WO2012121190A1 - Élément photoélectrique - Google Patents

Élément photoélectrique Download PDF

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WO2012121190A1
WO2012121190A1 PCT/JP2012/055516 JP2012055516W WO2012121190A1 WO 2012121190 A1 WO2012121190 A1 WO 2012121190A1 JP 2012055516 W JP2012055516 W JP 2012055516W WO 2012121190 A1 WO2012121190 A1 WO 2012121190A1
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transport layer
electrode
organic compound
sensitizing dye
electron transport
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PCT/JP2012/055516
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English (en)
Japanese (ja)
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直毅 林
理生 鈴鹿
関口　隆史
西出　宏之
研一 小柳津
文昭 加藤
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パナソニック株式会社
学校法人早稲田大学
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Publication of WO2012121190A1 publication Critical patent/WO2012121190A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
    • H01G9/2018—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte characterised by the ionic charge transport species, e.g. redox shuttles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
    • H01G9/2009—Solid electrolytes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/331—Metal complexes comprising an iron-series metal, e.g. Fe, Co, Ni
    • 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
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • 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
    • Y02E10/542—Dye sensitized solar 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a photoelectric element that converts light into electricity.
  • photoelectric elements photoelectric conversion elements
  • photoelectric conversion elements such as photovoltaic cells and solar cells
  • sensor elements for sensing temperature, light, and the like.
  • Such an electron transport layer has been conventionally formed from a metal, an organic semiconductor, an inorganic semiconductor, a conductive polymer, conductive carbon, or the like.
  • an electron transport layer for transporting electrons is formed of an organic substance using electrons as carriers, such as fullerene, a perylene derivative, a polyphenylene vinylene derivative, or pentacene.
  • electrons such as fullerene, a perylene derivative, a polyphenylene vinylene derivative, or pentacene.
  • Non-patent Document 5 As a molecular element type solar cell, there has been a report of forming a thin film on a substrate of a structure formed by chemically bonding an electron donating molecule (donor) and an electron accepting molecule (acceptor) (Non-patent Document 5). reference).
  • the present condition is that the electron transport layer for electron transport which has the more excellent electron transport characteristic and a sufficiently wide interface is desired.
  • the effective diffusion distance is a distance until the electrode reaches the electrode after the charge separation, and the conversion efficiency of the device increases as the effective diffusion distance increases.
  • conversion efficiency is sufficient because the interface area of charge separation is not sufficient, and the electron conduction potential affecting the open circuit voltage is uniquely determined by the constituent elements. is not.
  • the present invention has been made in view of the above points, and includes an electron transport layer having excellent electron transport characteristics and a sufficiently wide reaction interface, light having low resistance loss, and excellent light-to-electricity conversion efficiency.
  • An object is to provide an electrical element.
  • the photoelectric element according to the present invention includes a first electrode, a second electrode, an electron transport layer and a hole transport layer sandwiched between the first electrode and the second electrode, It comprises an electrolyte solution and a sensitizing dye.
  • the electron transport layer includes an organic compound having a redox portion capable of repeated redox, and the electrolyte solution has a function of stabilizing the reduced state of the redox portion, and the organic compound and the electrolyte
  • the solution forms a gel layer
  • the sensitizing dye is provided in contact with the electron transport layer
  • the hole transport layer is formed of an organic compound having a function of reducing an oxidant of the sensitizing dye. It contains a charge transport medium, and the charge transport medium has a redox potential of 0.3 V to 1.0 V with respect to the silver / silver chloride reference electrode.
  • the charge transport medium is formed of a ferrocene derivative.
  • the charge transport medium is formed of a triphenylamine derivative.
  • the charge transport medium is formed of a phenothiazine derivative.
  • the charge transport medium is formed of a TEMPO derivative.
  • an optoelectric device having an electron transport layer having excellent electron transport characteristics and a sufficiently wide reaction interface, having a low resistance loss, and excellent in conversion efficiency between light and electricity.
  • an electron transport layer 1 and a hole transport layer 5 are sandwiched between a pair of electrodes 3 and 4 (first electrode 3 and second electrode 4).
  • the electron transport layer 1 includes an organic compound having a redox portion capable of repeated redox. This organic compound swells including an electrolyte solution that stabilizes the reduced state of the redox portion, whereby the gel layer 2 is formed.
  • sensitizing dye is provided in contact with the electron transport layer 1.
  • a sensitizing dye is a dye having a function as a photosensitizer and is changed into an oxidant by a photosensitizing reaction.
  • the hole transport layer 5 contains a charge transport medium having a function of reducing the oxidant of the sensitizing dye.
  • the charge transport medium is formed of an organic compound, and its oxidation-reduction potential is 0.3 V or more and 1.0 V or less with respect to the silver / silver chloride reference electrode.
  • the organic compound and the electrolyte solution in the electron transport layer 1 constitute the gel layer 2 to increase the reaction interface, and the sensitizing dye in contact with the electron transport layer 1 has an oxidant that transports holes. Since it is rapidly reduced by the charge transport medium in the layer 5, the redox cycle of the sensitizing dye can be accelerated. For this reason, the conversion efficiency between light and electricity by the photoelectric element is improved.
  • the sensitizing dye may be in contact with the electron transport layer 1 and may be fixed by a physical or chemical action between the sensitizing dye and the organic compound constituting the gel layer 2. In this case, when the distance between the sensitizing dye and the organic compound approaches, the electron transport efficiency between the sensitizing dye and the organic compound is improved. That the sensitizing dye is in contact with the electron transport layer 1 includes a state in which the sensitizing dye exists in the interface region between the electron transport layer 1 and the hole transport layer 5.
  • FIG. 1 is an example of an embodiment of a photoelectric element.
  • a pair of base materials 6 and 7 (the first base material 6 and the second base material 7) are arranged to face each other.
  • the first electrode 3 is disposed on the inner surface of the first base material 6, and the second electrode 4 is disposed on the inner surface of the second base material 7.
