WO2014168163A1 - Elément de conversion photoélectrique, cellule à pigment photosensible, colorant de complexe métallique, solution de colorant, électrode à colorant adsorbé et procédé de fabrication de cellule à pigment photosensible - Google Patents

Elément de conversion photoélectrique, cellule à pigment photosensible, colorant de complexe métallique, solution de colorant, électrode à colorant adsorbé et procédé de fabrication de cellule à pigment photosensible Download PDF

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WO2014168163A1
WO2014168163A1 PCT/JP2014/060250 JP2014060250W WO2014168163A1 WO 2014168163 A1 WO2014168163 A1 WO 2014168163A1 JP 2014060250 W JP2014060250 W JP 2014060250W WO 2014168163 A1 WO2014168163 A1 WO 2014168163A1
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dye
group
anc
formula
ring
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PCT/JP2014/060250
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Japanese (ja)
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晃逸 佐々木
渡辺　康介
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
    • 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
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • 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
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
    • 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
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a photoelectric conversion element, a dye-sensitized solar cell, a metal complex dye, a dye solution, a dye-adsorbing electrode, and a method for producing a dye-sensitized solar battery.
  • Photoelectric conversion elements are used in various optical sensors, copiers, solar cells and the like.
  • Various types of photoelectric conversion elements have been put to practical use, such as those using metals, semiconductors, organic pigments and dyes, or combinations thereof.
  • 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.
  • Non-Patent Document 1 The dyes described in Patent Documents 1 and 2 and Non-Patent Document 1 are not always satisfactory in terms of spectral sensitivity characteristics and photoelectric conversion efficiency in the long wavelength region at a wavelength of 800 to 850 nm. Improvement was desired. In view of the above situation, the present invention improves the photoelectric conversion efficiency by improving the spectral sensitivity characteristic in the long wavelength region in the absorption characteristic of the metal complex dye, and in addition, the photoelectric conversion element and the dye excellent in durability It is an object of the present invention to provide a sensitized solar cell, a metal complex dye used for the sensitized solar cell, a dye solution, a dye adsorption electrode, and a method for producing a dye-sensitized solar cell.
  • the conventional metal complex dyes are not necessarily sufficient for the spectral sensitivity characteristic in the long wavelength region
  • the present inventors have found that the spectral sensitivity property in the long wavelength region, particularly the sensitivity characteristic at 800 to 850 nm, that is, the quantum yield (IPCE).
  • IPCE quantum yield
  • a nitrogen atom coordinated to the central metal ion via a lone pair As a result, as a ligand used together with a tridentate ligand having a function of adsorbing to the surface of the semiconductor fine particles, a nitrogen atom coordinated to the central metal ion via a lone pair, and The above nitrogen using a bidentate ligand formed by combining a nitrogen atom, an oxygen atom or a sulfur atom as a coordinating atom to which an anion coordinates, and coordinating with a central metal via a lone electron pair Spectral sensitivity characteristics in the long-wavelength region of the photoelectric conversion element are improved by making the atom a ring-constituting atom that forms a more electron-deficient nitrogen-containing aromatic ring that further includes an electron-withdrawing atom than the carbon atom.
  • the object of the present invention has been achieved by the following means.
  • a photoelectric conversion element having a conductive support, a photoreceptor layer containing an electrolyte, a charge transfer layer containing an electrolyte, and a counter electrode, The photoelectric conversion element in which this photoreceptor layer has the semiconductor fine particle by which the metal complex dye represented by following formula (I) was carry
  • M represents a metal ion.
  • LD represents a bidentate ligand represented by any of the following formulas (2L-1) to (2L-3).
  • LA represents a tridentate ligand represented by the following formula (AL-1) or (AL-2).
  • LX represents a monodentate ligand.
  • Y represents a counter ion necessary for neutralizing the electric charge.
  • n represents an integer of 0 to 4.
  • Ring D 1 represents a nitrogen-containing aromatic ring
  • ring D 2 represents an aromatic hydrocarbon ring or heteroaromatic ring.
  • a 12 and A 13 are each independently, N - R L, O - or S - represents a.
  • a 1 to A 4 each independently represent CR LD or N, and at least one of A 1 to A 4 represents N.
  • R L and R LD each independently represent a hydrogen atom or a substituent that does not have the following Anc 1 , Anc 2, and Anc 3 .
  • Anc 1 to Anc 3 each independently represent —CO 2 H, —SO 3 H, —PO 3 H 2, or a group in which any one of these protons is dissociated.
  • R AL represents a substituent other than Anc 1 to Anc 3
  • b1 represents an integer of 0 to 4.
  • R LDa represents a substituent having no Anc 1 , Anc 2, or Anc 3 , nL1 to nL3 each independently represents an integer of 0 to 3, and nL4 represents an integer of 0 to 2.
  • R A1 represents a substituent having an acidic group.
  • R A2 represents a substituent.
  • nA represents an integer of 0 or more.
  • M represents a metal ion.
  • LD represents a bidentate ligand represented by any of the following formulas (2L-1) to (2L-3).
  • LA represents a tridentate ligand represented by the following formula (AL-1) or (AL-2).
  • LX represents a monodentate ligand.
  • Y represents a counter ion necessary for neutralizing the electric charge.
  • n represents an integer of 0 to 4.
  • Ring D 1 represents a nitrogen-containing aromatic ring
  • ring D 2 represents an aromatic hydrocarbon ring or heteroaromatic ring.
  • a 12 and A 13 are each independently, N - R L, O - or S - represents a.
  • a 1 to A 4 each independently represent CR LD or N, and at least one of A 1 to A 4 represents N.
  • R L and R LD each independently represent a hydrogen atom or a substituent that does not have the following Anc 1 , Anc 2, and Anc 3 .
  • Anc 1 to Anc 3 each independently represent —CO 2 H, —SO 3 H, —PO 3 H 2, or a group in which any one of these protons is dissociated.
  • R AL represents a substituent other than Anc 1 to Anc 3
  • b1 represents an integer of 0 to 4.
  • R LDa represents a substituent having no Anc 1 , Anc 2, or Anc 3 , nL1 to nL3 each independently represents an integer of 0 to 3, and nL4 represents an integer of 0 to 2.
  • R A1 represents a substituent having an acidic group.
  • R A2 represents a substituent.
  • nA represents an integer of 0 or more.
  • a dye-adsorbing electrode for a dye-sensitized solar cell in which the metal complex dye according to (8) or (9) is supported on the surface of a semiconductor fine particle provided in a semiconductor electrode.
