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WO2014119782A1 - Couche tampon destinée à des cellules solaires en couche mince organique et cellule solaire en couche mince organique - Google Patents

Couche tampon destinée à des cellules solaires en couche mince organique et cellule solaire en couche mince organique Download PDF

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Publication number
WO2014119782A1
WO2014119782A1 PCT/JP2014/052432 JP2014052432W WO2014119782A1 WO 2014119782 A1 WO2014119782 A1 WO 2014119782A1 JP 2014052432 W JP2014052432 W JP 2014052432W WO 2014119782 A1 WO2014119782 A1 WO 2014119782A1
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film solar
organic thin
carbon atoms
thin film
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Japanese (ja)
Inventor
直樹 大谷
彰治 森山
卓司 吉本
寿郎 大島
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/41—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
    • C07C309/43—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton having at least one of the sulfo groups bound to a carbon atom of a six-membered aromatic ring being part of a condensed ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/20—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups being part of rings other than six-membered aromatic rings
    • C07C251/22—Quinone imines
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a buffer layer for an organic thin film solar cell and an organic thin film solar cell.
  • An organic solar cell is a solar cell element using an organic substance as an active layer or a charge transport material.
  • Organic thin-film solar cells developed by Tan are well known (Non-Patent Documents 1 and 2). All are lightweight, thin film, flexible, roll-to-roll, and other features that are different from the current mainstream inorganic solar cells. Formation is expected.
  • organic thin-film solar cells hereinafter abbreviated as OPV
  • OPV organic thin-film solar cells
  • PCE photoelectric conversion efficiency
  • an OPV element can improve initial characteristics and life characteristics by forming a thin film called a buffer layer on an anode or a cathode as a base layer of an active layer and forming a laminated structure together with the active layer.
  • a polythiophene-based material called PEDOT / PSS is often used as the anode buffer layer (Non-patent Documents 3 and 4).
  • PEDOT / PSS it exhibits high corrosiveness to anode materials and coating devices, is likely to cause an electrical short circuit in an OPV element, which is an extremely thin film element, due to aggregates generated during storage, and an aqueous solvent. Since it is used, it is difficult to adjust the physical properties of the solution, and it may be difficult to produce a thin film having a uniform coating surface.
  • organic electroluminescence (hereinafter abbreviated as “organic EL”) elements and OPVs weight reduction and high performance have been demanded. And since it occupies most weight of the glass substrate of a transparent electrode, a battery, etc., the trial which uses the board
  • organic compounds are generally inferior in heat resistance to glass, when a substrate made of an organic compound is used, it is necessary to produce a charge transporting thin film at a lower temperature than in the past. The development of charge transporting thin films is strongly desired.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide an organic thin film battery buffer layer that provides an organic thin film solar battery with high conversion efficiency, and an organic thin film sun having the same.
  • the inventors of the present invention have developed a charge transporting varnish containing an oligoaniline compound containing a quinoid moiety, an electron-accepting dopant material, and an organic solvent into an organic thin film solar cell. It was found that a buffer layer that gives an organic thin-film solar cell with high conversion efficiency can be formed by applying it on the anode of the battery or on any layer on the anode and baking it at 135 ° C. or lower. Completed the invention.
  • Either a charge transporting varnish comprising a charge transporting material comprising an oligoaniline compound represented by the formula (1), an electron accepting dopant material, and an organic solvent is either on the anode or on the anode of an organic thin film solar cell.
  • R 1 to R 19 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, aldehyde groups may be substituted with Z 1, an alkyl group having 1 to 20 carbon atoms, an alkenyl group or an alkynyl group having 2 to 20 carbon atoms having 2 to 20 carbon atoms may be substituted with Z 2, carbon atoms An aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms, —NHY 1 , —NY 2 Y 3 , —OY 4 , —SY 5 , —SO 3 Y 6 , —C (O) OY
  • R 1 is a hydrogen atom
  • R 2 and R 3 are each independently a hydrogen atom, a halogen atom, or an aryl having 6 to 20 carbon atoms in which Y 2 and Y 3 may be substituted with Z 2.
  • R 4 to R 19 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with Z 1 , or Y 4 1 or 2 of an organic thin film solar cell buffer layer, wherein —OY 4 is an alkyl group having 1 to 20 carbon atoms which may be substituted with Z 1 ; 4).
  • the organic thin-film solar cell buffer layer of any one of 1 to 3, wherein m is 1 or 2, and n is 1; 5.
  • the organic thin film solar cell according to 4 wherein R 1 and R 4 to R 19 are hydrogen atoms, R 2 and R 3 are simultaneously hydrogen atoms or diphenylamino groups, m is 1 and n is 1.
  • Battery buffer layer 6).
  • X represents O
  • A represents a naphthalene ring or an anthracene ring
  • B represents a divalent to tetravalent perfluorobiphenyl group
  • l represents the number of sulfonic acid groups bonded to A.
  • q represents the number of bonds between B and X, and is an integer satisfying 2 to 4.
