It is 1 ⁇ 10 6 .
  • the ink may contain only one p-type semiconductor material, or may contain two or more arbitrary proportions.
  • the n-type semiconductor material may be a low molecular weight compound or a high molecular weight compound.
  • n-type semiconductor materials which are low molecular weight compounds
  • n-type semiconductor materials which are low molecular weight compounds
  • n-type semiconductor materials which are low molecular weight compounds
  • oxadiazole derivatives anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyano Anthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, fullerenes such as C 60 fullerene and derivatives thereof, and phenanthrene derivatives such as vasocuproin Can be mentioned.
  • n-type semiconductor materials which are high molecular compounds include polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain, polyaniline and the like Derivatives, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, and polyfluorene and derivatives thereof can be mentioned.
  • the n-type semiconductor material is preferably at least one selected from fullerenes and fullerene derivatives, and more preferably fullerene derivatives.
  • fullerene examples include C 84 fullerene.
  • fullerene derivatives include derivatives of these fullerenes.
  • the fullerene derivative means a compound in which at least a part of the fullerene is modified.
  • Examples of the fullerene derivative include compounds represented by the following formulas (N-1) to (N-4).
  • R a represents an alkyl group, an aryl group, a monovalent heterocyclic group, or a group having an ester structure.
  • the plurality of Ras may be the same as or different from each other.
  • R b represents an alkyl group or an aryl group.
  • Plural R b 's may be the same as or different from each other.
  • Examples of the group having an ester structure represented by Ra include a group represented by the following formula (19).
  • u1 represents an integer of 1 to 6.
  • u2 represents an integer of 0 to 6;
  • R c represents an alkyl group, an aryl group or a monovalent heterocyclic group.
  • Examples of C 60 fullerene derivatives include the following compounds.
  • fullerene derivative examples include [6,6] -phenyl-C61 butyric acid methyl ester (C60PCBM, [6,6] -phenyl C61 butyric acid methyl ester), [6,6] -phenyl-C71 butyric acid methyl ester ( C70PCBM, [6,6] -Phenyl C71 butyric acid methyl ester, [6,6] -phenyl-C85 butyric acid methyl ester (C84PCBM, [6,6] -phenyl C85 butyric acid methyl ester), and [6,6] ] -Thienyl-C61 butyric acid methyl ester ([6,6] -Thienyl C61 butyric acid methyl ester).
  • the ink may contain only one n-type semiconductor material, or may contain two or more arbitrary proportions of combinations.
  • the weight ratio of the p-type semiconductor material to the n-type semiconductor material in the ink is preferably 1: 9 to 9: 1, and 1: 9 to 2: 1. Is more preferable, 1: 9 or more and 1: 1 or less is further preferable, and 1: 5 or more and 1: 1 or less is particularly preferable.
  • the ink may contain any component other than the first solvent, the second solvent, the p-type semiconductor material, and the n-type semiconductor material as long as the effects of the present invention are not impaired.
  • Optional components include, for example, solvents other than the first solvent and the second solvent as described above, propiophenone, methyl benzoate, ethyl benzoate and benzyl benzoate.
  • the total concentration of the p-type semiconductor material and the n-type semiconductor material in the ink is preferably 0.01% by weight or more and 20% by weight or less, and more preferably 0.01% by weight or more and 10% by weight or less More preferably, it is 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 p-type semiconductor material and the n-type semiconductor material may be dissolved or dispersed, but preferably at least a part is dissolved, and more preferably all is dissolved.
  • the ink can be produced by a known method. For example, a method of preparing a mixed solvent by mixing a first solvent and a second solvent, and adding a p-type semiconductor material and an n-type semiconductor material to the mixed solvent for production; a p-type semiconductor material in the first solvent And the n-type semiconductor material is added to the second solvent, and then the mixture is manufactured by mixing the first solvent and the second solvent to which each material is added; .
  • the first solvent and the second solvent, and the p-type semiconductor material and the n-type semiconductor material may be heated to a temperature equal to or lower than the boiling point of the solvent and mixed.
  • the resulting composition may be filtered using a filter, and the filtrate may be used as an ink.
  • a filter for example, a filter formed of a fluorine resin such as polytetrafluoroethylene (PTFE) can be used.
