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WO2011148717A1 - Élément organique de conversion photoélectrique, cellule solaire et réseau de capteurs optiques - Google Patents

Élément organique de conversion photoélectrique, cellule solaire et réseau de capteurs optiques Download PDF

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WO2011148717A1
WO2011148717A1 PCT/JP2011/058409 JP2011058409W WO2011148717A1 WO 2011148717 A1 WO2011148717 A1 WO 2011148717A1 JP 2011058409 W JP2011058409 W JP 2011058409W WO 2011148717 A1 WO2011148717 A1 WO 2011148717A1
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photoelectric conversion
organic photoelectric
layer
group
general formula
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Japanese (ja)
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貴宗 服部
大久保　康
晃矢子 和地
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Konica Minolta Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C01B32/00—Carbon; Compounds thereof
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    • C01B32/152—Fullerenes
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    • 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
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
    • 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
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • 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
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    • 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
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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    • H10K85/151—Copolymers
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to an organic photoelectric conversion element, a solar cell, and an optical sensor array, and more particularly to a bulk heterojunction type organic photoelectric conversion element, a solar cell using the organic photoelectric conversion element, and an optical sensor array.
  • an electron donor layer p-type semiconductor layer
  • an electron acceptor layer n-type
  • a bulk heterojunction photoelectric conversion element sandwiching a bulk heterojunction layer mixed with a semiconductor layer
  • these bulk heterojunction solar cells are formed by a coating process except for the anode and cathode, it is expected that they can be manufactured at high speed and at low cost, and may solve the above-mentioned problem of power generation cost. . Furthermore, unlike the above Si-based solar cells, compound semiconductor-based solar cells, dye-sensitized solar cells, etc., there is no process at a temperature higher than 160 ° C., so it is expected that it can be formed on a cheap and lightweight plastic substrate. Is done.
  • the power generation cost In addition to the initial manufacturing cost, the power generation cost must be calculated including the power generation efficiency and the durability of the element.
  • the power generation cost In order to efficiently absorb the solar spectrum, the power generation cost is about 900 nm. By using a low band gap organic polymer capable of absorbing up to 5%, conversion efficiency exceeding 5% has been achieved.
  • the efficiency of the solar cell is represented by the product of open circuit voltage (Voc) ⁇ short circuit current (Jsc) ⁇ curve factor (FF).
  • the short circuit current Jsc is a theoretical Jsc obtained when the solar spectrum is completely absorbed.
  • the external quantum efficiency of Non-Patent Document 1 is about 0.5.
  • the organic photoelectric conversion element using the conjugated polymer that can absorb up to such a long wavelength there is a tendency that a higher photoelectric conversion efficiency is obtained when the mixing ratio of the fullerene derivative that is an n-type semiconductor is larger. Since it is mainly a p-type semiconductor that absorbs light in the wavelength region substantially contained in sunlight, it is difficult to increase the external quantum efficiency, which hinders further improvement in efficiency.
  • organic polymers that are p-type semiconductor materials have relatively long molecular lengths, so they easily come into contact with each other, and the paths through which holes flow are easy to form, but they are amorphous materials with spherical molecular shapes. It is presumed that a fullerene derivative of a certain n-type semiconductor material is difficult to make a continuous path through which electrons flow, and in Non-Patent Document 2 and Non-Patent Document 3, a fullerene derivative having a structure in which fullerene units are easily arranged is proposed. Has been.
  • Patent Document 3 in which a compound polymer in which a thiophene polymer and fullerene are linked via an ethynyl group is used in a solar cell, but the fullerene derivative of the present invention is an invention limited to low molecular weight materials. The idea is different. Further, Patent Document 3 does not mention the effect when a bulk heterojunction layer is formed using a p-type semiconductor material and a fullerene derivative, and this point is also different from the present invention in this respect.
  • fullerene derivatives having a structure in which fullerene units are easily arranged as described in Non-Patent Document 2 and Non-Patent Document 3 are self-contained in a bulk heterojunction layer mixed with an organic polymer that is a p-type semiconductor material. Fullerene derivatives with insufficient alignment ability and higher self-alignment ability are expected.
  • the present invention has been made in view of the above problems, and an object thereof is to provide an organic photoelectric conversion element containing a fullerene derivative capable of providing a high fill factor in order to obtain a high photoelectric conversion efficiency by a low band gap polymer, a solar It is to provide a battery and an optical sensor array.
  • the present inventors have useful a structure in which a substituent is arranged via an ethynyl group on a fullerene unit having a spherical structure. I found out.
  • Such a structure is expected to have a strong self-alignment force by arranging the ethynyl group perpendicular to the spherical fullerene, thereby improving the intermolecular force to align with each other.
