WO2016047344A1 - Élément de conversion photoélectrique, cellule solaire sensibilisée par un colorant, colorant complexe métallique et solution de colorant - Google Patents

Élément de conversion photoélectrique, cellule solaire sensibilisée par un colorant, colorant complexe métallique et solution de colorant Download PDF

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WO2016047344A1
WO2016047344A1 PCT/JP2015/073871 JP2015073871W WO2016047344A1 WO 2016047344 A1 WO2016047344 A1 WO 2016047344A1 JP 2015073871 W JP2015073871 W JP 2015073871W WO 2016047344 A1 WO2016047344 A1 WO 2016047344A1
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group
formula
dye
represented
ring
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PCT/JP2015/073871
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Japanese (ja)
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征夫 谷
小林　克
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富士フイルム株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0083—Solutions of dyes
    • 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

Definitions

  • the present invention relates to a photoelectric conversion element, a dye-sensitized solar cell, a metal complex dye, and a dye solution.
  • Photoelectric conversion elements are used in various photosensors, photocopiers, photoelectrochemical cells such as solar cells, and the like.
  • Various methods such as a method using a metal, a method using a semiconductor, a method using an organic pigment or a dye, or a combination of these have been put to practical use for this photoelectric conversion element.
  • a solar cell using non-depleting solar energy does not require fuel, and full-scale practical use is highly expected as it uses inexhaustible clean energy.
  • silicon-based solar cells have been researched and developed for a long time, and are spreading due to the policy considerations of each country.
  • silicon is an inorganic material, there is a limit to improving throughput and cost.
  • Patent Document 1 and Non-Patent Document 1 disclose PRT dyes with an improved black die. Patent Document 1 and Non-Patent Document 1 describe that in the dye-sensitized solar cell using this PRT dye, the quantum yield of 400 to 550 nm is increased and the photoelectric conversion efficiency is improved.
  • An object of the present invention is to provide a photoelectric conversion element having excellent photoelectric conversion efficiency and excellent durability, and a dye-sensitized solar cell using the photoelectric conversion element.
  • the present invention provides a metal complex dye that can exhibit excellent durability in addition to excellent photoelectric conversion performance when used as a photoelectric conversion element or a sensitizing dye of a dye-sensitized solar cell, and the metal complex.
  • An object is to provide a dye solution containing a dye.
  • a photoelectric conversion element using, as a sensitizing dye, a metal complex dye having a tridentate ligand having a specific structure having an acidic group and a bidentate ligand having an atom having an unshared electron pair at a specific site It has been found that the photoelectric conversion efficiency of the obtained photoelectric conversion element is increased and that the photoelectric conversion efficiency is not easily lowered even by continuous light irradiation in a severe high temperature environment.
  • the present invention has been further studied based on these findings and has been completed.
  • a photoelectric conversion element having semiconductor fine particles carrying a dye M (LA) (LD) Z. (CI) n (I)
  • M represents a metal ion.
  • LA represents a tridentate ligand represented by the following formula (L1).
  • LD represents a bidentate ligand represented by any of the following formulas (L2-1) to (L2-5).
  • Z represents a monodentate ligand.
  • CI represents a counter ion necessary for neutralizing the charge of the metal complex dye, and n is an integer of 0 to 3.
  • ring Za, ring Zb and ring Zc represent a 5-membered ring or a 6-membered ring having a nonmetallic atom as a ring constituent atom. At least one of ring Za, ring Zb and ring Zc has an acidic group.
  • G 1 is a group represented by any of the following formulas (G1-1) to (G1-6), and G 2 is any one of the following formulas (G2-1) to (G2-3). It is group represented by these.
  • R represents a substituent, n1 is an integer of 0 to 3, and n2 is an integer of 0 to 5.
  • R 1 to R 3 are each a hydrogen atom, an alkyl group, a heteroaryl group, an aryl group, —COOH, —PO (OH) 2 , —PO (OR a ) (OH), or —CO (NHOH).
  • R a represents an alkyl group, a heteroaryl group, or an aryl group.
  • R 4 represents an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, or a halogen atom. * Represents a linking site.
  • [2] The photoelectric conversion element according to [1], wherein the LD is represented by the formula (L2-1) or (L2-2).
  • a dye-sensitized solar cell comprising the photoelectric conversion element according to any one of [6].
  • a metal complex dye represented by the following general formula (I).
  • M (LA) (LD) Z.
  • CI n (I)
  • M represents a metal ion.
  • LA represents a tridentate ligand represented by the following formula (L1).
  • LD represents a bidentate ligand represented by any of the following formulas (L2-1) to (L2-5).
  • Z represents a monodentate ligand.
  • CI represents a counter ion necessary for neutralizing the charge of the metal complex dye, and n is an integer of 0 to 3.
  • ring Za, ring Zb and ring Zc represent a 5-membered ring or a 6-membered ring having a nonmetallic atom as a ring constituent atom. At least one of ring Za, ring Zb and ring Zc has an acidic group.
  • G 1 is a group represented by any of the following formulas (G1-1) to (G1-6), and G 2 is any one of the following formulas (G2-1) to (G2-3). It is group represented by these.
  • R represents a substituent, n1 is an integer of 0 to 3, and n2 is an integer of 0 to 5.
  • R 1 to R 3 are each a hydrogen atom, an alkyl group, a heteroaryl group, an aryl group, —COOH, —PO (OH) 2 , —PO (OR a ) (OH), or —CO (NHOH).
  • R a represents an alkyl group, a heteroaryl group, or an aryl group.
  • R 4 represents an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, or a halogen atom. * Represents a linking site.
  • the metal complex dye according to [8], wherein the LD is represented by the formula (L2-1) or (L2-2).
  • G 1 is the formula (G1-1), (G1-2), or a metal complex dye according to represented by [8] or [9] in (G1-5).
  • the G 2 is the formula (G2-2) or (G2-3) represented by [8] in to [10] any one of the description of the metal complex dye.
  • the LD is a bidentate ligand represented by the formula (L2-1), the G 1 is represented by the formula (G1-2), and the G 2 is represented by the formula (G2-2).
  • the metal complex dye as described in any one of [8] to [11].
  • [14] [8] A dye solution containing the metal complex dye according to any one of [13] and a solvent.
  • the double bond may be any of E type and Z type in the molecule, or a mixture thereof.
  • substituents linking groups, ligands, etc. (hereinafter referred to as substituents, etc.) indicated by a specific symbol or formula, or when a plurality of substituents are specified simultaneously, unless otherwise specified
  • the respective substituents may be the same as or different from each other. The same applies to the definition of the number of substituents and the like.
  • a plurality of substituents and the like are close to each other (especially when they are adjacent to each other), they may be connected to each other to form a ring unless otherwise specified.
  • a ring for example, an aromatic ring or an aliphatic ring may be further condensed to form a condensed ring.
  • an aromatic ring refers to a ring exhibiting aromaticity, and is used to include an aromatic hydrocarbon ring and an aromatic heterocycle.
  • an aromatic group means group which shows aromaticity, and is used for the meaning containing an aryl group and heteroaryl group.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the photoelectric conversion element and the dye-sensitized solar cell of the present invention exhibit excellent photoelectric conversion efficiency and are excellent in durability.
  • the metal complex dye of this invention can be used suitably as a sensitizing dye of the photoelectric conversion element thru
  • the dye solution of the present invention comprises the metal complex dye of the present invention and a solvent, and can be suitably used for the preparation of semiconductor fine particles carrying the metal complex dye of the present invention.
  • the photoelectric conversion element of the present invention has a conductive support, a photoreceptor layer containing an electrolyte, a charge transfer body layer containing an electrolyte, and a counter electrode (counter electrode).
  • the photosensitive layer, the charge transfer layer, and the counter electrode are provided on the conductive support in this order.