  • PTFE polytetrafluoroethylene
  • the application of the ink of the present invention is optional.
  • the ink of the present invention can be used to form a film containing a p-type semiconductor material and an n-type semiconductor material.
  • the ink of the present invention is suitably used to form an active layer contained in a photoelectric conversion element.
  • the light detection element including the active layer formed using the ink of the present invention has improved EQE when a reverse bias voltage is applied. Therefore, the ink of the present invention is particularly suitably used to form an active layer contained in a light detection element.
  • the dimensions, such as thickness, of the solidified film of the ink are not particularly limited.
  • the solidified film of the ink is suitably used for the application described as the application of the ink.
  • the solidified film of the ink can be manufactured by any manufacturing method.
  • One embodiment of a method for producing a solidified film of ink includes a step (i) of applying an ink to an application target to obtain a coating, and a step (ii) of removing a solvent from the obtained coating.
  • the coating method is preferably a slit coating method, a knife coating method, a spin coating method, a microgravure coating method, a gravure coating method, a bar coating method, an ink jet coating method, a nozzle coating method or a capillary coating method.
  • 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 more preferable.
  • the ink is applied to any application target.
  • the ink may be applied on a functional layer of a photoelectric conversion element, such as an electrode (anode or cathode), an electron transport layer, or a hole transport layer, in a manufacturing process of the photoelectric conversion element.
  • a photoelectric conversion element such as an electrode (anode or cathode), an electron transport layer, or a hole transport layer, in a manufacturing process of the photoelectric conversion element.
  • Arbitrary methods can be used as a method of removing a solvent from a coating film.
  • the method of removing the solvent include drying methods such as a hot air drying method, an infrared heat drying method, a flash lamp annealing drying method, and a reduced pressure drying method.
  • the photoelectric conversion element of the present invention comprises a first electrode, an active layer containing a p-type semiconductor material and an n-type semiconductor material, and a second electrode in this order, and the active layer is a solidified film of ink. .
  • the active layer includes p-type semiconductor material and n-type semiconductor material.
  • the active layer is a solidified film of the above-mentioned ink. Examples and preferred examples of the p-type semiconductor material, the n-type semiconductor material, and the ink are the same as those described in [2. Ink] is the same as the example described in the section.
  • the EQE is improved by the active layer being a solidified film of the ink.
  • EQE improves when a reverse bias voltage is applied to the photoelectric conversion element. Therefore, the photoelectric conversion element of the present invention is suitable as a light detection element.
  • the photoelectric conversion element may have a plurality of active layers.
  • At least one of the first electrode and the second electrode is a transparent or translucent electrode.
  • the substrate is opaque, it is preferable that one of the first electrode and the second electrode which is farther from the substrate is transparent or translucent.
  • transparent or translucent electrodes include conductive metal oxide films and translucent metal thin films.
  • Specific examples of the transparent or translucent electrode material include, for example, indium oxide, zinc oxide, tin oxide, and a complex thereof (eg, indium tin oxide (ITO), indium zinc oxide), These include NESA, gold, platinum, silver and copper.
  • ITO indium tin oxide
  • the transparent or translucent electrode material one or more selected from ITO, indium zinc oxide and tin oxide are preferable.
  • Examples of the method for producing the electrode include a vacuum evaporation method, a sputtering method, an ion plating method, and a plating method.
  • a transparent conductive film composed of an organic compound such as polyaniline and a derivative thereof and polythiophene and a derivative thereof may be used as the transparent or translucent electrode.
  • One of the first electrode and the second electrode may be an electrode with low light transmittance.
  • the material of the low light transmitting electrode include metals and conductive polymers.
  • Specific examples of the electrode material include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium and the like And alloys of two or more of them; one or more of the above metals and one or more metals selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin Graphite; graphite intercalation compounds; polyaniline and its derivatives; polythiophene and its derivatives.
  • magnesium-silver alloy for example, magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminium alloy, indium-silver alloy, lithium-aluminium alloy, lithium-magnesium alloy, lithium-indium alloy, calcium- Aluminum alloy is mentioned.
  • the photoelectric conversion element may include elements other than the first electrode, the active layer, and the second electrode.