  • the buffer layer for organic thin film solar cells according to any one of 1 to 7, which is an anode buffer layer, 9.
  • An organic thin film solar cell comprising: a buffer layer for an organic thin film solar cell of any one of 1 to 8; and an active layer provided in contact therewith, 10. 9 organic thin-film solar cells in which the active layer contains a fullerene derivative, 11. 9 organic thin-film solar cells in which the active layer contains a polythiophene derivative, 12 9 organic thin-film solar cells in which the active layer contains a fullerene derivative and a polythiophene derivative, 13.
  • a charge transporting varnish comprising a charge transporting material comprising an oligoaniline compound represented by the formula (1), an electron accepting dopant material, and an organic solvent is used on either an anode or an anode of an organic thin film solar cell.
  • the buffer layer for an organic thin film solar cell of the present invention has a high hole transport property and can promote the p / n phase separation of the active layer to form an appropriate active layer structure.
  • the buffer layer for an organic thin film solar cell of the present invention is characterized by not only high heat resistance of the material itself but also low damage to moisture due to low hygroscopicity. . Therefore, it is possible to obtain an organic thin film solar cell having both excellent conversion efficiency and high durability by using the buffer layer for an organic thin film solar cell of the present invention.
  • the buffer layer for organic thin film solar cells of this invention can be manufactured at low temperature compared with the past, the manufacturing conditions of an organic thin film solar cell element can be made mild.
  • the present invention it is possible to apply a film substrate that contributes to reducing the weight, flexibility, and cost of the device, and it is also possible to apply an inexpensive film substrate such as PET.
  • the charge transportable varnish used by this invention can be prepared using various organic solvents, it can adjust and use liquid physical properties, such as the viscosity and surface tension, to suit various process conditions. Therefore, the buffer layer for an organic thin film solar cell of the present invention can be manufactured with good reproducibility even when various wet processes capable of forming a film on a large-area substrate such as a spin coating method and a slit coating method are used.
  • the buffer layer for an organic thin-film solar cell of the present invention comprises a charge transporting varnish containing a charge transporting material composed of an oligoaniline compound represented by the formula (1), an electron accepting dopant material, and an organic solvent. It is formed by coating on either the anode of the thin film solar cell or on the thin film on the anode and baking at 135 ° C. or lower.
  • the buffer layer for organic thin-film solar cells of the present invention is usually used as an anode buffer layer, but may be used as a cathode buffer layer.
  • the anode means the electrode on the side where holes mainly flow in the charge generated from the active layer
  • the cathode means the electrode on the side where electrons mainly flow in the charge generated from the active layer. means.
  • R 1 to R 19 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, or an aldehyde.
  • an alkyl group having 1 to 20 carbon atoms may be substituted with Z 1
  • an alkyl group having 1 to 20 carbon atoms may be substituted with Z 2
  • an alkyl group having ⁇ 20 or a heteroaryl group having 2 to 20 carbon atoms —NHY 1 , —NY 2 Y 3 , —OY 4 , —SY 5 , —SO 3 Y 6 , —C (O) OY 7 , or — C (O) Y 8 is represented.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, n- C1-C20 chain alkyl groups such as hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl A cyclic alkyl group having 3 to 20 carbon atoms such as a group, cyclooctyl group, cyclo
  • alkenyl group having 2 to 20 carbon atoms examples include ethenyl group, n-1-propenyl group, n-2-propenyl group, 1-methylethenyl group, n-1-butenyl group, n-2-butenyl group, n-3 -Butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, n-1-pentenyl Group, n-1-decenyl group, n-1-eicocenyl group and the like.
  • alkynyl group having 2 to 20 carbon atoms examples include ethynyl group, n-1-propynyl group, n-2-propynyl group, n-1-butynyl group, n-2-butynyl group, n-3-butynyl group, -Methyl-2-propynyl group, n-1-pentynyl group, n-2-pentynyl group, n-3-pentynyl group, n-4-pentynyl group, 1-methyl-n-butynyl group, 2-methyl-n -Butynyl group, 3-methyl-n-butynyl group, 1,1-dimethyl-n-propynyl group, n-1-hexynyl, n-1-decynyl group, n-1-pentadecynyl group, n-1-eicosinyl group Etc.
  • aryl group having 6 to 20 carbon atoms examples include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3 -Phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.
  • heteroaryl group having 2 to 20 carbon atoms examples include 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-imidazolyl, 4-imidazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl group and the like.
  • —NHY 1 is a group in which one of the hydrogen atoms of the amino group (—NH 2 ) is substituted with Y 1
  • —NY 2 Y 3 is a group in which the hydrogen atom of the amino group (—NH 2 ) is Y 2 and Y 3 -OY 4 is a group in which a hydrogen atom of a hydroxyl group (-OH) is substituted with Y 4
  • -SY 5 is a group in which a hydrogen atom of a thiol group (-SH) is substituted with Y 5
  • SO 3 Y 6 is a group in which a hydrogen atom of a sulfonic acid group (—SO 3 H) is substituted with Y 6
  • —C (O) OY 7 is a hydrogen atom in a carboxyl group (—COOH).