  • the semiconductor fine particles forming the photoreceptor layer carries a metal complex dye represented by the formula (I) described later as a sensitizing dye.
  • the aspect in which the metal complex dye is supported on the surface of the semiconductor fine particle 22 includes an aspect in which the metal complex dye is adsorbed on the surface of the semiconductor fine particle 22, an aspect in which the metal complex dye is deposited on the surface of the semiconductor fine particle 22, and an aspect in which these are mixed.
  • the adsorption includes chemical adsorption and physical adsorption, and chemical adsorption is preferable.
  • the semiconductor fine particles may carry another metal complex dye together with the metal complex dye of the formula (I) described later. It is preferable that the semiconductor fine particles carry a co-adsorbent described later together with the metal complex dye.
  • the photoreceptor layer contains an electrolyte.
  • the electrolyte contained in the photoreceptor layer may be the same as or different from the electrolyte of the charge transfer layer, but is preferably the same.
  • “the same type of electrolyte” means that the component contained in the electrolyte of the photoreceptor layer and the component contained in the electrolyte of the charge transfer layer are the same, and the content of each component is the same, and The components included in the electrolyte of the photoreceptor layer and the components included in the electrolyte of the charge transfer layer are the same, but include the aspects in which the content of each component is different.
  • the photoelectric conversion element of the present invention is not particularly limited in structure other than the structure defined in the present invention, and a known structure relating to the photoelectric conversion element can be adopted.
  • Each of the layers constituting the photoelectric conversion element of the present invention is designed according to the purpose, and may be formed in a single layer or multiple layers, for example. Moreover, you may have layers other than said each layer if needed.
  • the dye-sensitized solar cell of the present invention uses the photoelectric conversion element of the present invention.
  • preferred embodiments of the photoelectric conversion element and the dye-sensitized solar cell of the present invention will be described.
  • a system 100 shown in FIG. 1 is an application of the photoelectric conversion element 10 according to the first aspect of the present invention to a battery application in which an operation means M (for example, an electric motor) is caused to work by an external circuit 6.
  • the photoelectric conversion element 10 includes a conductive support 1, semiconductor fine particles 22 sensitized by supporting a dye (metal complex dye) 21, and a photoreceptor layer 2 including an electrolyte between the semiconductor fine particles 22, It consists of a charge transfer layer 3 that is a hole transport layer and a counter electrode 4.
  • the light receiving electrode 5 includes the conductive support 1 and the photoreceptor layer 2, and functions as a working electrode.
  • the light incident on the photoreceptor layer 2 excites the metal complex dye 21.
  • the excited metal complex dye 21 has high energy electrons, and these electrons are transferred from the metal complex dye 21 to the conduction band of the semiconductor fine particles 22 and reach the conductive support 1 by diffusion.
  • the metal complex dye 21 is an oxidant. Electrons that have reached the conductive support 1 work in the external circuit 6, reach the oxide of the metal complex dye 21 via the counter electrode 4 and the charge transfer layer 3, and reduce this oxide.
  • the system 100 functions as a solar cell.
  • the dye-sensitized solar cell 20 shown in FIG. 2 is configured by the photoelectric conversion element of the second aspect of the present invention.
  • the photoelectric conversion element used as the dye-sensitized solar cell 20 differs with respect to the photoelectric conversion element shown in FIG. 1 by the structure of the electroconductive support body 41 and the photoreceptor layer 42, and the point which has a spacer, those points are the same.
  • the configuration is the same as that of the photoelectric conversion element 10 shown in FIG. That is, the conductive support 41 has a two-layer structure including a substrate 44 and a transparent conductive film 43 formed on the surface of the substrate 44.
  • the photoreceptor layer 42 has a two-layer structure including a semiconductor layer 45 and a light scattering layer 46 formed adjacent to the semiconductor layer 45.
  • a spacer is provided between the conductive support 41 and the counter electrode 48.
  • reference numeral 40 denotes a light receiving electrode
  • 47 denotes a charge transfer body layer.
  • the dye-sensitized solar cell 20 functions as a solar cell when light enters the photoreceptor layer 42 as in the system 100 to which the photoelectric conversion element 10 is applied.
  • the photoelectric conversion element and the dye-sensitized solar cell of the present invention are not limited to the above-described preferred embodiments, and the configurations and the like of each embodiment can be appropriately combined between the respective embodiments without departing from the gist of the present invention.
  • materials and members used for the photoelectric conversion element or the dye-sensitized solar cell can be prepared by a conventional method.
  • the metal complex dye of the present invention is represented by the following formula (I).
  • M represents a metal ion.
  • M is a central metal of the metal complex dye, and examples thereof include ions of each element of groups 6 to 12 on the long periodic table. Examples of such metal ions include Ru, Fe, Os, Cu, W, Cr, Mo, Ni, Pd, Pt, Co, Ir, Rh, Re, Mn, and Zn ions.
  • two or more metal complex dyes having different metal ions M may be used.
  • the metal ion M is preferably Os 2+ , Ru 2+ or Fe 2+ , more preferably Os 2+ or Ru 2+ , and particularly preferably Ru 2+ . Note that in a state of being incorporated in the photoelectric conversion element, the valence of M may change due to an oxidation-reduction reaction with surrounding materials.
  • LA represents a tridentate ligand represented by the following formula (L1).
  • ring Za, ring Zb and ring Zc each independently represent a 5-membered or 6-membered ring having a nonmetallic atom as a ring-constituting atom. At least one of ring Za, ring Zb and ring Zc has an acidic group. Two or more of the rings Za, Zb and Zc preferably have an acidic group, and more preferably all three rings have an acidic group.
  • the number of acidic groups contained in the tridentate ligand represented by the formula (L1) is preferably 1 to 3, more preferably 2 or 3, and still more preferably 3.
  • an acidic group is a substituent having a dissociative proton, and a pKa of 11 or less.
  • the pKa of the acidic group is determined by J.M. Phys. Chem. A2011, 115, 6641-6645 can be obtained according to the “SMD / M05-2X / 6-31G * ” method.
  • the acidic group include acid groups exhibiting acidity such as a carboxy group, a phosphonyl group, a phosphoryl group, a sulfo group, and a boric acid group, or groups having these acid groups.
  • the group having an acid group include a group having an acid group and a linking group.
  • the linking group is not particularly limited, and examples thereof include a divalent group, and preferable examples include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, and a heteroarylene group.
  • the linking group may have as a substituent a group selected from Substituent Group T R to be described later.
  • the acidic group having an acid group and a linking group for example, carboxymethyl, carboxyvinylene, dicarboxyvinylene, cyanocarboxyvinylene, 2-carboxy-1-propenyl, 2-carboxy-1-butenyl, carboxyphenyl and the like are preferable.
  • the acidic group is preferably a group having a carboxy group, a phosphonyl group, a sulfo group, a phosphoric acid group or a carboxy group, and more preferably a carboxy group.
  • the ring constituent atoms of ring Za, ring Zb and ring Zc are preferably atoms selected from a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom.
  • Ring Za, ring Zb and ring Zc are preferably aromatic rings, and in particular, a ring selected from an imidazole ring, an oxazole ring, a thiazole ring, a triazole ring, a pyridine ring, a pyridazine ring, and a pyrazine ring is preferable, and an imidazole ring or a pyridine ring Is more preferable, and a pyridine ring is more preferable.
  • These rings may have a substituent, preferably a group selected from Substituent Group T R to be described later as the substituent. Further, these substituents may be connected to each other to form a ring.
  • the acidic group is preferably introduced into a carbon atom located in the para position with respect to the N atom that is the ring constituent atom.
  • LD- LD represents a bidentate ligand represented by any of the following formulas (L2-1) to (L2-5).