  • the first electrode 3 and the second electrode 4 are opposed to each other.
  • the electron transport layer 1 is provided on the surface of the first electrode 3 opposite to the first substrate 6.
  • the electron transport layer 1 may be in contact with the first electrode 3.
  • a hole transport layer 5 is provided on the surface of the second electrode 4 opposite to the second substrate 7.
  • the hole transport layer 5 may be in contact with the second electrode 4.
  • the electron transport layer 1 is formed from an organic compound having a redox portion.
  • the organic compound and the electrolyte solution in the electron transport layer 1 form the gel layer 2.
  • the first electrode 3 is formed by laminating a conductive material on an insulating first base material 7 formed of, for example, glass or a light-transmitting film.
  • the first electrode 3 may be formed from a single metal film.
  • Preferred examples of the conductive material include metals such as platinum, gold, silver, copper, aluminum, rhodium, and indium; carbon; indium-tin composite oxide, tin oxide doped with antimony, and tin oxide doped with fluorine. Examples thereof include conductive metal oxides; composites of the metals and compounds; materials obtained by coating the metals and compounds with silicon oxide, tin oxide, titanium oxide, zirconium oxide, aluminum oxide, and the like.
  • the surface resistance of the electrode 4 is preferably as low as possible, but the surface resistance is preferably 200 ⁇ / ⁇ or less, more preferably 50 ⁇ / ⁇ or less.
  • the lower limit of the surface resistance is not particularly limited, but is usually 0.1 ⁇ / ⁇ .
  • the light transmittance of the first substrate 6 is high. Is desirable.
  • the preferable light transmittance of the first substrate 6 in this case is 50% or more at a wavelength of 500 nm, and more preferably 80% or more.
  • the thickness of the first electrode 3 is preferably in the range of 0.1 to 10 ⁇ m. If it is in this range, the 1st electrode 3 will be easily formed in uniform thickness, and also the fall of the light transmittance of the 1st electrode 3 will be controlled. Thereby, sufficient light can be incident on the photoelectric element via the first electrode 3.
  • the first electrode 3 may be formed by a vacuum process such as a sputtering method or a vapor deposition method, or a transparent material composed of indium oxide, tin oxide, zinc oxide, or the like by a wet method such as a spin coating method, a spray method, or screen printing.
  • the first electrode 3 may be formed by forming a conductive oxide layer.
  • the second electrode 4 functions as a positive electrode of the photoelectric element.
  • the second electrode 4 is formed, for example, by laminating a conductive material on the second substrate 7.
  • the second electrode 4 may be formed from a single metal film.
  • the material for forming the second electrode 4 depends on the type of the photoelectric element including the second electrode 4, for example, a metal such as platinum, gold, silver, copper, aluminum, rhodium, indium, graphite, Carbon nanotubes, carbon materials such as carbon carrying platinum, indium-tin composite oxide, tin oxide doped with antimony, conductive metal oxides such as tin oxide doped with fluorine, polyethylene dioxythiophene, polypyrrole, polyaniline And the like, and the like.
  • a method for forming the second electrode 4 on the second substrate 7 the same method as that for forming the first electrode 3 on the first substrate 6 can be used.
  • the second base material 7 can be formed from the same material as the first base material 6. When the second electrode 4 is formed on the second base material 7, the second base material 7 may or may not have translucency.
  • the second substrate 7 is preferably transparent in that light can enter from both sides of the hole transport layer 5 side and the electron transport layer 1 side of the photoelectric element.
  • the light transmittance of the second substrate 7 can be set similarly to the light transmittance of the first substrate 6.
  • the electron transport layer 1 is composed of an organic compound.
  • the molecule of the organic compound has a redox portion that can be repeatedly redox, and also has a portion (hereinafter referred to as a gel portion) that becomes a gel by swelling with the electrolyte solution.
  • the redox moiety is chemically bonded to the gel site.
  • the positional relationship between the redox moiety and the gel part in the molecule is not particularly limited.
  • the gel part constitutes a skeleton such as the main chain of the molecule
  • the redox part is bonded to the main chain as a side chain. Yes.
  • the molecular skeleton that forms the gel part and the molecular skeleton that forms the redox moiety may be alternately bonded.
  • the gel layer 2 can hold the oxidation-reduction part so that the oxidation-reduction part stays at a position where it is easy to transport electrons.
  • the organic compound having a redox moiety and a gel part may be a low molecular weight substance or a high molecular weight substance.
  • an organic compound that forms a so-called low molecular gel through hydrogen bonding or the like can be used.
  • the organic compound is a polymer, an organic compound having a number average molecular weight of 1000 or more is preferable because it can spontaneously express a gelling function.
  • the upper limit of the molecular weight is not particularly limited, but is preferably 1,000,000 or less.
  • the gel state of the gel layer 2 is preferably, for example, konjac or an external shape such as an ion exchange membrane, but is not limited to these states.
  • An oxidation-reduction part means a site that is reversibly converted into an oxidant and a reductant in a redox reaction.
  • the redox moiety is not particularly limited as long as it is a site constituting a pair of redox systems composed of an oxidant and a reductant, but the oxidant and the reductant preferably have the same charge.
  • Swelling degree is a physical index that affects the size of the reaction interface related to the gel layer 2.
  • the swelling degree said here is represented by the following formula.
  • the gel dried body refers to a dried gel layer 2. Drying the gel layer 2 means removing the solution contained in the gel layer 2, especially removing the solvent. Examples of the method for drying the gel layer 2 include a method by heating, a method for removing the solution or solvent in a vacuum environment, a method for removing the solution or solvent contained in the gel layer 2 using another solvent, and the like. It is done.
  • the degree of swelling of the gel layer 2 is preferably 110 to 3000%, more preferably 150 to 500%.
  • the degree of swelling is less than 110%, the electrolyte component in the gel layer 2 is reduced, so that the redox part may not be sufficiently stabilized.
