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WO2013176156A1 - Matière organique donneuse d'électrons, matière pour élément de puissance photovoltaïque utilisant celle-ci et élément de puissance photovoltaïque utilisant celle-ci - Google Patents

Matière organique donneuse d'électrons, matière pour élément de puissance photovoltaïque utilisant celle-ci et élément de puissance photovoltaïque utilisant celle-ci Download PDF

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WO2013176156A1
WO2013176156A1 PCT/JP2013/064149 JP2013064149W WO2013176156A1 WO 2013176156 A1 WO2013176156 A1 WO 2013176156A1 JP 2013064149 W JP2013064149 W JP 2013064149W WO 2013176156 A1 WO2013176156 A1 WO 2013176156A1
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electron
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organic material
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渡辺伸博
北澤大輔
山本修平
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Toray Industries Inc
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    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
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    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
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    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
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    • C08G2261/90—Applications
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    • 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 electron donating organic material, a material for a photovoltaic device using the same, and a photovoltaic device using the material.
  • Solar cells are attracting attention as an effective solution to the increasing energy problem as an environmentally friendly electric energy source.
  • inorganic materials such as single crystal silicon, polycrystalline silicon, amorphous silicon, and compound semiconductors are used as semiconductor materials for photovoltaic elements of solar cells.
  • solar cells manufactured using inorganic semiconductors have not been widely used in general households because of high costs. The high cost factor is mainly in the process of manufacturing a semiconductor thin film under vacuum and high temperature. Therefore, organic solar cells using organic semiconductors and organic dyes such as conjugated polymers and organic crystals are being studied as semiconductor materials expected to simplify the manufacturing process.
  • an organic solar cell using a conjugated polymer or the like has the biggest problem that the photoelectric conversion efficiency is lower than that of a conventional solar cell using an inorganic semiconductor, and has not yet been put into practical use.
  • the photoelectric conversion efficiency of organic solar cells using conventional conjugated polymers is mainly due to the low solar absorption efficiency and the excitons that are difficult to separate the electrons and holes generated by sunlight. This is because a state is formed and a trap for trapping carriers (electrons and holes) is easily formed, so that the generated carriers are easily trapped in the trap and the mobility of carriers is low.
  • Conventional photoelectric conversion elements using organic semiconductors are Schottky type, electron accepting organic materials (n-type organic semiconductors) and electron donating properties, which join an electron donating organic material (p-type organic semiconductor) and a metal having a low work function. It can be classified into a heterojunction type in which an organic material (p-type organic semiconductor) is joined. In these elements, only the organic layer (about several molecular layers) at the junction contributes to the photocurrent generation, so that the photoelectric conversion efficiency is low, and its improvement is a problem.
  • a bulk heterojunction in which an electron-accepting organic material (n-type organic semiconductor) and an electron-donating organic material (p-type organic semiconductor) are mixed to increase the bonding surface contributing to photoelectric conversion There is a type (for example, see Non-Patent Document 1).
  • the conjugated polymer used as the electron donating organic material (p-type organic semiconductor), a fullerene or fullerene derivative, such as other C 60 of the conductive polymer having the semiconductor characteristics of the n-type as the electron accepting organic material The used photoelectric conversion material is reported (for example, refer nonpatent literature 2).
  • Narrow bandgap electron-donating organic material combining the above-described electron-withdrawing group with a thienopyrrole dione skeleton and the electron-donating group with an oligothiophene skeleton, a cyclopentadithiophene skeleton, or a benzodithiophene skeleton
  • Patent Document 1 Non-Patent Document
  • the solubility in an organic solvent necessary for coating the power generation layer is poor, and in order to improve the solubility, an alkyl side chain is introduced on the nitrogen of the thienopyrrole dione skeleton.
  • an excessive alkyl group having no carrier transporting ability would reduce the carrier mobility of the electron donating organic material.
  • Examples of the alkyl group on the nitrogen include a straight chain structure such as a butyl group, a hexyl group, an octyl group, and a dodecyl group (Patent Document 1, Non-Patent Documents 5 to 13), a 2-ethylhexyl group, a 3,7-dimethylhexyl group, A branched chain structure such as 2-butyloctyl group (Patent Document 1, Non-Patent Documents 6, 8 to 10, 14) is used.
  • a relatively short alkyl group such as a butyl group cannot secure sufficient solubility in an organic solvent, and the compatibility with an electron accepting material typified by fullerene also decreases, so that sufficient photoelectric conversion efficiency can be obtained. (Non-patent document 9).
  • the highest occupied molecular orbital (HOMO) level becomes shallow, and the open voltage of the solar cell characteristics decreases.
  • An object of the present invention is to provide a photovoltaic device having high photoelectric conversion efficiency, and to provide an electron-donating organic material satisfying all of solubility in an organic solvent, high carrier mobility, and deep HOMO.
  • the present invention relates to an electron donating organic material containing a thienopyrrole dione structural unit in which an aryl group or a heteroaryl group is introduced on the nitrogen represented by the general formula (1), and a photovoltaic device using the same. is there.
  • R 1 represents an optionally substituted aryl group or an optionally substituted heteroaryl group.