  • LD is preferably a bidentate ligand represented by the following formula (L2-1), (L2-2), (L2-4), or (L2-5), more preferably the following formula (L2- 1) or a bidentate ligand represented by (L2-2), more preferably a bidentate ligand represented by the following formula (L2-1).
  • G 1 is a group represented by any of the following formulas (G1-1) to (G1-6).
  • G 1 is preferably a group represented by the following formula (G1-1), (G1-2), (G1-3), (G1-5), or (G1-6), and more preferably A group represented by the formula (G1-1), (G1-2), (G1-5), or (G1-6), more preferably the following formula (G1-1), (G1-2) or A group represented by (G1-5), particularly preferably a group represented by the following formula (G1-2).
  • Any of the groups represented by the following formulas (G1-1) to (G1-6) is coordinated to a metal ion via an anion of a nitrogen atom shown in each formula.
  • G 2 is a group represented by any of the following formulas (G2-1) to (G2-3).
  • G 2 is preferably a group represented by the following formula (G2-2) or (G2-3), and more preferably a group represented by the following formula (G2-2).
  • R represents a substituent
  • n1 is an integer of 0 to 3
  • n2 is an integer of 0 to 5. This R is preferably a group selected from the substituent group T R described later.
  • n1 and n2 are preferably 0 or 1, and more preferably 0.
  • R 1 to R 3 each represents a hydrogen atom, an alkyl group, a heteroaryl group, an aryl group, —COOH, —PO (OH) 2 , —PO (OR a ) (OH), or —CO (NHOH).
  • R a represents an alkyl group, a heteroaryl group, or an aryl group. Preferred forms of the alkyl, heteroaryl group and aryl group that can be adopted as R a are the same as the forms of the alkyl, heteroaryl group, and aryl group that can be adopted by the substituent RA described later.
  • R 1 to R 3 are preferably a hydrogen atom or an alkyl group, and more preferably, at least one of R 1 to R 3 is an alkyl group having an electron withdrawing group as a substituent (preferably an electron seeking group).
  • the electron withdrawing group is preferably a fluorine atom.
  • R 1 to R 3 are alkyl groups, trifluoromethyl is particularly preferable.
  • Particularly preferred form in G 1 is G 1 is the formula (G1-2), and a said alkyl group R 1 has a substituent an electron withdrawing group, in the form R 2 is a hydrogen atom is there.
  • R 1 to R 3 are preferably not acidic groups.
  • R 4 represents an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, or a halogen atom.
  • R 4 is a group having an unshared electron pair, durability (light resistance) of the photoelectric conversion element can be improved. The reason for this is not clear, but it is thought that the unstable radical cation state of the dye can be delocalized by the resonance effect after electron injection from the dye to the semiconductor fine particles.
  • R 4 is an alkoxy group, it includes a straight-chain alkoxy group and a branched alkoxy group. From the viewpoint of improving durability, the carbon number is preferably 1 to 30, more preferably 2 to 25, still more preferably 3 to 20, further preferably 4 to 15, and further preferably 5 to 12.
  • alkoxy group examples include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy, n-pentoxy, n-hexyloxy, n-octyloxy, 2-ethylhexyloxy, 3,7-dimethyloctyloxy, n-decyloxy, isodecyloxy, s-decyloxy, 2-butyloctyloxy, n-dodecyloxy, n-hexadecyloxy, isohexadecyloxy, n-eicosyloxy, n-hexa Cosyloxy or isooctacosyloxy is mentioned.
  • the aryl group includes a carbocyclic aryloxy group in which the aryl group is a carbon aromatic ring group and a heteroaryloxy group in which the hetero aromatic ring group is present.
  • the aryloxy group preferably has 3 to 30 carbon atoms, more preferably 3 to 25 carbon atoms, still more preferably 3 to 20 carbon atoms, and particularly preferably 3 to 16 carbon atoms.
  • aryloxy group examples include phenoxy, naphthoxy, imidazolyloxy, benzoimidazolyloxy, pyridin-4-yloxy, pyrimidinyloxy, quinazolinyloxy, purinyloxy, thiophen-3-yloxy and the like.
  • a thiophene ring is preferred as the heterocycle of the heteroaryloxy group.
  • R 4 is an alkylthio group, it includes a linear alkylthio group and a branched alkylthio group. From the viewpoint of improving durability, the carbon number is preferably 1 to 30, more preferably 2 to 25, still more preferably 3 to 20, further preferably 4 to 15, and further preferably 5 to 12.
  • alkylthio group examples include methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, t-butylthio, n-pentylthio, n-hexylthio, n-octylthio, 2-ethylhexylthio, 3, 7-dimethyloctylthio, n-decylthio, isodecylthio, s-decylthio, n-dodecylthio, 2-butyloctylthio, n-hexadecylthio, isohexadecylthio, n-eicosylthio, n-hexacosylthio or isooctacosylthio It is done.
  • the aryl group includes a carbocyclic arylthio group in which the aryl group is a carbon aromatic ring group and a heteroarylthio group in which the heteroaromatic ring group is present.
  • the arylthio group preferably has 3 to 30 carbon atoms, more preferably 3 to 25 carbon atoms, still more preferably 3 to 20 carbon atoms, and particularly preferably 3 to 16 carbon atoms.
  • arylthio group examples include phenylthio, naphthylthio, imidazoylthio, benzimidazolylthio, pyridin-4-ylthio, pyrimidinylthio, quinazolinylthio, purinylthio, thiophen-3-ylthio and the like.
  • a thiophene ring is preferred as the heterocycle of the heteroarylthio group.
  • R 4 An amino group that can be used as R 4 is represented by —N (R A ) (R B ).
  • R A and R B each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.
  • the alkyl group that can be taken as R A and R B preferably has 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 3 to 10 carbon atoms. Further, the alkyl group may be either linear or branched.
  • alkyl group examples include methyl, ethyl, isopropyl, n-butyl, t-butyl, isobutyl, n-hexyl, n-octyl, 2-ethylhexyl, 3,7-dimethyloctyl, 2-butyloctyl and n-dodecyl.
  • N-hexadecyl and 2-hexyldecyl, and t-butyl, n-hexyl, 2-ethylhexyl and n-octyl are preferred.
  • the aryl group that can be used as R A and R B preferably has 6 to 24 carbon atoms, and more preferably 6 to 18 carbon atoms.
  • the aryl group may be a group consisting of an aromatic hydrocarbon ring, and may be a condensed ring group in which at least one of another aromatic hydrocarbon ring and an aliphatic hydrocarbon ring is condensed.
  • Aryl groups include phenyl, naphthyl, fluorenyl, biphenyl, anthracenyl.
  • the aryl group as R 1 and R 2 is preferably phenyl, naphthyl or fluorenyl, more preferably phenyl.
  • the heteroaryl group that can be employed as R 1 and R 2 preferably has 0 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, and still more preferably 2 to 16 carbon atoms.
  • This heteroaryl group is particularly preferably a 5-membered or 6-membered ring.
  • At least one of R A and R B is preferably an aryl group or a heteroaryl group, more preferably an aryl group or a heteroaryl group from the viewpoint of photoelectric conversion efficiency, and both are an aryl group. Particularly preferred.
  • R A and R B may combine with each other to form a ring.
  • the nitrogen-containing cyclic group formed by combining R A and R B is not particularly limited, and may be an aromatic group or an aliphatic cyclic group. Examples of such nitrogen-containing ring groups include morpholine ring groups, thiomorpholine ring groups, piperidine ring groups, and the following nitrogen-containing ring groups.
  • R DA3 and R DA4 each independently represent an alkyl group or an aryl group.
  • the alkyl group and aryl group has the same meaning as alkyl or aryl group can take as the R A and R B, it is preferable also the same.
  • R A and R B include a form in which the group described above as R A and R B further has a substituent (in addition, R A and R B are formed by bonding to each other).