  • this substituent is a planar aromatic compound, the intermolecular force in which planar plate-like ⁇ -conjugated structures are aligned with each other by ⁇ - ⁇ interaction is further improved.
  • An organic photoelectric conversion element comprising an organic layer containing a compound represented by the following general formula (1) having a molecular weight of 5000 or less between a counter electrode and a transparent electrode.
  • R 1 and R 2 represent a hydrogen atom or a substituent.
  • FLN represents a fullerene mother nucleus.
  • Ar represents a substituted or unsubstituted aromatic compound.
  • R 2 represents a hydrogen atom or a substituent.
  • FLN represents a fullerene mother nucleus.
  • Ar represents a substituted or unsubstituted aromatic compound.
  • R 3 represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group or cyano group.
  • FLN represents a fullerene mother nucleus.
  • a solar cell comprising the organic photoelectric conversion device as described in any one of 1 to 9 above.
  • An optical sensor array comprising the organic photoelectric conversion elements according to any one of 1 to 9 arranged in an array.
  • an organic photoelectric conversion element a solar cell, and a photosensor array having a high fill factor and photoelectric conversion efficiency could be provided.
  • the fullerene derivative of the present invention is useful as a fullerene derivative excellent in carrier mobility, that is, a fullerene derivative having a high self-alignment property. I found.
  • FIG. 1 is a cross-sectional view showing an example of a solar cell having a single configuration (a configuration having one bulk heterojunction layer) composed of a bulk heterojunction type organic photoelectric conversion element.
  • a bulk heterojunction type organic photoelectric conversion element 10 includes a transparent electrode (anode) 12, a hole transport layer 17, a photoelectric conversion unit 14 in a bulk heterojunction layer, an electron transport layer (or an electron transport layer) (Also referred to as a buffer layer) 18 and a counter electrode (cathode) 13 are sequentially stacked.
  • the substrate 11 is a member that holds the transparent electrode 12, the photoelectric conversion unit 14, and the counter electrode 13 that are sequentially stacked. In the present embodiment, since light that is photoelectrically converted enters from the substrate 11 side, the substrate 11 can transmit the light that is photoelectrically converted, that is, with respect to the wavelength of the light to be photoelectrically converted. It is a transparent member.
  • the substrate 11 for example, a glass substrate or a resin substrate is used.
  • the substrate 11 is not essential.
  • the bulk heterojunction type organic photoelectric conversion element 10 may be configured by forming the transparent electrode 12 and the counter electrode 13 on both surfaces of the photoelectric conversion unit 14.
  • the photoelectric conversion unit 14 is a layer that converts light energy into electric energy, and includes a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed.
  • the p-type semiconductor material functions relatively as an electron donor (donor)
  • the n-type semiconductor material functions relatively as an electron acceptor (acceptor).
  • the electron donor and the electron acceptor are “an electron donor in which, when light is absorbed, electrons move from the electron donor to the electron acceptor to form a hole-electron pair (charge separation state)”.
  • an electron acceptor which does not simply donate or accept electrons like an electrode, but donates or accepts electrons by a photoreaction.
  • FIG. 1 light incident from the transparent electrode 12 through the substrate 11 is absorbed by the electron acceptor or electron donor in the bulk heterojunction layer of the photoelectric conversion unit 14, and electrons move from the electron donor to the electron acceptor.
  • a hole-electron pair charge separation state
  • the generated electric charge is caused by an internal electric field, for example, when the work functions of the transparent electrode 12 and the counter electrode 13 are different, the electrons pass between the electron acceptors and the holes are electron donors by the potential difference between the transparent electrode 12 and the counter electrode 13.
  • the photocurrent is detected by passing through different electrodes. For example, when the work function of the transparent electrode 12 is larger than the work function of the counter electrode 13, electrons are transported to the transparent electrode 12 and holes are transported to the counter electrode 13. If the work function is reversed, electrons and holes are transported in the opposite direction.
  • the transport direction of electrons and holes can be controlled.
  • a hole blocking layer such as a hole blocking layer, an electron blocking layer, an electron injection layer, a hole injection layer, or a smoothing layer may be included.
  • FIG. 2 is a cross-sectional view showing a solar cell composed of an organic photoelectric conversion element including a tandem type bulk heterojunction layer.
  • the transparent electrode 12 and the first photoelectric conversion unit 14 ′ are sequentially stacked on the substrate 11, the charge recombination layer 15 is stacked, the second photoelectric conversion unit 16, and then the counter electrode 13. By stacking layers, a tandem configuration can be obtained.
