WO2022202188A1 - 光電変換素子および撮像装置 - Google Patents

光電変換素子および撮像装置 Download PDF

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WO2022202188A1
WO2022202188A1 PCT/JP2022/009124 JP2022009124W WO2022202188A1 WO 2022202188 A1 WO2022202188 A1 WO 2022202188A1 JP 2022009124 W JP2022009124 W JP 2022009124W WO 2022202188 A1 WO2022202188 A1 WO 2022202188A1
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photoelectric conversion
substituent
conversion element
compound
electrode
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French (fr)
Japanese (ja)
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有子 岸本
浩章 飯島
雅哉 平出
眞澄 井土
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to JP2023508886A priority Critical patent/JPWO2022202188A1/ja
Priority to EP22774984.3A priority patent/EP4318623A4/en
Priority to CN202280019452.7A priority patent/CN117083995A/zh
Publication of WO2022202188A1 publication Critical patent/WO2022202188A1/ja
Priority to US18/455,667 priority patent/US20230403929A1/en
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    • 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
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • 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
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
    • H10F39/10—Integrated devices
    • H10F39/12—Image sensors
    • 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
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/311—Phthalocyanine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2604/00—Fullerenes, e.g. C60 buckminsterfullerene or C70
    • 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
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • 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
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present disclosure relates to photoelectric conversion elements and imaging devices.
  • Photoelectric conversion elements that convert light energy into electrical energy are widely used as solar cells or light sensors.
  • many photoelectric conversion elements using inorganic semiconductor materials such as silicon single crystals or silicon polycrystals have been developed.
  • Non-Patent Document 1 organic semiconductor materials with physical properties and functions not found in conventional inorganic materials have been actively researched.
  • An organic photoelectric conversion element which is a photoelectric conversion element using an organic semiconductor material as a photoelectric conversion material for a photoelectric conversion layer, has also been developed.
  • the photoelectric conversion element can be used as an optical sensor such as an imaging device by extracting electric charges generated by light as an electric signal.
  • a photoelectric conversion layer using an organic semiconductor material whose molecules aggregate with weak van der Waals forces is heated to a high temperature after formation. There is a problem that the photoelectric conversion layer deteriorates and the device characteristics deteriorate.
  • the present disclosure provides a photoelectric conversion element or the like that can suppress deterioration in element characteristics when exposed to high temperatures.
  • a photoelectric conversion element includes a first electrode, a second electrode facing the first electrode, a donor organic compound positioned between the first electrode and the second electrode, and and a photoelectric conversion layer including a bulk heterojunction layer containing an acceptor organic compound.
  • the donor organic compound includes a first substituent.
  • the acceptor organic compound includes an aromatic moiety and a second substituent group bonded to the aromatic moiety and exhibiting dipolar interaction with the first substituent group.
  • An imaging device includes a substrate, a charge detection circuit provided on the substrate, a photoelectric conversion unit provided on the substrate, and an electrical connection between the charge detection circuit and the photoelectric conversion unit. and a pixel including a charge storage node connected to the .
  • the photoelectric conversion section includes the photoelectric conversion element.
  • deterioration of device characteristics when exposed to high temperatures can be suppressed.
  • FIG. 1 is a schematic cross-sectional view showing an example of a photoelectric conversion element according to an embodiment.
  • FIG. 2 is a schematic cross-sectional view showing another example of the photoelectric conversion element according to the embodiment.
  • FIG. 3 is an exemplary energy band diagram in the photoelectric conversion element shown in FIG.
  • FIG. 4 is a diagram illustrating an example of a circuit configuration of an imaging device according to an embodiment;
  • FIG. 5 is a schematic cross-sectional view showing an example of the device structure of pixels in the imaging device according to the embodiment. 6 is a diagram showing measurement results of spectral sensitivity characteristics of photoelectric conversion elements in Example 1 and Comparative Example 1.
  • FIG. 1 is a schematic cross-sectional view showing an example of a photoelectric conversion element according to an embodiment.
  • FIG. 2 is a schematic cross-sectional view showing another example of the photoelectric conversion element according to the embodiment.
  • FIG. 3 is an exemplary energy band diagram in the photoelectric conversion element shown in FIG.
  • FIG. 4 is a diagram illustrating
  • a bulk heterojunction layer having a bulk heterojunction structure of a donor organic semiconductor and an acceptor organic semiconductor can achieve high photoelectric conversion efficiency, it is useful as a photoelectric conversion layer of a photoelectric conversion element, and has been studied in recent years. ing.
  • excitons generated by light absorption migrate in the donor organic semiconductor or acceptor organic semiconductor as excitons, and at the interface between the donor organic semiconductor and the acceptor organic semiconductor, form holes and It is known to be charge-separated into electrons.
  • the exciton diffusion length through which excitons can diffuse varies depending on the material.
  • the exciton-generated donor organic semiconductor and acceptor organic semiconductor domains are shorter than the exciton diffusion length, and the distance between the domains is close enough to enable band conduction or hopping conduction for separated charges.
  • High photoelectric conversion efficiency can be achieved by having a domain structure such that
  • the bulk heterojunction layer has the following problems.
  • the donor organic semiconductors and the acceptor organic semiconductors have high affinity, so when heat is applied to the bulk heterojunction layer, the donor organic semiconductors and the acceptor organic semiconductors aggregate and/or Or crystallization is promoted.
  • the domain structure of the bulk heterojunction layer changes greatly from the structure immediately after film formation. For example, aggregation and/or crystallization of donor organic semiconductors and/or acceptor organic semiconductors progresses, making the domain larger than the exciton diffusion length, and sufficient charge separation efficiency cannot be obtained.
  • an energetically trough trap level is generated between the domains, and the extraction efficiency of the charge-separated charges is lowered.
  • the photoelectric conversion efficiency of the photoelectric conversion element decreases when exposed to high temperatures. Furthermore, the aggregation and/or crystallization of the donor organic semiconductors and the acceptor organic semiconductors causes the surface of the bulk heterojunction layer to become rough, which becomes a leak source when an electric field is applied to the bulk heterojunction layer. Dark current is likely to occur in the conversion element. As described above, when the bulk heterojunction layer is exposed to high temperature, the photoelectric conversion efficiency and the device characteristics such as dark current are likely to be deteriorated due to aggregation of donor organic semiconductors and acceptor organic semiconductors.
  • Non-Patent Document 2 [60]PCBM ([6,6]-Phenyl-C61-Butyric Acid Methyl Ester) used as an acceptor organic compound [70]PCBM ([6,6]-Phenyl -C71-Butyric Acid Methyl Ester) is disclosed as an organic thin film solar cell using an organic photoelectric conversion film.
  • fullerene derivatives with different carbon numbers such as [60]PCBM and [70]PCBM, it is difficult to sufficiently suppress deterioration of the photoelectric conversion layer.
  • the present inventors have found that in a photoelectric conversion device, by increasing the affinity between the donor organic semiconductor and the acceptor organic semiconductor in the bulk heterojunction layer, the donor organic semiconductors and the acceptor organic semiconductors Focusing on the ability to suppress the aggregation of, etc., one aspect of the present disclosure has been obtained.
  • the present disclosure provides a photoelectric conversion element or the like that can suppress the deterioration of element characteristics when exposed to high temperatures even if it has a bulk heterojunction layer.