  • a photovoltaic device with high photoelectric conversion efficiency can be provided.
  • the electron donating organic material of the present invention includes a structural unit represented by the general formula (1).
  • R 1 represents an optionally substituted aryl group or an optionally substituted heteroaryl group.
  • the aryl group or heteroaryl group introduced onto the nitrogen of this thienopyrrole dione skeleton makes it possible to partially destroy the planarity of the conjugated polymer, so that both solubility in organic solvents and high carrier mobility can be achieved. It will be possible.
  • the partial planarity of the conjugated polymer is partially broken by the twist between the aryl group or heteroaryl group introduced on the nitrogen of the conjugated polymer main chain skeleton and the thienopyrrole dione skeleton. This means that the planarity of the whole conjugated polymer is slightly lowered while maintaining the pi-conjugated plane of the case.
  • an electron-withdrawing group on the aryl group or heteroaryl group on nitrogen it is considered possible to deepen the HOMO level of the conjugated polymer (this may be called deep HOMO). .
  • the aryl group refers to, for example, an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, an anthryl group, a terphenyl group, a pyrenyl group, a fluorenyl group, and a perylenyl group.
  • an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, an anthryl group, a terphenyl group, a pyrenyl group, a fluorenyl group, and a perylenyl group.
  • a phenyl group having a small molecular size is particularly preferably used.
  • the heteroaryl group includes, for example, thienyl group, furyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, oxazolyl group, pyridyl group, pyrazyl group, pyrimidyl group, quinolinyl group, isoquinolyl group, quinoxalyl group, acridinyl group, indolyl group.
  • a heteroaromatic cyclic group having an atom other than carbon such as a group, a carbazolyl group, a benzofuran group, a dibenzofuran group, a benzothiophene group, a dibenzothiophene group, a benzodithiophene group, a silole group, a benzosilole group, and a dibenzosilole group;
  • the number of carbon atoms in the heteroaryl group is preferably 2 or more and 8 or less in order to maintain carrier mobility.
  • the carbon number of the heteroaryl group represents the number of carbon atoms contained in the aromatic ring, and even if a non-aromatic carbon is included as a substituent, it is not included in the carbon number of the heteroaryl group.
  • Examples of the substituent of the aryl group or heteroaryl group when the aryl group or heteroaryl group has a substituent include an alkyl group (R 1S1 ), an alkoxy group (R 1S2 ), and a halogen (R 1S3 ).
  • R 1S1 alkyl group
  • R 1S2 alkoxy group
  • R 1S3 halogen
  • halogen is not a group, but in the present invention, it is treated as one type of group (hereinafter, the same applies to substituents on other structural formulas).
  • the position of the substituent is preferably in the ortho position or the meta position, and since an appropriate twist can be generated in the phenyl group and the main chain structure, an excessive alkyl side chain is introduced.
  • the solubility of the conjugated polymer can be improved.
  • the alkyl group (R 1S1 ) is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, or a dodecyl group.
  • the saturated aliphatic hydrocarbon group may be linear, branched, or cyclic, and may be unsubstituted or substituted. Examples of the substituent when substituted include an alkoxy group and halogen.
  • the number of carbon atoms of the alkyl group (R 1S1 ) is preferably 6 or less in order to maintain sufficient carrier mobility of the electron donating organic material.
  • carbon contained in the substituent in the alkyl group is not included in the number of carbon atoms of the alkyl group (R 1S1 ).
  • fluorine is particularly preferably used to deepen the HOMO level of the conjugated polymer.
  • the alkoxy group (R 1S2 ) is a group in which an aliphatic hydrocarbon group is bonded via an ether bond such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group, and the alkoxy group (R 1S2 )
  • the aliphatic hydrocarbon group may be unsubstituted or may have a substituent.
  • the substituent in the case of having a substituent include the above aryl group, the above heteroaryl group, and halogen.
  • the preferable carbon number range of the alkoxy group (R 1S2 ) is preferably 6 or less as in the case of the alkyl group (R 1S1 ). In this case as well, the carbon number contained in the substituent of the aliphatic hydrocarbon group is not included in the number of carbon atoms of the alkoxy group (R 1S2 ).
  • the halogen (R 1S3 ) that can be applied to the present invention is any one of fluorine, chlorine, bromine, and iodine.
  • fluorine is particularly preferably used because it can deepen the HOMO level of the electron-donating organic material by being introduced as a substituent of the aryl group or heteroaryl group.
  • the electron donating organic material including the structure represented by the general formula (1) is preferably composed of the structure represented by the general formula (2).
  • X represents a divalent linking group capable of maintaining a conjugated structure.
  • N represents the degree of polymerization and represents a range of 2 to 1,000.
  • n is preferably less than 100.
  • the degree of polymerization can be determined by dividing the weight average molecular weight by the molecular weight (calculated value) of the repeating unit. The weight average molecular weight can be determined by measuring using GPC (gel permeation chromatography) and converting to a polystyrene standard sample.
  • X is a divalent linking group capable of maintaining a conjugated structure.
  • the divalent linking group capable of maintaining a conjugated structure is a linking group that itself has a conjugated structure, and the conjugated structures on both sides of two bonding sites can be continued through the linking group.