  • the second photoelectric conversion unit 16 may be a layer that absorbs the same spectrum as the absorption spectrum of the first photoelectric conversion unit 14 ′ or may be a layer that absorbs a different spectrum.
  • the tandem organic photoelectric conversion element When multiple layers generate different amounts of current, the total amount of current is limited to the element with the smallest generated current. Therefore, in order to make the same amount of generated power uniform in each bulk heterojunction layer, preferably different. A layer that absorbs the spectrum is preferable.
  • Examples of different spectral combinations include, for example, a combination in which the first bulk heterojunction layer absorbs sunlight up to 1.9 ev and the second bulk heterojunction layer absorbs sunlight up to 1.3 eV, Or a combination in which the first bulk heterojunction layer absorbs sunlight up to 1.6 ev, the second bulk heterojunction layer absorbs sunlight up to 1.1 eV, and so on.
  • the organic photoelectric conversion device of the present invention is characterized by having an organic layer containing a compound represented by the general formula (1) having a molecular weight of 5000 or less between a counter electrode and a transparent electrode.
  • R 1 and R 2 represent a hydrogen atom or a substituent.
  • FLN represents a fullerene mother nucleus.
  • substituents examples include alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, acyl group, alkoxycarbonyl group, amino group, alkoxy group, cycloalkyloxy group, aryloxy group, aryloxycarbonyl Group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, silyl group, sulfonyl group, sulfinyl group, ureido group, phosphoric acid amide Groups, halogen atoms, hydroxyl groups, mercapto groups, cyano groups, sulfo groups, carboxyl groups, nitro groups, hydroxamic acid groups, sulfino groups
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms.
  • the cycloalkyl group preferably has 4 to 8 carbon atoms, and examples thereof include cyclopentyl and cyclohexyl.
  • the alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, and 3-pentenyl. .
  • the alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include propargyl and 3-pentenyl.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, and naphthyl.
  • the heteroaryl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl, Examples include pyridyl, quinolyl, furyl, piperidyl, benzoxazolyl, benzimidazolyl, benzthiazolyl and the like.
  • the acyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include acetyl, benzoyl, formyl, and pivaloyl.
  • the alkoxycarbonyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonyl and ethoxycarbonyl.
  • the amino group preferably has 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino, dibenzylamino and the like. It is done.
  • the alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy and the like.
  • the cycloalkyloxy group preferably has 4 to 8 carbon atoms, and examples thereof include cyclopentyloxy and cyclohexyloxy.
  • the aryloxy group preferably has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyloxy and 2-naphthyloxy.
  • the aryloxycarbonyl group preferably has 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably 7 to 10 carbon atoms, and examples thereof include phenyloxycarbonyl.
  • the acyloxy group preferably has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include acetoxy and benzoyloxy.
  • the acylamino group preferably has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino.
  • the alkoxycarbonylamino group preferably has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino.
  • the aryloxycarbonylamino group preferably has 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino.
  • the sulfonylamino group preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfonylamino and benzenesulfonylamino.
  • the sulfamoyl group preferably has 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms.
  • sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamo Moyl etc. are mentioned.
  • the carbamoyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. Examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl.
  • the alkylthio group preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include methylthio and ethylthio.
  • the arylthio group preferably has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenylthio.
  • the sulfonyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include mesyl and tosyl.
  • the sulfinyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl.
  • the ureido group preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include ureido, methylureido, and phenylureido.
  • the phosphoric acid amide group preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include diethyl phosphoric acid amide and phenyl phosphoric acid amide. .
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • substituents include a hydroxy group, mercapto group, cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group and the like. These substituents may be further substituted.
  • fullerene mother nucleus represented by FLN examples include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C84, fullerene C240, etc.
  • Fullerene C60 and C70 are preferable from the viewpoint of photoelectric conversion efficiency. From the above viewpoint, fullerene C60 is preferable.
  • the molecular weight of the compound represented by the general formula (1) in the present invention is 5000 or less.
  • the molecular weight exceeds 5000, the solubility in a solvent is lowered, and it is difficult to produce an organic photoelectric conversion device.
  • the molecular weight is preferably 4000 or less, and more preferably 3000 or less.
  • Ar represents a substituted or unsubstituted aromatic compound.
  • R 2 represents a hydrogen atom or a substituent.
  • FLN represents a fullerene mother nucleus.
  • aromatic compounds include aromatic carbocyclic compounds and aromatic heterocyclic compounds.
  • the aromatic carbocyclic compound preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, and naphthyl. .
  • the aromatic heterocyclic compound preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, Examples include imidazolyl, pyridyl, quinolyl, furyl, piperidyl, benzoxazolyl, benzimidazolyl, benzthiazolyl and the like. Furthermore, naphthyl, quinolyl, benzoxazolyl, benzimidazolyl, benzthiazolyl and the like, which are these condensed rings, can be mentioned.