  • a photoelectric conversion element includes a first electrode, a second electrode facing the first electrode, a donor organic compound positioned between the first electrode and the second electrode, and and a photoelectric conversion layer including a bulk heterojunction layer containing an acceptor organic compound.
  • the donor organic compound includes a first substituent.
  • the acceptor organic compound includes an aromatic moiety and a second substituent group bonded to the aromatic moiety and exhibiting dipolar interaction with the first substituent group.
  • the affinity between the donor organic compound and the acceptor organic compound increases due to the dipolar interaction between the first substituent and the second substituent.
  • the second substituent is bonded to the aromatic site, the cohesive force between the aromatic sites of the acceptor organic compound, which tends to aggregate easily, can be reduced.
  • the photoelectric conversion device according to this aspect can suppress degradation of device characteristics when exposed to high temperatures.
  • each of the first substituent and the second substituent may be an alkoxy group, an alkylsulfanyl group, or a cyano group.
  • each of the first substituent and the second substituent may be an alkoxy group or a cyano group.
  • the dipolar interaction between the first substituent and the second substituent is more likely to occur, and aggregation between donor organic compounds and between acceptor organic compounds can be more effectively suppressed.
  • the donor organic compound may be a phthalocyanine derivative or a naphthalocyanine derivative.
  • the donor organic compound may be a phthalocyanine derivative represented by the following general formula (1) or a naphthalocyanine derivative represented by the following general formula (2).
  • Y 1 to Y 16 are each independently the first substituent
  • M is Si, Sn or Ge
  • R 1 to R 4 are each independently the following general formulas (3) to (5) any one of the substituents represented by R 5 to R 7 are each independently an alkyl group or an aryl group
  • R 8 to R 10 are each independently an aryl group.
  • the acceptor organic compound may be a fullerene derivative.
  • the fullerene derivative is C60 fullerene bonded to the second substituent, or [6,6]-phenyl-C61-butyric acid methyl ester ([60]PCBM) bonded to the second substituent.
  • the photoelectric conversion element may further include a buffer layer positioned between at least one selected from the group consisting of the first electrode and the second electrode and the photoelectric conversion layer.
  • the photoelectric conversion element further includes a first buffer layer positioned between the first electrode and the photoelectric conversion layer, and a second buffer layer positioned between the second electrode and the photoelectric conversion layer. good too.
  • the buffer layer suppresses dark current due to charge injection from the electrode, or alleviates damage and stress during electrode formation, thereby improving the characteristics of the photoelectric conversion layer.
  • an imaging device includes a substrate, a charge detection circuit provided on the substrate, a photoelectric conversion unit provided on the substrate, and the charge detection circuit and the photoelectric conversion unit. and a pixel including a charge storage node electrically connected thereto.
  • the photoelectric conversion section includes the photoelectric conversion element.
  • the imaging device includes the photoelectric conversion element, deterioration of element characteristics due to heating can be suppressed.
  • the terms “upper” and “lower” do not refer to the upward direction (vertically upward) and the downward direction (vertically downward) in absolute spatial recognition, but are based on the stacking order in the stacking structure. It is used as a term defined by a relative positional relationship. Specifically, the light-receiving side of the imaging device is defined as “upper”, and the side opposite to the light-receiving side is defined as “lower”. Note that terms such as “upper” and “lower” are used only to specify the mutual arrangement of members, and are not intended to limit the orientation of the imaging apparatus when it is used.
  • FIG. 1 is a schematic cross-sectional view showing a photoelectric conversion element 10A, which is an example of a photoelectric conversion element according to this embodiment.
  • a photoelectric conversion element 10A includes an upper electrode 4 and a lower electrode 2, which are a pair of electrodes arranged to face each other, and a photoelectric conversion layer 3 positioned between the pair of electrodes.
  • the photoelectric conversion layer 3 is composed of a bulk heterojunction layer containing a donor organic compound and an acceptor organic compound.
  • the bulk heterojunction layer is a layer having a bulk heterojunction structure of a donor organic semiconductor containing a donor organic compound and an acceptor organic semiconductor containing an acceptor organic compound, for example, a bulk heterojunction structure as a whole.
  • a photoelectric conversion element 10A according to the present embodiment is supported by a support substrate 1, for example.
  • the support substrate 1 is, for example, transparent to light having a wavelength that can be absorbed by the photoelectric conversion layer 3 , and light enters the photoelectric conversion element 10A through the support substrate 1 .
  • the support substrate 1 may be a substrate used in general photoelectric conversion elements, such as a glass substrate, a quartz substrate, a silicon substrate, a semiconductor substrate, or a plastic substrate.
  • transparent in this specification means that at least part of light having a wavelength that can be absorbed by the photoelectric conversion layer 3 is transmitted, and it is not essential that light be transmitted over the entire wavelength range.
  • the photoelectric conversion layer 3 absorbs light incident on the photoelectric conversion element 10A and generates a pair of charges (excitons) by photoelectric conversion.
  • the generated charge pairs are separated and collected in the upper electrode 4 and the lower electrode 2 .
  • the photoelectric conversion layer 3 is composed of a bulk heterojunction layer in which a donor organic semiconductor containing a donor organic compound and an acceptor organic semiconductor containing an acceptor organic compound are mixed. In the bulk heterojunction layer, the generation of charge pairs may occur in either the donor organic semiconductor or the acceptor organic semiconductor, or in both the donor organic semiconductor and the acceptor organic semiconductor.
  • the donor organic semiconductor and the acceptor organic semiconductor according to the present embodiment will be specifically described below.
  • Donor organic semiconductors are mainly represented by hole-transporting organic compounds and are composed of donor organic compounds that have the property of easily donating electrons. More specifically, the donor organic compound is the organic compound with the smaller ionization potential when the two organic materials are used in contact. Moreover, the donor organic compound has a first substituent group that exhibits a dipole interaction with a second substituent group described later. Also, the donor organic compound has, for example, an aromatic moiety. A 1st substituent is a substituent couple
  • donor organic compounds include triarylamine compounds, benzidine compounds, pyrazoline compounds, styrylamine compounds, hydrazone compounds, triphenylmethane compounds, carbazole compounds, polysilane compounds, thiophene compounds, phthalocyanine compounds, naphthalocyanine compounds, and cyanine compounds.
  • merocyanine compounds oxonol compounds
  • polyamine compounds indole compounds, pyrrole compounds, pyrazole compounds, polyarylene compounds, condensed aromatic carbocyclic compounds (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives ), a metal complex having a nitrogen-containing heterocyclic compound as a ligand, or the like can be used.
  • Acceptor organic semiconductors are mainly represented by electron-transporting organic compounds, and are composed of acceptor organic compounds that easily accept electrons. More specifically, the acceptor organic compound is the organic compound with the higher electron affinity when two organic compounds are used in contact. Also, the acceptor organic compound has the first substituent and the second substituent that exhibits dipolar interaction. Also, the acceptor organic compound has, for example, an aromatic moiety. A 2nd substituent is a substituent couple
  • Acceptor organic compounds include, for example, fullerene derivatives, condensed aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives), 5- to 7-membered heterocyclic compounds.
  • a heterocyclic compound containing a nitrogen atom, an oxygen atom or a sulfur atom e.g.