  • the nitrogen-containing ring group includes a form in which the group described as the nitrogen-containing ring group further has a substituent). Examples of the substituent group is not particularly limited, it includes groups selected from Substituent Group T R to be described later.
  • an alkyl group, an aryl group, an alkoxy group, an alkylthio group, a silyl group, a halogen atom, and an amino group are preferable, an alkyl group, an alkoxy group, and an alkylthio group are more preferable, and an alkyl group is further preferable.
  • the N, N-dialkylamino group in which R A and R B are both alkyl groups is not particularly limited, and examples thereof include N, N-dimethylamino, N, N-diethylamino, N, N-dipentylamino, N, N-bis (n-hexyl) amino, N-methyl-Nn-hexylamino, N, N-bis (2-ethylhexyl) amino, N, N-bis (n-octyl) amino, N, N-bis (N-decyl) amino and the like.
  • N, N-diarylamino group in which R A and R B are both aryl groups is not particularly limited, and examples thereof include N, N-diphenylamino, N, N-di (4-methylphenyl) amino, N, N-di (4- (t-butyl) phenyl) amino, N, N-di (4- (n-hexyl) phenyl) amino, N, N-di (4-methoxyphenyl) amino, N, N-di (4- (n-octyloxy) phenyl) amino, N, N-di (4-trimethylsilylphenyl) amino, N, N-di (3,5-dimethylphenyl) amino, N, N-di (4-dimethyl) Aminophenyl) amino, N, N-di (4-methylthiophenyl) amino, N, N-di (4-biphenyl) amino, N, N-dinaphthylamino, N,
  • N, N-diheteroarylamino groups in which R A and R B are both heteroaryl groups include N, N-di (4-alkylthienyl) amino, N, N-di (4- (n-hexyl) Thienyl) amino, N, N-di (3-pyridyl) amino and the like.
  • the halogen atom which can be taken as R 4 is a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom or a bromine atom, and more preferably a bromine atom.
  • R 4 is preferably an alkylthio group, an alkoxy group, an amino group or a halogen atom, more preferably an alkylthio group or an amino group, and even more preferably an alkylthio group.
  • LD is represented by the above formula (L2-1)
  • G 1 is represented by the above formula (G1-2)
  • G 2 is represented by the above formula (G2-2).
  • the form represented by is especially preferable.
  • Z is a monodentate ligand.
  • Z is, for example, a ligand coordinated by a group selected from a selenocyanate group, an isoselenocyanate group, a thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, an alkylthio group, and an arylthio group, or a halogen.
  • Examples include ligands selected from atoms, carbonyls, dialkyl ketones and thioureas. Of these, Z is preferably an isothiocyanate group or a cyano group, and more preferably an isothiocyanate group.
  • -Charge neutralization counter ion CI- CI represents a counter ion when a counter ion is required to neutralize the charge.
  • a metal complex dye is a cation or an anion or has a net ionic charge depends on the metal, ligand and substituent in the metal complex dye.
  • the metal complex dye may be dissociated and have a negative charge because the substituent has a dissociable group. In this case, the entire charge of the metal complex dye is electrically neutralized by CI.
  • the counter ion CI is a positive counter ion
  • the counter ion CI is an inorganic or organic ammonium ion (for example, tetraalkylammonium ion, pyridinium ion, etc.), phosphonium ion (for example, tetraalkylphosphonium ion, alkyltriphenylphosphonium ion). Etc.), alkali metal ions, metal complex ions or protons.
  • the positive counter ion is preferably an inorganic or organic ammonium ion (such as triethylammonium or tetrabutylammonium ion) or a proton.
  • the counter ion CI may be an inorganic anion or an organic anion.
  • hydroxide ion, halogen anion eg, fluoride ion, chloride ion, bromide ion, iodide ion, etc.
  • substituted or unsubstituted alkylcarboxylate ion acetate ion, trifluoroacetic acid etc.
  • substituted Or an unsubstituted aryl carboxylate ion (benzoate ion, etc.)
  • a substituted or unsubstituted alkyl sulfonate ion methane sulfonate, trifluoromethane sulfonate ion, etc.
  • a substituted or unsubstituted aryl sulfonate ion for example, p- Toluenesulfonic acid ion,
  • an ionic polymer or another dye having a charge opposite to that of the dye may be used as the charge balance counter ion, and a metal complex ion (for example, bisbenzene-1,2-dithiolatonickel (III)) can also be used. is there.
  • Negative counter ions include halogen anions, substituted or unsubstituted alkyl carboxylate ions, substituted or unsubstituted alkyl sulfonate ions, substituted or unsubstituted aryl sulfonate ions, aryl disulfonate ions, perchlorate ions , Hexafluorophosphate ions are preferred, and halogen anions and hexafluorophosphate ions are more preferred.
  • n indicating the number of CIs is an integer of 0 to 3, with 0 being preferred.
  • the dye represented by the above formula (I) has a maximum absorption wavelength in an ethanol solution of preferably 500 to 700 nm, more preferably 550 to 650 nm.
  • Examples of the metal complex dye represented by the above formula (I) include a method described in JP2013-084594A, a method described in Japanese Patent No. 4298799, US Patent Application Publication No. 2013 / 0018189A1, and US Patent Application. Methods described in published 2012 / 0073660A1, published US 2012 / 0111410A1 and published published US 2010 / 0258175A1, Angew. Chem. Int. Ed. , 2011, 50, 2054-2058, the method described in the reference cited in this document, the above-mentioned patent document relating to solar cells, a known method, or a method according to these methods. it can.
  • each alkyl group represented by —C m H 2m + 1 may be linear or branched, but is preferably a linear alkyl group.
  • Me represents methyl.
  • substituents include groups selected from Substituent Group T R.
  • substituent group T R when simply not listed only as a substituent are those referring to the substituent group T R, also, each of the groups, for example, an alkyl group, the only have been described If, preferable range of the corresponding group of the substituent group T R, the embodiment is applied.
  • the group contained in the substituent group T R including the like groups below.
  • An alkyl group preferably having 1 to 20 carbon atoms such as methyl, ethyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxyl.
  • alkenyl groups preferably having 2 to 20 carbon atoms, such as vinyl, allyl, butenyl or oleyl
  • alkynyl groups preferably having 2 to 20 carbon atoms, such as ethynyl, butynyl or phenylethynyl
  • a cycloalkyl group preferably having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl or 4-methylcyclohexyl
  • a cycloalkenyl group preferably having 5 to 20 carbon atoms such as cyclopentenyl or cyclohexenyl
  • Aryl groups Preferably it has 6 to 26 carbon atoms, for example, phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, difluorophenyl or tetrafluorophenyl
  • alkoxycarbonyl group preferably having 2 to 20 carbon atoms, such as ethoxycarbonyl or 2-ethylhexyloxycarbonyl
  • a cycloalkoxycarbonyl group preferably having 4 to 20 carbon atoms, such as cyclopropyloxycarbonyl, cyclopentyloxycarbonyl or Cyclohexyloxycarbonyl
  • aryloxycarbonyl group preferably having 6 to 20 carbon atoms, for example, phenyloxycarbonyl or naphthyloxycarbonyl
  • amino group preferably having 0 to 20 carbon atoms, alkylamino group, alkenylamino group, Including alkynylamino group, cycloalkylamino group, cycloalkenylamino group, arylamino group, heterocyclic amino group, such as amino, N, N-dimethylamino, N, N-diethylamino, N Ethylamino, N-
  • An acylamino group (preferably an acylamino group having 1 to 20 carbon atoms, such as acetylamino, cyclohexylcarbonylamino or benzoylamino), a sulfonamide group (preferably an alkyl, cycloalkyl or aryl sulfonamide group having 0 to 20 carbon atoms)
  • a sulfonamide group preferably an alkyl, cycloalkyl or aryl sulfonamide group having 0 to 20 carbon atoms
  • an alkylthio group preferably having 1 to 20 carbon atoms, for example, methylthio, ethylthio , Isopropylthio, pentylthio
  • a silyl group (preferably a silyl group having 1 to 20 carbon atoms and substituted with alkyl, aryl, alkoxy and aryloxy is preferable, for example, trimethylsilyl, triethylsilyl, triisopropylsilyl, triphenylsilyl, diethylbenzylsilyl or dimethylphenylsilyl.