  • aromatic compound a substituted or unsubstituted 6-membered aromatic compound is preferable.
  • the aromatic compound is substituted with an electron donating group such as an alkyl group, an alkoxy group, an amino group, or an alkylthio group. Due to the electron donating property of the substituent, the LUMO of the fullerene derivative of the present invention becomes shallow and Voc is improved.
  • the alkyl group or alkoxy group is preferably C6 or more.
  • Substituents represented by R 2 has the same meaning as the substituents represented by R 2 in the general formula (1).
  • R 2 is preferably a substituent other than a hydrogen atom.
  • R 2 is a substituent other than a hydrogen atom, the solubility of the fullerene derivative is improved.
  • the fullerene mother nucleus represented by FLN has the same meaning as the fullerene mother nucleus represented by FLN in the general formula (1).
  • Ar represents a substituted or unsubstituted aromatic compound.
  • R 3 represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group or cyano group.
  • FLN represents a fullerene mother nucleus.
  • the aromatic compound represented by Ar has the same meaning as the aromatic compound represented by Ar in the general formula (2).
  • the alkyl group, alkenyl group and alkynyl group represented by R 3 have the same meanings as the alkyl group, alkenyl group and alkynyl group exemplified as the substituent represented by R 1 and R 2 in the general formula (1).
  • the substituent of the substituted alkyl group, alkenyl group, and alkynyl group represented by R 3 has the same definition as the substituent represented by R 1 and R 2 in the general formula (1).
  • the fullerene mother nucleus represented by FLN has the same meaning as the fullerene mother nucleus represented by FLN in the general formula (1).
  • Such a fullerene derivative of the present invention is formed as a single layer as a hole blocking layer or an n layer having a pin structure on a bulk heterojunction layer containing a conventional fullerene derivative such as ordinary PCBM.
  • a conventional fullerene derivative such as ordinary PCBM.
  • it is preferably contained in a bulk heterojunction layer in which a conjugated polymer and a fullerene derivative are mixed.
  • a single body may be sufficient and a mixture with a well-known fullerene derivative may be sufficient.
  • the mixture with a compound (for example, C60 and C70) from which carbon number of a fullerene structure differs may be sufficient.
  • the n-type semiconductor material according to the present invention may be used by mixing a known n-type semiconductor material for the purpose of controlling crystallization, controlling the phase separation structure, controlling the morphology, or the like.
  • Known n-type semiconductor materials include, for example, fullerene, octaazaporphyrin and the like, p-type semiconductor perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.), naphthalene tetracarboxylic anhydride, naphthalene tetracarboxylic acid diimide, perylene.
  • aromatic carboxylic acid anhydrides such as tetracarboxylic acid anhydride and perylenetetracarboxylic acid diimide, and polymer compounds containing the imidized product thereof as a skeleton.
  • Examples of the p-type semiconductor material used in the bulk heterojunction layer of the present invention include various condensed polycyclic aromatic low-molecular compounds and conjugated polymers.
  • the tandem organic photoelectric conversion device of the present invention includes two or more types. Since it has a bulk heterojunction layer, it is preferable to use a p-type semiconductor material suitable for each layer.
  • Examples of the p-type semiconductor material used for the bulk heterojunction layer of the present invention include various condensed polycyclic aromatic low molecular compounds and conjugated polymers.
  • condensed polycyclic aromatic low-molecular compound examples include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, circumanthracene, bisanthene, zeslen, Compounds such as heptazeslen, pyranthrene, violanthene, isoviolanthene, cacobiphenyl, anthradithiophene, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTTF ) -Perchloric acid complexes, and derivatives and precursors thereof.
  • TTF tetra
  • Examples of the derivative having the above condensed polycycle include WO 03/16599 pamphlet, WO 03/28125 pamphlet, US Pat. No. 6,690,029, JP 2004-107216 A.
  • conjugated polymer for example, polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, polysilane, polygermane, etc.
  • Polythiophene such as poly-3-hexylthiophene (P3HT) and oligomers thereof, or polythiophene having a polymerizable group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225, Nature Materia 200 vol.
  • PCDTBT polythiophene-carbazole-benzothiadiazole copolymer
  • Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed include a vapor deposition method and a coating method (including a casting method and a spin coating method).
  • the coating method is preferable in order to increase the area of the interface where charges and electrons are separated from each other as described above and to produce a device having high photoelectric conversion efficiency.
  • the coating method is also excellent in production speed.
  • the bulk heterojunction layer can have an appropriate phase separation structure. As a result, the carrier mobility of the bulk heterojunction layer is improved and high efficiency can be obtained.