  • pyridine pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, Tetrazole, pyrazole, imidazole, thiazole, oxazole, indazole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, triazolopyridazine, triazolopyrimidine, tetrazaindene, oxadiazole, imidazopyridine, pyrrolidine, pyrrolo pyridine, thiadiazolopyridine, dibenzazepine, tribenzazepine, etc.), polyarylene compounds, fluorene compounds, cyclopentadiene compounds, silyl compounds, and nitrogen-containing heterocyclic compounds
  • the first substituent and the second substituent will be explained.
  • the first substituent and the second substituent exhibit a dipolar interaction.
  • the affinity between the donor organic compound and the acceptor organic compound is increased, and even when the photoelectric conversion layer 3 is exposed to high temperatures, the aggregation of the donor organic compounds and the acceptor organic compounds is suppressed. .
  • the first substituent and the second substituent each bind to, for example, an aromatic moiety.
  • the first substituent and the second substituent are bonded to the aromatic sites that are particularly likely to aggregate due to the ⁇ - ⁇ interaction. Aggregation or the like between acceptor organic compounds is effectively suppressed.
  • the first substituent and the second substituent are each, for example, an oxygen atom (O), a nitrogen atom (N), a sulfur atom (S), a selenium atom (Se), a boron atom (B), a phosphorus atom (P), A substituent containing at least one atom selected from the group consisting of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), and an iodine atom (I).
  • each of the first substituent and the second substituent are an alkoxy group, an alkylsulfanyl group, a cyano group, a nitro group, a halogen group, an amino group, an alkylamino group, a dialkylamino group, a carbonyl group, a hydroxyl group and the like.
  • Each of the first substituent and the second substituent may be an alkyl group in which at least one hydrogen atom is substituted with a halogen atom, such as a trifluoromethyl group.
  • the first substituent and the second substituent may each be an alkoxy group, an alkylsulfanyl group or a cyano group, and among these, an alkoxy group or It may be a cyano group.
  • first substituent and the second substituent may each be an acyclic substituent, oxygen (O), nitrogen (N), sulfur (S), selenium (Se), boron (B), It may be a substituent having a cyclic skeleton containing at least one selected from the group consisting of phosphorus (P).
  • Each of the first substituent and the second substituent has, for example, a cyclic skeleton such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, thiazole, oxazole, indazole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, triazolopyridazine, triazolopyrimidine, tetrazaindene, oxadiazole, imidazopyridine, pyrrolidine , pyrrolopyridine, thiadiazolopyridine, dibenzazepine or tribenzazepine.
  • first substituent and the second substituent may be, for example, substituents having the same structural formula, or may be substituents having the same classification as exemplified in the above specific examples, and the structural formula may be different substituents, or may be substituents of different classifications. From the viewpoint of ease of occurrence of dipole interaction, the first substituent and the second substituent may be substituents of the same classification.
  • the donor organic compound may have a plurality of first substituents.
  • the plurality of first substituents may all have the same structural formula, may all have the same classification, may have at least one different structural formula, or may have at least one different classification good too. From the viewpoint of ease of synthesis, the plurality of first substituents may all have the same structural formula.
  • the acceptor organic compound may have a plurality of second substituents.
  • the plurality of second substituents may all have the same structural formula, may all have the same classification, may have at least one different structural formula, or may have at least one different classification good too. From the viewpoint of ease of synthesis, the plurality of second substituents may all have the same structural formula.
  • the donor organic compound is, for example, a phthalocyanine derivative having a first substituent or a naphthalocyanine derivative having a first substituent.
  • the photoelectric conversion efficiency of the photoelectric conversion device can be improved, and even when a phthalocyanine derivative or naphthalocyanine derivative that easily aggregates is used as the donor organic compound, the donor organic Aggregation of compounds can be suppressed.
  • the first substituent is bonded, for example, to the aromatic moiety.
  • the phthalocyanine derivative and the naphthalocyanine derivative each have, for example, the first substituent on the ⁇ -side chain. Further, each of the phthalocyanine derivative and the naphthalocyanine derivative may have a first substituent on a part of the axial ligand coordinated to the central metal.
  • each of the phthalocyanine derivative and naphthalocyanine derivative may have a plurality of first substituents.
  • the donor organic semiconductor contains a phthalocyanine derivative or a naphthalocyanine derivative as a main component.
  • the donor organic compound is, for example, a phthalocyanine derivative represented by the following general formula (1) or a naphthalocyanine derivative represented by the following general formula (2).
  • Y 1 to Y 16 are each independently a first substituent
  • M is Si, Sn or Ge
  • R 1 to R 4 are each independently represented by the following general formulas (3) to (5). Any one of the substituents represented.
  • Each of Y 1 to Y 8 and Y 9 to Y 16 may be a first substituent group having the same structural formula, may be a first substituent group having the same classification, or may be first substituent groups having different structural formulas.
  • a substituent may be included, and a first substituent group different in classification from each other may be included. From the viewpoint of ease of synthesis, each of Y 1 to Y 8 and Y 9 to Y 16 may be the first substituent of the same structural formula.
  • R5 to R7 are each independently an alkyl group or an aryl group
  • R8 to R10 are each independently an aryl group.
  • at least one selected from the group consisting of R 5 to R 7 in the general formula (3), at least one selected from the group consisting of R 8 and R 9 in the general formula (4), and At least one hydrogen atom of each of R 10 in the general formula (5) may be substituted with a first substituent.
  • each of Y 1 to Y 8 and Y 9 to Y 16 may be a substituent other than the first substituent such as hydrogen or a hydrocarbon group.
  • each of the first substituents Y1 to Y16 may be an alkoxy group or an alkylsulfanyl group.
  • each of the first substituents Y 1 to Y 8 may be an alkylsulfanyl group.
  • each of the first substituents Y9 to Y16 may be an alkoxy group. This makes it possible to easily synthesize a phthalocyanine derivative or a naphthalocyanine derivative.
  • it since it has an electron-donating alkoxy group or alkylsulfanyl group in the ⁇ -side chain, the absorption wavelength tends to be longer, and the absorbance coefficient tends to increase in the near-infrared region.
  • At least one selected from the group consisting of R 5 to R 7 in the general formula (3), at least one selected from the group consisting of R 8 and R 9 in the general formula (4), and , and R 10 in the general formula (5) may each have at least one hydrogen atom substituted with an electron-withdrawing group. This increases the electron-withdrawing property of the axial ligand of the phthalocyanine derivative or naphthalocyanine derivative, reduces the electron density of the phthalocyanine ring or naphthalocyanine ring, and narrows the energy bandgap of the phthalocyanine derivative or naphthalocyanine derivative.
  • Electron withdrawing groups include, for example, cyano groups, fluoro groups and carbonyl groups.
  • the electron-withdrawing group may be a cyano group or a fluoro group from the viewpoint of high electron-withdrawing properties.
  • the phthalocyanine derivative or naphthalocyanine derivative may be, for example, any one of the compounds represented by the following structural formulas (6) to (15).
  • the phthalocyanine derivative or naphthalocyanine derivative is any one of the compounds represented by the structural formulas (6) to (15), high photoelectric conversion efficiency can be obtained in the near-infrared region.
  • the compounds represented by the structural formulas (6) to (15) can be synthesized by known synthetic methods or synthetic methods shown in the following examples.
  • the donor organic semiconductor may contain materials other than the phthalocyanine derivative and the naphthalocyanine derivative.
  • the donor organic semiconductor may contain at least one of the organic compounds exemplified as the donor organic compounds described above.