  • Preferred examples of the linking group X include thiophene derivatives such as oligothiophene, benzodithiophene, and cyclopentadithiophene.
  • the band gap can be narrowed and high carrier mobility can be maintained.
  • the benzodithiophene or cyclopentadithiophene represented by 3) is more preferably used.
  • R 2 to R 5 may be the same or different and each represents an optionally substituted alkyl group, alkoxy group, aryl group, or heteroaryl group.
  • the alkyl group, alkoxy group, aryl group, and heteroaryl group are as described above except for the preferred carbon number range.
  • R 2 to R 5 are particularly preferably an alkyl group or alkoxy group having 12 or less carbon atoms.
  • n is preferably in the range of 2 or more and 1,000 or less for the same reason as in the case of the general formula (2).
  • the electron-donating organic material containing the structural unit represented by the general formula (1) is, for example, the polymerization method described in Non-Patent Document 5 or the polymerization method described in Non-Patent Document 8. Obtainable.
  • the electron donating organic material containing the structural unit represented by the general formula (1) of the present invention is a material exhibiting p-type semiconductor characteristics, and is used as a photovoltaic element material in an organic semiconductor layer in a photovoltaic element.
  • the electron donating organic material containing the structural unit represented by the general formula (1) of the present invention may be used as a material for a photovoltaic device comprising (i-1) alone, or (i-2) It may be used as a photovoltaic device material in combination with other electron-donating organic materials, or (ii) used as a photovoltaic device material in combination with an electron-accepting organic material exhibiting n-type semiconductor characteristics. Also good.
  • an electron-accepting organic material (the embodiment (ii)) because higher photoelectric conversion efficiency can be obtained.
  • other electron donating organic materials in the embodiment (i-2) may be used in combination.
  • the specific aspect of the organic-semiconductor layer and photovoltaic element using these materials for photovoltaic elements is mentioned later.
  • the electron donating organic material containing the structural unit represented by the general formula (1) is used as a material for a photovoltaic device in combination with another electron donating organic material (the embodiment (i-2))
  • examples of other electron-donating organic materials that can be used in combination include polythiophene polymers, benzothiadiazole-thiophene derivatives, benzothiadiazole-thiophene copolymers, poly-p-phenylene vinylene polymers, poly- Conjugated polymers such as p-phenylene polymer, polyfluorene polymer, polypyrrole polymer, polyaniline polymer, polyacetylene polymer, polythienylene vinylene polymer, H 2 phthalocyanine (H 2 Pc ), Phthalocyanine derivatives such as copper phthalocyanine (CuPc) and zinc phthalocyanine (ZnPc), porphyrin Derivatives, N, N′-diphenyl-N, N′-di (3-methylphenyl
  • the electron-donating organic material containing the structural unit represented by the general formula (1) is used as a material for a photovoltaic device in combination with an electron-accepting organic material exhibiting n-type semiconductor characteristics (the mode (ii) above) ),
  • NTCDA 1,4,5,8-naphthalenetetracarboxylic dianhydride
  • NTCDA 3,4,9,10-perylenetetracarboxylic dianhydride
  • PTCBI 3,4,9,10-perylenetetracarboxylic bisbenzimidazole
  • PTCBI 3,4,9,10-perylenetetracarboxylic bisbenzimidazole
  • PTCBI 3,4,9,10-perylenetetracarboxylic bisbenzimidazole
  • PTCBI 3,4,9,10-perylenetetracarboxylic bisbenzimidazole
  • PTCBI 3,4,9,10-perylenetetracarboxylic bisbenzimidazole
  • PTCBI 3,4,9,
  • fullerene compounds are preferably used because of their high charge separation speed and electron transfer speed.
  • C 70 derivatives such as the above PC 70 BM are more preferable because they are excellent in light absorption characteristics and can obtain higher photoelectric conversion efficiency.
  • the content ratio (weight fraction) of the electron-donating organic material and the electron-accepting organic material is not particularly limited, but the weight fraction of the electron-donating organic material: electron-accepting organic material is 1:99 to 99. Is preferably in the range of 1:90, more preferably in the range of 10:90 to 90:10, and still more preferably in the range of 20:80 to 60:40.
  • the electron-donating organic material containing the structural unit represented by the general formula (1) is used as a material for a photovoltaic device in combination with an electron-accepting organic material exhibiting n-type semiconductor characteristics (the mode (ii) above)
  • the preferred form of the organic semiconductor layer in the organic semiconductor layer will be described later.
  • the mixing method in the case of adopting the form used by mixing, but after adding it to the solvent at a desired ratio, one or more methods such as heating, stirring and ultrasonic irradiation are combined. And a method of dissolving in a solvent.
  • Electron-donating organic material in the case of a mixed form The weight fraction of the electron-accepting organic material is as described above, and in the case of a form in which the electron-donating organic material and the electron-accepting organic material are stacked. (Including the case of a laminated structure of two or more layers) means the content ratio of the electron donating organic material and the electron accepting organic material in the entire laminated layer.