  • a group in which an atom is substituted with Y 7 , and —C (O) Y 8 represents a group in which a hydrogen atom of an aldehyde group (—C (O) H) is substituted with Y 8 , respectively.
  • Y 1 to Y 8 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, which may be substituted with Z 1
  • Z 2 represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with 2
  • an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heteroaryl group having Y 1 to Y 8 The same as those mentioned above.
  • R 1 is a hydrogen atom
  • R 2 and R 3 may each independently be a hydrogen atom, a halogen atom, or Y 2 and Y 3 may be substituted with Z 2.
  • —NY 2 Y 3 which is an aryl group having 6 to 20 carbon atoms
  • R 4 to R 19 are each independently a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms which may be substituted with Z 1
  • An alkyl group or —OY 4 which is an alkyl group having 1 to 20 carbon atoms which Y 4 may be substituted with Z 1 is preferable
  • R 1 is a hydrogen atom
  • R 2 and R 3 are respectively Independently a hydrogen atom, a fluorine atom, or a diphenylamino group
  • R 4 to R 19 are each independently a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 20 carbon atoms that may be substituted with fluorine.
  • the alkyl group, alkenyl group and alkynyl group of R 1 to R 19 and Y 1 to Y 8 are a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, an amino group, and a phosphate group.
  • Z 1 is a halogen atom, a nitro group, a cyano group, or an aryl group having 6 to 20 carbon atoms that may be substituted with Z 3.
  • it is preferably a halogen atom or a phenyl group which may be substituted with Z 3 , and more preferably not present (that is, R 1 to R 19 and Y 1 to Y 8 are unsubstituted).
  • Z 2 is preferably a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with Z 3 , and may be substituted with a halogen atom or Z 3. It is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably absent (that is, R 1 to R 19 and Y 1 to Y 8 are unsubstituted).
  • Z 3 is preferably a halogen atom, more preferably fluorine, and even more preferably not present (that is, Z 1 and Z 2 are unsubstituted).
  • n and n are each independently an integer of 1 or more and satisfy m + 2n ⁇ 20.
  • m is preferably 1 to 2
  • n is preferably 1 to 4
  • m is 1 or More preferably, n is 1 to 3, and m is 1, and n is even more preferable.
  • a compound containing an oxidized oligoaniline structure represented by the formula (3) is particularly suitable.
  • R 1 to R 19 have the same meaning as described above.
  • part which exists in the compound containing the oligoaniline structure of this invention exists in the arbitrary positions of structural formula by tautomerism.
  • the compound represented by the formula (1) is such that R 1 to R 19 are all hydrogen atoms, m is 2, and n is 1, the compound represented by the formula (4) And (5) are meant to be included.
  • the charge transporting varnish containing such an oligoaniline compound does not mean that only one tautomer is included, but means that one or two or more tautomers can be included. .
  • the molecular weight of the oligoaniline compound represented by the formula (1) is not particularly limited. However, in consideration of increasing the solubility of the oligoaniline compound in an organic solvent, the upper limit is usually 5000 or less, preferably 2000. It is as follows. In the present invention, an oligoaniline compound having no molecular weight distribution (dispersity of 1) is preferred. In addition, molecular weight distribution says the measured value by gel permeation chromatography (polystyrene conversion).
  • the electron-accepting dopant material which is the other component contained in the charge transporting varnish used in the present invention is not particularly limited as long as it is soluble in at least one solvent used for the charge transporting varnish.
  • the electron-accepting dopant material include inorganic strong acids such as hydrogen chloride, sulfuric acid, nitric acid and phosphoric acid; aluminum chloride (III) (AlCl 3 ), titanium tetrachloride (IV) (TiCl 4 ), boron tribromide (BBr 3 ), boron trifluoride ether complex (BF 3 ⁇ OEt 2 ), iron chloride (III) (FeCl 3 ), copper (II) chloride (CuCl 2 ), antimony pentachloride (V) (SbCl 5 ), Lewis acids such as arsenic pentafluoride (V) (AsF 5 ), phosphorus pentafluoride (PF 5 ), tris (4-bromophenyl) aluminum hexachloroantimonate (TBPAH); benzenesulfonic acid, tosylic acid, camphorsulfonic acid Hydroxybenzenesulfonic acid, 5-sulfo
  • aryl sulfonic acid compounds particularly aryl sulfonic acid compounds represented by the formula (2)
  • heteropoly acid compounds particularly phosphomolybdic acid and phosphotungstic acid are suitable.
  • X represents O
  • A represents a naphthalene ring or an anthracene ring
  • B represents a divalent to tetravalent perfluorobiphenyl group
  • l represents the number of sulfonic acid groups bonded to A.
  • arylsulfonic acid compounds examples include the following compounds (formula (6)).