  • the acceptor organic compound is, for example, a fullerene derivative having a second substituent.
  • the acceptor organic semiconductor contains a fullerene derivative as a main component.
  • the fullerene derivative may have a plurality of second substituents.
  • the second substituent is attached, for example, to the aromatic moiety.
  • the acceptor organic semiconductor contains a fullerene derivative as a main component.
  • the second substituent in the fullerene derivative may be an alkoxy group.
  • Fullerene derivatives are, for example, fullerenes such as C60 fullerene and C70 fullerene to which a second substituent is attached.
  • the second substituent is attached to the fullerene moiety.
  • Fullerenes in which the second substituent is bonded to the fullerene moiety can be synthesized by addition reaction of the second substituent to fullerenes, such as the method described in Non-Patent Document 3, for example.
  • fullerene derivatives are, for example, PCBMs such as [60]PCBM and [70]PCBM to which a second substituent is attached.
  • PCBMs are compounds in which phenylbutyric acid methyl ester is added to a fullerene moiety having various carbon numbers via a three-membered ring structure.
  • the second substituent is attached to the phenyl group of the phenylbutyric acid methyl ester moiety or the fullerene moiety.
  • the second substituent may be bonded to the phenyl group of the phenylbutyric acid methyl ester moiety.
  • each of the plurality of second substituents is bonded to either the phenyl group of the phenylbutyric acid methyl ester moiety or the fullerene moiety.
  • the PCBMs may have a plurality of phenylbutyric acid methyl esters attached to the fullerene site via a three-membered ring structure.
  • PCBMs in which a second substituent is bonded to the phenyl group of the phenylbutyric acid methyl ester site are, for example, nucleophilic addition reactions of phenylbutyric acid methyl ester derivatives in which the second substituent is bonded to the phenyl group in advance to fullerenes.
  • nucleophilic addition reactions of phenylbutyric acid methyl ester derivatives in which the second substituent is bonded to the phenyl group in advance to fullerenes. can be synthesized by
  • the fullerene derivative is C60 fullerene with a second substituent attached or [60]PCBM with a second substituent attached. Thereby, a fullerene derivative can be easily synthesized.
  • the fullerene derivative may be, for example, any one of the compounds represented by the following structural formulas (16) to (19).
  • the compounds represented by the following structural formulas (16) to (19) are each [60]PCBM to which a second substituent is attached.
  • the fullerene moiety in the structural formulas of fullerene derivatives and the like not all carbon atoms are shown, and some carbon atoms are omitted for the sake of flat representation.
  • the acceptor organic semiconductor may contain materials other than the fullerene derivative.
  • the acceptor organic semiconductor may contain at least one of the organic compounds exemplified as the acceptor organic compounds described above.
  • a coating method such as spin coating, or a vacuum deposition method in which a film material is vaporized by heating under vacuum and deposited on a substrate, or the like can be used.
  • a vapor deposition method may be used in order to prevent the contamination of impurities and to perform multi-layering with a higher degree of freedom for higher functionality.
  • a commercially available device may be used as the vapor deposition device.
  • the temperature of the deposition source during deposition may be 100° C. or higher and 500° C. or lower, or may be 150° C. or higher and 400° C. or lower.
  • the degree of vacuum during vapor deposition may be 1 ⁇ 10 ⁇ 4 Pa or more and 1 Pa or less, or 1 ⁇ 10 ⁇ 3 Pa or more and 0.1 Pa or less.
  • a method of adding metal fine particles or the like to the vapor deposition source to increase the vapor deposition rate may be used.
  • the mixing ratio of the materials of the photoelectric conversion layer 3 is indicated by weight ratio in the coating method and by volume ratio in the vapor deposition method. More specifically, in the coating method, the blending ratio of each material is determined by the weight of each material when the solution is prepared. stipulate.
  • At least one of the upper electrode 4 and the lower electrode 2 is a transparent electrode made of a conductive material transparent to light of the response wavelength. Only the upper electrode 4 may be a transparent electrode, only the lower electrode 2 may be a transparent electrode, or both the upper electrode 4 and the lower electrode 2 may be transparent electrodes.
  • a bias voltage is applied to the lower electrode 2 and the upper electrode 4 through wiring (not shown). For example, the polarity of the bias voltage is determined such that electrons move to the upper electrode 4 and holes move to the lower electrode 2 among the charges generated in the photoelectric conversion layer 3 . Further, the bias voltage may be set such that holes move to the upper electrode 4 and electrons move to the lower electrode 2 among the charges generated in the photoelectric conversion layer 3 .
  • the bias voltage is such that the electric field generated in the photoelectric conversion element 10A, that is, the strength of the value obtained by dividing the applied voltage value by the distance between the lower electrode 2 and the upper electrode 4 is 1.0 ⁇ 10 3 V/. cm or more and 1.0 ⁇ 10 7 V/cm or less, or 1.0 ⁇ 10 4 V/cm or more and 1.0 ⁇ 10 6 V/cm or less. may By adjusting the magnitude of the bias voltage in this way, it becomes possible to efficiently move the charge to the upper electrode 4 and extract a signal corresponding to the charge to the outside.
  • a transparent conducting oxide (TCO) having a high transmittance of light in the near-infrared region and a small resistance value may be used as a material of the lower electrode 2 and the upper electrode 4.
  • a thin metal film such as Au can be used as a transparent electrode.
  • a transparent electrode is manufactured so as to obtain a transmittance of 60% to 80%. The resistance value may increase significantly compared to when Therefore, TCO has higher transparency to near-infrared light than a metal material such as Au, and a transparent electrode with a small resistance value can be obtained.
  • TCO is not particularly limited, but for example, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), AZO (Aluminum-doped Zinc Oxide), FTO (Florine-doped Tin Oxide), SnO 2 , TiO 2 , ZnO 2 etc.
  • the lower electrode 2 and the upper electrode 4 may be made of a single metal material such as TCO and Au, or a combination of a plurality of them, depending on the desired transmittance.
  • the material of the lower electrode 2 and the upper electrode 4 is not limited to the conductive material transparent to near-infrared light, and other materials may be used.
  • Various methods are used for producing the lower electrode 2 and the upper electrode 4 depending on the materials used.
  • a chemical reaction method such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, a sol-gel method, or a method such as application of an indium tin oxide dispersion may be used.
  • further UV-ozone treatment, plasma treatment, or the like may be performed.
  • photoelectric conversion occurs in the photoelectric conversion layer 3 by light incident through the support substrate 1 and the lower electrode 2 and/or light incident through the upper electrode 4, for example.
  • the holes are collected in the lower electrode 2 and the electrons are collected in the upper electrode 4 . Therefore, for example, by measuring the potential of the lower electrode 2, the light incident on the photoelectric conversion element 10A can be detected.
  • the photoelectric conversion element 10A may further include a buffer layer 5 (see FIG. 2) and a buffer layer 6 (see FIG. 2), which will be described later.
  • a buffer layer 5 see FIG. 2
  • a buffer layer 6 see FIG. 2
  • the donor organic compound having the first substituent and the second substituent exhibiting dipole interaction with the first substituent are bonded to the aromatic site. and a photoelectric conversion layer 3 having a bulk heterojunction layer containing an acceptor organic compound.