  • the photoelectric conversion part (bulk heterojunction layer) 14 may be composed of a single layer in which the electron acceptor and the electron donor are uniformly mixed, but a plurality of the mixture ratios of the electron acceptor and the electron donor are changed. It may consist of layers.
  • the organic photoelectric conversion element positive and negative charges generated in the bulk heterojunction layer are taken out from the transparent electrode and the counter electrode via the p-type organic semiconductor material and the n-type organic semiconductor material, respectively, and function as a battery. To do.
  • Each electrode is required to have characteristics suitable for carriers passing through the electrode.
  • the counter electrode is preferably an electrode for taking out electrons.
  • the conductive material may be a single layer, or in addition to a conductive material, a resin that holds these may be used in combination.
  • the counter electrode material is required to have sufficient conductivity, a work function close to the extent that no Schottky barrier is formed when bonded to the n-type semiconductor material, and no deterioration. That is, it is preferably a metal having a work function 0 to 0, 3 eV deeper than the LUMO of the n-type semiconductor material used for the bulk heterojunction layer, and the preferred LUMO of the n-type semiconductor material used for the second bulk heterojunction layer of the present invention. Since the level is ⁇ 4.3 to ⁇ 4.6 eV, the work function is preferably ⁇ 4.3 to ⁇ 4.9 eV.
  • the work function is deeper than that of the transparent electrode (anode) for extracting holes, and a metal having a work function shallower than that of the n-type semiconductor material may cause interlayer resistance.
  • a metal having a work function of ⁇ 4.8 eV is preferable. Therefore, aluminum, gold, silver, copper, indium, or oxide materials such as zinc oxide, ITO, and titanium oxide are also preferable. More preferably, they are aluminum, silver, and copper, More preferably, it is silver.
  • the work function of these metals can be similarly measured using ultraviolet photoelectron spectroscopy (UPS).
  • UPS ultraviolet photoelectron spectroscopy
  • An alloy may be used if necessary.
  • a magnesium / silver mixture, a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al 2 O 3 ) mixture, a lithium / aluminum mixture, and aluminum are preferable. It is.
  • the counter electrode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the counter electrode side is made light transmissive
  • a conductive material suitable for the counter electrode such as aluminum and aluminum alloy
  • silver and silver compound is made thin with a film thickness of about 1 to 20 nm, and then the conductive light
  • a film of a transmissive material By providing a film of a transmissive material, a light transmissive counter electrode can be obtained.
  • the transparent electrode is preferably an electrode for extracting holes.
  • the transparent electrode when used as an anode, it is preferably an electrode that transmits light of 380 to 800 nm.
  • transparent conductive metal oxides such as indium tin oxide (ITO), SnO 2 and ZnO, metal thin films such as gold, silver and platinum, metal nanowires and carbon nanotubes can be used.
  • Conductive polymers can also be used. A plurality of these conductive compounds can be combined to form a transparent electrode.
  • the intermediate electrode material required in the case of the tandem structure is preferably a layer using a compound having both transparency and conductivity, and the materials (ITO, AZO, FTO, etc.) used in the transparent electrode , Transparent metal oxides such as titanium oxide, very thin metal layers such as Ag, Al, Au, or layers containing nanoparticles / nanowires, conductive polymer materials such as PEDOT: PSS, polyaniline, etc.) Can do.
  • Transparent metal oxides such as titanium oxide, very thin metal layers such as Ag, Al, Au, or layers containing nanoparticles / nanowires, conductive polymer materials such as PEDOT: PSS, polyaniline, etc.
  • PEDOT such as trade name BaytronP manufactured by Stark Vitec, polyaniline and its doped material, cyan compounds described in WO2006 / 019270, etc.
  • the hole transport layer having a LUMO level shallower than the LUMO level of the n-type semiconductor material used for the bulk heterojunction layer has a rectifying effect that prevents electrons generated in the bulk heterojunction layer from flowing to the transparent electrode side.
  • the electronic block function is provided.
  • Such a hole transport layer is also called an electron block layer, and it is preferable to use a hole transport layer having such a function.
  • triarylamine compounds described in JP-A-5-271166 metal oxides such as molybdenum oxide, nickel oxide, and tungsten oxide can be used.
  • a layer made of a single p-type semiconductor material used for the bulk heterojunction layer can also be used.
  • the means for forming these layers may be either a vacuum deposition method or a solution coating method, but is preferably a solution coating method. Forming the coating film in the lower layer before forming the bulk heterojunction layer is preferable because it has the effect of leveling the coating surface and reduces the influence of leakage and the like.