  • the preferred combination of the charge transporting substance and the electron accepting dopant substance is an oligoaniline compound represented by the formula (1), preferably an oligoaniline compound represented by the formula (3), and an aryl.
  • a sulfonic acid compound preferably an aryl sulfonic acid compound represented by formula (2), more preferably an aryl sulfonic acid compound represented by formula (6).
  • organic solvent used for the preparation of the charge transporting varnish a highly soluble solvent capable of satisfactorily dissolving the oligoaniline compound and the electron-accepting dopant substance can be used.
  • Highly soluble solvents can be used singly or in combination of two or more, and the amount used can be 5-100% by mass with respect to the total solvent used in the varnish.
  • Examples of such highly soluble solvents include N-methylformamide (183 ° C.), N, N-dimethylformamide (153 ° C.), N, N-diethylformamide (178 ° C.), N-methylacetamide (206 ° C.). ), N, N-dimethylacetamide (166 ° C.), N-methylpyrrolidone (202 ° C.), 1,3-dimethyl-2-imidazolidinone (225 ° C.), and the like.
  • the value in parentheses is the boiling point of the solvent under 1.01 ⁇ 10 5 Pa (atmospheric pressure) (the same applies hereinafter).
  • N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, N-methylacetamide, and N, N-dimethylacetamide are preferred, and N, N-dimethylacetamide is more preferred. preferable.
  • both the charge transporting substance and the electron-accepting dopant substance are completely dissolved or uniformly dispersed in the organic solvent to give an organic thin film solar cell with high conversion efficiency.
  • these substances are completely dissolved in the organic solvent.
  • the charge transporting varnish used in the present invention has a viscosity of 10 to 200 mPa ⁇ s at 25 ° C., particularly 35 to 150 mPa ⁇ s, and a high viscosity organic solvent having a boiling point of 50 to 300 ° C., particularly 150 to 250 ° C. at normal pressure. It is preferable to contain at least one kind.
  • the high-viscosity organic solvent is not particularly limited.
  • cyclohexanol (161 ° C.), ethylene glycol (198 ° C.), 1,3-octylene glycol (245 ° C.), diethylene glycol (245 ° C.), dipropylene Glycol (138 ° C), triethylene glycol (166 ° C), tripropylene glycol (268 ° C), 1,3-butanediol (207 ° C), 2,3-butanediol (182 ° C), 1,4-butanediol (230 ° C.), propylene glycol (107 ° C.), hexylene glycol (198 ° C.), and the like.
  • the addition ratio of the high-viscosity organic solvent to the whole solvent used in the varnish is preferably within a range where no solid precipitates, and the addition ratio is preferably 5 to 80% by mass as long as no solid precipitates. .
  • adjusting the surface tension of the solvent, adjusting the polarity, adjusting the boiling point, etc. 1 to 90% by mass, preferably 1 to 50% by mass, can be mixed.
  • Examples of such a solvent include butyl cellosolve (171 ° C.), diethylene glycol diethyl ether (187 ° C.), diethylene glycol dimethyl ether (162 ° C.), diethylene glycol monoethyl ether acetate (217 ° C.), diethylene glycol monobutyl ether acetate (247 ° C.), diethylene glycol Propylene glycol monomethyl ether (189 ° C), propylene glycol monomethyl ether (120 ° C), propylene glycol monomethyl ether acetate (146 ° C), ethyl carbitol (202 ° C), diacetone alcohol (166 ° C), ⁇ -butyrolactone (204 ° C) ), Ethyl lactate (154 ° C.), n-hexyl acetate (169 ° C.) and the like, but are not limited thereto.
  • the boiling point of the organic solvent contained in the charge transporting varnish is not particularly limited, but it is included in the charge transporting varnish in consideration of obtaining a buffer layer that gives an organic thin film solar cell with high conversion efficiency with good reproducibility.
  • the boiling point of all organic solvents is preferably 200 ° C. or lower, more preferably 190 ° C. or lower.
  • the solid content concentration of the charge transporting varnish used in the present invention is appropriately set in consideration of the viscosity and surface tension of the varnish and the thickness of the thin film to be produced. It is about 0% by mass, preferably 0.5 to 5.0% by mass, more preferably 1.0 to 3.0% by mass.
  • the substance amount (mol) ratio between the charge transporting substance and the electron-accepting dopant substance is also appropriately set in consideration of the type of charge transporting property, charge transporting substance, etc. that are expressed.
  • the electron-accepting dopant material is 0.1 to 10, preferably 0.5 to 5.0, more preferably 1.0 to 3.0.
  • the viscosity of the charge transporting varnish used in the present invention is appropriately adjusted according to the coating method in consideration of the thickness of the thin film to be produced and the solid content concentration, but is usually 0.1 mPa ⁇ s to about 50 mPa ⁇ s.