  • a silyloxy group (preferably a silyloxy group having 1 to 20 carbon atoms and substituted with alkyl, aryl, alkoxy and aryloxy, such as triethylsilyloxy, triphenylsilyloxy, diethylbenzylsilyloxy or dimethylphenylsilyloxy ), A hydroxy group, a cyano group, a nitro group, and a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom).
  • Group selected from Substituent Group T R is more preferably an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, cycloalkoxy group, aryloxy group, alkoxycarbonyl group, cycloalkoxy carbonyl group Amino group, acylamino group, cyano group or halogen atom, particularly preferably an alkyl group, alkenyl group, heterocyclic group, alkoxy group, alkoxycarbonyl group, amino group, acylamino group or cyano group.
  • a compound or a substituent when a compound or a substituent includes an alkyl group, an alkenyl group, etc., these may be linear or branched, and may be substituted or unsubstituted. When an aryl group, a heterocyclic group, or the like is included, they may be monocyclic or condensed, and may be substituted or unsubstituted.
  • the conductive support is not particularly limited as long as it has conductivity and can support the photoreceptor layer 2 and the like.
  • the conductive support includes the conductive support 1 made of a conductive material, for example, a metal, or a glass or plastic substrate 44 and a transparent conductive film 43 formed on the surface of the substrate 44.
  • a conductive support 41 is preferred.
  • the conductive support 41 in which a conductive metal oxide is coated on the surface of the substrate 44 to form a transparent conductive film 43 is more preferable.
  • the substrate 44 made of plastic include a transparent polymer film described in paragraph No. 0153 of JP-A-2001-291534.
  • ceramic Japanese Patent Laid-Open No. 2005-135902
  • conductive resin Japanese Patent Laid-Open No. 2001-160425
  • tin oxide As the metal oxide, tin oxide (TO) is preferable, and fluorine-doped tin oxide such as indium-tin oxide (tin-doped indium oxide; ITO) and fluorine-doped tin oxide (FTO) is particularly preferable.
  • the coating amount of the metal oxide at this time is preferably 0.1 to 100 g per 1 m 2 of the surface area of the substrate 44.
  • light is preferably incident from the substrate 44 side.
  • Conductive supports 1 and 41 are preferably substantially transparent. “Substantially transparent” means that the transmittance of light (wavelength 300 to 1200 nm) is 10% or more, preferably 50% or more, and particularly preferably 80% or more. .
  • the thickness of the conductive supports 1 and 41 is not particularly limited, but is preferably 0.05 ⁇ m to 10 mm, more preferably 0.1 ⁇ m to 5 mm, and particularly preferably 0.3 ⁇ m to 4 mm. .
  • the thickness of the transparent conductive film 43 is preferably 0.01 to 30 ⁇ m, more preferably 0.03 to 25 ⁇ m, and particularly preferably 0.05 to 20 ⁇ m. .
  • the conductive supports 1 and 41 may have a light management function on the surface.
  • a light management function on the surface.
  • an antireflection film in which high refractive films and low refractive index oxide films described in JP-A-2003-123859 are alternately laminated may be provided on the surface, as described in JP-A-2002-260746.
  • the light guide function may be provided.
  • Photoreceptor layer Other configurations are not particularly limited as long as the photoreceptor layer includes the semiconductor fine particles 22 on which the dye 21 is supported and an electrolyte.
  • the photoreceptor layer 2 and the photoreceptor layer 42 are used.
  • the semiconductor fine particles 22 are preferably fine particles of a metal chalcogenide (eg, oxide, sulfide, selenide, etc.) or a compound having a perovskite crystal structure.
  • a metal chalcogenide eg, oxide, sulfide, selenide, etc.
  • the metal chalcogenide include titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium or tantalum oxide, cadmium sulfide, and cadmium selenide.
  • Preferred examples of the compound having a perovskite crystal structure include strontium titanate and calcium titanate. Of these, titanium oxide (titania), zinc oxide, tin oxide, and tungsten oxide are particularly preferable.
  • titania examples include anatase type, brookite type, and rutile type, and anatase type and brookite type are preferable. Titania nanotubes, nanowires, and nanorods can be used alone or mixed with titania fine particles.
  • the particle diameters of the semiconductor fine particles 22 are 0.001 to 1 ⁇ m as primary particles and 0.01 to 100 ⁇ m as the average particle diameter of the dispersion in terms of the average particle diameter when the projected area is converted into a circle. Is preferred.
  • Examples of a method for coating the semiconductor fine particles 22 on the conductive support 1 or 41 include a wet method, a dry method, and other methods.
  • the semiconductor fine particles 22 preferably have a large surface area so that a large amount of the dye 21 can be adsorbed.
  • the surface area thereof is preferably 10 times or more, more preferably 100 times or more the projected area.
  • it is about 5000 times.
  • the diffusion distance of the generated electrons increases, the loss due to charge recombination also increases.
  • the preferred thickness of the semiconductor layer 45 is not uniquely determined depending on the use of the photoelectric conversion element, but is typically 0.1 to 100 ⁇ m. When used as a dye-sensitized solar cell, the thickness is more preferably 1 to 50 ⁇ m, further preferably 3 to 30 ⁇ m.
  • the semiconductor fine particles 22 are preferably applied to the conductive support 1 or 41 and then baked at a temperature of 100 to 800 ° C. for 10 minutes to 10 hours to bring the particles into close contact with each other.
  • the film forming temperature is preferably 60 to 600 ° C. when glass is used as the material of the conductive support 1 or the substrate 44.
  • the coating amount of the semiconductor fine particles 22 per 1 m 2 of the surface area of the conductive support 1 or 41 is preferably 0.5 to 500 g, more preferably 5 to 100 g.
  • a short-circuit prevention layer In order to prevent contact between the light receiving electrode 5 or 40 and the counter electrode 4 or 48, it is preferable to use a spacer S (see FIG. 2) or a separator.
  • At least one metal complex dye represented by the above formula (I) is used as a sensitizing dye.
  • the metal complex dye represented by the formula (I) is as described above.
  • examples of the dye that can be used in combination with the metal complex dye of the above formula (I) include a Ru complex dye, a squarylium cyanine dye, an organic dye, a porphyrin dye, and a phthalocyanine dye.
  • Ru complex dye examples include Ru complex dyes described in JP-A-7-500630 (especially synthesized in Examples 1 to 19 on page 5, lower left column, line 5 to page 7, upper right column, line 7). Dyes), Ru complex dyes described in JP-T-2002-512729 (especially dyes synthesized in Examples 1 to 16 on the third line to the 29th line from the bottom of page 20), JP, Ru complex dyes described in JP 2001-59062 (particularly dyes described in paragraphs 0087 to 0104), Ru complex dyes described in JP 2001-6760 A (particularly, dyes described in paragraphs 0093 to 0102) ), Ru complex dyes described in JP-A No. 2001-253894 (particularly dyes described in paragraph Nos.
  • Ru complex dyes described in JP-A No. 2003-212851 particularly paragraph No. 0005 Described
  • Ru complex dyes described in WO 2007/91525 pamphlet particularly the dye described in [0067]
  • Ru complex dyes described in JP-A No. 2001-291534 particularly, paragraph number 0120) To 0144
  • Ru complex dyes described in JP2012-012570A in particular, dyes described in paragraphs 0095 to 0103
  • Ru metal complex dyes described in JP2013-084594A In particular, the dye described in Paragraph Nos. 0072 to 0081, etc.