  • the degree of swelling exceeds 3000%, the redox part in the gel layer 2 is reduced, and the electron transport ability may be reduced. In either case, the characteristics of the photoelectric element are deteriorated.
  • An organic compound having a redox moiety and a gel site as described above in one molecule can be represented by the following general formula.
  • (X i ) nj : Y k (X i ) n represents a gel site, and X i represents a monomer of a compound constituting the gel site.
  • the gel site can be formed from a polymer backbone.
  • Y represents a redox moiety bonded to (X i ) n .
  • j and k are each an arbitrary integer representing the number of (X i ) n and Y contained in one molecule, and both are preferably in the range of 1 to 100,000.
  • the redox moiety Y may be bonded to any part of the polymer skeleton that forms the gel part (X i ) n .
  • the oxidation-reduction part Y may contain different types of sites, and in this case, a site with a near redox potential is preferable from the viewpoint of the electron exchange reaction.
  • Examples of the organic compound having such a redox moiety Y and a gel site (X i ) n in one molecule include a polymer having a quinone derivative skeleton formed by chemically bonding quinones, and an imide derivative skeleton containing an imide.
  • the polymer skeleton is a gel site, and the quinone derivative skeleton, the imide derivative skeleton, the phenoxyl derivative skeleton, and the viologen derivative skeleton are redox portions.
  • examples of polymers having a quinone derivative skeleton formed by chemically bonding quinones include those having the following chemical structures [Chemical Formula 1] to [Chemical Formula 4].
  • R represents methylene, ethylene, propane-1,3-dienyl, ethylidene, propane-2,2-diyl, alkanediyl, benzylidene, propylene, vinylidene, propene-1,3- Saturated or unsaturated hydrocarbons such as diyl, but-1-ene-1,4-diyl; cyclic hydrocarbons such as cyclohexanediyl, cyclohexenediyl, cyclohexadienediyl, phenylene, naphthalene, biphenylene; oxalyl, malonyl, succinyl, Glutanyl, adipoyl, al
  • [Chemical Formula 1] is an example of an organic compound formed by chemically bonding anthraquinone to the polymer main chain.
  • [Chemical Formula 2] is an example of an organic compound constituted by incorporating anthraquinone as a repeating unit into a polymer main chain.
  • [Chemical Formula 3] is an example of an organic compound in which anthraquinone is a cross-linking unit.
  • [Chemical Formula 4] is an example of an anthraquinone having a proton donating group that forms an intramolecular hydrogen bond with an oxygen atom.
  • the above quinone polymer is capable of high-speed redox reaction that is not limited by proton transfer, and there is no electronic interaction between quinone groups, which are redox sites (redox sites), and chemical stability that can withstand long-term use. Have sex. Moreover, since the quinone polymer does not elute in the electrolyte solution, it is useful in that the electron transport layer 1 can be formed by being held by the first electrode 3.
  • Examples of the polymer having an imide derivative skeleton containing imide include polyimides represented by [Chemical Formula 5] and [Chemical Formula 6].
  • R 1 to R 3 are an aromatic group such as a phenylene group, an aliphatic group such as an alkylene group or an alkyl ether, or an ether group.
  • the polyimide polymer skeleton may be cross-linked at the R 1 to R 3 portions, but may not have a cross-linked structure as long as the polyimide polymer skeleton swells in the solvent and does not elute. In the case of crosslinking, the portion where the crosslinking occurs corresponds to the gel site (X i ) n .
  • an imide group may be contained in the crosslinking unit.
  • the imide group phthalimide, pyromellitic imide, or the like is preferably used as long as it shows electrochemically reversible redox characteristics.
  • Examples of the polymer having a phenoxyl derivative skeleton containing phenoxyl include a galbi compound (galbi polymer) represented by [Chemical Formula 7].
  • the galbi compound represented by [Chemical Formula 7]
  • the galvinoxyl group corresponds to the redox site Y
  • the polymer skeleton corresponds to the gel site (X i ) n .
  • Examples of the polymer having a viologen derivative skeleton containing viologen include polyviologen polymers as shown in [Chemical 9] and [Chemical 10].
  • the site represented by [Chemical Formula 11] corresponds to the redox moiety Y
  • the polymer skeleton corresponds to the gel site (X i ) n .
  • m and n represent the degree of polymerization of the monomer, and the values are 1 to A range of 100,000 is preferred.
  • the electron transport layer 1 of the photoelectric element includes at least one of an imide derivative, a quinone derivative, a viologen derivative, and a phenoxyl derivative as an organic compound. These are compounds in which exchange of electrons in a molecule is performed at high speed, and by using these, an electron transport layer having a high electron transport capability can be formed.
  • the gel layer 2 is formed by the electrolyte solution being contained and swollen between the polymer skeleton of the organic compound having the above-described oxidation-reduction portion and the gel portion composed of the polymer skeleton.
  • the electrolyte solution is contained in the electron transport layer 1 formed from the organic compound, so that the ionic state formed by the redox reaction of the redox part is compensated by the counter ion in the electrolytic solution, and the redox part is Stabilized.
  • the electrolyte solution only needs to contain an electrolyte and a solvent.
  • the electrolyte is either one or both of a supporting salt and a pair of redox constituents composed of an oxidant and a reductant.
  • the supporting salt supporting electrolyte
  • examples of the supporting salt include tetrabutylammonium perchlorate, tetraethylammonium hexafluorophosphate, ammonium salts such as imidazolium salt and pyridinium salt, alkali metals such as lithium perchlorate and potassium tetrafluoroborate. Examples include salt.
  • the redox-based constituent material means a pair of substances that are present reversibly in the form of an oxidized form and a reduced form in a redox reaction.