  • Optional elements include, for example, a substrate, a hole transport layer, an electron transport layer, and a sealing layer.
  • the photoelectric conversion element is usually formed on a substrate (supporting substrate).
  • the substrate is preferably formed of a material that does not change chemically when forming the electrode and forming the organic layer. Examples of substrate materials include glass, plastic, polymer films, and silicon.
  • the substrate may have low light transmittance, but in the photoelectric conversion element, for example, when taking in light from the substrate, the substrate is preferably transparent or translucent.
  • the substrate In the case of manufacturing a photoelectric conversion element on a substrate with low light transmittance, light can not be taken in from the electrode side closer to the substrate, so a transparent or semitransparent electrode is used for the electrode far from the substrate. It is preferred to use.
  • a transparent or translucent electrode for the electrode far from the substrate light can be taken in from the electrode far from the substrate, even if a substrate with low light transmittance is used.
  • a hole transport layer In the photoelectric conversion element, a hole transport layer may be provided between an electrode which is an anode and an 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 electrode may be particularly referred to as a hole injection layer.
  • the hole transport layer (hole injection layer) provided in contact with the electrode has a function of promoting the injection of holes into the electrode.
  • the hole transport layer (hole injection layer) may be in contact with the active layer.
  • the hole transport layer contains a hole transport material.
  • the hole transporting material include polythiophene and derivatives thereof, an aromatic amine compound, a polymer compound containing a constitutional unit having an aromatic amine residue, CuSCN, CuI, NiO, and molybdenum oxide (MoOx). .
  • an electron transport layer may be provided between an electrode which is a cathode and an active layer.
  • the electron transport layer has a function of transporting electrons from the active layer to the electrode.
  • the electron transport layer may be in contact with the electrode.
  • the electron transport layer may be in contact with the active layer.
  • the electron transport layer contains an electron transport material.
  • electron transporting materials include zinc oxide nanoparticles, gallium-doped zinc oxide nanoparticles, aluminum-doped zinc oxide nanoparticles, polyethyleneimine, polyethyleneimine ethoxylated, and PFN-P2.
  • the photoelectric conversion element may include a sealing layer.
  • the sealing layer is provided, for example, on the electrode side far from the substrate.
  • the sealing layer can be formed of a material having a moisture blocking property (water vapor barrier property) or an oxygen blocking property (oxygen barrier property).
  • FIG. 1 is a schematic view showing an embodiment of the photoelectric conversion element of the present invention.
  • the photoelectric conversion element 10 of the present embodiment is provided on the support substrate 11 and includes the first electrode 12 as an anode, the hole transport layer 13, the active layer 14, the electron transport layer 15, And the two electrodes 16 in this order.
  • the first electrode 12 is provided to be in contact with one of two main surfaces of the support substrate 10.
  • a hole transport layer 13 is provided in contact with the first electrode 12.
  • An active layer 14 is provided in contact with the hole transport layer 13.
  • An electron transport layer 15 is provided in contact with the active layer 14.
  • a second electrode 16 as a cathode is provided in contact with the electron transport layer 15.
  • the material constituting the supporting substrate 11 and the material constituting each element (the first electrode 12, the hole transport layer 13, the active layer 14, the electron transport layer 15, the second electrode 16) included in the photoelectric conversion element 10 are as follows.
  • the material mentioned as an example as a material which constitutes each above-mentioned element may be sufficient.
  • the photoelectric conversion element of the present invention can be produced by any method.
  • the photoelectric conversion element of the present invention is, for example, the above item [4. Method of Producing Solidified Film of Ink]
  • the method can be produced by the method including the method of producing a solidified film of ink described in the above.
  • the photoelectric conversion element of the present invention can be manufactured by a method including the above-mentioned step (i) and step (ii).
  • the photoelectric conversion element of the present invention generates photovoltaic power between electrodes by being irradiated with light such as sunlight, and can be operated as a solar cell. Further, by integrating a plurality of solar cells, it can also be used as a thin film solar cell module.
  • the photoelectric conversion element of the present invention can flow a photocurrent by irradiating light to a transparent or semi-transparent electrode in a state where a voltage is applied between the electrodes, and as a light sensor (light detection element) It can be operated. It can also be used as an image sensor by integrating a plurality of light sensors.