  • the charge transporting material, the electron accepting dopant material, and the organic solvent can be mixed in any order as long as the solid content is uniformly dissolved or dispersed in the solvent. That is, for example, after dissolving an oligoariin compound in an organic solvent, an electron-accepting dopant substance is dissolved in the solution. After dissolving an electron-accepting dopant substance in an organic solvent, the oligoaniline compound is dissolved in the solution. Any method that mixes an oligoaniline compound and an electron-accepting dopant substance and then dissolves the mixture in an organic solvent is used as long as the solid content is uniformly dissolved or dispersed in the organic solvent. be able to.
  • varnish preparation is usually performed in an inert gas atmosphere at normal temperature and pressure, but in an air atmosphere (in the presence of oxygen) unless the compounds in the varnish are decomposed or the composition changes significantly. It may be performed while heating.
  • the method for applying the above-described charge transporting varnish on the thin film on the anode or on the anode of the organic thin film solar cell is not particularly limited.
  • Specific examples of any thin film on the anode include an anode buffer layer, an active layer, a carrier block layer, and the like.
  • the film thickness is not particularly limited, but is preferably about 5 to 200 nm when used as an anode buffer layer of an organic thin film solar cell.
  • a method of changing the film thickness there are methods such as changing the solid content concentration in the varnish or changing the amount of the solution at the time of application.
  • the buffer layer for an organic thin-film solar cell of the present invention is formed by baking the charge transporting varnish applied according to the above method at 135 ° C. or lower.
  • the temperature at the time of baking means the temperature at the time of applying heat to the coated varnish from the outside.
  • baking at 135 ° C. is 135 when a hot plate is used. It means that a varnish is subjected to a heat treatment at 135 ° C. by placing a substrate coated with the varnish on a plate set at ° C. for a certain period of time.
  • the upper limit of the firing temperature of the present invention is 135 ° C.
  • the upper limit of the firing temperature is preferably 130 ° C. or less, more preferably 125 ° C. or less, even more preferably 120 ° C. or less, considering that a buffer layer that gives an organic thin film solar cell with high conversion efficiency can be obtained with good reproducibility. It is.
  • the lower limit of the firing temperature is appropriately determined in consideration of the type and concentration of solids such as a charge transporting material and an electron-accepting dopant material, as well as varnish coating conditions and desired film thickness. Therefore, it cannot be generally specified, but it is usually 40 ° C. or higher, preferably 50 ° C. or higher.
  • an appropriate apparatus may be used in consideration of the size and shape of the element to be heated, and specific examples thereof include a hot plate and an oven.
  • the temperature may be changed in two or more steps for the purpose of exhibiting a higher uniform film forming property or allowing the reaction to proceed after coating within a range where the baking temperature does not exceed 135 ° C.
  • the buffer layer for organic thin film solar cells of the present invention is particularly suitable for an anode buffer layer used by being directly laminated on the anode of an organic thin film solar cell. Since the buffer layer for an organic thin film solar cell of the present invention can contribute to the improvement of charge transportability in the device, an organic thin film solar cell with high conversion efficiency can be realized by using this as an anode buffer layer of the organic thin film solar cell. .
  • an organic thin film solar cell having the buffer layer for an organic thin film solar cell of the present invention as an anode buffer layer will be described, but the present invention is not limited thereto.
  • Formation of anode layer A step of forming a layer of anode material on the surface of the transparent substrate to produce a transparent electrode.
  • the anode material metal oxide such as indium tin oxide (ITO) and indium zinc oxide (IZO) is used. And high charge transporting organic compounds such as polythiophene derivatives and polyaniline derivatives can be used.
  • the transparent substrate a substrate made of glass or transparent resin can be used.
  • the method for forming the anode material layer (anode layer) is appropriately selected according to the properties of the anode material, and is usually a dry process using a sublimation compound (evaporation method) or a wet process using a varnish containing a charge transporting compound. Either process (especially spin coating or slit coating) is employed.
  • the manufacturing method of the organic thin-film solar cell of this invention does not include the process of forming an anode layer.
  • the transparent electrode to be used is preferably used after being washed with a detergent, alcohol, pure water or the like.
  • the anode substrate is preferably subjected to a surface treatment such as UV ozone treatment or oxygen-plasma treatment immediately before use (when the anode material is mainly composed of an organic substance, the surface treatment may not be performed).
  • Step of forming an anode buffer layer on the formed anode material layer Step of forming an anode buffer layer on the formed anode material layer According to the above method, the buffer layer of the present invention is formed on the anode material layer.
  • the active layer includes an n layer which is a thin film made of an n-type semiconductor material, and a p layer which is a thin film made of a p-type semiconductor material. Or a non-laminated thin film made of a mixture of these materials.
  • n-type semiconductor materials include fullerene, [6,6] -phenyl-C 61 -butyric acid methyl ester (PC 61 BM), [6,6] -phenyl-C 71 -butyric acid methyl ester (PC 71 BM), and the like. Can be mentioned.
  • the p-type semiconductor material is described in regioregular poly (3-hexylthiophene) (P3HT), PTB7 represented by the following formula, JP 2009-158921 A and International Publication No. 2010/008672.