  • the carbon-carbon double bond may be either E-type or Z-type in the molecule, or a mixture thereof.
  • substituents, etc. linking groups, ligands, etc.
  • substituents etc.
  • a special notice is given.
  • each substituent etc. may mutually be same or different. The same applies to the definition of the number of substituents and the like.
  • substituents and the like when 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 such as an alicyclic ring, an aromatic ring, or a hetero ring may be further condensed to form a condensed ring.
  • each substituent may be further substituted with a substituent unless otherwise specified.
  • the photoelectric conversion efficiency is improved by improving the spectral sensitivity characteristic in a long wavelength region, and in addition, the photoelectric conversion element, the dye-sensitized solar cell, which are excellent in durability, It is possible to provide a method for producing a metal complex and a metal complex dye, a dye solution, a dye-adsorbing electrode, and a dye-sensitized solar cell used in the above.
  • 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.
  • This photoreceptor layer has semiconductor fine particles carrying a metal complex dye represented by the following formula (I).
  • the metal complex dye of the present invention is represented by the following formula (I).
  • M represents a metal ion.
  • LD represents a bidentate ligand represented by any of the following formulas (2L-1) to (2L-3).
  • LA represents a tridentate ligand represented by the following formula (AL-1) or (AL-2).
  • LX represents a monodentate ligand.
  • Y represents a counter ion necessary for neutralizing the electric charge.
  • n represents an integer of 0 to 4.
  • Ring D 1 represents a nitrogen-containing aromatic ring
  • ring D 2 represents an aromatic hydrocarbon ring or heteroaromatic ring.
  • a 12 and A 13 are each independently, N - R L, O - or S - represents a.
  • a 1 to A 4 each independently represent CR LD or N, and at least one of A 1 to A 4 represents N.
  • R L and R LD each independently represent a hydrogen atom or a substituent that does not have the following Anc 1 , Anc 2, and Anc 3 .
  • Anc 1 to Anc 3 each independently represent —CO 2 H, —SO 3 H, —PO 3 H 2, or a group in which any one of these protons is dissociated.
  • R AL represents a substituent other than Anc 1 to Anc 3
  • b1 represents an integer of 0 to 4.
  • M-M is a central metal ion of the metal complex dye, and examples of these metals include atoms in groups 6 to 12 of the long-period periodic table. Specific examples of such atoms include Ru, Fe, Os, Cu, W, Cr, Mo, Ni, Pd, Pt, Co, Ir, Rh, Re, Mn, and Zn.
  • M is preferably Os 2+ , Ru 2+ or Fe 2+ , and Ru 2+ is particularly preferable.
  • the valence of M may change due to an oxidation-reduction reaction with surrounding materials.
  • the ligand LD is a ligand that binds to the metal ion M in a bidentate, and is classified as a donor ligand.
  • the ligand LD is coordinated to the metal ion M by a nitrogen atom having a lone electron pair and an anion.
  • the nitrogen atom having a lone electron pair is a nitrogen atom coordinated to the metal ion M through the lone electron pair, and further includes an atom having a stronger electron withdrawing property than the carbon atom, and is further deficient in electrons.
  • the anion that coordinates to the metal ion M is a nitrogen anion, an oxygen atom anion, or a sulfur anion.
  • the lone electron pair is an electron pair (a set of two electrons) that does not participate in a covalent bond among the outermost electron pairs of the nitrogen atom, and the nitrogen atom has one pair of the lone electron pair.
  • the anion is also preferred.
  • an anion of a nitrogen atom, an oxygen atom, or a sulfur atom is regarded as a coordination atom that coordinates to the metal ion M as an anion even if it has a lone pair.
  • the anion is regarded as a coordinating atom as the stable coordination structure. That is, in the case of> NH, —OH, —SH, it is considered that the anions of> N ⁇ , —O ⁇ , —S 2 — are coordinated.
  • the nitrogen atom coordinated through the lone pair is a nitrogen atom having no hydrogen atom.
  • the atom whose coordination atom is an anion is a nitrogen atom, an oxygen atom and a sulfur atom, and a nitrogen atom is preferable.
  • These atoms may be ring-constituting atoms or atoms contained in a simple group (substituent, preferably an atom in a substituent that is substituted with a ring structure).
  • a nitrogen atom it can be a ring constituent atom constituting a heteroaromatic ring, and such a heterocyclic constituent atom is preferable.
  • each atom serving as an anion is preferably a heterocyclic atom or a substituent on the ring.
  • this ring is preferably an aromatic hydrocarbon ring or a heteroaromatic ring
  • the heteroaromatic ring is a nitrogen-containing heteroaromatic ring (including a heteroaromatic ring having a heteroatom other than a nitrogen atom). Further preferred.
  • Such bidentate ligand LD is specifically represented by any of the following formulas (2L-1) to (2L-3).
  • Ring D 1 represents a nitrogen-containing aromatic ring
  • ring D 2 represents an aromatic hydrocarbon ring or heteroaromatic ring.
  • a 12 and A 13 are each independently, N - R L, O - or S - represents a.
  • a 1 to A 4 each independently represent CR LD or N, and at least one of A 1 to A 4 represents N.
  • R L and R LD each independently represent a hydrogen atom or a substituent that does not have the following Anc 1 , Anc 2, and Anc 3 .
  • the ring D 1 is a nitrogen-containing aromatic ring, has an active hydrogen on at least one nitrogen atom of the ring (—NH—), and the —NH— moiety is an anion ( ⁇ N ⁇ ⁇ ) and can be bonded to the metal ion M.
  • —N ⁇ — on ring D 1 in formula (2L-1) is a nitrogen anion from which a hydrogen atom bonded to the nitrogen atom constituting ring D 1 is eliminated.
  • a nitrogen-containing aromatic ring is preferably a 5- to 7-membered ring and may be condensed.
  • Examples include an imidazole ring, a triazole ring, a tetrazole ring, a benzimidazole ring, a 1H-indazole ring, a purine ring, a pyrrole ring, and a pyrazole ring in which the atom bonded to the metal ion M is a nitrogen atom at the 1st position.
  • a triazole ring, a tetrazole ring, a pyrrole ring, and a pyrazole ring in which the atom bonded to the metal ion M is a nitrogen atom at the 1-position is preferable.
  • the nitrogen-containing aromatic ring is preferably a group represented by the following formulas (a-1) to (a-6) derived from an imidazole ring, a pyrazole ring, a triazole ring, a tetrazole ring or a pyrrole ring.
  • (A-1), (a-2) or a group represented by (a-5) is more preferred, and a group represented by (a-2) is particularly preferred.