  • the electron-donating organic material and / or the electron-accepting organic material preferably has a small amount of impurities that can trap carriers, and the electron-donating organic material It is preferable to remove as much as possible in the production process of the electron-accepting organic material.
  • the electron-donating organic material containing the structural unit represented by the general formula (1) and the purification method for removing impurities from the electron-accepting organic material are not particularly limited.
  • a crystal method, a sublimation method, a reprecipitation method, a Soxhlet extraction method, a molecular weight fractionation method by GPC, a filtration method, an ion exchange method, a chelate method and the like can be used.
  • a column chromatography method, a recrystallization method, and a sublimation method are preferably used for purification of a low molecular weight organic material.
  • reprecipitation method, Soxhlet extraction method, molecular weight fractionation method by GPC is preferably used when removing low molecular weight components, and reprecipitation method or the like when removing metal components.
  • a chelate method or an ion exchange method is preferably used. A plurality of these methods may be combined.
  • FIG. 1 is a schematic view showing an example of the photovoltaic element of the present invention.
  • reference numeral 1 is a substrate
  • reference numeral 2 is a positive electrode
  • reference numeral 3 is an organic semiconductor layer containing the photovoltaic element material of the present invention
  • reference numeral 4 is a negative electrode.
  • the organic semiconductor layer 3 contains the photovoltaic element material of the present invention. That is, the electron-donating organic material containing the structural unit represented by the general formula (1) is included.
  • the electron donating organic material containing the structural unit represented by the general formula (1) is used in combination with an electron accepting organic material exhibiting n-type semiconductor characteristics (the embodiment (ii)), these There are modes in which organic materials are mixed and used, but it is preferable to adopt a mode in which they are used in combination. That is, a bulk heterojunction photovoltaic device that can increase the bonding surface between an electron-donating organic material and an electron-accepting organic material that contribute to photoelectric conversion efficiency by mixing an electron-donating organic material and an electron-accepting organic material Is preferable.
  • the electron-donating organic material containing the structural unit represented by the general formula (1) and the electron-accepting organic material are phase-separated in a nanometer size.
  • the domain size of this phase separation structure is not particularly limited, but is usually 1 nm or more and 50 nm or less.
  • the electron-donating organic material containing the structural unit represented by the general formula (1) is used in combination with an electron-accepting organic material exhibiting n-type semiconductor characteristics (the embodiment (ii))
  • the layer containing the electron-donating organic material exhibiting p-type semiconductor characteristics is on the positive electrode side, and the electron-accepting property exhibiting n-type semiconductor characteristics
  • the layer containing an organic material is preferably on the negative electrode side. An example of the photovoltaic element in such a case is shown in FIG.
  • Reference numeral 5 denotes a layer containing an electron donating organic material containing the structural unit represented by the general formula (1)
  • reference numeral 6 denotes a layer containing an electron accepting organic material.
  • the organic semiconductor layer preferably has a thickness of 5 nm to 500 nm, more preferably 30 nm to 300 nm.
  • the layer containing the electron-donating organic material of the present invention preferably has a thickness of 1 nm to 400 nm, more preferably 15 nm to 150 nm.
  • the positive electrode 2 or the negative electrode 4 has light transmittance.
  • the light transmittance of the electrode is not particularly limited as long as incident light reaches the organic semiconductor layer 3 and an electromotive force is generated.
  • the electrode represents a positive electrode or a negative electrode.
  • the light transmittance in the present invention is a value obtained by [transmitted light intensity (W / m 2 ) / incident light intensity (W / m 2 )] ⁇ 100 (%).
  • the thickness of the electrode may be in a range having light transmittance and conductivity, and is preferably 20 nm to 300 nm although it varies depending on the electrode material.
  • the other electrode is not necessarily light-transmitting as long as it has conductivity, and the thickness is not particularly limited.
  • the electrode material it is preferable to use a conductive material having a high work function for one electrode and a conductive material having a low work function for the other electrode.
  • An electrode using a conductive material having a large work function is a positive electrode.
  • Conductive materials with a large work function include metals such as gold, platinum, chromium and nickel, transparent metal oxides such as indium, tin and molybdenum, and composite metal oxides (indium tin oxide (ITO)). Indium zinc oxide (IZO) and the like are preferably used.
  • the conductive material used for the positive electrode 2 is preferably one that is in ohmic contact with the organic semiconductor layer 3. Furthermore, when a hole transport layer described later is used, it is preferable that the conductive material used for the positive electrode 2 is in ohmic contact with the hole transport layer.
  • An electrode using a conductive material with a low work function is a negative electrode, but as the conductive material with a low work function, alkali metal or alkaline earth metal, specifically lithium, magnesium, calcium, etc. are used. . Tin, silver, and aluminum are also preferably used. Furthermore, an electrode made of an alloy made of the above metal or a laminate of the above metal is also preferably used. Further, it is possible to improve the extraction current by introducing a metal fluoride such as lithium fluoride or cesium fluoride into the interface between the negative electrode 4 and the electron transport layer.
  • the conductive material used for the negative electrode 4 is preferably one that is in ohmic contact with the organic semiconductor layer 3.