  • the photoelectric conversion device according to the embodiment of the present invention described above is suitably applied to detection units included in various electronic devices such as workstations, personal computers, portable information terminals, room access control systems, digital cameras, and medical devices. can do.
  • the photoelectric conversion element (light detection element) of the present invention is included in the electronic device illustrated above, for example, an image detection unit (image sensor) for a solid-state imaging device such as an X-ray imaging device and a CMOS image sensor, a fingerprint detection unit
  • an image detection unit image sensor
  • a detection unit that detects predetermined features of a part of a living body such as a face detection unit, a vein detection unit, and an iris detection unit
  • a detection unit of an optical biosensor such as a pulse oximeter.
  • FIG. 2 is a view schematically showing a configuration example of an image detection unit for a solid-state imaging device.
  • the image detection unit 1 includes a CMOS transistor substrate 20, an interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20, and photoelectric conversion according to an embodiment of the present invention provided on the interlayer insulating film 30. It is provided so as to penetrate element 10 and interlayer insulating film 30, and is provided so as to cover photoelectric conversion element 10 and interlayer wiring portion 32 electrically connecting CMOS transistor substrate 20 and photoelectric conversion element 10. And a color filter 50 provided on the sealing layer.
  • the CMOS transistor substrate 20 has any suitable configuration known in the art according to the design.
  • the CMOS transistor substrate 20 includes transistors, capacitors and the like formed within the thickness of the substrate, and is equipped with functional elements such as a CMOS transistor circuit (MOS transistor circuit) for realizing various functions.
  • MOS transistor circuit CMOS transistor circuit
  • Examples of the functional element include a floating diffusion, a reset transistor, an output transistor, and a selection transistor.
  • a signal readout circuit or the like is built in the CMOS transistor substrate 20 by such functional elements, wirings, and the like.
  • the interlayer insulating film 30 can be made of, for example, any conventionally known suitable insulating material such as silicon oxide or insulating resin.
  • the interlayer wiring portion 32 can be made of, for example, any conventionally known suitable conductive material (wiring material) such as copper, tungsten or the like.
  • the interlayer wiring section 32 may be, for example, an in-hole wiring formed simultaneously with the formation of the wiring layer, or may be a buried plug formed separately from the wiring layer.
  • the sealing layer 40 is made of any conventionally known suitable material, on the condition that penetration of harmful substances such as oxygen and water which may cause the photoelectric conversion element 10 to be functionally deteriorated can be prevented or suppressed. Can.
  • color filter 50 for example, a primary color filter that is made of any suitable material known in the related art and corresponds to the design of the image detection unit 1 can be used. Further, as the color filter 50, a complementary color filter which can be thinner than the primary color filter can be used. As complementary color filters, for example, 3 types of (yellow, cyan, magenta), 3 types of (yellow, cyan, transparent), 3 types of (yellow, transparent, magenta), and 3 of (transparent, cyan, magenta) Color filters of different types can be used. These can be arranged in any suitable manner 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 through the color filter 50 is converted by the photoelectric conversion element 10 into an electrical signal according to the amount of light received, and the light reception signal outside the photoelectric conversion element 10 through the electrode, ie, an imaging target Is output as an electrical signal corresponding to
  • the light reception signal output from the photoelectric conversion element 10 is input to the CMOS transistor substrate 20 through the interlayer wiring portion 32, and is read by a signal readout circuit built in the CMOS transistor substrate 20, and further not shown.
  • Signal processing is performed by any suitable conventional known functional unit to generate image information based on an imaging target.
  • FIG. 3 is a view schematically showing a configuration example of a fingerprint detection unit configured integrally with the display device.
  • the display device 2 of the portable 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. And a unit 200.
  • the fingerprint detection unit 100 is provided in an area substantially corresponding to the display area 200 a of the display panel unit 200.
  • the display panel unit 200 is integrally stacked above the fingerprint detection unit 100.
  • the fingerprint detection unit 100 may be provided in correspondence with 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 essential functions.
  • the fingerprint detection unit 100 may be any desired conventionally known member such as a protection film (protection film), a support substrate, a sealing substrate, a sealing member, a barrier film, a band pass filter, an infrared cut film, etc. not shown. It can be provided in a manner corresponding to the design to obtain the characteristics.