  • 2013/0888898 (particularly, the dye described in [0286] to [0293]), or International Publication No. 2013 Ru complex dyes described in pamphlet of / 47615 (especially the dyes described in [0078] to [0082]) It is below.
  • squarylium cyanine dyes described in JP-A No. 11-214730 particularly dyes described in paragraphs 0036 to 0047
  • squarylium cyanine dyes described in JP-A No. 2012-144688 in particular, And dyes described in paragraphs 0039 to 0046 and 0054 to 0060
  • squarylium cyanine dyes described in JP 2012-84503 A in particular, dyes described in paragraphs 0066 to 0076 and the like.
  • organic dyes described in JP-A No. 2004-063274 particularly dyes described in paragraph Nos. 0017 to 0021
  • organic dyes described in JP-A No. 2005-123033 particularly paragraph numbers.
  • porphyrin dyes examples include Angew. Chem. Int. Ed. , 49, 1-5 (2010), and the like, and examples of the phthalocyanine dye include Angew. Chem. Int. Ed. , 46, 8358 (2007), and the like.
  • the dye that can be used in combination is preferably a Ru complex dye, a squarylium cyanine dye, or an organic dye.
  • the total amount of the dye used is preferably 0.01 to 100 mmol, more preferably 0.1 to 50 mmol, particularly preferably 0.1 to 10 mmol per 1 m 2 of the surface area of the conductive support 1 or 41. is there.
  • the amount of the dye 21 adsorbed on the semiconductor fine particles 22 is preferably 0.001 to 1 mmol, more preferably 0.1 to 0.5 mmol, with respect to 1 g of the semiconductor fine particles 22. By using such a dye amount, the sensitizing effect in the semiconductor fine particles 22 can be sufficiently obtained.
  • the ratio of the mass of the metal complex dye represented by the formula (I) / the mass of the other dye is 95/5 to 10/90. Is preferred, 95/5 to 50/50 is more preferred, 95/5 to 60/40 is more preferred, 95/5 to 65/35 is particularly preferred, and 95/5 to 70/30 is most preferred.
  • the surface of the semiconductor fine particles 22 may be treated with an amine compound.
  • Preferable amine compounds include pyridine compounds (for example, 4-t-butylpyridine, polyvinylpyridine) and the like. In the case of a liquid, these may be used as they are, or may be used after being dissolved in an organic solvent.
  • a coadsorbent in the present invention, it is preferable to use a coadsorbent together with the metal complex dye represented by the formula (I) or a dye used in combination as necessary.
  • a co-adsorbent a co-adsorbent having at least one acidic group (preferably, a carboxy group or a salt thereof) is preferable, and examples thereof include a compound having a fatty acid or a steroid skeleton.
  • the fatty acid may be a saturated fatty acid or an unsaturated fatty acid, and examples thereof include butanoic acid, hexanoic acid, octanoic acid, decanoic acid, hexadecanoic acid, dodecanoic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid.
  • Examples of the compound having a steroid skeleton include cholic acid, glycocholic acid, chenodeoxycholic acid, hyocholic acid, deoxycholic acid, lithocholic acid, ursodeoxycholic acid and the like. Preferred are cholic acid, deoxycholic acid and chenodeoxycholic acid, and more preferred are chenodeoxycholic acid.
  • a preferred co-adsorbent is a compound represented by the following formula (CA).
  • R A1 represents an acidic group.
  • R A2 represents a substituent.
  • nA represents an integer of 0 or more.
  • An acidic group is synonymous with the acidic group which the tridentate ligand represented by the said formula (L1) has, and its preferable form is also the same.
  • R A1 is preferably a carboxy group, a sulfo group, or an alkyl group substituted by a salt thereof, and —CH (CH 3 ) CH 2 CH 2 CO 2 H, —CH (CH 3 ) CH 2 CH 2 CONHCH More preferred is 2 CH 2 SO 3 H.
  • the R A2 include groups selected from the above substituent group T R. Among these, an alkyl group, a hydroxy group, an acyloxy group, an alkylaminocarbonyloxy group, or an arylaminocarbonyloxy group is preferable, and an alkyl group, a hydroxy group, or an acyloxy group is more preferable.
  • nA is preferably 2 to 4.
  • the co-adsorbent has an effect of suppressing inefficient association of the metal complex dye by adsorbing to the semiconductor fine particles 22 and an effect of preventing reverse electron transfer from the surface of the semiconductor fine particles to the redox system in the electrolyte.
  • the amount of the co-adsorbent used is not particularly limited, but from the viewpoint of effectively expressing the above action, it is preferably 1 to 200 mol, more preferably 10 to 150 mol, relative to 1 mol of the metal complex dye. Particularly preferred is 20 to 50 mol.
  • the light scattering layer is different from the semiconductor layer in that it has a function of scattering incident light.
  • the light scattering layer 46 preferably contains rod-like or plate-like metal oxide particles. Examples of the metal oxide particles used in the light scattering layer 46 include the metal chalcogenide (oxide) particles.
  • the thickness of the light scattering layer is preferably 10 to 50% of the thickness of the photoreceptor layer 42.
  • the light scattering layer 46 is preferably a light scattering layer described in JP-A No. 2002-289274, and the description of JP-A No. 2002-289274 is preferably incorporated in the present specification as it is.
  • the charge transfer body layers 3 and 47 used in the photoelectric conversion element of the present invention are layers having a function of replenishing electrons to the oxidant of the dye 21 and are provided between the light receiving electrode 5 or 40 and the counter electrode 4 or 48. It is done.
  • the charge transfer layer 3 and 47 contains an electrolyte.
  • “the charge transfer layer contains an electrolyte” means to include both modes of the mode in which the charge transfer layer is made of only an electrolyte and the mode containing an electrolyte and a substance other than the electrolyte.
  • the charge transfer body layers 3 and 47 may be solid, liquid, gel, or a mixed state thereof.
  • Electrolytes examples include a liquid electrolyte in which a redox couple is dissolved in an organic solvent, a molten salt containing a redox couple, and a so-called gel electrolyte in which a polymer matrix is impregnated with a liquid in which a redox couple is dissolved in an organic solvent. .
  • a liquid electrolyte is preferable at the point of photoelectric conversion efficiency.
  • iodine and iodide As an oxidation-reduction pair, for example, iodine and iodide (iodide salt, ionic liquid is preferable, lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, methylpropylimidazolium iodide are preferable)
  • iodine and iodide iodide salt, ionic liquid is preferable
  • lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, methylpropylimidazolium iodide are preferable
  • a combination of an alkyl viologen eg, methyl viologen chloride, hexyl viologen bromide, benzyl viologen tetrafluoroborate
  • polyhydroxybenzene e
  • the cobalt complex is preferably a complex represented by the formula (CC) described in paragraphs 0144 to 0156 of JP2014-82189A, and described in paragraphs 0144 to 0156 of JP2014-82189A. It is preferably incorporated in the present specification as it is.
  • iodine and iodide When a combination of iodine and iodide is used as the electrolyte, it is preferable to further use an iodine salt of a 5-membered or 6-membered nitrogen-containing aromatic cation.
  • the organic solvent used for the liquid electrolyte and the gel electrolyte is not particularly limited, but an aprotic polar solvent (for example, acetonitrile, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl sulfoxide, sulfolane, 1,3-dimethylimidazolinone, 3 -Methyloxazolidinone etc.) are preferred.
  • the organic solvent used for the liquid electrolyte is preferably a nitrile compound, an ether compound, an ester compound, more preferably a nitrile compound, and particularly preferably acetonitrile or methoxypropionitrile.