  • Appropriate domain sizes and inter-domain distances in the donor organic compound and the acceptor organic compound contained in the bulk heterojunction layer enable high device characteristics to be exhibited as described above. That is, in the bulk heterojunction layer, the donor organic compound and the acceptor organic compound are appropriately dispersed, so that high device characteristics can be exhibited.
  • donor organic compounds and acceptor organic compounds have high affinity with each other.
  • the photoelectric conversion element 10A since the first substituent and the second substituent exhibit dipole interaction, the affinity between the donor organic compound and the acceptor organic compound increases. Therefore, even when the photoelectric conversion element 10A is exposed to a high temperature, aggregation or the like of the donor organic compounds and the acceptor organic compounds is suppressed, and the donor organic compounds and the acceptor organic compounds are appropriately dispersed. state is maintained. Therefore, the photoelectric conversion element 10A can suppress the deterioration of the element characteristics due to the aggregation of the donor organic compounds and the aggregation of the acceptor organic compounds.
  • FIG. 2 is a schematic cross-sectional view showing a photoelectric conversion element 10B, which is another example of the photoelectric conversion element according to this embodiment.
  • a photoelectric conversion element 10B has a pair of electrodes, a lower electrode 2 and an upper electrode 4, and a photoelectric conversion layer 3 provided between the pair of electrodes. Further, the photoelectric conversion element 10B includes a buffer layer 5 arranged between the lower electrode 2 and the photoelectric conversion layer 3 and a buffer layer 6 arranged between the upper electrode 4 and the photoelectric conversion layer 3 .
  • the details of the lower electrode 2, the upper electrode 4, and the photoelectric conversion layer 3 are the same as those described in the description of the photoelectric conversion element 10A, so descriptions thereof will be omitted here.
  • the buffer layer 5 is provided, for example, to reduce dark current due to injection of electrons from the lower electrode 2 , and suppresses injection of electrons from the lower electrode 2 into the photoelectric conversion layer 3 . That is, the buffer layer 5 may be an electron blocking layer. The buffer layer 5 also has a function of transporting holes generated in the photoelectric conversion layer 3 to the lower electrode 2 .
  • a donor semiconductor such as the materials listed above for the donor organic semiconductor or a hole-transporting organic compound can be used.
  • the buffer layer 5 may be a protective layer for protecting the photoelectric conversion layer 3 from stress, chemical substances, heat, and the like when forming electrodes and the like.
  • the buffer layer 6 is provided, for example, to reduce dark current due to injection of holes from the upper electrode 4, and suppresses injection of holes from the upper electrode 4 into the photoelectric conversion layer 3. do. That is, the buffer layer 6 may be a hole blocking layer.
  • the buffer layer 6 also has a function of transporting electrons generated in the photoelectric conversion layer 3 to the upper electrode 4 .
  • Materials for the buffer layer 6 include, for example, copper phthalocyanine, ClAlPc (chloroaluminum phthalocyanine), PTCDA (3,4,9,10-perylenetetracarboxylic dianhydride), acetylacetonate complex, BCP (bathocuproine), Alq (Tris(8-quinolinolate) aluminum) or organic-metal compounds or inorganics such as MgAg, MgO can be used.
  • acceptor semiconductors such as the materials listed above for the acceptor organic semiconductor or electron-transporting organic compounds can also be used.
  • the buffer layer 6 may be a protective layer for protecting the photoelectric conversion layer 3 from stress, chemical substances, heat, and the like when forming electrodes and the like.
  • the buffer layer 6 may have a high transmittance of light in the wavelength region for photoelectric conversion, or may be made of a material that does not absorb light in the visible light region. Well, the thickness of the buffer layer 6 may be reduced. The thickness of the buffer layer 6 depends on the configuration of the photoelectric conversion layer 3, the thickness of the upper electrode 4, and the like, but may be, for example, 2 nm or more and 50 nm or less.
  • the material of the lower electrode 2 is selected from among the materials described above in consideration of adhesion with the buffer layer 5, electron affinity, ionization potential, stability, and the like. The same applies to the upper electrode 4 when the buffer layer 6 is provided.
  • FIG. 3 shows an example of a schematic energy band diagram of the photoelectric conversion element 10B having the configuration shown in FIG.
  • the HOMO energy level of the buffer layer 5 is lower than the highest occupied molecular orbital (HOMO) energy level of the donor organic semiconductor 3A included in the photoelectric conversion layer 3. .
  • the LUMO energy level of the buffer layer 5 is higher than the lowest unoccupied molecular orbital (LUMO) energy level of the donor organic semiconductor 3A.
  • the LUMO level of the buffer layer 6 is higher than the LUMO energy level of the acceptor organic semiconductor 3B included in the photoelectric conversion layer 3, for example.
  • the positions of the buffer layer 5 and the buffer layer 6 may be interchanged in the photoelectric conversion element 10B. That is, the buffer layer 5 may be arranged between the upper electrode 4 and the photoelectric conversion layer 3 and the buffer layer 6 may be arranged between the lower electrode 2 and the photoelectric conversion layer 3 . Moreover, the photoelectric conversion element 10B may include only one of the buffer layer 5 and the buffer layer 6 .
  • the imaging device according to the present embodiment is, for example, a charge reading type imaging device.
  • FIG. 4 is a diagram showing an example of the circuit configuration of the imaging device 100 according to this embodiment.
  • FIG. 5 is a schematic cross-sectional view showing an example of the device structure of the pixel 24 in the imaging device 100 according to this embodiment.
  • the imaging device 100 includes a semiconductor substrate 40 which is an example of a substrate, a charge detection circuit 35 provided on the semiconductor substrate 40, a photoelectric conversion section 10C provided on the semiconductor substrate 40, and a charge detection circuit. 35 and a pixel 24 including a charge storage node 34 electrically connected to the photoelectric conversion unit 10C.
  • the photoelectric conversion unit 10C of the pixel 24 includes, for example, the photoelectric conversion element 10A or the photoelectric conversion element 10B. In the example shown in FIG. 5, the photoelectric conversion unit 10C includes a photoelectric conversion element 10B.
  • the charge storage node 34 stores the charge generated by the photoelectric conversion unit 10C, and the charge detection circuit 35 detects the charge stored in the charge storage node 34.
  • the charge detection circuit 35 provided on the semiconductor substrate 40 may be provided on the semiconductor substrate 40 or may be provided in the semiconductor substrate 40 .
  • the imaging device 100 includes a plurality of pixels 24 and peripheral circuits.
  • the imaging device 100 is an organic image sensor realized by a one-chip integrated circuit, and has a pixel array including a plurality of pixels 24 arranged two-dimensionally.
  • a plurality of pixels 24 are arranged two-dimensionally on a semiconductor substrate 40, that is, in row and column directions to form a photosensitive region, which is a pixel region.
  • FIG. 4 shows an example in which the pixels 24 are arranged in a matrix of two rows and two columns.
  • FIG. 4 omits illustration of a circuit (for example, a pixel electrode control circuit) for individually setting the sensitivity of the pixels 24 .
  • the imaging device 100 may be a line sensor.
  • the plurality of pixels 24 may be arranged one-dimensionally.
  • the terms row direction and column direction refer to directions in which rows and columns extend, respectively. That is, in FIG. 4, the vertical direction on the paper surface is the column direction, and the horizontal direction is the row direction.
  • each pixel 24 includes a photoelectric conversion portion 10C, a charge detection circuit 35, and a charge accumulation node 34 electrically connected to the photoelectric conversion portion 10C and the charge detection circuit 35.