  • Rd represents a substituent.
  • b1 represents an integer of 0 to 2
  • b2 represents an integer of 0 to 3
  • b3 represents 0 or 1.
  • Rd include a substituent T described later.
  • Rd and b1 to b3 have the same meanings as Rd and b1 to b3 in the formulas (a-1) to (a-6) described above, and the preferred ranges are also the same.
  • b4 represents an integer of 0 to 4
  • b5 represents an integer of 0 to 5.
  • Rd may be present not only on the benzene ring but also on the pyrrole ring.
  • Rd is preferably a linear or branched alkyl group, a cycloalkyl group, an alkenyl group, a fluoroalkyl group, an aryl group, a halogen atom, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, or a group formed by combining these, more preferably A straight chain or branched alkyl group, a cycloalkyl group, an alkenyl group, a fluoroalkyl group, an aryl group or a group formed by combining these, particularly preferably a linear or branched alkyl group, a cycloalkyl group, an alkenyl group, a fluoro group. An alkyl group and a group formed by a combination thereof.
  • Rd preferably does not have an adsorbing group that adsorbs to the surface of the semiconductor fine particles.
  • the adsorbing group adsorbed on the surface of the semiconductor fine particles is a group represented by Anc 1 to Anc 3 in the ligand LA described later. Even if Rd contains a group corresponding to the adsorbing group, it is included as a group that binds to the metal ion M and is not adsorbed on the surface of the semiconductor fine particles.
  • a 1 to A 4 each independently represent CR LD (R LD is a hydrogen atom or a substituent not having the following Anc 1 , Anc 2 and Anc 3 ) or N, and A 1 At least one of A 4 represents N. That is, the ring structure represented by the formula (2L R ), which will be described later, which includes a ring-constituting nitrogen atom coordinated to the metal ion M via a lone pair and A 1 to A 4 , It has 2 to 5 nitrogen atoms among ring members.
  • a ring structure formed by including a plurality of nitrogen atoms having electron withdrawing properties stronger than carbon atoms as ring constituent atoms becomes a nitrogen-containing aromatic ring having fewer electrons than a pyridine ring structure.
  • the ring-constituting nitrogen atom constituting such a nitrogen-containing aromatic ring is coordinated to the metal ion M via a lone electron pair, in combination with the ligands LA and LX described later, a photoelectric conversion element Both the spectral sensitivity characteristics and the durability in the long wavelength region can be improved. From the viewpoint of improving spectral sensitivity characteristics and durability, one to three of A 1 to A 4 are preferably N, and more preferably one or two are N.
  • Such a nitrogen-containing aromatic ring has two or more N as ring constituent atoms and does not have a nitrogen atom that becomes an anion.
  • a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine Preferable examples include a ring, a tetrazine ring, and a ring in which benzene is condensed.
  • R LDa is a substituent that does not have the following Anc 1 to Anc 3 .
  • Examples of the substituent R LD and the substituent R LDa include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, and a cycloalkyl group.
  • Oxy group, aryloxy group, heterocyclic oxy group, amino group, alkylthio group, cycloalkylthio group, arylthio group, heteroarylthio group, polyalkylene ether group, halogen atom are preferred, alkyl group, alkenyl group, alkynyl group, aryl Group, heterocyclic group, alkoxy group, aryloxy group, amino group, alkylthio group and arylthio group are more preferable, and alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, amino group, alkylthio group and arylthio group are More preferred Ku, alkyl group, alkenyl group, alkynyl group, an aryl group, a heterocyclic group is particularly preferred.
  • the substituents R LD and R LDa may be a group formed by combining a plurality of the above-described substituents.
  • an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic ring A group selected from the group consisting of a group, an aryloxy group and an alkylthio group, a group consisting of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an aryloxy group, an alkylthio group, an amino group and a cycloalkyl group
  • a group to which at least one selected from the above is bonded.
  • the substituents R LD and R LDa are not an anionic functional group and partly an anion in that the above-described ring-constituting nitrogen atom is easily coordinated to the metal ion M through a lone pair. It is preferably not included.
  • nL1 to nL3 are each independently an integer of 0 to 3
  • nL4 is an integer of 0 to 2.
  • nL1 to nL3 are all preferably integers of 0 to 2
  • nL1 to nL4 are particularly preferably 0 or 1, and most preferably 1.
  • the ring D 2 is an aromatic hydrocarbon ring or a heteroaromatic ring, preferably a 5- to 7-membered ring, and may be condensed.
  • the aromatic hydrocarbon ring include an aromatic ring group corresponding to the aryl group of the substituent T described later
  • examples of the heteroaromatic ring include a heterocyclic group corresponding to the heterocyclic group of the substituent T described later.
  • aromatic hydrocarbon ring or heteroaromatic ring a benzene ring, a naphthalene ring, a thiophene ring, a furan ring, a pyridine ring, a pyrazole ring, and a pyrrole ring are preferable, and a benzene ring is particularly preferable.
  • a 12 is, N - R L, O - or S - a and is present as a substituent on the ring D2 (substituted) amino group, the same meanings as residues obtained by removing active hydrogen from hydroxyl or thiol group.
  • R L is a hydrogen atom or a substituent not having the following Anc 1 to Anc 3 ; an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, an alkoxy group, Alkenyloxy group, alkynyloxy group, cycloalkyloxy group, aryloxy group, heterocyclic oxy group, (substituted or unsubstituted) amino group, alkylthio group, cycloalkylthio group, arylthio group, halogen atom are preferred, alkyl group, alkenyl group Group, alkynyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, (substituted or unsubstituted) amino group, alkylthio group, arylthio group are more preferable, alkyl group, al
  • Examples of the substituted amino group include —NHSO 2 Ry (Ry represents an alkyl group).
  • —NHSO 2 Ry include —NHSO 2 CH 3 , —NHSO 2 C 2 H 5 , —NHSO 2 C 3 H 7 and the like.
  • Ring D 2 may further have a substituent T in addition to A 12 .
  • the substitution position o, m and p of the benzene rings represent the position relative to A 12.
  • the ring structure in formula (2L-2) is synonymous with the ring structure in formula (2L-1), and preferred ones are also the same.
  • the divalent linking group L LD represents —C ( ⁇ O) —, —C ( ⁇ S) —, —C ( ⁇ NR L ) —, —C (R L ) 2 —.
  • R L has the same meaning as R L of formula (2L-2), is a preferred also the same, particularly preferred are hydrogen atom.