  • Examples thereof include polymers having a thiophene skeleton in the main chain, such as thienothiophene unit-containing polymers, phthalocyanines such as CuPC and ZnPC, and porphyrins such as tetrabenzoporphyrin.
  • thiophene skeleton in the main chain refers to a divalent aromatic ring composed solely of thiophene, or thienothiophene, benzothiophene, dibenzothiophene, benzodithiophene, naphthothiophene, naphthodithiophene, anthrathiophene, anthracodi. It represents a divalent fused aromatic ring containing one or more thiophenes such as thiophene, and these may be substituted with a substituent represented by R 1 to R 8 above.
  • the formation method of the active layer is appropriately selected according to the properties of the n-type semiconductor or the p-type semiconductor material, and is usually a dry process using a sublimation compound (particularly vapor deposition method) or a wet process using a varnish containing a material ( In particular, either a spin coat method or a slit coat method is employed.
  • Step of forming a cathode buffer layer on the formed active layer A cathode buffer between the active layer and the cathode layer for the purpose of improving the efficiency of charge transfer, if necessary.
  • a layer may be formed.
  • Materials for forming the cathode buffer layer include lithium oxide (Li 2 O), magnesium oxide (MgO), alumina (Al 2 O 3 ), lithium fluoride (LiF), magnesium fluoride (MgF 2 ), and strontium fluoride. (SrF 2 ) and the like.
  • the formation method of the cathode buffer layer is appropriately selected according to the properties of the material, and is usually a dry process using a sublimation compound (particularly vapor deposition method) or a wet process using a varnish containing the material (particularly spin coating method). Or slit coat method) is employed.
  • Step of forming a cathode layer on the formed cathode buffer layer As cathode materials, aluminum, magnesium-silver alloy, aluminum-lithium alloy, lithium, sodium, potassium, cesium, calcium, barium Silver, gold and the like, and a plurality of cathode materials can be laminated or mixed for use.
  • the method for forming the cathode layer is appropriately selected according to the properties of the material, but usually a dry process (especially vapor deposition) is employed.
  • a carrier block layer may be provided between arbitrary layers for the purpose of controlling photocurrent rectification.
  • the material for forming the carrier block layer include titanium oxide, zinc oxide, bathocuproine (BCP) and the like.
  • the method for forming the carrier block layer is appropriately selected according to the properties of the material. Usually, the vapor deposition method is used when a sublimation compound is used, and the spin coating method or the slit coating method is used when a varnish in which the material is dissolved is used. Either one is adopted.
  • the OPV device manufactured by the method exemplified above is again introduced into the glove box and sealed in an inert gas atmosphere such as nitrogen in order to prevent device deterioration due to the atmosphere.
  • the function as a solar cell can be exhibited, or the solar cell characteristics can be measured.
  • a sealing method a concave glass substrate with a UV curable resin attached to the end is attached to the film forming surface side of the organic thin film solar cell element in an inert gas atmosphere, and the resin is cured by UV irradiation. Examples of the method include performing a film sealing type sealing by a technique such as sputtering under vacuum.
  • Glove box Sanpachi Bussan Co., Ltd., VAC glove box system
  • Deposition equipment Aoyama Engineering Co., Ltd., vacuum deposition equipment
  • Solar simulator Spectrometer Co., Ltd., OTENTOUN-III AM1.5G filter, radiation intensity: 100 mW / cm 2
  • Source measure unit 2612A, manufactured by Keithley Instruments Co., Ltd.
  • oligoaniline compound B2 An oligoaniline compound represented by the formula (1-2) (hereinafter also referred to as oligoaniline compound B2) was synthesized according to the following reaction formula based on the description in WO2010 / 058777. The measurement results of the obtained oligoaniline compound by 1 H-NMR and mass spectrometry are shown below.
  • 1 H-NMR 300 MHz, DMSO-d6): ⁇ 5.75 (1H, s, NH), 6.8-7.4 (36H, m, Ar—H) (mixture of E and Z forms)
  • PEDOT / PSS (Clevios P VP AI4083 manufactured by Heraeus) was dispersed with ultrasonic waves and filtered through a syringe filter having a pore diameter of 0.45 ⁇ m to obtain a charge transporting varnish C4.
  • buffer layer and organic thin film solar cell [Example 1] A glass substrate of 25 mm ⁇ 25 mm obtained by patterning an ITO transparent conductive layer serving as a positive electrode into a 2 mm ⁇ 25 mm stripe pattern was subjected to UV / ozone treatment for 30 minutes, and then the charge transporting varnish C1 prepared on the substrate was applied by spin coating. The applied charge transporting varnish was heated at 50 ° C. for 15 minutes using a hot plate (manufactured by ASONE Co., Ltd., model number TH-900) to form a buffer layer having a thickness of 30 nm.
  • a hot plate manufactured by ASONE Co., Ltd., model number TH-900
  • the active layer composition D1 was dropped on the formed buffer layer, and an active layer having a thickness of 90 nm was formed by a spin coating method.