  • redox-based constituent materials include chlorine compound-chlorine, iodine compound-iodine, bromine compound-bromine, thallium ion (III) -thallium ion (I), mercury ion (II) -mercury ion (I ), Ruthenium ion (III) -ruthenium ion (II), copper ion (II) -copper ion (I), iron ion (III) -iron ion (II), nickel ion (II) -nickel ion (III), Examples thereof include, but are not limited to, vanadium ion (III) -vanadium ion (II), manganate ion-permanganate ion, and the like. These redox constituents function differently from the
  • the solvent constituting the electrolyte solution includes at least one of water, an organic solvent, and an ionic liquid.
  • organic solvent examples include carbonate compounds such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, and propylene carbonate, ester compounds such as methyl acetate, methyl propionate, and ⁇ -butyrolactone, diethyl ether, 1, Ether compounds such as 2-dimethoxyethane, 1,3-dioxosilane, tetrahydrofuran, 2-methyl-tetrahydrofuran, heterocyclic compounds such as 3-methyl-2-oxazodilinone, 2-methylpyrrolidone, acetonitrile, methoxyacetonitrile, propionitrile, etc.
  • carbonate compounds such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, and propylene carbonate
  • ester compounds such as methyl acetate, methyl propionate, and ⁇ -butyrolactone
  • diethyl ether 1, Ether compounds such
  • aprotic polar compounds such as nitrile compounds, sulfolane, dimethyl sulfoxide and dimethylformamide. These can be used alone or in combination of two or more.
  • carbonate compounds such as ethylene carbonate and propylene carbonate, ⁇ -butyrolactone, 3-methyl-2-oxazozirinone, 2-methyl Heterocyclic compounds such as pyrrolidone, and nitrile compounds such as acetonitrile, methoxyacetonitrile, propionitrile, 3-methoxypropionitrile, and valeric nitrile are preferred.
  • the redox part is stabilized, and the ionic liquid is not volatile and has high flame retardancy, so that it has excellent stability.
  • known ionic liquids in general can be used.
  • imidazolium-based such as 1-ethyl-3-methylimidazolium tetracyanoborate
  • pyridine-based alicyclic amine-based, aliphatic amine-based
  • Azonium amine-based ionic liquids European Patent No. 718288, International Publication WO95 / 18456, Pamphlet 65, 11 (923), J. Electrochem. Soc. 143, 10 No., 3099 (1996), Inorg. Chem. 35, 1168 (1996).
  • the electron transport layer 1 is formed by providing the gel layer 2 formed of the organic compound having an oxidation-reduction portion and the electrolyte solution as described above on the surface of the electrode 4. In the electron transport layer 1 formed in this way, electrons behave as dopants.
  • the electron transport layer 1 has an oxidation-reduction potential lower than +100 mV with respect to the silver / silver chloride reference electrode 4. It has a reducing part.
  • the thickness of the electron transport layer 1 is preferably in the range of 10 nm to 10 mm from the viewpoint of maintaining good electron transport properties. Particularly preferably, the thickness is 100 nm to 100 ⁇ m. With this thickness, good electron transport characteristics of the electron transport layer 1 and an increase in the area of the interface can be achieved at a higher level.
  • a wet forming method in which the electron transport layer 1 is formed by applying a solution or the like is preferable because it is a simpler and lower cost manufacturing method.
  • a wet forming method is preferable from the viewpoint of moldability.
  • the wet process include a spin coating method, a drop cast method in which droplets are dropped and then dried, and a printing method such as screen printing and gravure printing.
  • vacuum processes such as sputtering and vapor deposition can also be employed.
  • Sensitizing dye functions as a photosensitizer that efficiently absorbs visible light and near infrared light.
  • the sensitizing dye is provided in contact with the electron transport layer 1, and in this case, may be provided at the interface between the electron transport layer 1 and the hole transport layer 5.
  • the gel layer 2 is formed by swelling an organic compound having a redox moiety in the electron transport layer 1 with an electrolyte solution, and the hole transport layer 5 is formed with a similar electrolyte solution.
  • the electrolyte solution contained therein also forms part of the hole transport layer 5. Therefore, the sensitizing dye is present in the gel layer 2 by adhering, adsorbing, or bonding to the surface of the organic compound that forms the electron transport layer 1, so that the sensitizing dye is transported by electrons. It is provided at the interface between the layer 1 and the hole transport layer 5. When the sensitizing dye is thus provided, a dye-sensitized photoelectric conversion element is produced.
  • sensitizing dye known materials can be used.
  • 9-phenylxanthene dye, coumarin dye, acridine dye, triphenylmethane dye, tetraphenylmethane dye, quinone dye, azo dye examples thereof include dyes, indigo dyes, cyanine dyes, merocyanine dyes, and xanthene dyes.
  • RuL 2 (H 2 O) 2 type ruthenium-cis-diaqua-bipyridyl complex (where L represents 4,4′-dicarboxyl-2,2′-bipyridine), ruthenium -Transition metal complexes of types such as tris (RuL 3 ), ruthenium-bis (RuL 2 ), osnium-tris (OsL 3 ), osnium-bis (OsL 2 ), zinc-tetra (4-carboxyphenyl) porphyrin, iron -Hexacyanide complexes, phthalocyanines and the like.
  • the sensitizing dye for example, a dye as described in the DSSC chapter of “FPD / DSSC / Optical memory and the latest technology and material development of functional dye” (NTS Inc.) may be applied.
  • dyes having associative properties are preferable from the viewpoint of promoting charge separation during photoelectric conversion.
  • a dye having an effect by forming an aggregate for example, a dye represented by the structure of [Chemical Formula 12] is preferable.
  • X 1 and X 2 are an organic group having at least one alkyl group, alkenyl group, aralkyl group, aryl group, or heterocyclic ring, and each may have a substituent. It is known that a dye such as the above [Chemical Formula 12] is associative. In this case, the recombination of electrons and holes existing in the electron transport layer 1 and the hole transport layer 5 is dramatically reduced, and the conversion efficiency of the photoelectric conversion element obtained thereby is improved.