  • the substrate 1 is a substrate on which an electrode material and an organic semiconductor layer can be laminated according to the type and application of the photoelectric conversion material, for example, inorganic materials such as alkali-free glass and quartz glass, polyester, polycarbonate, polyolefin, polyamide, polyimide, polyphenylene A film or plate produced by an arbitrary method from an organic material such as sulfide, polyparaxylene, epoxy resin or fluorine resin can be used. In the case where light is incident from the substrate side, it is preferable that each substrate described above has a light transmittance of about 80%.
  • a hole transport layer may be provided between the positive electrode 2 and the organic semiconductor layer 3.
  • the material for forming the hole transport layer include conductive polymers such as polythiophene polymers, poly-p-phenylene vinylene polymers, polyfluorene polymers, phthalocyanine derivatives (H 2 Pc, CuPc, ZnPc, etc.) ), Low molecular organic compounds exhibiting p-type semiconductor properties such as porphyrin derivatives are preferably used.
  • PEDOT polyethylenedioxythiophene
  • PEDOT polyethylenedioxythiophene
  • PEDOT polyethylenedioxythiophene
  • PEDOT polystyrene sulfonate
  • the thickness of the hole transport layer is preferably 5 nm to 600 nm, more preferably 30 nm to 200 nm.
  • an electron transport layer may be provided between the organic semiconductor layer 3 and the negative electrode 4.
  • the material for forming the electron transport layer is not particularly limited, but the above-described electron-accepting organic materials (NTCDA, PTCDA, PTCDI-C8H, oxazole derivatives, triazole derivatives, phenanthroline derivatives, phosphine oxide derivatives, fullerene compounds, Organic materials exhibiting n-type semiconductor properties such as CNT and CN-PPV are preferably used.
  • the thickness of the electron transport layer is preferably 5 nm to 600 nm, more preferably 30 nm to 200 nm.
  • the photovoltaic element of the present invention may form a series junction by laminating two or more organic semiconductor layers via one or more intermediate electrodes.
  • a laminated structure of substrate / positive electrode / first organic semiconductor layer / intermediate electrode / second organic semiconductor layer / negative electrode can be given.
  • Such a configuration is sometimes called a tandem configuration.
  • the open circuit voltage can be improved.
  • the hole transport layer described above may be provided between the positive electrode and the first organic semiconductor layer and between the intermediate electrode and the second organic semiconductor layer, and between the first organic semiconductor layer and the intermediate electrode.
  • the above-described electron transport layer may be provided between the second organic semiconductor layer and the negative electrode.
  • At least one of the organic semiconductor layers contains the photovoltaic device material of the present invention, and the other layers are represented by the general formula (1) in order not to reduce the short-circuit current. It is preferable to include an electron-donating organic material having a different band gap from the electron-donating organic material containing a structural unit. Examples of the electron-donating organic material used in such a case include the above-described polythiophene polymer, benzothiadiazole-thiophene derivative, benzothiadiazole-thiophene copolymer, poly-p-phenylene vinylene polymer, poly-p.
  • -Conjugated polymers such as phenylene polymers, polyfluorene polymers, polypyrrole polymers, polyaniline polymers, polyacetylene polymers, polythienylene vinylene polymers, phthalocyanine derivatives, porphyrin derivatives, triaryls
  • Low molecular organic compounds such as amine derivatives, carbazole derivatives, oligothiophene derivatives and the like can be mentioned.
  • the material for the intermediate electrode used here is preferably a material having high conductivity, for example, the above-mentioned metals such as gold, platinum, chromium, nickel, lithium, magnesium, calcium, tin, silver, aluminum, and transparent Metal oxides such as indium, tin, and molybdenum, composite metal oxides (indium tin oxide (ITO), indium zinc oxide (IZO), etc.), alloys composed of the above metals, and laminates of the above metals , Polyethylenedioxythiophene (PEDOT), and those obtained by adding polystyrene sulfonate (PSS) to PEDOT.
  • the intermediate electrode preferably has a light transmission property, but even a material such as a metal having a low light transmission property can often ensure a sufficient light transmission property by reducing the film thickness.
  • a transparent electrode such as ITO (corresponding to a positive electrode in this case) is formed on the substrate by sputtering or the like.
  • a solution is prepared by dissolving an electron-donating organic material containing the structural unit represented by the general formula (1) and, if necessary, a material for a photoelectric conversion element containing an electron-accepting organic material in a solvent. To form an organic semiconductor layer.
  • the solvent used at this time is preferably an organic solvent, for example, methanol, ethanol, butanol, toluene, xylene, o-chlorophenol, acetone, ethyl acetate, ethylene glycol, tetrahydrofuran, dichloromethane, chloroform, dichloroethane, chlorobenzene, dichlorobenzene, Examples include chlorobenzene, chloronaphthalene, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and ⁇ -butyrolactone. Two or more of these may be used.
  • organic solvent for example, methanol, ethanol, butanol, toluene, xylene, o-chlorophenol, acetone, ethyl acetate, ethylene glycol, tetrahydrofuran, dichloromethane, chloroform, dichloroethane, chlorobenzene, dichlorobenzene
  • the organic semiconductor layer is formed by mixing the electron-donating organic material containing the structural unit represented by the general formula (1) and the electron-accepting organic material, the structural unit represented by the general formula (1) is included.