  • a 13 is synonymous with the residue obtained by removing the active hydrogen from the (substituted) amino group, hydroxyl group or thiol group bonded to the linking group L LD , and specifically has the same meaning as A 12 and is preferably A. 12 is the same.
  • the ring structure in formula (2L-3) is synonymous with the ring structure in formula (2L-1), and preferred ones are also the same.
  • Me in specific examples represents a methyl group
  • Et represents an ethyl group
  • t-Bu represents a t-butyl group
  • Ph represents a phenyl group.
  • ligands LD are disclosed in, for example, US Patent Application Publication No. 2010/0258175, Japanese Patent No. 4298799, Angew. Chem. Int. Ed. , 2011, 50, 2054-2058, and the methods described in the references cited in these documents, or a method according to these methods.
  • the ligand LA is a tridentate ligand represented by the following formula (AL-1) or (AL-2). This ligand LA has adsorbing groups Anc 1 to Anc 3 adsorbed on the surface of the semiconductor fine particles.
  • Anc 1 to Anc 3 each independently represent —CO 2 H, —SO 3 H, —PO 3 H 2, or a group in which these protons are dissociated.
  • the proton-dissociated group is, for example, the above-mentioned anions (for example, —CO 2 ⁇ , —SO 3 ⁇ , —PO 3 H ⁇ , —PO 3 2 ⁇ ) or a salt thereof.
  • —CO 2 H or a group in which its proton is dissociated is preferable.
  • R AL represents a substituent other than Anc 1 to Anc 3 .
  • R AL includes the substituent T described later.
  • R AL is an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaromatic ring group, a substituted amino group (especially an alkylsulfonamide group (the carbon number of the alkyl group is Although not particularly limited, it is preferably 1 to 6.))) is preferred, and an aryl group is more preferred.
  • the heteroaromatic ring group is preferably a thiophene ring group, a furan ring group, or a thiazole ring group, and more preferably a thiophene ring group.
  • R AL may be a group in which a plurality of these groups are bonded, may form a ring by combining at least two groups if R AL there are multiple.
  • b1 represents an integer of 0 to 4, preferably 0 or 1, and more preferably 1.
  • ligand LA Specific examples of the ligand LA are shown below, but the present invention is not limited thereto.
  • Anc 1 to Anc 3 are shown in a state where dissociable protons are not dissociated. However, these protons dissociate, for example, tetrabutylammonium ion ( + NBu 4 ).
  • Triethylammonium ion ( + NHEt 3 ) lithium ion, sodium ion, potassium ion, cesium ion, and the like may form a salt that forms an ion pair.
  • ligand LA represented by the formula (AL-2) are shown below.
  • the ligand LA can be synthesized by a metal-halogen exchange reaction, a cross coupling reaction, a Kunafener gel condensation reaction, or the like.
  • LX represents a monodentate ligand and is an acyloxy anion, acylthioanion, thioacyloxyanion, thioacylthioanion, acylaminooxyanion, thiocarbamate anion, dithiocarbamate anion, thiocarbonate anion, dithiocarbonate Nate anion, trithiocarbonate anion, acyl anion, thiocyanate anion, isothiocyanate anion, cyanate anion, isocyanate anion, alkylthioanion, (hetero) arylthioanion, alkoxy anion, (hetero) aryloxyanion, saturated or unsaturated hetero A thioanion or oxyanion bonded to a ring, an amide anion or imide anion bonded to a saturated or unsaturated heterocycle, a silylthioan On, silyl oxyanion, silyl
  • Examples of the atomic group having a lone pair include triarylphosphine (for example, triphenylphosphine) and nitrogen-containing aromatic ring (for example, pyridine).
  • triarylphosphine for example, triphenylphosphine
  • nitrogen-containing aromatic ring for example, pyridine
  • the ligand LX contains an alkyl group, an alkenyl group, an alkynyl group, an alkylene group or the like, these may be linear or branched, and may be substituted or unsubstituted.
  • an aryl group, a heterocyclic group, a cycloalkyl group, etc. may be substituted or unsubstituted, and may be monocyclic or condensed.
  • the ligand LX is preferably a cyanate anion, an isocyanate anion, a thiocyanate anion, an isothiocyanate anion, a selenocyanate anion, an isoselenocyanate anion, more preferably an isocyanate anion, an isothiocyanate anion, an isoselenocyanate anion, An isothiocyanate anion is particularly preferred.
  • ligand LX Specific examples of the ligand LX are shown below, but the present invention is not limited to these.
  • Me represents a methyl group
  • Et represents an ethyl group
  • Ph represents a phenyl group.
  • -Counter ion Y- Y represents a counter ion when a counter ion is necessary to neutralize the charge.
  • a 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, for example, because the substituent has a dissociable group. In this case, the charge of the entire metal complex dye is electrically neutralized by Y.
  • the counter ion Y is a positive counter ion
  • the counter ion Y is an inorganic or organic ammonium ion (for example, tetraalkylammonium ion such as tetrabutylammonium ion, triethylbenzylammonium ion, pyridinium ion, etc.), phosphonium ion (For example, tetraalkylphosphonium ions such as tetrabutylphosphonium ions, alkyltriphenylphosphonium ions, triethylphenylphosphonium ions, 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 Y 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 eg, benzoate ion
  • a substituted or unsubstituted alkyl sulfonate ion eg, methane sulfonate, trifluoromethane sulfonate ion
  • a substituted or unsubstituted aryl sulfonate ion eg, 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- N in the formula (I) represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.
  • ⁇ Substituent T> In this specification, about the display of a compound (a complex and a pigment
  • a substituent that does not specify substitution / non-substitution means that the group may have an arbitrary substituent. This is also synonymous for compounds that do not specify substitution / non-substitution.
  • Preferred substituents include the following substituent T. Further, in the present specification, when only described as a substituent, it refers to this substituent T, and each group, for example, an alkyl group, is only described. The preferred range and specific examples of the corresponding group of the substituent T are applied.
  • substituent T examples include the following groups.
  • An alkyl group preferably having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, trifluoromethyl, etc.
  • Alkenyl groups preferably having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.
  • alkynyl groups preferably having 2 to 20 carbon atoms, such as ethynyl, butynyl, phenylethynyl, etc.
  • cycloalkyl groups preferably Has 3 to 20 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl and the like, cycloalkenyl group (preferably having 5 to 20 carbon atom
  • alkoxycarbonyl group preferably having 2 to 20 carbon atoms such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.
  • a cycloalkoxycarbonyl group preferably having 4 to 20 carbon atoms such as cyclopropyloxycarbonyl, cyclopentyloxycarbonyl, etc.