  • Molten salts include ionic liquids containing imidazolium or triazolium cations, ionic liquids containing oxazolium cations, ionic liquids containing pyridinium cations, ionic liquids containing guanidinium cations, and these A combination is preferred. Moreover, you may combine a specific anion with respect to these cations. Additives may be added to these molten salts.
  • the molten salt may have a liquid crystalline substituent.
  • the molten salt of a quaternary ammonium salt can also be used as the molten salt.
  • molten salts other than these for example, flowability at room temperature was imparted by mixing polyethylene oxide with lithium iodide and at least one other lithium salt (for example, lithium acetate, lithium perchlorate, etc.). And the like.
  • the amount of the polymer added is 1 to 50% by mass.
  • ⁇ -butyrolactone may be included in the electrolytic solution, thereby increasing the diffusion efficiency of iodide ions and improving the photoelectric conversion efficiency.
  • polymer (polymer matrix) used for the gel electrolyte matrix examples include polyacrylonitrile and polyvinylidene fluoride.
  • the electrolyte may be made pseudo-solid by adding a gelling agent to an electrolyte solution composed of an electrolyte and a solvent to cause gelation (the pseudo-solid electrolyte is also referred to as “pseudo-solid electrolyte” hereinafter).
  • the gelling agent include organic compounds having a molecular weight of 1000 or less, Si-containing compounds having a molecular weight in the range of 500 to 5000, organic salts made of a specific acidic compound and a basic compound, sorbitol derivatives, and polyvinylpyridine.
  • a method of confining a polymer matrix, a crosslinkable polymer compound or monomer, a crosslinking agent, an electrolyte, and a solvent in the polymer may be used.
  • the polymer matrix is preferably a polymer having a nitrogen-containing heterocycle in the main chain or side chain repeating unit and a crosslinked product obtained by reacting these with an electrophilic compound, a polymer having a triazine structure, or a polymer having a ureido structure.
  • Molecules compounds containing liquid crystal compounds, polymers having an ether bond, polyvinylidene fluoride, methacrylates, acrylates, thermosetting resins, crosslinked polysiloxanes, polyvinyl alcohol (PVA), inclusion compounds such as polyalkylene glycols and dextrins, Examples include systems to which oxygen-containing or sulfur-containing polymers are added, natural polymers, and the like.
  • An alkali swelling polymer, a polymer having a compound capable of forming a charge transfer complex of a cation moiety and iodine in one polymer, and the like may be added to these.
  • a system containing a crosslinked polymer obtained by reacting a bifunctional or higher functional isocyanate group with a functional group such as a hydroxy group, an amino group, or a carboxy group may be used.
  • a crosslinking method in which a crosslinked polymer composed of a hydrosilyl group and a double bond compound, polysulfonic acid, polycarboxylic acid, or the like is reacted with a divalent or higher valent metal ion compound may be used.
  • Examples of the solvent that can be preferably used in combination with the quasi-solid electrolyte include a specific phosphate ester, a mixed solvent containing ethylene carbonate, a solvent having a specific dielectric constant, and the like.
  • the liquid electrolyte solution may be held in the solid electrolyte membrane or the pores.
  • a preferred method for holding the liquid electrolyte solution is a method using a cloth-like solid such as a conductive polymer film, a fibrous solid, or a filter.
  • electrolytes include aminopyridine compounds, benzimidazole compounds, aminotriazole compounds and aminothiazole compounds, imidazole compounds, aminotriazine compounds, urea compounds, amide compounds, and pyrimidines. It may contain a compound or a nitrogen-free heterocycle.
  • Preferred methods for controlling moisture include a method for controlling the concentration and a method in which a dehydrating agent is allowed to coexist. It is preferable to adjust the water content (content ratio) of the electrolytic solution to 0 to 0.1% by mass.
  • Iodine can also be used as an inclusion compound of iodine and cyclodextrin. Cyclic amidine may be used, and an antioxidant, hydrolysis inhibitor, decomposition inhibitor, and zinc iodide may be added.
  • a solid charge transport layer such as a p-type semiconductor or a hole transport material, for example, CuI, CuNCS or the like can be used. Also, Nature, vol. 486, p. The electrolyte described in 487 (2012) or the like may be used.
  • An organic hole transport material may be used as the solid charge transport layer.
  • the organic hole transport material is preferably a conductive polymer such as polythiophene, polyaniline, polypyrrole and polysilane, and a spiro compound in which two rings share a central element having a tetrahedral structure such as C and Si, and an aromatic such as triarylamine. Group amine derivatives, triphenylene derivatives, nitrogen-containing heterocyclic derivatives, and liquid crystalline cyano derivatives.
  • the redox couple becomes an electron carrier, it is preferably contained at a certain concentration.
  • a preferable concentration is 0.01 mol / L or more in total, more preferably 0.1 mol / L or more, and particularly preferably 0.3 mol / L or more.
  • the upper limit in this case is not particularly limited, but is usually about 5 mol / L.
  • the counter electrodes 4 and 48 preferably function as positive electrodes of the dye-sensitized solar cell.
  • the counter electrodes 4 and 48 can usually have the same configuration as that of the conductive support 1 or 41, but the substrate 44 is not necessarily required in a configuration in which the strength is sufficiently maintained.
  • As the structure of the counter electrodes 4 and 48 a structure having a high current collecting effect is preferable.
  • At least one of the conductive support 1 or 41 and the counter electrode 4 or 48 must be substantially transparent.
  • the conductive support 1 or 41 is preferably transparent, and sunlight is preferably incident from the conductive support 1 or 41 side.
  • the counter electrodes 4 and 48 have a property of reflecting light.
  • a glass or plastic on which a metal or conductive oxide is vapor-deposited is preferable, and a glass on which platinum is vapor-deposited is particularly preferable.
  • the present invention includes, for example, Japanese Patent No. 4260494, Japanese Patent Application Laid-Open No. 2004-146425, Japanese Patent Application Laid-Open No. 2000-340269, Japanese Patent Application Laid-Open No. 2002-289274, Japanese Patent Application Laid-Open No. 2004-152613, and Japanese Patent Application Laid-Open No. 9-27352. It can be applied to the photoelectric conversion element and the dye-sensitized solar cell described in the publication.
  • the photoelectric conversion element and the dye-sensitized solar cell of the present invention can be produced using the dye solution (the dye solution of the present invention) containing the metal complex dye of the present invention.
  • the metal complex dye of the present invention is dissolved in a solvent and may contain other components as necessary.
  • the solvent to be used examples include, but are not limited to, the solvents described in JP-A No. 2001-291534.
  • an organic solvent is preferable, and an alcohol solvent, an amide solvent, a nitrile solvent, a hydrocarbon solvent, and a mixed solvent of two or more of these are more preferable.
  • a mixed solvent of an alcohol solvent and a solvent selected from an amide solvent, a nitrile solvent, or a hydrocarbon solvent is preferable. More preferred are alcohol solvents and amide solvents, mixed solvents of alcohol solvents and hydrocarbon solvents, and particularly preferred are mixed solvents of alcohol solvents and amide solvents.
  • a mixed solvent of at least one of methanol, ethanol, propanol and butanol and at least one of dimethylformamide, dimethylacetamide and acetonitrile is preferable.
  • the dye solution preferably contains a co-adsorbent.
  • the co-adsorbent the above-mentioned co-adsorbent is preferable, and among them, the compound represented by the above formula (CA) is preferable.
  • the dye solution of the present invention is a dye solution in which the concentration of the metal complex dye or coadsorbent is adjusted so that the solution can be used as it is when producing a photoelectric conversion element or a dye-sensitized solar cell. Is preferred.
  • the metal complex dye of the present invention is preferably contained in an amount of 0.001 to 0.1% by mass. The amount of coadsorbent used is as described above.