  • the organic photoelectric conversion device of the present invention more efficiently extracts charges generated in the bulk heterojunction layer by forming an electron transport layer, a hole blocking layer, and a buffer layer between the bulk heterojunction layer and the counter electrode. Therefore, it is preferable to have these layers.
  • the electron transport layer As the electron transport layer, octaazaporphyrin and p-type semiconductor perfluoro (perfluoropentacene, perfluorophthalocyanine, etc.) can be used. Similarly, HOMO of p-type semiconductor material used for the bulk heterojunction layer.
  • the electron transport layer having a HOMO level deeper than the level is given a hole blocking function having a rectifying effect so that holes generated in the bulk heterojunction layer do not flow to the counter electrode side.
  • Such an electron transport layer is also called a hole blocking layer, and it is preferable to use an electron transport layer having such a function.
  • n-type semiconductor materials such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and titanium oxide.
  • n-type inorganic oxide such as zinc oxide or gallium oxide, a layer made of a single n-type semiconductor material used for the bulk heterojunction layer, or the like can also be used.
  • alkali metal compounds such as lithium fluoride, sodium fluoride, cesium fluoride, and the like can be used.
  • an alkali metal compound that has a function of further doping an organic semiconductor molecule and improving electrical junction with the metal electrode (cathode).
  • an alkali metal compound layer it may be called a buffer layer.
  • the intermediate layer include a hole block layer, an electron block layer, a hole injection layer, an electron injection layer, an exciton block layer, a UV absorption layer, a light reflection layer, and a wavelength conversion layer.
  • the substrate is preferably a member that can transmit the light that is photoelectrically converted, that is, a member that is transparent to the wavelength of the light to be photoelectrically converted.
  • a transparent resin film from the viewpoint of light weight and flexibility.
  • the material, a shape, a structure, thickness, etc. can be suitably selected from well-known things.
  • polyolefins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyester resin film such as modified polyester, polyethylene (PE) resin film, polypropylene (PP) resin film, polystyrene resin film, cyclic olefin resin, etc.
  • Resin films vinyl resin films such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin films, polysulfone (PSF) resin films, polyether sulfone (PES) resin films, polycarbonate (PC) resin films , Polyamide resin film, polyimide resin film, acrylic resin film, triacetyl cellulose (TAC) resin film, and the like.
  • the resin film transmittance of 80% or more at 0 ⁇ 800 nm can be preferably applied to a transparent resin film according to the present invention.
  • a transparent resin film according to the present invention is preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, or a polycarbonate film, and biaxially stretched. More preferred are polyethylene terephthalate films and biaxially stretched polyethylene naphthalate films.
  • the transparent substrate used in the present invention can be subjected to a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesion of the coating solution.
  • a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesion of the coating solution.
  • a conventionally well-known technique can be used about a surface treatment or an easily bonding layer.
  • the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.
  • Examples of the easy adhesion layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, and epoxy copolymer.
  • a barrier coat layer may be formed in advance on the transparent substrate for the purpose of suppressing the permeation of oxygen and water vapor.
  • the organic photoelectric conversion element of the present invention may have various optical functional layers for the purpose of more efficient reception of sunlight.
  • a light condensing layer such as an antireflection film or a microlens array, or a light diffusion layer that can scatter the light reflected by the counter electrode and enter the bulk heterojunction layer again can be provided. Good.
  • the antireflection layer can be provided as the antireflection layer.
  • the refractive index of the easy adhesion layer adjacent to the film is 1.57. It is more preferable to set it to ⁇ 1.63 because the transmittance can be improved by reducing the interface reflection between the film substrate and the easy adhesion layer.
  • the method for adjusting the refractive index can be carried out by appropriately adjusting the ratio of the oxide sol having a relatively high refractive index such as tin oxide sol or cerium oxide sol and the binder resin.
  • the easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.
  • the condensing layer for example, it is processed so as to provide a structure on the microlens array on the sunlight receiving side of the support substrate, or the amount of light received from a specific direction is increased by combining with a so-called condensing sheet. Conversely, the incident angle dependency of sunlight can be reduced.
  • quadrangular pyramids having a side of 30 ⁇ m and an apex angle of 90 degrees are arranged two-dimensionally on the light extraction side of the substrate.
  • One side is preferably 10 to 100 ⁇ m. If it is smaller than this, the effect of diffraction is generated and colored.
  • the light scattering layer examples include various antiglare layers, layers in which nanoparticles or nanowires such as metals or various inorganic oxides are dispersed in a colorless and transparent polymer, and the like.
  • the method and process for patterning the electrode, the power generation layer, the hole transport layer, the electron transport layer, and the like according to the present invention are not particularly limited, and known methods can be appropriately applied.