  • An electron-donating organic material and an electron-accepting organic material are added to a solvent in a desired ratio, dissolved by using a method such as heating, stirring, and ultrasonic irradiation to form a solution, which is applied onto a transparent electrode.
  • a method such as heating, stirring, and ultrasonic irradiation to form a solution, which is applied onto a transparent electrode.
  • the photoelectric conversion efficiency of the photovoltaic element can be improved by using a mixture of two or more solvents.
  • a structure in which an electron-donating organic material and an electron-accepting material are phase-separated at a nanometer size is preferable for improving the conversion efficiency, and such a phase-separated structure can be formed by a solvent.
  • an optimal combination type can be selected depending on the types of the electron donating organic material and the electron accepting organic material to be used.
  • chloroform and chlorobenzene are mentioned as preferred solvents to be combined among the above.
  • an organic semiconductor layer is formed by stacking an electron donating organic material and an electron accepting organic material containing the structural unit represented by the general formula (1), for example, a solution of an electron donating organic material is applied. After forming a layer having an electron-donating organic material, a solution of the electron-accepting organic material is applied to form a layer.
  • the electron-donating organic material and the electron-accepting organic material are low molecular weight substances having a molecular weight of about 1000 or less, it is possible to form a layer using a vapor deposition method.
  • the formation method may be selected according to the characteristics of the organic semiconductor layer to be obtained, such as film thickness control and orientation control.
  • the electron donating organic material containing the structural unit represented by the general formula (1) and the electron accepting organic material have a concentration of 1 to 20 g / l (in the general formula (1)).
  • the electron donating organic material and the electron accepting organic material having the structure represented by the general formula (1) with respect to the volume of the solution containing the electron donating organic material, the electron accepting organic material and the solvent having the structure represented by Weight) is preferable, and by setting this concentration, a homogeneous organic semiconductor layer having a thickness of 5 to 200 nm can be easily obtained.
  • the formed organic semiconductor layer may be annealed under reduced pressure or under an inert atmosphere (in a nitrogen or argon atmosphere).
  • a preferable temperature for the annealing treatment is 40 ° C to 300 ° C, more preferably 50 ° C to 200 ° C. Further, by performing the annealing process that applies heat, the effective area where the stacked layers permeate and contact each other at the interface increases, and the short-circuit current can be increased. This annealing treatment may be performed after the formation of the negative electrode.
  • a metal electrode such as Al (corresponding to a negative electrode in this case) is formed on the organic semiconductor layer by vacuum deposition or sputtering.
  • the metal electrode is vacuum-deposited using a low molecular organic material for the electron transport layer, it is preferable that the metal electrode is continuously formed while maintaining the vacuum.
  • a desired p-type organic semiconductor material such as PEDOT
  • PEDOT p-type organic semiconductor material
  • the solvent is removed using a vacuum thermostat or a hot plate to form a hole transport layer.
  • a vacuum vapor deposition method using a vacuum vapor deposition machine.
  • a desired n-type organic semiconductor material such as fullerene derivatives
  • an n-type inorganic semiconductor material such as titanium oxide gel
  • the solvent is removed using a vacuum thermostat or a hot plate to form an electron transport layer.
  • a vacuum deposition method using a vacuum deposition machine.
  • the photovoltaic element of the present invention can be applied to various photoelectric conversion devices using a photoelectric conversion function, an optical rectification function, and the like.
  • photovoltaic cells such as solar cells
  • electronic devices such as optical sensors, optical switches, phototransistors
  • optical recording materials such as optical memories
  • ITO indium tin oxide
  • PEDOT polyethylene dioxythiophene
  • PSS polystyrene sulfonate
  • PC 70 BM phenyl C71 butyric acid methyl ester
  • Eg band gap HOMO: highest occupied molecular orbital
  • Isc short circuit current density
  • Voc open circuit voltage
  • FF fill Factor ⁇ : Photoelectric conversion efficiency
  • an FT-NMR apparatus JEOL JNM-EX270 manufactured by JEOL Ltd.
  • the average molecular weight (number average molecular weight, weight average molecular weight) was calculated by an absolute calibration curve method using a polystyrene standard sample using a GPC apparatus (manufactured by TOSOH Co., Ltd., which was fed with chloroform, high-speed GPC apparatus HLC-8320GPC). .
  • the band gap (Eg) was calculated from the light absorption edge wavelength by the following equation. The light absorption edge wavelength was measured using a U-3010 type spectrophotometer manufactured by Hitachi, Ltd.
  • Synthesis example 1 Compound A-1 was synthesized by the method shown in Formula 1.
  • the compound of formula 1 (1-g) was synthesized with reference to the method described in Advanced Functional Materials, 2011, Vol. 21, pp. 718-728.
  • the obtained solid was dissolved in chloroform, passed through Celite (manufactured by Nacalai Tesque), and then a silica gel column (free solution, chloroform), and then the solvent was distilled off under reduced pressure.
  • the obtained solid was dissolved again in chloroform and then reprecipitated in methanol to obtain Compound A-1 (84 mg).