  • the water content of the dye solution is preferably adjusted.
  • the water content is preferably adjusted to 0 to 0.1% by mass.
  • the photoreceptor layer is preferably prepared by supporting the metal complex dye represented by the formula (I) or a dye containing the same on the surface of the semiconductor fine particles using the dye solution. That is, the photoreceptor layer is preferably formed by applying the above dye solution (including a dip method) to semiconductor fine particles provided on a conductive support, and drying or curing.
  • the photoelectric conversion element or the dye-sensitized solar cell of the present invention can be obtained by further providing a charge transfer layer, a counter electrode, and the like on the light-receiving electrode provided with the photoreceptor layer thus prepared.
  • the dye-sensitized solar cell is manufactured by connecting the external circuit 6 to the conductive support 1 and the counter electrode 4 of the photoelectric conversion element manufactured as described above.
  • Example 1 [Synthesis of Metal Complex Dye]
  • the metal complex dyes D-1 to D-9 synthesized in this example are shown below.
  • each alkyl group represented by —C m H 2m + 1 (m is a natural number) is a linear alkyl group.
  • Example 2 [Production of dye-sensitized solar cell] Using each of the metal complex dyes D-1 to D-9 synthesized in Example 1 and the following comparative dyes C1 to C9, a dye-sensitized solar cell 20 (5 mm ⁇ 5 mm scale) shown in FIG. 2 was produced. This manufacture was performed by the method shown below. About each manufactured dye-sensitized solar cell 20, the following performance was evaluated.
  • a fluorine-doped SnO 2 conductive film (transparent conductive film 43, film thickness: 500 nm) was formed on a glass substrate (substrate 44, thickness 4 mm) to produce a conductive support 41.
  • titania paste “18NR-T” (manufactured by DyeSol) was screen printed on the SnO 2 conductive film and dried at 120 ° C.
  • the titania paste “18NR-T” was screen-printed again and dried at 120 ° C. for 1 hour. Thereafter, the dried titania paste was baked in air at 500 ° C. to form a semiconductor layer 45 (layer thickness: 10 ⁇ m).
  • a titania paste “18NR-AO” manufactured by DyeSol was screen-printed on the semiconductor layer 45 and dried at 120 ° C. for 1 hour. Thereafter, the dried titania paste was baked at 500 ° C., and a light scattering layer 46 (layer thickness: 5 ⁇ m) was formed on the semiconductor layer 45. In this manner, the photoreceptor layer 42 (light receiving surface area: 5 mm ⁇ 5 mm, layer thickness: 15 ⁇ m, metal complex dye not supported) is formed on the SnO 2 conductive film, and the metal complex dye is not supported.
  • a light receiving electrode precursor [A] was prepared.
  • each metal complex dye synthesized in Example 1 (above D-1 to D-9) or each comparison dye (below C1 to C9) is added to the photoreceptor layer 42 not carrying the metal complex dye. It was made to support as follows. First, the above metal complex dye is dissolved in a 1: 1 (volume ratio) mixed solvent of t-butanol and acetonitrile so that the concentration of the metal complex dye is 2 ⁇ 10 ⁇ 4 mol / L. 30 mol of cholic acid was added to 1 mol of the above metal complex dye to prepare each dye solution. Next, the light-receiving electrode precursor [A] was immersed in each dye solution at 25 ° C. for 45 hours, and then dried after being pulled up. In this manner, 18 types of light receiving electrodes 40 in which different metal complex dyes were supported on the light receiving electrode precursor [A] were produced.
  • a platinum electrode (Pt thin film thickness: 100 nm) having the same shape and size as the conductive support 41 was prepared.
  • an electrolytic solution iodine 0.1M (mol / L), lithium iodide 0.1M, 4-t-butylpyridine 0.5M and 1,2-dimethyl-3-propylimidazolium iodide 0.6M were used.
  • a liquid electrolyte was prepared by dissolving in acetonitrile.
  • a spacer S “Surlin” (trade name, manufactured by DuPont) having a shape matched to the size of the photoreceptor layer 42 was prepared.
  • Each of the light-receiving electrodes 40 and the counter electrode 48 manufactured as described above are thermocompression-bonded so as to face each other via the spacer S, and then the electrolyte solution injection port is interposed between the photoreceptor layer 42 and the counter electrode 48.
  • the charge transfer layer 47 was formed by filling the liquid electrolyte.
  • the outer periphery and the electrolyte injection port of the battery thus produced were sealed and cured using Resin XNR-5516 (manufactured by Nagase Chemtech), and each dye-sensitized solar cell (sample numbers 101 to 109, c01). To c09).
  • Descent rate ⁇ L is less than 2%
  • Descent rate ⁇ L is 2% or more and less than 4%
  • Descent rate ⁇ L is 4% or more and less than 6%
  • D: Descent rate ⁇ L is 6% or more and less than 8%
  • the dye-sensitized solar cell using the dye specified in the present invention has excellent photoelectric conversion efficiency and high durability even under severe high temperature environment.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Hybrid Cells (AREA)
  • Photovoltaic Devices (AREA)
  • Pyridine Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

L'invention concerne : un élément de conversion photoélectrique et une cellule solaire sensibilisée par un colorant dont le colorant sensibilisant est un colorant complexe métallique de formule (I); le colorant complexe métallique de formule (I); et une solution de colorant contenant le colorant. M(LA)(LD)Z·(CI)n (I) M représente un ion de métal. LA représente un ligand tridenté de structure spécifique comportant un groupe acide. LD représente un ligand bidenté représenté par une des formules (L2-1)-(L2-5). Z représente un ligand monodenté. CI représente un contre-ion nécessaire à la neutralisation de la charge du colorant complexe métallique, et n est un entier compris entre 0 et 3. G1 et G2 représentent des groupes spécifiques. R représente un substituant, n1 est un entier compris entre 0 et 3, et n2 est un entier compris entre 0 et 5.
PCT/JP2015/073871 2014-09-22 2015-08-25 Élément de conversion photoélectrique, cellule solaire sensibilisée par un colorant, colorant complexe métallique et solution de colorant WO2016047344A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3273456A4 (fr) * 2015-03-17 2018-01-24 FUJI-FILM Corporation Élément de conversion photoélectrique, cellule solaire sensibilisé au colorant, colorant de complexe de ruthénium, et solution de colorant

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013072080A (ja) * 2011-09-29 2013-04-22 Fujifilm Corp 光電変換素子及び光電気化学電池、これらに用いられる色素
JP2013206874A (ja) * 2012-03-29 2013-10-07 Fujifilm Corp 光電変換素子、色素増感太陽電池用色素吸着組成液、色素増感太陽電池用半導体電極、色素増感太陽電池の製造方法および光電変換素子用金属錯体色素
JP2013229285A (ja) * 2011-12-15 2013-11-07 Fujifilm Corp 金属錯体色素、光電変換素子、色素増感太陽電池、色素溶液および化合物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013072080A (ja) * 2011-09-29 2013-04-22 Fujifilm Corp 光電変換素子及び光電気化学電池、これらに用いられる色素
JP2013229285A (ja) * 2011-12-15 2013-11-07 Fujifilm Corp 金属錯体色素、光電変換素子、色素増感太陽電池、色素溶液および化合物
JP2013206874A (ja) * 2012-03-29 2013-10-07 Fujifilm Corp 光電変換素子、色素増感太陽電池用色素吸着組成液、色素増感太陽電池用半導体電極、色素増感太陽電池の製造方法および光電変換素子用金属錯体色素

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3273456A4 (fr) * 2015-03-17 2018-01-24 FUJI-FILM Corporation Élément de conversion photoélectrique, cellule solaire sensibilisé au colorant, colorant de complexe de ruthénium, et solution de colorant

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