  • the sensitizing dye in contact with the electron transport layer 1 may be immobilized on the surface or inside of the gel layer 2 by physical or chemical action with the organic compound constituting the gel layer 2. Furthermore, the sensitizing dye may be present in the gel layer 2, and in this case, it may be present throughout the entire gel layer 2.
  • the sensitizing dye is present in the gel layer 2 means that the sensitizing dye is present not only in the surface layer of the gel layer 2 but also in the inside thereof. As a result, the amount of the sensitizing dye present in the gel layer 2 is continuously maintained in a state of a certain value or more, thereby bringing about an effect of improving the output of the photoelectric element.
  • the state in which the sensitizing dye is present in the gel layer 2 includes “the state in which the sensitizing dye is present in the electrolyte solution constituting the gel layer 2” and “the sensitizing dye is in the gel layer 2”. In a state of being held in the gel layer 2 by physically or chemically interacting with an organic compound constituting “.
  • the state in which the sensitizing dye is held in the gel layer 2 by physically interacting with the organic compound constituting the gel layer 2 means, for example, sensitization as an organic compound constituting the gel layer 2
  • an organic compound having a structure that prevents the movement of molecules in the dye gel layer 2 By using an organic compound having a structure that prevents the movement of molecules in the dye gel layer 2, the movement of the molecules of the sensitizing dye is prevented in the gel layer 2.
  • Structures that prevent the movement of sensitizing dye molecules include structures in which various molecular chains such as alkyl chains of organic compounds exhibit steric hindrance, and the size of voids that exist between the molecular chains of organic compounds. For example, a structure that is small enough to suppress the above.
  • the sensitizing dye It is also effective to bring a factor that develops a physical interaction to the sensitizing dye side. Specifically, it is also effective to give the sensitizing dye a structure that expresses steric hindrance due to various molecular chains such as an alkyl chain, and to link two or more sensitizing dye molecules.
  • a sulfur-containing group such as sulfanyl and sulfonyl, a nitrogen-containing group such as imino, nitrilo, hydrazo, azo, azino, diazoamino, urylene and amide, a silicon-containing group such as silanediyl and disilane-1,2-diyl, or a terminal thereof. It is effective to utilize a substituted group or a complex group.
  • Said moiety may be a substituted, linear or branched alkyl group such as methyl, ethyl, i-propyl, butyl, t-butyl, octyl, 2-ethylhexyl, 2-methoxyethyl, benzyl, Trifluoromethyl, cyanomethyl, ethoxycarbonylmethyl, propoxyethyl, 3- (1-octylpyridinium-4-yl) propyl, 3- (1-butyl-3-methylpyridinium-4-yl) propyl, etc.
  • it is desirable to bind to the sensitizing dye via an alkenyl group which may be linear or branched, for example, vinyl or allyl.
  • the state in which the sensitizing dye is held in the gel layer 2 by chemically interacting with the organic compound constituting the gel layer 2 means, for example, sharing between the sensitizing dye and the organic compound In the gel layer 2 due to chemical interaction such as bond, coordination bond, ionic bond, hydrogen bond, van der Waals bond, hydrophobic interaction, hydrophilic interaction, force based on electrostatic interaction, etc.
  • the sensitizing dye is retained.
  • the sensitizing dye is fixed in the gel layer 2 by the chemical interaction between the sensitizing dye and the organic compound constituting the gel layer 2, the distance between the sensitizing dye and the organic compound approaches. For this reason, electrons move more efficiently.
  • the sensitizing dye is fixed in the gel layer 2 by chemical interaction between the organic compound and the sensitizing dye
  • functional groups are appropriately introduced into the organic compound and the sensitizing dye
  • the sensitizing dye is fixed to the organic compound by a chemical reaction or the like.
  • functional groups include hydroxyl groups, carboxyl groups, phosphate groups, sulfo groups, nitro groups, alkyl groups, carbonate groups, aldehyde groups, thiol groups, and the like.
  • the reaction format of the chemical reaction via the functional group include a condensation reaction, an addition reaction, and a ring-opening reaction.
  • a functional group in the sensitizing dye is introduced in the vicinity of a site where the electron density is increased in a state where the sensitizing dye is photoexcited, and the gel It is preferable that the functional group in the organic compound in the layer 2 is introduced in the vicinity of a site involved in electron transport in the organic compound. In this case, the efficiency of electron transfer from the sensitizing dye to the organic compound and the efficiency of electron transport in the organic compound can be improved.
  • the sensitizing dye and the organic compound constituting the gel layer 2 are bonded with a bonding group having a high electron transporting property that connects the electron cloud of the sensitizing dye and the electron cloud of the organic compound, it is more efficient. Electrons can move from the sensitizing dye to the organic compound. Specifically, an example in which an ester bond having a ⁇ electron system or the like is used as a chemical bond that links a ⁇ electron cloud of a sensitizing dye and a ⁇ electron cloud of an organic compound.
  • the timing when the sensitizing dye and the organic compound are combined is when the organic compound is in a monomer state, when the organic compound is polymerized, when the organic compound is gelated after the organic compound is polymerized, and the organic compound is gelled. Any of these may be used.
  • Specific examples of the method include a method in which the electron transport layer 1 formed of an organic compound is immersed in a bath containing a sensitizing dye, and a coating solution containing the organic compound and the sensitizing dye is applied to the electrode 4.
  • a method of forming the electron transport layer 1 by forming a film may be used, and a plurality of methods may be combined.
  • the sensitizing dye When the sensitizing dye is immobilized by a physical or chemical action between the organic compound constituting the gel layer 2 as described above, the distance between the sensitizing dye and the organic compound is increased. Electron transport efficiency between the dye-sensitive material and the organic compound is improved.
  • the content of the sensitizing dye in the gel layer 2 is set as appropriate.
  • the content of the sensitizing dye is 0.1 parts by mass or more with respect to 100 parts by mass of the organic compound, the unit film of the gel layer 2
  • the amount of the sensitizing dye per thickness becomes sufficiently high, thereby improving the light absorption capability of the sensitizing dye and obtaining a high current value.