  • the fingerprint detection unit 100 may adopt the configuration of the image detection unit described above.
  • the photoelectric conversion element 10 can be included in any mode in 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 or the sealing substrate, and the support substrate 11 is provided with an electrode (anode or cathode) in a matrix, for example.
  • the light received by the photoelectric conversion element 10 is converted by the photoelectric conversion element 10 into an electric signal according to the amount of light received, and the light reception signal outside the photoelectric conversion element 10 through the electrodes, that is, the electric 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 in this configuration example.
  • the display panel unit 200 may be configured of, for example, 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 instead of the organic EL display panel.
  • the display panel unit 200 is provided on the fingerprint detection unit 100 described above.
  • the display panel unit 200 includes an organic electroluminescent element (organic EL element) 220 as a functional part that performs essential functions.
  • the display panel unit 200 further includes any substrate such as a conventionally known glass substrate (support substrate 210 or sealing substrate 240), sealing member, barrier film, polarizing plate such as circular polarizing plate, touch sensor panel 230, etc. Suitable previously known components can be provided in a manner corresponding to the desired properties.
  • the organic EL element 220 is used not only as a light source for pixels in the display area 200 a but also as a light source for capturing a fingerprint in the fingerprint detection unit 100.
  • the fingerprint detection unit 100 detects a fingerprint using light emitted from the organic EL element 220 of the display panel unit 200. Specifically, light emitted from the organic EL element 220 is transmitted through components existing between the organic EL element 220 and the photoelectric conversion element 10 of the fingerprint detection unit 100, and the display is in the display region 200a. The light is reflected by the skin (finger surface) of the fingertip of the finger placed in contact with the surface of the panel unit 200. At least a part of the light reflected by the finger surface is transmitted through the component present between them, received by the photoelectric conversion element 10, and converted into an electrical signal according to the amount of light received by the photoelectric conversion element 10. Then, from the converted electrical signal, image information on the fingerprint on the finger surface is constructed.
  • the portable information terminal provided with the display device 2 performs fingerprint authentication by comparing the obtained image information with fingerprint data for fingerprint authentication recorded in advance by any conventionally known and suitable steps.
  • the method for producing a photoelectric conversion element of the present invention is a method for producing a photoelectric conversion element comprising, in order, a first electrode, an active layer containing a p-type semiconductor material and an n-type semiconductor material, and a second electrode. And the step of forming the active layer, wherein the step of forming the active layer is a step (i) of applying the ink to a target to be coated to obtain a coating, and removing the solvent from the coating obtained Step (ii) is included.
  • the step of forming an active layer preferably includes step (i) and step (ii) in this order.
  • Any application method can be used as a method of applying the ink to the application target.
  • a more preferable coating method, and a further preferable coating method the items [4. Method of Producing Solidified Film of Ink] The same method as the method described in [Step (i)] may be mentioned.
  • Arbitrary methods can be used as a method of removing a solvent from the obtained coating film.
  • the above item [4. Method of Producing Solidified Film of Ink]
  • the same method as the method described in [Step (ii)] may be mentioned.
  • the step of forming the active layer may include an optional step other than the above step (ii) and step (ii).
  • the ink is applied over the layer to form the active layer. Therefore, the application object of the ink differs depending on the layer configuration of the photoelectric conversion element to be manufactured and the order of lamination. For example, when the photoelectric conversion element has a layer configuration of substrate / anode / hole transport layer / active layer / electron transport layer / cathode and is laminated in the order of the elements described on the left, the application of the ink The subject is usually a hole transport layer. Also, for example, when the photoelectric conversion element has a layer configuration of substrate / cathode / electron transport layer / active layer / hole transport layer / anode, and is stacked in the order of the elements described on the left, the ink The object of application is usually the electron transport layer.
  • the method of manufacturing a photoelectric conversion device may be a method of manufacturing a photoelectric conversion device having a plurality of active layers, and even if step (i) and step (ii) are repeated a plurality of times. Good.
  • the method of manufacturing a photoelectric conversion element of the present invention can improve the EQE of the photoelectric conversion element.