  • the charge detection circuit 35 includes an amplification transistor 21 , a reset transistor 22 and an address transistor 23 .
  • the photoelectric conversion unit 10C includes a lower electrode 2 provided as a pixel electrode and an upper electrode 4 provided as a counter electrode facing the pixel electrode. A predetermined bias voltage is applied to the upper electrode 4 through the counter electrode signal line 26 .
  • the lower electrode 2 is an array of multiple pixel electrodes provided for each of the multiple pixels 24 .
  • the lower electrode 2 is connected to the gate electrode 21G of the amplification transistor 21, and the signal charge collected by the lower electrode 2 is accumulated in the charge accumulation node 34 located between the lower electrode 2 and the gate electrode 21G of the amplification transistor 21. be done.
  • the signal charges are holes, but the signal charges may be electrons.
  • the signal charge accumulated in the charge accumulation node 34 is applied to the gate electrode 21G of the amplification transistor 21 as a voltage corresponding to the amount of signal charge.
  • the amplification transistor 21 amplifies this voltage.
  • the amplified voltage is selectively read out by the address transistor 23 as a signal voltage.
  • the reset transistor 22 has its source/drain electrodes connected to the lower electrode 2 and resets the signal charge accumulated in the charge accumulation node 34 . In other words, the reset transistor 22 resets the potentials of the gate electrode 21 ⁇ /b>G and the lower electrode 2 of the amplification transistor 21 .
  • the imaging device 100 has power supply wiring 31, vertical signal line 27, address signal line 36, and reset signal line 37, and these lines are are connected to each pixel 24 respectively.
  • the power supply wiring 31 is connected to the source/drain electrodes of the amplification transistor 21
  • the vertical signal line 27 is connected to the source/drain electrodes of the address transistor 23 .
  • the address signal line 36 is connected to the gate electrode 23G of the address transistor 23.
  • FIG. Also, the reset signal line 37 is connected to the gate electrode 22G of the reset transistor 22 .
  • the peripheral circuits include a vertical scanning circuit 25, a horizontal signal readout circuit 20, a plurality of column signal processing circuits 29, a plurality of load circuits 28, and a plurality of differential amplifiers 32.
  • the vertical scanning circuit 25 is also called a row scanning circuit.
  • the horizontal signal readout circuit 20 is also called a column scanning circuit.
  • the column signal processing circuit 29 is also called a row signal storage circuit.
  • Differential amplifier 32 is also called a feedback amplifier.
  • the vertical scanning circuit 25 is connected to an address signal line 36 and a reset signal line 37, selects a plurality of pixels 24 arranged in each row in units of rows, and reads signal voltages and resets the potential of the lower electrode 2. conduct.
  • a power supply line 31 that is a source follower power supply supplies a predetermined power supply voltage to each pixel 24 .
  • the horizontal signal readout circuit 20 is electrically connected to a plurality of column signal processing circuits 29 .
  • the column signal processing circuit 29 is electrically connected to the pixels 24 arranged in each column via vertical signal lines 27 corresponding to each column.
  • a load circuit 28 is electrically connected to each vertical signal line 27 .
  • the load circuit 28 and the amplification transistor 21 form a source follower circuit.
  • a plurality of differential amplifiers 32 are provided corresponding to each column.
  • a negative input terminal of the differential amplifier 32 is connected to the corresponding vertical signal line 27 .
  • the output terminal of the differential amplifier 32 is connected to the pixels 24 via the feedback line 33 corresponding to each column.
  • the vertical scanning circuit 25 applies a row selection signal for controlling ON/OFF of the address transistor 23 to the gate electrode 23G of the address transistor 23 through the address signal line 36 . This scans and selects the row to be read. A signal voltage is read out to the vertical signal line 27 from the pixels 24 in the selected row. Also, the vertical scanning circuit 25 applies a reset signal for controlling ON/OFF of the reset transistor 22 to the gate electrode 22G of the reset transistor 22 via the reset signal line 37 . This selects a row of pixels 24 to be reset. The vertical signal line 27 transmits the signal voltage read from the pixel 24 selected by the vertical scanning circuit 25 to the column signal processing circuit 29 .
  • the column signal processing circuit 29 performs noise suppression signal processing typified by correlated double sampling and analog-digital conversion (AD conversion).
  • the horizontal signal readout circuit 20 sequentially reads signals from the plurality of column signal processing circuits 29 to a horizontal common signal line (not shown).
  • the differential amplifier 32 is connected to the drain electrode of the reset transistor 22 via the feedback line 33. Therefore, differential amplifier 32 receives the output value of address transistor 23 at its negative terminal when address transistor 23 and reset transistor 22 are in a conducting state.
  • the differential amplifier 32 performs a feedback operation so that the gate potential of the amplification transistor 21 becomes a predetermined feedback voltage. At this time, the output voltage value of the differential amplifier 32 is 0V or a positive voltage near 0V.
  • Feedback voltage means the output voltage of the differential amplifier 32 .
  • the pixel 24 includes a semiconductor substrate 40, a charge detection circuit 35, a photoelectric conversion section 10C, and a charge storage node 34 (see FIG. 4).
  • the semiconductor substrate 40 may be an insulating substrate or the like having a semiconductor layer provided on the surface on which the photosensitive region is formed, such as a p-type silicon substrate.
  • the semiconductor substrate 40 has impurity regions 21D, 21S, 22D, 22S and 23S, and an isolation region 41 for electrical isolation between the pixels 24 .
  • Impurity regions 21D, 21S, 22D, 22S and 23S are, for example, n-type regions.
  • the element isolation region 41 is also provided between the impurity region 21D and the impurity region 22D. This suppresses leakage of signal charges accumulated in the charge accumulation node 34 .
  • the element isolation region 41 is formed, for example, by implanting acceptor ions under predetermined implantation conditions.
  • the impurity regions 21D, 21S, 22D, 22S and 23S are diffusion layers formed in the semiconductor substrate 40, for example.
  • amplification transistor 21 includes impurity regions 21S and 21D and gate electrode 21G.
  • Impurity region 21S and impurity region 21D function as, for example, a source region and a drain region of amplifying transistor 21, respectively.
  • a channel region of amplification transistor 21 is formed between impurity region 21S and impurity region 21D.
  • the address transistor 23 includes impurity regions 23S and 21S and a gate electrode 23G connected to the address signal line 36.
  • amplification transistor 21 and address transistor 23 are electrically connected to each other by sharing impurity region 21S.
  • the impurity region 23S functions as a source region of the address transistor 23, for example.
  • Impurity region 23S has a connection with vertical signal line 27 shown in FIG.
  • the reset transistor 22 includes impurity regions 22D and 22S and a gate electrode 22G connected to the reset signal line 37.
  • the impurity region 22S functions as a source region of the reset transistor 22, for example.
  • Impurity region 22S has a connection with reset signal line 37 shown in FIG.
  • An interlayer insulating layer 50 is laminated on the semiconductor substrate 40 so as to cover the amplification transistor 21 , the address transistor 23 and the reset transistor 22 .
  • a wiring layer (not shown) may be arranged in the interlayer insulating layer 50 .
  • the wiring layer is made of metal such as copper, and may include wiring such as the vertical signal lines 27 described above.
  • the number of insulating layers in the interlayer insulating layer 50 and the number of layers included in the wiring layers arranged in the interlayer insulating layer 50 can be set arbitrarily.