  • Cyclohexyloxycarbonyl, etc. aryloxycarbonyl groups (preferably having 6 to 20 carbon atoms, such as phenyloxycarbonyl, naphthyloxycarbonyl, etc.)
  • amino groups preferably having 0 to 20 carbon atoms, alkylamino groups, alkenyls
  • An acyl group preferably having 1 to 20 carbon atoms such as acetyl, cyclohexylcarbonyl, benzoyl, etc.
  • an acyloxy group preferably having 1 to 20 carbon atoms such as acetyloxy, cyclohexylcarbonyloxy).
  • Benzoyloxy, etc. carbamoyl group (preferably an carbamoyl group having 1 to 20 carbon atoms, alkyl, cycloalkyl or aryl, such as N, N-dimethylcarbamoyl, N-cyclohexylcarbamoyl, N-phenylcarbamoyl, etc.)
  • N, N-dimethylcarbamoyl, N-cyclohexylcarbamoyl, N-phenylcarbamoyl, etc.
  • An acylamino group (preferably an acylamino group having 1 to 20 carbon atoms, such as acetylamino, cyclohexylcarbonylamino, benzoylamino, etc.), a sulfonamide group (preferably an alkyl, cycloalkyl or aryl sulfonamide having 0 to 20 carbon atoms) Groups such as methanesulfonamide, benzenesulfonamide, N-methylmethanesulfonamide, N-cyclohexylsulfonamide, N-ethylbenzenesulfonamide, etc., alkylthio groups (preferably having 1 to 20 carbon atoms, for example, Methylthio, ethylthio, isopropylthio, benzylthio, etc.), cycloalkylthio groups (preferably having 3 to 20 carbon atoms, such as cyclopropylthio, cyclopen
  • a silyl group (preferably a silyl group having 1 to 20 carbon atoms and substituted by alkyl, aryl, alkoxy and aryloxy, such as triethylsilyl, triphenylsilyl, diethylbenzylsilyl, dimethylphenylsilyl, etc.), silyloxy group ( Preferably, it is a silyloxy group having 1 to 20 carbon atoms and substituted with alkyl, aryl, alkoxy and aryloxy, such as triethylsilyloxy, triphenylsilyloxy, diethylbenzylsilyloxy, dimethylphenylsilyloxy, etc.), hydroxyl group Cyano group, nitro group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group, sulfo group, phosphonyl group, phosphoryl group, boric acid group.
  • the compound or the substituent includes an alkyl group, an alkenyl group, etc.
  • these may be linear or branched, and may be substituted or unsubstituted.
  • an aryl group, a heterocyclic group, or the like may be monocyclic or condensed, and may be substituted or unsubstituted.
  • the maximum absorption wavelength in the solution is preferably in the range of 300 to 1000 nm, more preferably in the range of 350 to 950 nm, and particularly preferably in the range of 370 to 900 nm.
  • the metal complex dye represented by the formula (I) of the present invention is a method according to each method described in Patent Documents 1 and 2 and Non-Patent Document 1 described above, and a synthesis method in Examples described later. It can be synthesized by a similar method.
  • the photoelectric conversion element 10 of the present invention includes, for example, as shown in FIG. 1, a conductive support 1, a photoreceptor layer 2 containing semiconductor fine particles sensitized by a dye (metal complex dye) 21, and a hole transport layer. It consists of a certain charge transfer layer 3 and a counter electrode 4.
  • the co-adsorbent is adsorbed on the semiconductor fine particles 22 together with the dye (metal complex dye) 21.
  • the conductive support 1 provided with the photoreceptor layer 2 functions as a working electrode in the photoelectric conversion element 10.
  • the photoelectric conversion element 10 is shown as a system 100 using a dye-sensitized solar cell that can be used for a battery for causing the operating means M to work with the external circuit 6.
  • the light-receiving electrode 5 includes a conductive support 1 and a photoreceptor layer 2 containing semiconductor fine particles adsorbed with a dye (metal complex dye) 21.
  • the photoreceptor layer 2 is designed according to the purpose, and may be a single layer structure or a multilayer structure.
  • the dye (metal complex dye) 21 in one photosensitive layer may be one kind or a mixture of various kinds, but at least one of them uses the metal complex dye of the present invention described above.
  • the light incident on the photoreceptor layer 2 excites the dye (metal complex dye) 21.
  • the excited dye has high energy electrons, and the electrons are transferred from the dye (metal complex dye) 21 to the conduction band of the semiconductor fine particles 22 and reach the conductive support 1 by diffusion.
  • the dye (metal complex dye) 21 is an oxidant, but the electrons on the electrode work in the external circuit 6 and pass through the counter electrode 4 so that the oxidant of the dye (metal complex dye) 21 and By returning to the photoreceptor layer 2 where the electrolyte is present, it functions as a solar cell.
  • the material used for the photoelectric conversion element or the dye-sensitized solar cell and the method for producing each member may be any ordinary material and each member used in the photoelectric conversion element or the dye-sensitized solar cell.
  • the conductive support is preferably a support made of glass or plastic having a conductive film layer on the surface, such as a metal, which is conductive in itself.
  • a support in addition to glass and plastic, ceramic (Japanese Patent Laid-Open No. 2005-135902) or conductive resin (Japanese Patent Laid-Open No. 2001-160425) may be used.
  • the surface On the support, the surface may have a light management function.
  • an antireflection film in which high refractive films and low refractive index oxide films described in JP-A-2003-123859 are alternately laminated, A light guide function described in JP-A-2002-260746 can be mentioned.
  • the thickness of the conductive film layer is preferably 0.01 to 30 ⁇ m, more preferably 0.03 to 25 ⁇ m, and particularly preferably 0.05 to 20 ⁇ m.
  • the conductive support is substantially transparent. “Substantially transparent” means that the light transmittance is 10% or more, preferably 50% or more, and particularly preferably 80% or more.
  • a glass or plastic coated with a conductive metal oxide is preferable.
  • the metal oxide tin oxide is preferable, and indium-tin oxide and fluorine-doped oxide are particularly preferable.
  • the coating amount of the conductive metal oxide at this time is preferably 0.1 to 100 g per 1 m 2 of the glass or plastic support. When a transparent conductive support is used, light is preferably incident from the support side.
  • the semiconductor fine particles are preferably metal chalcogenide (for example, oxide, sulfide, selenide, etc.) or perovskite fine particles.
  • metal chalcogenide for example, oxide, sulfide, selenide, etc.