  • the content of the sensitizing dye is 1000 parts by mass or less with respect to 100 parts by mass of the organic compound, it is suppressed that an excessive amount of the sensitizing dye is interposed between the organic compounds, and electron transfer in the organic compound is prevented. Inhibition by the sensitizing dye is suppressed, and high conductivity is ensured.
  • the hole transport layer 5 is formed including a charge transport medium having a function of reducing the oxidized form of the sensitizing dye.
  • a material for forming the hole transport layer 5 an organic compound may be contained, and an electrolyte solution in which an electrolyte such as a redox couple is dissolved in a solvent, a solid electrolyte such as a molten salt, triphenyl, or the like.
  • an electrolyte solution in which an electrolyte such as a redox couple is dissolved in a solvent, a solid electrolyte such as a molten salt, triphenyl, or the like.
  • examples thereof include amine derivatives such as amines, and conductive polymers such as polyacetylene, polyaniline, and polythiophene.
  • the hole transport layer 5 When the hole transport layer 5 is formed of an electrolyte solution, the hole transport layer 5 can also be formed of an electrolyte solution that constitutes the gel layer 2. In this case, the electrolyte solution constituting the gel layer 2 constitutes a part of the hole transport layer 5.
  • the electrolyte solution may be held in a polymer matrix.
  • a polyvinylidene fluoride polymer compound used as the polymer matrix a homopolymer of vinylidene fluoride or a copolymer of vinylidene fluoride and another polymerizable monomer (preferably a radical polymerizable monomer) may be used.
  • polymerizable monomers copolymerized with vinylidene fluoride hereinafter referred to as copolymerizable monomers
  • copolymerizable monomers include hexafluoropropylene, tetrafluoroethylene, trifluoroethylene, ethylene, propylene, acrylonitrile, vinylidene chloride.
  • an organic charge transport medium can be used as the charge transport medium contained in the hole transport layer 5.
  • the redox potential of the organic charge transport medium is not less than 0.3V and not more than 1.0V. This is equal to or higher than the oxidation-reduction potential of iodine, which is a conventional inorganic charge transport medium (0.3 V with respect to the silver / silver chloride reference electrode), and the HOMO level of the dye (silver / silver chloride) It is the range which is the same as or lower than 1.0 V) with respect to the reference electrode.
  • the open-circuit voltage defined by the difference in redox potential between the charge transport medium and the electron transport material can be improved.
  • the potential difference between the HOMO level of the dye and the oxidation-reduction potential of the charge transport medium is reduced, the charge separation efficiency between the dye and the charge transport medium is improved, and the short-circuit current density can be improved.
  • the conversion efficiency of the photoelectric element can be improved.
  • the oxidation-reduction potential of the charge transport medium becomes nobler than the HOMO level of the dye, charge separation does not occur from the viewpoint of the energy level. Therefore, the redox potential of the organic charge-transport medium is lower than the HOMO level of the dye. It is preferable that In addition, HOMO is Highest Occupied Molecular Orbital (the highest occupied orbit).
  • the silver / silver chloride reference electrode is also referred to as a silver-silver chloride electrode, and is a reference electrode that uses silver and silver chloride as electrodes (an electrode that provides a potential reference point when measuring the electrode potential).
  • the typical structure is a silver surface covered with silver chloride.
  • Open-circuit voltage (V) Redox potential of charge transport medium (V)-Redox potential of electron transport material (V)
  • V Open-circuit voltage
  • (V) in the above formula is a unit: volt.
  • the redox potential is unambiguous and fixed because it is an inorganic substance, whereas the organic charge transport medium changes the substituent effect and redox center. It can be considered that the redox potential can be controlled. From the above formula, it is considered that the open circuit voltage is improved by applying an organic charge transport medium having a more noble redox potential.
  • the organic compound forming the electron transport layer contains an electrolyte solution that stabilizes the reduced state of the redox portion, and thus the electron life in the reduced state is extremely long. .
  • an electron transport material having a long electron lifetime reverse electron transfer is suppressed and loss of open circuit voltage is reduced. That is, it is considered that the open-circuit voltage in the photoelectric element is greatly influenced by the oxidation-reduction potential of the charge transport medium or the electron transport material. Therefore, it is considered that it is particularly effective to use a charge transport medium having a more noble redox potential in the photoelectric element.
  • charge separation efficiency is a factor that determines the short-circuit current density, it is important to design the interface according to the electrical properties such as potential and the structural properties such as molecular size. Since the organic charge transport medium has a noble redox potential than conventional iodine, the level difference from the HOMO level of the dye is reduced, the charge separation efficiency is improved, and the short-circuit current density can be improved. Conceivable. However, when the redox potential of the charge transport medium becomes nobler than the HOMO level of the dye, charge separation does not occur from the viewpoint of the energy level. Therefore, the redox potential of the organic charge transport medium is lower than the HOMO level of the dye. It is preferable that
  • the charge transport medium contained in the hole transport layer 5 is preferably at least one selected from ferrocene derivatives, triphenylamine derivatives, phenothiazine derivatives, and TEMPO derivatives.
  • the ferrocene derivative is a ferrocene derivative represented by [Chemical Formula 13].
  • Derivatives include those in which a hydrogen atom is substituted with a hydrocarbon group.
  • the triphenylamine derivative is represented by [Chemical Formula 14].
  • the substituents R 1 , R 2 and R 3 are independently of each other a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic C1-C30 hydrocarbon group, an alkoxy group, a hydroxyl group, a nitro group, A substituent selected from a group, a nitroso group, a cyano group, an aryloxy group, and an acyl group.
  • the phenothiazine derivative is a phenothiazine derivative represented by [Chemical 15].
  • Derivatives include those in which a hydrogen atom is substituted with a hydrocarbon group.
  • the TEMPO derivative is represented by [Chemical Formula 16].