  • the substrate on which the organic semiconductor layer is formed and the mask for the cathode are placed in a vacuum deposition apparatus, and the exhaust is exhausted again until the degree of vacuum in the apparatus becomes 1 ⁇ 10 ⁇ 3 Pa or less.
  • An aluminum layer serving as a negative electrode was deposited to a thickness of 100 nm.
  • an OPV element having an area where the stripe-shaped ITO layer and the aluminum layer intersect with each other was 2 mm ⁇ 2 mm was manufactured.
  • Example 2 instead of heating at 50 ° C. for 15 minutes, an OPV device was fabricated in the same manner as in Example 1, except that heating was performed at 50 ° C. for 5 minutes and further heating was performed at 80 ° C. for 10 minutes.
  • Examples 3 and 4 instead of heating at 80 ° C. for 10 minutes, an OPV element was fabricated in the same manner as in Example 2 except that heating was performed at 120 ° C. and 130 ° C. for 10 minutes, respectively.
  • Example 5 An OPV device was produced in the same manner as in Example 3 except that instead of the charge transporting varnish C1, charge transporting varnishes C2 and C3 were used, respectively.
  • Example 7 After using the charge transporting varnish C2 instead of the charge transporting varnish C1 and the active layer composition D2 instead of the active layer composition D1, heating at 50 ° C for 5 minutes instead of heating at 50 ° C for 15 minutes An OPV element was fabricated in the same manner as in Example 1 except that the film was further heated at 120 ° C. for 10 minutes.
  • Example 8 An OPV device was produced in the same manner as in Example 7 except that the charge transporting varnish C3 was used instead of the charge transporting varnish C2.
  • the elements (Examples 1 to 6) having a firing temperature of 135 ° C. or less at the time of forming the thin film had higher conversion efficiency than the elements having a firing temperature exceeding 135 ° C. (Comparative Examples 1 to 3).
  • the characteristics of the device after being stored for a long time in a dark place, that is, the lifetime characteristics of the device were also better than those of the device using PEDOT / PSS.
  • the conversion efficiency of the element having the buffer layer baked at 125 ° C. or less was a high value of 3.3% or more (Examples 1 to 3, 5, and 6).
  • the device (Example 7) having a firing temperature of 135 ° C. or lower during the production of the thin film showed higher conversion efficiency than the device (Comparative Example 5) having a firing temperature exceeding 135 ° C.
  • the conversion efficiency of the OPV device (Example 8) produced using the charge transporting varnish C3 containing phosphotungstic acid n-hydrate showed a higher value (5.5%).

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Abstract

La présente invention concerne une cellule solaire en couche mince organique possédant une efficacité de conversion photoélectrique élevée, qui peut être obtenue par l'utilisation d'une couche tampon destinée à des cellules solaires en couche mince organique, ladite couche tampon étant formée par l'application d'un vernis de transport de charge, qui contient un matériau de transport de charge qui est composé d'un composé oligoaniline représenté, par exemple, par la formule (3), un matériau dopant acceptant les électrons et un solvant organique, sur une électrode positive de la cellule solaire en couche mince organique ou d'une quelconque couche mince sur l'électrode positive et par la cuisson du vernis à une température inférieure ou égale à 135 °C. (Dans la formule, chacun de R1 à R19 représente indépendamment un atome d'hydrogène ou analogue.)
PCT/JP2014/052432 2013-02-04 2014-02-03 Couche tampon destinée à des cellules solaires en couche mince organique et cellule solaire en couche mince organique Ceased WO2014119782A1 (fr)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017077883A1 (fr) * 2015-11-06 2017-05-11 日産化学工業株式会社 Composition pour couche de piégeage de trous d'élément de conversion photoélectrique organique
WO2017135117A1 (fr) 2016-02-03 2017-08-10 日産化学工業株式会社 Vernis de transport de charges