  • perovskite fine particles Preferred examples of the metal chalcogenide include titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, tantalum oxide, cadmium sulfide, cadmium selenide, and the like.
  • Preferred perovskites 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 may be mixed with titania fine particles or used as a semiconductor electrode.
  • the particle diameters of the semiconductor fine particles are 0.001 to 1 ⁇ m as primary particles and 0.01 to 100 ⁇ m as the average particle diameter of the dispersion as the average particle diameter using the diameter when the projected area is converted into a circle. preferable.
  • Examples of the method for coating the semiconductor fine particles on the conductive support include a wet method, a dry method, and other methods.
  • the semiconductor fine particles preferably have a large surface area so that many dyes can be adsorbed.
  • the surface area is preferably 10 times or more, more preferably 100 times or more the projected area.
  • the preferred thickness of the photoreceptor layer which is a semiconductor layer, varies depending on the use of the device, but is typically 0.1 to 100 ⁇ m. When used as a dye-sensitized solar cell, the thickness is preferably 1 to 50 ⁇ m, more preferably 3 to 30 ⁇ m.
  • the semiconductor fine particles may be fired at a temperature of 100 to 800 ° C. for 10 minutes to 10 hours in order to adhere the particles to each other after being applied to the support. When glass is used as the support, the film forming temperature is preferably 400 to 60 ° C.
  • the coating amount of semiconductor fine particles per 1 m 2 of support is preferably 0.5 to 500 g, more preferably 5 to 100 g.
  • the total amount of the dye used is preferably 0.01 to 100 mmol, more preferably 0.1 to 50 mmol, and particularly preferably 0.1 to 10 mmol per 1 m 2 of the support.
  • the amount of the metal complex dye of the present invention is preferably 5 mol% or more.
  • the adsorption amount of the dye to the semiconductor fine particles 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. By using such a dye amount, the sensitizing effect in the semiconductor fine particles can be sufficiently obtained.
  • the counter ion of the specific metal complex dye is not particularly limited, and examples thereof include alkali metal ions and quaternary ammonium ions.
  • the semiconductor fine particles are adsorbed with the added metal complex dye represented by the above formula (I).
  • a method of adsorption will be described later.
  • the surface of the semiconductor fine particles may be treated with amines.
  • Preferable amines include pyridines (for example, 4-tert-butylpyridine, polyvinylpyridine) and the like. These may be used as they are in the case of a liquid, or may be used by dissolving in an organic solvent.
  • the photoelectric conversion element for example, the photoelectric conversion element 10
  • the dye-sensitized solar cell for example, the photoelectrochemical cell 20
  • at least the metal complex dye of the present invention is used.
  • the metal complex dye of the present invention may be used in combination with another dye.
  • the dye used in combination include Japanese Patent No. 3731852, Japanese Patent Publication No. 2002-512729, Japanese Patent Application Laid-Open No. 2001-59062, Japanese Patent Application Laid-Open No. 2001-6760, Japanese Patent No. 3430254, Japanese Patent Application Laid-Open No. 2003-212851, and International Publication No. 2007/91525.
  • the squarylium cyanine dyes described in each of the above publications such as JP2004-063274, JP2005-123033, JP2007-287694, Organic dyes described in JP-A-2008-71648, JP-A-2007-287694, and International Publication No. 2007/119525 pamphlet or specification, Angew. Chem. Int. Ed. , 49, 1-5 (2010), etc., Angew. Chem. Int. Ed. , 46, 8358 (2007), and the like.
  • the dye used in combination is preferably a Ru complex dye, a squarylium cyanine dye, or an organic dye.
  • the ratio of the mass of the metal complex dye of the present invention to the mass of the other dye is preferably 95/5 to 10/90, and 95/5 to 50/50. Is more preferable, 95/5 to 60/40 is further preferable, 95/5 to 65/35 is particularly preferable, and 95/5 to 70/30 is most preferable.
  • the charge transfer layer used in the photoelectric conversion element of the present invention is a layer having a function of replenishing electrons to the oxidant of the dye, and is provided between the light receiving electrode (photoelectrode) and the counter electrode (counter electrode).
  • Typical examples include a liquid electrolyte in which a redox couple is dissolved in an organic solvent, a so-called gel electrolyte in which a polymer matrix is impregnated with a liquid in which the redox couple is dissolved in an organic solvent, and a molten salt containing the redox couple. It is done.
  • a liquid electrolyte is preferred for increasing efficiency.
  • Nitrile compounds, ether compounds, ester compounds and the like are used as the organic solvent for the liquid electrolyte, but nitrile compounds are preferred, and acetonitrile and methoxypropionitrile are particularly preferred.
  • iodine and iodide iodide salt, ionic liquid is preferable, lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, methylpropylimidazolium iodide are preferable
  • alkyl viologens for example, methyl viologen chloride, hexyl viologen bromide, benzyl viologen tetrafluoroborate
  • polyhydroxybenzenes for example, hydroquinone, naphthohydroquinone, etc.
  • divalent And combinations of trivalent iron complexes for example, combinations of red blood salts and yellow blood salts
  • divalent and trivalent cobalt complexes and the like.
  • a combination of iodine and iodide iodide salt, ionic liquid is preferable, lithium iodide, tetrabutylammonium io
  • the cobalt complex is preferably a complex represented by the following formula (CC).
  • LL represents a bidentate or tridentate ligand.
  • X represents a monodentate ligand.
  • ma represents an integer of 0 to 3.
  • mb represents an integer of 0-6.
  • CI represents a counter ion when a counter ion is required to neutralize the charge.
  • CI includes Y in the formula (I).
  • LL is preferably a ligand represented by the following formula (LC).
  • Z LC1 , Z LC2 and Z LC3 each independently represent a nonmetallic atom group necessary for forming a 5- or 6-membered ring.
  • Z LC1 , Z LC2 and Z LC3 may have a substituent and may be closed with an adjacent ring via the substituent.
  • X LC1 and X LC3 represent a carbon atom or a nitrogen atom.
  • q represents 0 or 1; Examples of the substituent include the above-described substituent T.
  • X is preferably a halogen ion.
  • the ligand represented by the above formula (LC) is more preferably a ligand represented by the following formulas (LC-1) to (LC-3).
  • R LC1 to R LC9 each represents a substituent.
  • q1, q2, q6 and q7 each independently represents an integer of 0 to 4.
  • q3 and q5 each independently represents an integer of 0 to 3.
  • q4 represents an integer of 0-2.
  • examples of the substituent for R LC1 to R LC9 include an aliphatic group, an aromatic group, and a heterocyclic group.