  • a contact plug 54 connected to the impurity region 22D of the reset transistor 22 a contact plug 53 connected to the gate electrode 21G of the amplification transistor 21, a contact plug 51 connected to the lower electrode 2, and A wiring 52 is arranged to connect the contact plug 51, the contact plug 54, and the contact plug 53 together.
  • the impurity region 22D of the reset transistor 22 is electrically connected to the gate electrode 21G of the amplification transistor 21. As shown in FIG.
  • the charge detection circuit 35 detects signal charges captured by the lower electrode 2 and outputs a signal voltage. That is, the charge detection circuit 35 reads the charge generated by the photoelectric conversion unit 10C.
  • the charge detection circuit 35 includes an amplification transistor 21 , a reset transistor 22 and an address transistor 23 and is formed on a semiconductor substrate 40 .
  • the amplification transistor 21 is formed in the semiconductor substrate 40 and includes an impurity region 21D and an impurity region 21S functioning as a drain region and a source region, respectively, a gate insulating layer 21X formed on the semiconductor substrate 40, and a gate insulating layer 21X formed on the gate insulating layer 21X. and a gate electrode 21G formed on the .
  • the reset transistor 22 is formed in the semiconductor substrate 40 and includes an impurity region 22D and an impurity region 22S functioning as a drain region and a source region, respectively, a gate insulating layer 22X formed on the semiconductor substrate 40, and a gate insulating layer 22X on the gate insulating layer 22X. and a gate electrode 22G formed on the .
  • Address transistor 23 is formed in semiconductor substrate 40 and formed on impurity regions 21S and 23S functioning as a drain region and a source region, respectively, gate insulating layer 23X formed on semiconductor substrate 40, and gate insulating layer 23X. and a gate electrode 23G.
  • the impurity region 21S is shared by the amplification transistor 21 and the address transistor 23, whereby the amplification transistor 21 and the address transistor 23 are connected in series.
  • the photoelectric conversion section 10C described above is arranged on the interlayer insulating layer 50 .
  • a plurality of pixels 24 forming a pixel array are formed on the semiconductor substrate 40 .
  • a plurality of pixels 24 arranged two-dimensionally on the semiconductor substrate 40 form a photosensitive region.
  • the distance between two adjacent pixels 24 (that is, pixel pitch) may be, for example, about 2 ⁇ m.
  • the photoelectric conversion unit 10C has the structure of the photoelectric conversion element 10A or the photoelectric conversion element 10B described above.
  • a color filter 60 is formed above the photoelectric conversion unit 10C, and a microlens 61 is formed thereabove.
  • the color filter 60 is formed as an on-chip color filter by patterning, for example.
  • a photosensitive resin or the like in which dyes or pigments are dispersed is used to form the color filter 60 .
  • the microlens 61 is formed, for example, as an on-chip microlens.
  • An ultraviolet photosensitive material or the like is used for forming the microlenses 61 .
  • the imaging device 100 can be manufactured using a general semiconductor manufacturing process.
  • a silicon substrate is used as the semiconductor substrate 40, it can be manufactured by using various silicon semiconductor processes.
  • the photoelectric conversion unit 10C includes the photoelectric conversion element 10A or the photoelectric conversion element 10B capable of suppressing deterioration of element characteristics due to heating, deterioration of characteristics of the manufactured imaging device 100 can be suppressed.
  • reaction solution 449 mg of compound (A-2) synthesized above, 25 ml of dehydrated pyridine, and 60 mg of sodium methoxide were added to an argon-substituted three-necked 200 mL reaction vessel (hereinafter referred to as the first reaction vessel). , the reaction solution was stirred for 30 minutes. 735 mg of C60 fullerene and 75 ml of deoxygenated o-dichlorobenzene were added to another three-necked 200 mL reaction vessel (hereinafter referred to as a second reaction vessel) which was purged with argon, and the reaction solution was stirred.
  • a second reaction vessel three-necked 200 mL reaction vessel
  • reaction solution in the second reaction vessel was added to the first reaction vessel, and argon was bubbled through the reaction solution in the first reaction vessel for 30 minutes. Then, the first reaction vessel was irradiated with a 150 W sodium lamp, the distance between the first reaction vessel and the 150 W sodium lamp was adjusted so that the reaction solution reached 86° C., and the reaction solution was stirred for 12 hours. After cooling the reaction solution to room temperature, the reaction solution was concentrated to obtain a crude product. The crude product was purified by silica gel column chromatography using o-dichlorobenzene as a developing solvent, and the resulting purified product was reprecipitated with methanol. The resulting precipitate was dried under reduced pressure at 40° C. for 24 hours to obtain the desired compound (A-3). The yield of compound (A-3) was 432 mg, and the yield was 39%.
  • the compound (A-3) is methyl phenylbutyrate. It is possible to synthesize fullerene derivatives with different substituents attached to the phenyl group of the ester moiety.
  • reaction solution was allowed to cool to room temperature, 20 mL of distilled water was added to the reaction solution, and the mixture was stirred for 1 hour.
  • the reaction solution was extracted four times with 60 mL of toluene. After washing the extracted organic layer with distilled water, the organic layer was concentrated to obtain 48 mg of crude product.
  • the resulting crude product was purified with a neutral alumina column to obtain the desired compound (A-5) as a brown solid.
  • the yield of compound (A-5) was 25 mg, and the yield was 49%.
  • the obtained compounds were identified by 1 H NMR and MALDI-TOF-MS (Matrix Assisted Laser Desorption/Ionization Time Of Flight Mass Spectrometry). The results are shown below.
  • the compound (A-6) has a chemical formula of C 86 H 80 N 10 O 10 Si and an Exact Mass of 1441.82.
  • the solid component collected by filtration was purified by silica gel column chromatography using dichloromethane as a developing solvent, and the purified product was reprecipitated with heptane.
  • the obtained precipitate was dried under reduced pressure at 100° C. for 3 hours to obtain the desired compound (A-7).
  • the yield of compound (A-7) was 528 mg, and the yield was 68%.
  • the compound (A-7) has a chemical formula of C 88 H 78 N 12 O 10 Si and an Exact Mass of 1491.75.
  • reaction solution was allowed to cool to room temperature, 360 mL of distilled water was added to the reaction solution, and the mixture was stirred for 1 hour. 180 mL of triethylamine was added thereto, and extracted four times with 100 mL of toluene. The extracted organic layer was washed with distilled water, and the washed organic layer was concentrated to obtain 1.54 g of crude product. The resulting crude product was purified with a neutral alumina column to obtain the desired compound (A-9) as a brown solid. The yield of compound (A-9) was 0.53 g, and the yield was 50%.
  • the compound (A-10) has a chemical formula of C 94 H 96 N 10 O 10 Si and an Exact Mass of 1553.71.
  • reaction solution in the second reaction vessel was added to the first reaction vessel, and argon was bubbled through the reaction solution in the first reaction vessel for 30 minutes. Then, the first reaction vessel was irradiated with a 180 W sodium lamp, the distance between the first reaction vessel and the 180 W sodium lamp was adjusted so that the temperature of the reaction solution reached 95° C. to 105° C., and the reaction solution was stirred for 7 hours. After cooling the reaction solution to room temperature, the reaction solution was concentrated to obtain a crude product. The crude product was purified by silica gel column chromatography using o-dichlorobenzene as a developing solvent, and the resulting purified product was reprecipitated with a 1:1 mixed solution of methanol and acetone. The resulting precipitate was suspended and washed twice with acetone, and then dried under reduced pressure at 60° C. for 4 hours to obtain the desired compound (A-13). The yield of compound (A-13) was 473 mg, and the yield was 30%.