WO2017164158A1 (fr) 2016-03-24 2017-09-28 日産化学工業株式会社 Dérivé d'arylamine et utilisation correspondante
JPWO2016208506A1 (ja) * 2015-06-22 2017-12-21 富士フイルム株式会社 光電変換素子、光電変換素子の製造方法、および太陽電池
JPWO2016148184A1 (ja) * 2015-03-17 2017-12-28 日産化学工業株式会社 光センサ素子の正孔捕集層形成用組成物および光センサ素子
WO2018216507A1 (fr) 2017-05-25 2018-11-29 日産化学株式会社 Procédé de fabrication de film mince de transport de charge
CN109390473A (zh) * 2018-10-17 2019-02-26 华中科技大学 基于双官能团单分子修饰层的钙钛矿电池及其制备方法
CN110073509A (zh) * 2016-12-16 2019-07-30 日产化学株式会社 有机光电转换元件的空穴捕集层用组合物
WO2020066979A1 (fr) 2018-09-25 2020-04-02 日産化学株式会社 Procédé de fabrication de substrat comportant un film fonctionnel organique appliqué

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008010474A1 (fr) * 2006-07-18 2008-01-24 Nissan Chemical Industries, Ltd. Vernis contenant des charges
WO2010058777A1 (fr) * 2008-11-19 2010-05-27 日産化学工業株式会社 Matériau et vernis contenant des charges
JP2011054631A (ja) * 2009-08-31 2011-03-17 Orient Chemical Industries Co Ltd 有機・ナノ炭素複合系薄膜太陽電池
JP2012182370A (ja) * 2011-03-02 2012-09-20 National Institute Of Advanced Industrial & Technology 有機薄膜太陽電池用セル及びその製造方法、並びに有機薄膜太陽電池
JP2012186343A (ja) * 2011-03-07 2012-09-27 Kyushu Univ 有機薄膜太陽電池
JP2012244014A (ja) * 2011-05-20 2012-12-10 Osaka Gas Chem Kk 光電変換材料および太陽電池

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008010474A1 (fr) * 2006-07-18 2008-01-24 Nissan Chemical Industries, Ltd. Vernis contenant des charges
WO2010058777A1 (fr) * 2008-11-19 2010-05-27 日産化学工業株式会社 Matériau et vernis contenant des charges
JP2011054631A (ja) * 2009-08-31 2011-03-17 Orient Chemical Industries Co Ltd 有機・ナノ炭素複合系薄膜太陽電池
JP2012182370A (ja) * 2011-03-02 2012-09-20 National Institute Of Advanced Industrial & Technology 有機薄膜太陽電池用セル及びその製造方法、並びに有機薄膜太陽電池
JP2012186343A (ja) * 2011-03-07 2012-09-27 Kyushu Univ 有機薄膜太陽電池
JP2012244014A (ja) * 2011-05-20 2012-12-10 Osaka Gas Chem Kk 光電変換材料および太陽電池

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EP3273498A4 (fr) * 2015-03-17 2018-11-14 Nissan Chemical Corporation Composition de formation de couche de collecte de trous d'élément de photocapteur, et élément de photocapteur
EP4109573A1 (fr) 2015-03-17 2022-12-28 Nissan Chemical Corporation Élément de photocapteur
JP2022153435A (ja) * 2015-03-17 2022-10-12 日産化学株式会社 光センサ素子
JPWO2016148184A1 (ja) * 2015-03-17 2017-12-28 日産化学工業株式会社 光センサ素子の正孔捕集層形成用組成物および光センサ素子
JP7141826B2 (ja) 2015-03-17 2022-09-26 日産化学株式会社 光センサ素子の正孔捕集層形成用組成物および光センサ素子
US10340461B2 (en) 2015-03-17 2019-07-02 Nissan Chemical Industries, Ltd. Composition for forming hole collecting layer of photosensor element, and photosensor element
JPWO2016208506A1 (ja) * 2015-06-22 2017-12-21 富士フイルム株式会社 光電変換素子、光電変換素子の製造方法、および太陽電池
CN108352452A (zh) * 2015-11-06 2018-07-31 日产化学工业株式会社 有机光电转换元件的空穴捕集层用组合物
WO2017077883A1 (fr) * 2015-11-06 2017-05-11 日産化学工業株式会社 Composition pour couche de piégeage de trous d'élément de conversion photoélectrique organique
CN108352452B (zh) * 2015-11-06 2022-04-15 日产化学工业株式会社 有机光电转换元件的空穴捕集层用组合物
JPWO2017077883A1 (ja) * 2015-11-06 2018-08-23 日産化学株式会社 有機光電変換素子の正孔捕集層用組成物
TWI715657B (zh) * 2015-11-06 2021-01-11 日商日產化學工業股份有限公司 有機光電變換元件之電洞捕集層用組成物
US10770659B2 (en) 2015-11-06 2020-09-08 Nissan Chemical Industries, Ltd. Composition for hole trapping layer of organic photoelectric conversion element
WO2017135117A1 (fr) 2016-02-03 2017-08-10 日産化学工業株式会社 Vernis de transport de charges
WO2017164158A1 (fr) 2016-03-24 2017-09-28 日産化学工業株式会社 Dérivé d'arylamine et utilisation correspondante
EP3544072A4 (fr) * 2016-12-16 2019-11-27 Nissan Chemical Corporation Composition pour couche collectrice de trous d'élément de conversion photoélectrique organique
CN110073509A (zh) * 2016-12-16 2019-07-30 日产化学株式会社 有机光电转换元件的空穴捕集层用组合物
US11563176B2 (en) 2016-12-16 2023-01-24 Nissan Chemical Corporation Composition for hole collecting layer of organic photoelectric conversion element
WO2018216507A1 (fr) 2017-05-25 2018-11-29 日産化学株式会社 Procédé de fabrication de film mince de transport de charge
WO2020066979A1 (fr) 2018-09-25 2020-04-02 日産化学株式会社 Procédé de fabrication de substrat comportant un film fonctionnel organique appliqué
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