  • Specific examples of the substituent include alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, and heterocyclic rings.
  • Preferred examples include alkyl groups (eg methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl, cyclohexyl, benzyl etc.), aryl groups (eg phenyl, tolyl, naphthyl).
  • alkyl groups eg methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl, cyclohexyl, benzyl etc.
  • aryl groups eg phenyl, tolyl, naphthyl
  • alkoxy groups eg methoxy, ethoxy, isopropoxy, butoxy etc.
  • alkylthio groups eg methylthio, n-butylthio, n-hexylthio, 2-ethylhexylthio etc.
  • aryloxy groups eg phenoxy, naphthoxy etc.
  • arylthio groups eg, phenylthio, naphthylthio, etc.
  • heterocyclic groups eg, 2-thienyl, 2-furyl, etc.
  • cobalt complex represented by the formula (LC) include the following complexes.
  • 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.
  • organic solvent for dissolving the redox couple these are aprotic polar solvents (for example, acetonitrile, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl sulfoxide, sulfolane, 1,3-dimethylimidazolinone, 3-methyloxazolidinone, etc. ) Is preferred.
  • aprotic polar solvents for example, acetonitrile, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl sulfoxide, sulfolane, 1,3-dimethylimidazolinone, 3-methyloxazolidinone, etc.
  • the polymer (polymer matrix) used in the gel electrolyte matrix include polyacrylonitrile and polyvinylidene fluoride.
  • the molten salt include those imparted with fluidity at room temperature by mixing polyethylene oxide with lithium iodide and at least one other lithium salt (such as lithium acetate and lithium perchlor
  • aminopyridine compounds As an additive to the electrolyte, in addition to the aforementioned 4-tert-butylpyridine, aminopyridine compounds, benzimidazole compounds, aminotriazole compounds and aminothiazole compounds, imidazole compounds, aminotriazine compounds, urea derivatives, Amide compounds, pyrimidine compounds and nitrogen-free heterocycles can be added.
  • a method of controlling the water content of the electrolytic solution may be taken.
  • Preferred methods for controlling moisture include a method for controlling the concentration and a method in which a dehydrating agent is allowed to coexist.
  • an inclusion compound of iodine and cyclodextrin may be used, and conversely, a method of constantly supplying water may be used.
  • Cyclic amidine may be used, and an antioxidant, hydrolysis inhibitor, decomposition inhibitor, and zinc iodide may be added.
  • a molten salt may be used as the electrolyte, and preferred molten salts include ionic liquids containing imidazolium or triazolium type cations, oxazolium-based, pyridinium-based, guanidinium-based, and combinations thereof. These cationic systems may be combined with specific anions. Additives may be added to these molten salts. You may have a liquid crystalline substituent. Further, a quaternary ammonium salt-based molten salt may be used.
  • lithium iodide and at least one other lithium salt are mixed with polyethylene oxide to give fluidity at room temperature. Etc.
  • 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 the matrix polymer, the crosslinkable polymer compound or monomer, the crosslinking agent, the electrolyte, and the solvent in the polymer may be used.
  • a matrix polymer a polymer having a nitrogen-containing heterocyclic ring in the main chain or side chain repeating unit, a crosslinked product obtained by reacting these with an electrophilic compound, a polymer having a triazine structure, or having a ureido structure
  • Polymers liquid crystalline compounds, ether-bonded polymers, polyvinylidene fluoride, methacrylate / acrylate, thermosetting resins, cross-linked polysiloxane, polyvinyl alcohol (PVA), polyalkylene glycol and dextrin, etc.
  • Examples include inclusion compounds, systems to which oxygen-containing or sulfur-containing polymers are added, and natural polymers.
  • An alkali swelling polymer, a polymer having a compound capable of forming a charge transfer complex between a cation moiety and iodine in one polymer may be added to these.
  • a system containing a cross-linked polymer obtained by reacting a bifunctional or higher functional isocyanate with a functional group such as a hydroxyl group, an amino group, or a carboxyl 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, and a solvent having a specific dielectric constant.
  • the liquid electrolyte solution may be held in a solid electrolyte membrane or pores, and preferred methods thereof include conductive polymer membranes, fibrous solids, and cloth solids such as filters.
  • 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 or polysilane, and a spiro compound in which two rings share a tetrahedral structure such as C or Si, or 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.
  • the total concentration is preferably 0.01 mol / 1 or more, more preferably 0.1 mol / 1, and particularly preferably 0.3 mol / 1 or more.
  • the upper limit in this case is not particularly limited, but is usually about 5 mol / 1.
  • a coadsorbent In the photoelectric conversion element of this invention, it is preferable to use a coadsorbent with the metal complex dye of this invention or the pigment
  • a coadsorbent a coadsorbent having at least one acidic group (preferably a carboxyl group or a salt group thereof) is preferable, Examples include compounds 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 a substituent having an acidic group.
  • R A2 represents a substituent.
  • nA represents an integer of 0 or more.
  • an acidic group is a substituent having a dissociable proton.
  • the acidic group include a carboxy group, a phosphonyl group, a phosphoryl group, a sulfo group, a boric acid group, and the like, or a group having any one of these.
  • a carboxy group, a phosphonyl group or a group having this is preferred.
  • the acidic group may take a form of releasing a proton and dissociating, or may be a salt.
  • the counter ion is not particularly limited, and examples thereof include positive ions in the counter ion Y.
  • the acidic group may be a group bonded through a linking group, and examples thereof include carboxyvinylene group, dicarboxyvinylene group, cyanocarboxyvinylene group, carboxyphenyl group and the like as preferable acidic groups.
  • nA is preferably 2 to 4.
  • These specific compounds include the compounds exemplified as the compounds having the steroid skeleton described above.
  • the co-adsorbent used in the present invention has an effect of suppressing inefficient association of dyes by adsorbing to semiconductor fine particles 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 coadsorbent used is not particularly limited, but it is preferably 1 to 200 mol, more preferably 10 to 150 mol, and particularly preferably 20 to 50 mol with respect to 1 mol of the dye. It is preferable from the viewpoint of being effectively expressed.
  • the counter electrode (also referred to as a counter electrode) preferably serves as a positive electrode for a dye-sensitized solar cell (photoelectrochemical cell).
  • the counter electrode is usually synonymous with the conductive support described above, but the support is not necessarily required in a configuration in which the strength is sufficiently maintained.
  • As the structure of the counter electrode a structure having a high current collecting effect is preferable.
  • at least one of the conductive support and the counter electrode must be substantially transparent.