  • EQE can be improved when a reverse bias voltage is applied to the photoelectric conversion element. Therefore, the method for producing a photoelectric conversion element of the present invention is suitable as a method for producing a light detection element.
  • semiconductor material used in the embodiment In this embodiment, p-type semiconductor materials and n-type semiconductor materials described in the following table are used.
  • As the material P-1 a material synthesized with reference to the method described in WO2013 / 051676 was used.
  • As the material P-2 a product manufactured by 1-material, product name: PCE10 is used.
  • As a material P-3 a 1-material company make, brand name: PDTSTPD is used.
  • As the material P-4 Lumtec's product name: PDPP3T is used.
  • As the material P-5 a material synthesized with reference to the method described in JP-A-2010-74127 is used.
  • As the material P-6 a material synthesized using the method described in WO 2011/052709 as a reference was used.
  • a trade name: E100 manufactured by Frontier Carbon, Inc. was used as the material N-1.
  • As the material N-2 a product manufactured by American Die Source, trade name: ADS71 BFA is used.
  • Example 1 [A. Preparation of ink] A mixed solvent was prepared using 2-methylquinoline as the first solvent, pseudocumene as the second solvent, and a weight ratio of the first solvent to the second solvent of 10:90. In the mixed solvent, 2 wt% of the material P-1 as p-type semiconductor material with respect to the total weight of the composition and 3 wt% of the material N-1 as n-type semiconductor material with respect to the total weight of the composition are mixed. After stirring at 12 ° C. for 12 hours, the mixture was filtered through a PTFE filter with a pore size of 5 ⁇ m to obtain a composition (I-1) as an ink.
  • a PTFE filter with a pore size of 5 ⁇ m
  • a glass substrate on which an ITO film was formed to a thickness of 150 nm by sputtering was prepared.
  • the glass substrate on which the ITO film was formed was subjected to surface treatment by ozone UV treatment.
  • composition (I-1) was spin-coated on the hole transport layer and then dried in a vacuum dryer (0.1 mbar) to form an active layer.
  • the thickness of the active layer after drying was about 400 nm.
  • the photoelectric conversion elements of Examples 1 to 6 had higher external quantum efficiency when a reverse bias voltage of 3 V was applied, as compared with the photoelectric conversion elements of Comparative Examples 1 to 3.
  • compositions (I-7) to (I-11) and (C-4) to (C-6) were used instead of the composition (I-1), [B. Production and Evaluation of Photoelectric Conversion Element]
  • the photoelectric conversion element was produced and evaluated in the same manner as the procedure described in the section. The results are shown in Table 8.
  • the photoelectric conversion elements of Examples 7 to 11 had higher external quantum efficiency when a reverse bias voltage of 3 V was applied, as compared with the photoelectric conversion elements of Comparative Examples 4 to 6.

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  • Light Receiving Elements (AREA)

Abstract

Selon la présente invention, Il existe une demande d'amélioration de l'efficacité quantique externe d'un élément de conversion photoélectrique. Cette encre contient un matériau semi-conducteur de type p, un matériau semi-conducteur de type n, un premier solvant qui est un composé hétérocyclique contenant de l'azote, et un second solvant qui est un hydrocarbure aromatique. Une couche active dans cet élément de conversion photoélectrique est un film solidifié de l'encre.
PCT/JP2018/039195 2017-10-23 2018-10-22 Encre, film solidifié d'encre et élément de conversion photoélectrique Ceased WO2019082844A1 (fr)

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CN201880068520.2A CN111263982A (zh) 2017-10-23 2018-10-22 油墨、油墨的固化膜以及光电转换元件
JP2019551121A JP7129995B2 (ja) 2017-10-23 2018-10-22 インク、インクの固化膜、及び光電変換素子

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JP2022148301A (ja) * 2021-03-24 2022-10-06 住友化学株式会社 インク組成物の製造方法
EP4116381A4 (fr) * 2021-03-24 2024-04-24 Sumitomo Chemical Company, Limited Procédé de production d'une composition d'encre
US12043749B2 (en) 2021-03-24 2024-07-23 Sumitomo Chemical Company, Limited Method for producing ink composition

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JP7129995B2 (ja) 2022-09-02
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