  • the electrode can be subjected to mask vapor deposition during vacuum deposition or patterned by a known method such as etching or lift-off.
  • the pattern may be formed by transferring a pattern formed on another substrate.
  • the produced organic photoelectric conversion element is not deteriorated by oxygen, moisture, or the like in the environment, it is preferable to seal not only the organic photoelectric conversion element but also an organic electroluminescence element by a known method.
  • a method of sealing a cap made of aluminum or glass by bonding with an adhesive, a plastic film on which a gas barrier layer such as aluminum, silicon oxide, or aluminum oxide is formed and an organic photoelectric conversion element are pasted with an adhesive.
  • optical sensor array Next, an optical sensor array to which the bulk heterojunction type organic photoelectric conversion element described above is applied will be described in detail.
  • the optical sensor array is produced by arranging the photoelectric conversion elements in a fine pixel form by utilizing the fact that the bulk heterojunction type organic photoelectric conversion elements generate a current upon receiving light, and projected onto the optical sensor array.
  • FIG. 3 is a diagram showing a configuration of the optical sensor array.
  • 3A is a top view
  • FIG. 3B is a cross-sectional view taken along the line A-A ′ of FIG. 3A.
  • an optical sensor array 20 is paired with an anode 22 as a lower electrode, a photoelectric conversion unit 24 for converting light energy into electric energy, and an anode 22 on a substrate 21 as a holding member.
  • the cathode 23 is sequentially laminated.
  • the photoelectric conversion unit 24 includes two layers, a photoelectric conversion layer 24b having a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed, and a buffer layer 24a. In the example shown in FIG. 3, six bulk heterojunction organic photoelectric conversion elements are formed.
  • the substrate 21, the anode 22, the photoelectric conversion layer 24b, and the cathode 23 have the same configuration and role as the anode 12, the photoelectric conversion unit 14, and the cathode 13 in the bulk heterojunction photoelectric conversion element 10 described above.
  • the buffer layer 24a is made of PEDOT (poly-3,4-ethylenedioxythiophene) -PSS (polystyrene sulfonic acid) conductive polymer (trade name BaytronP, manufactured by Stark Vitec).
  • PEDOT poly-3,4-ethylenedioxythiophene
  • PSS polystyrene sulfonic acid
  • Such an optical sensor array 20 was manufactured as follows.
  • An ITO film was formed on the glass substrate by sputtering and processed into a predetermined pattern shape by photolithography.
  • the thickness of the glass substrate was 0.7 mm
  • the thickness of the ITO film was 200 nm
  • the measurement area (light receiving area) of the ITO film after photolithography was 0.5 mm ⁇ 0.5 mm.
  • P3HT was mixed with a chlorobenzene solvent at a ratio of 1: 1, and a mixture obtained by stirring (5 minutes) was used.
  • annealing was performed by heating in an oven at 130 ° C. for 30 minutes in a nitrogen gas atmosphere. The thickness of the coating film after the annealing treatment was 70 nm.
  • the optical sensor array 20 was produced as described above.
  • Example 1 of the bulk heterojunction layer a low bandgap polymer described in Macromolecules 2007, 40, 1981, PCPDTBT was synthesized and used with reference to the document described in Non-Patent Document 1. Further, as an n-type material, comparative examples of PCBM (purchased from Frontier Carbon), bis-PCBM (purchased from Sollen) and fullerene polymer (terthiophene-C60 linking compound) described in Example 1 of Patent Document 3, The fullerene derivative of the present invention was used.
  • PCBM purchased from Frontier Carbon
  • bis-PCBM purchasedd from Sollen
  • fullerene polymer terthiophene-C60 linking compound
  • a transparent electrode was formed by patterning an indium tin oxide (ITO) transparent conductive film having a thickness of 140 nm on a glass substrate to a width of 2 mm using a normal photolithography technique and hydrochloric acid etching.
  • ITO indium tin oxide
  • the patterned transparent electrode was cleaned in the order of ultrasonic cleaning with a surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, dried by nitrogen blowing, and finally subjected to ultraviolet ozone cleaning.
  • Baytron P4083 manufactured by Starck Vitec, which is a conductive polymer, was spin-coated with a film thickness of 60 nm, and then dried by heating at 140 ° C. for 10 minutes in the air.
  • the substrate was brought into the glove box and worked in a nitrogen atmosphere.
  • the substrate was heat-treated at 140 ° C. for 10 minutes in a nitrogen atmosphere.