  • reaction solution 611 mg of the compound (A-15) synthesized above, 20 ml of dehydrated pyridine, and 80 mg of sodium methoxide were added to an argon-substituted three-necked 200 mL reaction vessel (hereinafter referred to as the first reaction vessel). , the reaction solution was stirred for 30 minutes. 1.0 g of C60 fullerene and 100 ml of deoxygenated o-dichlorobenzene were added to another three-necked 200 mL reaction vessel (hereinafter referred to as a second reaction vessel) which was purged with argon, and the reaction solution was stirred.
  • a second reaction vessel three-necked 200 mL reaction vessel
  • reaction solution in the second reaction vessel was added to the first reaction vessel, and argon was bubbled through the reaction solution in the first reaction vessel for 30 minutes. Then, the first reaction vessel was irradiated with a 180 W sodium lamp, the distance between the first reaction vessel and the 180 W sodium lamp was adjusted so that the reaction solution reached 86° C., and the reaction solution was stirred for 7 hours. After cooling the reaction solution to room temperature, the reaction solution was concentrated to obtain a crude product. After the crude product was dissolved in o-dichlorobenzene and filtered, the filtered solution was purified by silica gel column chromatography using o-dichlorobenzene as a developing solvent, and the obtained purified product was further treated with methanol.
  • reaction solution in the second reaction vessel was added to the first reaction vessel, and argon was bubbled through the reaction solution in the first reaction vessel for 30 minutes. Then, the first reaction vessel was irradiated with a 180 W sodium lamp, the distance between the first reaction vessel and the 150 W sodium lamp was adjusted so that the reaction solution reached 86° C., and the reaction solution was stirred for 7 hours. After cooling the reaction solution to room temperature, the reaction solution was concentrated to obtain a crude product. After the crude product was dissolved in o-dichlorobenzene and filtered, the filtered solution was purified by silica gel column chromatography using o-dichlorobenzene as a developing solvent, and the obtained purified product was further treated with methanol.
  • Example 1 and Comparative Example 1 will be shown, and the photoelectric conversion device according to the present disclosure will be described more specifically.
  • Example 1 ⁇ Production of photoelectric conversion element> A photoelectric conversion device was produced by the following procedure. All of the photoelectric conversion elements were produced in a nitrogen atmosphere.
  • a glass substrate having a thickness of 0.7 mm and having an ITO film having a thickness of 150 nm as a lower electrode on one main surface was prepared.
  • VNPB(N4,N4'-di(Naphthalen-1-yl)-N4,N4'-bis(4-vinylphenyl)biphenyl-4,4 is used as a buffer layer that functions as an electron blocking layer in a nitrogen atmosphere glove box.
  • a 10 mg/ml o-xylene solution of '-diamine, manufactured by LUMTEC Co., Ltd.) was applied onto the lower electrode by a spin coating method to form a film. After the film formation, the VNPB was crosslinked by heating at 200° C.
  • a mixed film to be a photoelectric conversion layer was formed by spin coating using a chloroform mixed solution containing compound (A-6) as the donor organic compound and compound (A-3) as the acceptor organic compound.
  • the thickness of the mixed film obtained at this time was approximately 175 nm.
  • the weight ratio of compound (A-6) and compound (A-3) in the chloroform mixed solution was 1:9.
  • ClAlPc Chloroaluminum Phthalocyanine
  • Example 1 a photoelectric conversion device of Example 1 was obtained.
  • a methoxy group that exhibits a dipolar interaction with the propioxy group of compound (A-6), which is the donor organic compound, is bound to the aromatic site of compound (A-3), which is the acceptor organic compound. ing. In other words, an attractive force due to dipole interaction is likely to occur between the donor organic compound and the acceptor organic compound.
  • the photoelectric conversion efficiency of the obtained photoelectric conversion element was measured. Specifically, a photoelectric conversion element is introduced into a measurement jig that can be sealed in a glove box under a nitrogen atmosphere, and a long-wavelength compatible spectral sensitivity measurement device (CEP-25RR, manufactured by Spectroscopy Instruments) is used under a voltage condition of 10 V. , the external quantum efficiency was measured. The measurement results are shown in FIG. In the legend in FIG. 6 , the numerical value is the temperature at which the photoelectric conversion element was heated, "OMePCBM” indicates the photoelectric conversion element in Example 1, and "PCBM” indicates the photoelectric conversion element in Comparative Example 1. show.
  • Comparative example 1 A photoelectric conversion element was fabricated in the same manner as in Example 1, except that [60]PCBM was used instead of the compound (A-3) as the acceptor organic compound in forming the photoelectric conversion layer.
  • a substituent exhibiting a dipolar interaction with the propioxy group of compound (A-6), which is the donor organic compound, is bonded to the aromatic site of [60]PCBM, which is the acceptor organic compound. do not have. In other words, an attractive force due to dipole interaction is less likely to occur between the donor organic compound and the acceptor organic compound.
  • the photoelectric conversion element in Comparative Example 1 was heated to 200° C. (PCBM-200 in legend), and when heated to 150° C. and 170° C. (PCBM-150 and PCBM-170 in legend). Compared to , the external quantum efficiency is greatly reduced.
  • the photoelectric conversion element in Example 1 was heated to 200° C. (OMePCBM-200 in the legend) and when heated to 150° C. and 170° C. (OMePCBM-150 and OMePCBM-170 in the legend). In comparison, the decrease in external quantum efficiency is suppressed more than the photoelectric conversion element in Comparative Example 1.
  • a photoelectric conversion layer composed of a bulk heterojunction layer containing a donor organic compound and an acceptor organic compound in which a substituent of the donor organic compound that exhibits a dipolar interaction is bonded to an aromatic site. It has been confirmed that the photoelectric conversion element having the layer can suppress the deterioration of the element characteristics when exposed to high temperatures.
  • the photoelectric conversion element according to the present disclosure may be used in a solar cell by extracting the charge generated by light as energy.
  • the photoelectric conversion element and imaging device according to the present disclosure are applicable to image sensors and the like, and are suitable for image sensors that may be exposed to high temperatures, for example.
  • Reference Signs List 1 support substrate 2 lower electrode 3 photoelectric conversion layer 3A donor organic semiconductor 3B acceptor organic semiconductor 4 upper electrode 5, 6 buffer layer 10A, 10B photoelectric conversion element 10C photoelectric conversion section 20 horizontal signal readout circuit 21 amplification transistor 21D, 21S, 22D, 22S, 23S impurity region 21G, 22G, 23G gate electrode 21X, 22X, 23X gate insulating layer 22 reset transistor 23 address transistor 24 pixel 25 vertical scanning circuit 26 counter electrode signal line 27 vertical signal line 28 load circuit 29 column signal processing Circuit 31 power supply wiring 32 differential amplifier 33 feedback line 34 charge storage node 35 charge detection circuit 36 address signal line 37 reset signal line 40 semiconductor substrate 41 element isolation region 50 interlayer insulating layer 51, 53, 54 contact plug 52 wiring 60 color filter 61 microlens 100 imaging device

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