  • the substituents R A to R E are independently of each other a hydrogen atom, a substituted or unsubstituted aliphatic or aromatic C1-C30 hydrocarbon group, an alkoxy group, a halogen group, a hydroxyl group, a nitro group, Selected from a group, a nitroso group, a cyano group, an aryloxy group and an acyl group.
  • TEMPO derivatives include TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl).
  • the ferrocene derivative is a complex of iron and an aromatic compound, and since the ⁇ electron cloud spreads widely, reversible and quick electron transfer can be expected. Since the dye cation is rapidly reduced by rapid electron transfer, reverse electron transfer to the dye cation is suppressed, and an improvement in open circuit voltage is expected.
  • the triphenylamine derivative has a phenyl group, and it is easy to synthesize derivatives into which various substituents are introduced. For example, when an electron-withdrawing substituent is introduced into the p-position of a phenyl group, the redox potential can be shifted preciously, and when an electron-donating substituent is introduced, the redox potential can be shifted basely. Since the open circuit voltage is caused by the redox potential of the mediator, it is expected that the open circuit voltage can be improved by using triphenylamine derivatives having different redox potentials.
  • Phenothiazine derivatives have high solubility in general-purpose organic solvents.
  • the TEMPO derivative can efficiently transport the generated holes to the counter electrode by the very fast electron transfer reaction of the stable radical compound, and can improve the conversion efficiency.
  • the stable radical compound can be used without particular limitation as long as it is a chemical species having an unpaired electron, that is, a compound having a radical. Among them, a radical compound having nitroxide (NO.) In the molecule is used. preferable.
  • the radical compound preferably has a molecular weight (number average molecular weight) of 1000 or more. A molecular weight of 1000 or more is preferable from the viewpoint of the stability of the device because it becomes difficult to volatilize at or near a solid at room temperature.
  • examples of the charge transporter include materials having p-type redox properties such as a tetrathiafulvalene derivative and a nitronyl nitroxide derivative.
  • the electron transport layer 1 is formed by laminating an organic compound on the first electrode 3 provided on the first substrate 6 by a wet method or the like.
  • a hole transport layer 5 and a second electrode 4 are laminated on the electron transport layer 1.
  • the hole transport layer 5 is formed from an electrolyte solution, for example, the electron transport layer 1 and the second electrode 4 are sealed with a sealing material between the electron transport layer 1 and the second electrode 4.
  • the hole transport layer 5 can be formed by filling the electrolyte solution in the gap between the second electrode 4. At this time, a part of the electrolyte solution penetrates into the electron transport layer 1, so that the organic compound constituting the electron transport layer 1 swells, and thereby the gel layer 2 can be formed.
  • the organic compound of the electron transport layer 1 and the electrolyte solution form the gel layer 2, thereby increasing the reaction interface and increasing the amount in contact with the electron transport layer 1. Since the oxidized form of the dye is rapidly reduced by the charge transport medium in the hole transport layer 5, the oxidation-reduction cycle of the sensitizing dye can be accelerated. For this reason, the conversion efficiency between light and electricity of the photoelectric element is improved.
  • the sensitizing dye absorbs light and is excited, and the generated excited electrons flow into the electron transport layer 1.
  • holes are taken out through the first electrode 3 and holes in the sensitizing dye are taken out from the hole transport layer 5 through the second electrode 4.
  • the organic compound of the electron transport layer 1 and the electrolyte solution form the gel layer 2, so that the reaction interface becomes sufficiently wide, and the oxidant of the sensitizing dye exists in the hole transport layer 5.
  • the sensitizing dye becomes reexcitable again.
  • the sensitizing dye absorbs light again and is excited, and electrons and holes are taken out again.
  • Such a redox cycle of the sensitizing dye is repeated continuously at a high speed.
  • methyl 4-bromobenzoate (1.08 g; 0.005 mol, Mw: 215.0, TCI) dissolved in tetrahydrofuran (75 ml) was added, and the mixture was stirred at ⁇ 78 ° C. to room temperature overnight.
  • the reaction solution changed from yellow to light yellow to dark blue indicating the generation of anions.
  • a saturated ammonium chloride aqueous solution was added until the reaction solution became completely yellow, and liquid separation extraction was performed with ether / water to obtain a yellow viscous liquid.
  • the p-hydrogalvinoxyl styrene (1.54 g; 2.93 mmol) indicated by reference numeral 3 in [Scheme 1] was obtained as orange microcrystals.
  • a conductive glass substrate having a thickness of 0.7 mm and a sheet resistance of 100 ⁇ / ⁇ was prepared as the substrate 6 on which the first electrode 3 was provided.
  • This conductive glass substrate is composed of a glass substrate and a coating film made of fluorine-doped SnO 2 laminated on one side of the glass substrate. It becomes the first electrode 3.
  • the above galbi polymer was dissolved in chlorobenzene at a ratio of 2% by mass to prepare a galbi polymer solution. Then, this galbipolymer solution is spin-coated at 2000 rpm on the surface of the conductive glass substrate on which the electrode is formed, and dried at 60 ° C. and 0.01 MPa for 1 hour, thereby forming a galbipolymer layer having a thickness of 60 nm. Formed.
  • the electron transport layer 3 thus formed was immersed in an acetonitrile solution containing a sensitizing dye (D131) represented by [Chemical Formula 18] at a concentration of 0.3 mM for 1 hour and then washed with water. Thereby, a sensitizing dye was provided in the electron transport layer 3.
  • a sensitizing dye represented by [Chemical Formula 18]
  • a conductive glass substrate having the same configuration as that of the conductive glass substrate used in forming the electron transport layer 3 was prepared. Further, chloroplatinic acid was dissolved in isopropyl alcohol so that its concentration was 5 mM. The solution thus obtained was spin-coated on the surface of the conductive glass substrate on the side of the coating film, and then baked at 400 ° C. for 30 minutes, whereby the second electrode 4 was formed.
  • the conductive glass substrate provided with the electron transport layer 3 and the conductive glass substrate provided with the second electrode 4 are arranged so that the electron transport layer 3 and the second electrode 4 face each other.