  • PCPDTBT As a p-type semiconductor material, 1.0 mass% of PCPDTBT is added to chlorobenzene, 2.0 mass% of PCBM (manufactured by Frontier Carbon, NANOM SPECTRA E100H) as an n-type semiconductor material, and 2.4 mass of 1,8-octanedithiol. % was dissolved, spin-coated at 1200 rpm for 60 seconds while being filtered with a 0.45 ⁇ m filter, and dried at room temperature for 30 minutes to obtain a photoelectric conversion layer.
  • PCBM manufactured by Frontier Carbon, NANOM SPECTRA E100H
  • the substrate on which the organic layer was formed was placed in a vacuum evaporation apparatus.
  • the element was set so that the shadow mask with a width of 2 mm was orthogonal to the transparent electrode, and the inside of the vacuum deposition apparatus was depressurized to 10 ⁇ 3 Pa or less, and then 0.5 nm of lithium fluoride and 80 nm of Al were evaporated.
  • the heating for 30 minutes was performed at 120 degreeC, and the comparative organic photoelectric conversion element 1 was obtained.
  • the vapor deposition rate was 2 nm / second for all, and the size was 2 mm square.
  • the obtained organic photoelectric conversion element 1 was sealed with an aluminum cap and a UV curable resin (manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570-B1) in a nitrogen atmosphere.
  • a UV curable resin manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570-B1
  • organic photoelectric conversion elements 2 to 17 In the production of the organic photoelectric conversion element 1, the organic photoelectric conversion element 1 is the same as the organic photoelectric conversion element 1 except that PCBM of the n-type semiconductor material is changed to the comparative example described in Table 1 and the exemplary compound according to the present invention. 2 to 17 were produced.
  • the organic photoelectric conversion element 3 could not be produced because the molecular weight of the fullerene polymer (terthiophene-C60 linking compound) was larger than 5000 and the solubility in a solvent was low.
  • the obtained organic photoelectric conversion elements 2, 4 to 17 were sealed using an aluminum cap and a UV curable resin in a nitrogen atmosphere in the same manner as the organic photoelectric conversion element 1 described above.
  • Table 1 shows the evaluation results.
  • Table 1 shows that the organic photoelectric conversion element using the fullerene derivative according to the present invention has higher maximum EQE and photoelectric conversion efficiency than the organic photoelectric conversion element using the n-type semiconductor material of the comparative example.

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Abstract

L'invention concerne un élément organique de conversion photoélectrique contenant un dérivé de fullerène, qui peut assurer un facteur de remplissage élevé afin d'atteindre une efficacité élevée de la conversion photoélectrique avec un polymère à bande interdite basse. L'invention concerne en outre une cellule solaire et un réseau de capteurs optiques. L'élément organique de conversion photoélectrique est caractérisé en ce qu'il comprend une contre-électrode, une électrode transparente et une couche organique qui est formée entre la contre-électrode et l'électrode transparente et qui contient un composé représenté par la formule générale (1) et ayant un poids moléculaire de 5 000 ou moins. (Dans la formule, R1 et R2 représentent indépendamment un atome d'hydrogène ou un substitut ; et « FLN » représente un noyau mère de fullerène.)
PCT/JP2011/058409 2010-05-28 2011-04-01 Élément organique de conversion photoélectrique, cellule solaire et réseau de capteurs optiques Ceased WO2011148717A1 (fr)

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JP2014034542A (ja) * 2012-08-08 2014-02-24 Mitsubishi Corp 酸解離型重合性フラーレン誘導体及びその製造方法
JP2014055256A (ja) * 2012-09-13 2014-03-27 Sumitomo Chemical Co Ltd 組成物および光電変換素子
WO2014167860A1 (fr) * 2013-04-10 2014-10-16 富士フイルム株式会社 Élément d'imagerie à semi-conducteurs et dispositif d'imagerie
JP2014204102A (ja) * 2013-04-10 2014-10-27 富士フイルム株式会社 固体撮像素子および撮像装置
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WO2016190217A1 (fr) * 2015-05-28 2016-12-01 ソニーセミコンダクタソリューションズ株式会社 Élément de conversion photoélectrique, dispositif d'imagerie à semi-conducteurs et dispositif électronique
WO2018110050A1 (fr) * 2016-12-16 2018-06-21 ソニー株式会社 Élément de conversion photoélectrique, élément d'imagerie, élément d'imagerie stratifié, et dispositif d'imagerie à semiconducteur
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JPWO2020188959A1 (ja) * 2019-03-20 2021-10-14 株式会社ジャパンディスプレイ 検出装置
JP7220775B2 (ja) 2019-03-20 2023-02-10 株式会社ジャパンディスプレイ 検出装置
CN113234100A (zh) * 2021-05-06 2021-08-10 吉林奥来德光电材料股份有限公司 一种含硅单体、封装组合物、封装结构及光电器件
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