  • the weight average molecular weight was 29,800, the number average molecular weight was 14,200, and the degree of polymerization n was 43.
  • the light absorption edge wavelength was 680 nm, the band gap (Eg) was 1.82 eV, and the highest occupied molecular orbital (HOMO) level was ⁇ 5.34 eV.
  • Synthesis example 2 Compound A-2 was synthesized by the method shown in Formula 2.
  • the obtained solid was dissolved in chloroform, passed through Celite (manufactured by Nacalai Tesque), and then a silica gel column (free solution, chloroform), and then the solvent was distilled off under reduced pressure.
  • the obtained solid was dissolved again in chloroform and then reprecipitated in methanol to obtain Compound A-2 (79 mg).
  • the weight average molecular weight was 42,800, the number average molecular weight was 21,200, and the degree of polymerization n was 61.
  • the light absorption edge wavelength was 680 nm, the band gap (Eg) was 1.82 eV, and the highest occupied molecular orbital (HOMO) level was ⁇ 5.41 eV.
  • the obtained solid was dissolved in chloroform, passed through Celite (manufactured by Nacalai Tesque), and then a silica gel column (free solution, chloroform), and then the solvent was distilled off under reduced pressure.
  • the obtained solid was dissolved again in chloroform and then reprecipitated in methanol to obtain Compound A-3 (80 mg).
  • the weight average molecular weight was 34,100, the number average molecular weight was 12,200, and the degree of polymerization n was 46.
  • the light absorption edge wavelength was 672 nm, the band gap (Eg) was 1.85 eV, and the highest occupied molecular orbital (HOMO) level was ⁇ 5.46 eV.
  • Synthesis example 4 Compound A-4 was synthesized by the method shown in Formula 4. The compound (4-d) described in Formula 4 was synthesized with reference to the method described in Macromolecules 2007, 40, 1981-1986.
  • the obtained solid was dissolved in chloroform, passed through Celite (manufactured by Nacalai Tesque), then a silica gel column (free solution: chloroform), and then the solvent was distilled off under reduced pressure.
  • the obtained solid was dissolved again in chloroform and then reprecipitated in methanol to obtain Compound A-4 (68 mg).
  • the weight average molecular weight was 32,000, the number average molecular weight was 12,200, and the degree of polymerization n was 50.
  • the light absorption edge wavelength was 739 nm, the band gap (Eg) was 1.68 eV, and the highest occupied molecular orbital (HOMO) level was ⁇ 5.49 eV.
  • Synthesis example 5 Compound B-1 was synthesized by the method shown in Formula 5.
  • the compound (5-a) described in Formula 5 was synthesized with reference to the method described in Advanced Functional Materials, 2011, Vol. 21, pp. 71-728.
  • the obtained solid was dissolved in chloroform, passed through Celite (manufactured by Nacalai Tesque), and then a silica gel column (free solution, chloroform), and then the solvent was distilled off under reduced pressure.
  • the obtained solid was dissolved again in chloroform and then reprecipitated in methanol to obtain Compound B-1 (79 mg).
  • the weight average molecular weight was 65,000, the number average molecular weight was 26,100, and the degree of polymerization n was 91.
  • the light absorption edge wavelength was 670 nm, the band gap (Eg) was 1.85 eV, and the highest occupied molecular orbital (HOMO) level was -5.23 eV.
  • a toluene / dimethylformamide solution (50 ml / 10 ml) of 1.18 g (2.0 mmol) of the above compound (6-a) and 2.2 g (6.0 mmol) of tributyl (2-thienyl) tin (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 100 mg of dichlorobis (triphenylphosphine) palladium catalyst (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and refluxed for 8 hours under nitrogen. The reaction solution was cooled to room temperature, 50 ml of water was added, and the organic layer was washed twice with water and then with saturated brine.
  • the obtained solid was dissolved in chloroform, passed through Celite (manufactured by Nacalai Tesque), and then a silica gel column (free solution, chloroform), and then the solvent was distilled off under reduced pressure.
  • the obtained solid was dissolved again in chloroform and then reprecipitated in methanol to obtain Compound B-2 (72 mg).
  • the weight average molecular weight was 45,300, the number average molecular weight was 22,000, and the degree of polymerization n was 44.
  • the light absorption edge wavelength was 658 nm, the band gap (Eg) was 1.88 eV, and the highest occupied molecular orbital (HOMO) level was ⁇ 5.35 eV.
  • the obtained solid was dissolved in chloroform, passed through Celite (manufactured by Nacalai Tesque), and then a silica gel column (free solution, chloroform), and then the solvent was distilled off under reduced pressure.
  • the obtained solid was dissolved again in chloroform and then reprecipitated in methanol to obtain Compound B-3 (50 mg).
  • the weight average molecular weight was 19,400, the number average molecular weight was 11,000, and the degree of polymerization n was 29.
  • the light absorption edge wavelength was 752 nm, the band gap (Eg) was 1.65 eV, and the highest occupied molecular orbital (HOMO) level was ⁇ 5.28 eV.