  • a hot-melt adhesive having a width of 1 mm and a thickness of 50 ⁇ m (Bunel, manufactured by DuPont) was interposed between the outer edges of the two. And while heating this hot-melt adhesive, the above-mentioned two conductive glass substrates were pressurized in the thickness direction, thereby joining the two conductive glass substrates via the hot-melt adhesive. At this time, voids serving as electrolyte injection ports were formed in the hot-melt adhesive.
  • an electrolytic solution was filled between the electron transport layer 3 and the second electrode 4 from the above injection port.
  • ferrocene represented by [Chemical Formula 19] was added at a concentration of 0.1M
  • bis (trifluoromethanesulfonyl) imidolithium (LiTFSI) was added at a concentration of 0.5M
  • 4-tert-butylpyridine was added at 0.025M.
  • An acetonitrile solution containing at a concentration of was used. Note that 4-tert-butylpyridine is added as a stabilizer for the oxidation-reduction reaction of the electron transport layer 3 (galbi polymer) when producing a photoelectric conversion element.
  • the injection port was filled by irradiating UV light to cure the UV curable resin.
  • the hole transport layer 5 made of an electrolytic solution is formed, and the electrolytic solution penetrates into the electron transport layer 1 to swell the organic compound (galbi polymer) constituting the electron transport layer 1 to form the gel layer 2. did.
  • Example 2 As an electrolytic solution, tris (4-methoxyphenyl) amine represented by [Chemical Formula 20] is contained at a concentration of 0.1M, LiTFSI at a concentration of 0.5M, and 4-tert-butylpyridine at a concentration of 0.025M. Acetonitrile solution was used. Except for this, a photoelectric element was fabricated in the same manner as in Example 1.
  • Example 3 As the electrolytic solution, an acetonitrile solution containing phenothiazine represented by [Chemical Formula 21] at a concentration of 0.1 M, LiTFSI at a concentration of 0.5 M, and 4-tert-butylpyridine at a concentration of 0.025 M was used. Except for this, a photoelectric element was fabricated in the same manner as in Example 1.
  • Example 4 As an electrolytic solution, 2,2,6,6-tetramethylpiperidine-1-oxyl represented by [Chemical Formula 22] was added at a concentration of 0.1M, LiTFSI at a concentration of 0.5M, and 4-tert-butylpyridine. An acetonitrile solution containing a concentration of 0.025M was used. Except for this, a photoelectric element was fabricated in the same manner as in Example 1.
  • the measurement is performed under the condition that 4-tert-butylpyridine is not included, because 4-tert-butylpyridine is considered not to affect the redox potential. is there.

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Abstract

L'invention concerne un élément photoélectrique qui présente une faible perte ohmique et un excellent rendement de conversion photoélectrique et qui est muni d'une couche de transport d'électrons possédant d'excellentes caractéristiques de transport d'électrons et une interface de réaction suffisamment large. Ledit élément photoélectrique est muni de ce qui suit : une première électrode (3) ; une deuxième électrode (4) ; une couche de transport d'électrons (1) et une couche de transport de trous (5) prise en sandwich entre la première et la deuxième électrodes (3 et 4) ; une solution d'électrolyte ; et un colorant de sensibilisation. La couche de transport d'électrons (1) contient un composé organique qui comprend une partie d'oxydoréduction pouvant être soumise à une oxydoréduction répétée. La solution d'électrolyte sert à stabiliser l'état de réduction de la partie d'oxydoréduction. Le composé organique mentionné précédemment et la solution d'électrolyte forment une couche de gel (2). Le colorant de sensibilisation est mis en contact avec la couche de transport d'électrons (1). La couche de transport de trous (5) contient un milieu de transport de charge comprenant un composé organique servant à réduire ce qui est obtenu lorsque le colorant de sensibilisation est oxydé. Le potentiel de réduction dudit milieu de transport de charge par rapport à une électrode de référence en argent/argent-chlorure est compris entre 0,3 et 1,0 V inclus.
PCT/JP2012/055516 2011-03-10 2012-03-05 Élément photoélectrique WO2012121190A1 (fr)

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CN103779100A (zh) * 2012-10-23 2014-05-07 中国科学院化学研究所 离子/空穴双传输通道分子有机导体复合电解质及其制备方法与应用
JP2018018905A (ja) * 2016-07-26 2018-02-01 三菱ケミカル株式会社 光電変換素子及び太陽電池モジュール

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WO2014148016A1 (fr) * 2013-03-22 2014-09-25 パナソニック株式会社 Élément de conversion photoélectrique

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WO2010024090A1 (fr) * 2008-08-28 2010-03-04 パナソニック電工株式会社 Élément photoélectrique
WO2011013760A1 (fr) * 2009-07-31 2011-02-03 パナソニック電工株式会社 Élément photoélectrique
JP2011023344A (ja) * 2009-06-19 2011-02-03 Panasonic Electric Works Co Ltd 光電気素子
JP2011034813A (ja) * 2009-07-31 2011-02-17 Panasonic Electric Works Co Ltd 光電気素子

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WO2010024090A1 (fr) * 2008-08-28 2010-03-04 パナソニック電工株式会社 Élément photoélectrique
JP2011023344A (ja) * 2009-06-19 2011-02-03 Panasonic Electric Works Co Ltd 光電気素子
WO2011013760A1 (fr) * 2009-07-31 2011-02-03 パナソニック電工株式会社 Élément photoélectrique
JP2011034813A (ja) * 2009-07-31 2011-02-17 Panasonic Electric Works Co Ltd 光電気素子

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103779100A (zh) * 2012-10-23 2014-05-07 中国科学院化学研究所 离子/空穴双传输通道分子有机导体复合电解质及其制备方法与应用
JP2018018905A (ja) * 2016-07-26 2018-02-01 三菱ケミカル株式会社 光電変換素子及び太陽電池モジュール

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