  • Example 1 The above A-1 (1 mg) and PC 70 BM (4 mg, manufactured by Solenne) were added to a sample bottle containing 0.25 ml of chlorobenzene, and an ultrasonic cleaner (US-2 manufactured by Inoue Seieido Co., Ltd.) Name), and output 120W) for 30 minutes to obtain a solution A.
  • an ultrasonic cleaner US-2 manufactured by Inoue Seieido Co., Ltd.
  • a glass substrate on which a 120-nm thick ITO transparent conductive layer serving as a positive electrode was deposited by sputtering was cut into 38 mm ⁇ 46 mm, and then ITO was patterned into a 38 mm ⁇ 13 mm rectangular shape by photolithography.
  • the obtained substrate was subjected to ultrasonic cleaning for 10 minutes with an alkali cleaning solution (“Semico Clean” EL56 (trade name), manufactured by Furuuchi Chemical Co., Ltd.), and then washed with ultrapure water.
  • an alkali cleaning solution (“Semico Clean” EL56 (trade name), manufactured by Furuuchi Chemical Co., Ltd.
  • a PEDOT: PSS aqueous solution (0.8% by weight of PEDOT, 0.5% by weight of PPS) serving as a hole transport layer was formed on the substrate to a thickness of 60 nm by spin coating. did.
  • the above solution A was dropped onto the PEDOT: PSS layer, and an organic semiconductor layer having a thickness of 100 nm was formed by spin coating.
  • the substrate on which the organic semiconductor layer is formed and the cathode mask are placed in a vacuum vapor deposition apparatus, and the vacuum in the apparatus is exhausted again until the vacuum level becomes 1 ⁇ 10 ⁇ 3 Pa or less, and the negative electrode is formed by resistance heating.
  • the aluminum layer to be formed was deposited so as to have a thickness of 80 nm and an area intersecting with the stripe-like ITO layer was 5 mm ⁇ 5 mm.
  • a photovoltaic element having a power generation layer area of 5 mm ⁇ 5 mm was produced.
  • a photovoltaic device having an area where the stripe-shaped ITO layer intersects with the aluminum layer was 5 mm ⁇ 5 mm was produced.
  • the positive and negative electrodes of the photovoltaic device thus fabricated were connected to a picoammeter / voltage source 4140B manufactured by Hewlett-Packard Co., and simulated sunlight (from Yamashita Denso Co., Ltd., simplified) from the ITO layer side in the atmosphere.
  • the short-circuit current density (value of the current density when the applied voltage is 0 V) is 6.45 A / cm 2
  • the open circuit voltage value of the applied voltage when the current density is 0
  • the fill factor (FF) was 0.60
  • the photoelectric conversion efficiency calculated from these values was 3.75%.
  • the fill factor and photoelectric conversion efficiency were calculated by the following equations.
  • Example 2 A photovoltaic device was prepared in the same manner as in Example 1 except that A-2 was used in place of A-1, and current-voltage characteristics were measured. At this time, the short-circuit current density was 7.83 mA / cm 2 , the open-circuit voltage was 0.98 V, and the fill factor (FF) was 0.54. The photoelectric conversion efficiency calculated from these values was 4.14%. .
  • Example 3 A photovoltaic device was prepared in the same manner as in Example 1 except that A-3 was used in place of A-1, and current-voltage characteristics were measured. At this time, the short-circuit current density was 7.23 mA / cm 2 , the open-circuit voltage was 0.98 V, the fill factor (FF) was 0.50, and the photoelectric conversion efficiency calculated from these values was 3.54%. .
  • Example 4 A photovoltaic device was produced in the same manner as in Example 1 except that A-4 was used instead of A-1, and current-voltage characteristics were measured. At this time, the short-circuit current density was 7.68 mA / cm 2 , the open-circuit voltage was 0.94 V, the fill factor (FF) was 0.46, and the photoelectric conversion efficiency calculated from these values was 3.32%. .
  • Comparative Example 1 A photovoltaic device was prepared in the same manner as in Example 1 except that B-1 was used instead of A-1, and current-voltage characteristics were measured.
  • the short-circuit current density at this time was 6.10 mA / cm 2
  • the open-circuit voltage was 0.96 V
  • the fill factor (FF) was 0.45.
  • the photoelectric conversion efficiency calculated from these values was 2.64%. .
  • Comparative Example 2 A photovoltaic device was produced in the same manner as in Example 1 except that B-2 was used in place of A-1, and current-voltage characteristics were measured. At this time, the short-circuit current density was 2.45 mA / cm 2 , the open-circuit voltage was 0.76 V, the fill factor (FF) was 0.56, and the photoelectric conversion efficiency calculated from these values was 1.04%. .
  • Comparative Example 3 A photovoltaic device was produced in the same manner as in Example 1 except that B-3 was used in place of A-1, and current-voltage characteristics were measured. At this time, the short-circuit current density was 5.43 mA / cm 2 , the open-circuit voltage was 0.80 V, the fill factor (FF) was 0.41, and the photoelectric conversion efficiency calculated from these values was 1.78%. .
  • Substrate 2 Positive electrode 3: Organic semiconductor layer 4: Negative electrode 5: Layer having an electron-donating organic material 6: Layer having an electron-accepting organic material

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