  • the conductive support is preferably transparent, and sunlight is preferably incident from the support side. In this case, it is more preferable that the counter electrode has a property of reflecting light.
  • the counter electrode of the dye-sensitized solar cell glass or plastic on which metal or conductive oxide is vapor-deposited is preferable, and glass on which platinum is vapor-deposited is particularly preferable.
  • the dye-sensitized solar cell it is preferable to seal the side surface of the battery with a polymer, an adhesive or the like in order to prevent the constituents from evaporating.
  • the characteristics of the dye-sensitized solar cell of the present invention thus obtained are preferably an open circuit voltage of 0.01 to 1.5 V and a short-circuit current density of 0.001 to 20 mA / cm when AM 1.5G is 100 mW / cm 2. cm 2 , form factor 0.1 to 0.9, conversion efficiency 0.001 to 25%.
  • the present invention relates to 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, and Japanese Patent Application Laid-Open No. 2004-15. It can be applied to the photoelectric conversion elements and dye-sensitized solar cells described in Japanese Patent No. 2613 and Japanese Patent Laid-Open No. 9-27352.
  • a semiconductor electrode also referred to as a dye adsorption electrode
  • the metal complex dye of the present invention is dissolved in a solvent and may contain a co-adsorbent and other components as necessary.
  • the solvent to be used include, but are not particularly limited to, the solvents described in JP-A No. 2001-291534.
  • an organic solvent is preferable, and alcohols, amides, nitriles, hydrocarbons, and a mixed solvent of two or more of these are preferable.
  • the mixed solvent is preferably a mixed solvent of an alcohol and a solvent selected from amides, nitriles or hydrocarbons. Further preferred are alcohols and amides, mixed solvents of alcohols and hydrocarbons, and particularly preferred are mixed solvents of alcohols and amides. Specifically, methanol, ethanol, propanol, butanol, dimethylformamide, and dimethylacetamide are 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 formula (CA) is preferable.
  • the dye solution of the present invention is one in which the concentration of the metal complex dye or coadsorbent is adjusted so that the solution can be used as it is when a photoelectric conversion element or a dye-sensitized solar cell is produced. preferable.
  • the metal complex dye of the present invention is preferably contained in an amount of 0.001 to 0.1% by mass.
  • the water content of the dye solution is particularly preferably adjusted. Therefore, in the present invention, the content (content) of water is preferably adjusted to 0 to 0.1% by mass. Similarly, adjustment of the water content of the electrolytic solution in the photoelectric conversion element or the dye-sensitized solar cell is also preferable for effectively achieving the effects of the present invention. For this reason, the water content (content rate) of the electrolytic solution is preferable. Is preferably adjusted to 0 to 0.1% by mass.
  • the electrolytic solution is particularly preferably adjusted with a dye solution. In the present invention, a dye-sensitized solar cell semiconductor electrode in which a metal complex dye is supported on the surface of a semiconductor fine particle provided in the semiconductor electrode using the dye solution is preferable. Moreover, it is preferable to manufacture the dye-sensitized solar cell by which the metal complex pigment
  • Example 1 [Synthesis of Metal Complex Dye] The following metal complex dyes Dye-1-5, 12, 24, 26, 29, 31, 34, 36 and 41, Dye-2-2, and Dye-3-2, 3 and 6 were obtained as follows. Synthesized.
  • Compound LD-1-9a (2-acetyl-5-bromopyrimidine) (25 g) synthesized by the method described in International Publication No. 2012/126672 is dissolved in 1000 mL of THF (tetrahydrofuran) under a nitrogen atmosphere, and 200 mL of water, 63 g of 5-hexylthiophene-2-boronic acid pinacol ester, 86 g of potassium carbonate, and 7 g of tetrakis (triphenylphosphine) palladium were added, and the mixture was heated to reflux for 7 hours.
  • THF tetrahydrofuran
  • LD-1-9b Under a nitrogen atmosphere, 25 g of LD-1-9b was dissolved in 500 mL of THF (tetrahydrofuran), and while stirring at 0 ° C., 12 g of sodium ethoxide was added and stirred for 15 minutes. Thereafter, 37 g of ethyl trifluoroacetate was added dropwise thereto and stirred at 70 ° C. for 20 hours. The solution after stirring was returned to room temperature, and then an aqueous ammonium chloride solution was dropped to separate the solution. The organic phase was concentrated to obtain 34 g of a crude product LD-1-9c.
  • THF tetrahydrofuran
  • the obtained crude product was dissolved in 600 mL of ethanol under a nitrogen atmosphere, 9 g of hydrazine monohydrate was added with stirring at room temperature, and the mixture was heated at an external temperature of 90 ° C. for 12 hours. Thereafter, 20 mL of concentrated hydrochloric acid was added thereto and stirred for 1 hour. The solution after stirring was concentrated, 150 mL of sodium bicarbonate water and 150 mL of ethyl acetate were added, the reaction product was extracted into ethyl acetate, and after separation, the organic phase was concentrated. After recrystallization from acetonitrile, 24 g of ligand LD-1-9 was obtained.
  • a metal complex dye Dye-1-5 was synthesized according to the following scheme using the obtained ligand LD-1-9.
  • the reaction solution was cooled to room temperature, and the precipitated black solid was collected by filtration.
  • the obtained black solid was purified by silica gel column chromatography to obtain 4.6 g of Dye-1-5b.
  • the mixture was stirred as it was at room temperature for 1 hour, and a 1N solution of trifluoromethanesulfonic acid in methanol was slowly added dropwise thereto until the pH reached 3.0.
  • the gradually precipitated crystals were collected by filtration, and the obtained crystals were washed with methanol and dried to obtain 1.3 g of the target metal complex dye Dye-1-5.
  • LD-1-25c was synthesized in the same manner as the synthesis of the ligand LD-1-9 except that LD-1-25a was used instead of LD-1-9b.
  • This LD-1-25a is disclosed in Acta Chem. Scand. , 43, 62 (1989). Subsequently, 125 mL of 1.6M n-butyllithium hexane solution was added dropwise with stirring 22.2 g of diisopropylamine and 104 mL of tetrahydrofuran at ⁇ 40 ° C. in a nitrogen atmosphere, and then stirred for 30 minutes.
  • a metal complex dye Dye-1-12 was synthesized in the same manner as the synthesis of the metal complex dye Dye-1-5.
  • LD-2-16a and N- (tert A coupling product was obtained in the same manner as the synthesis of LD-1-9b except that -butoxycarbonyl) indole-2-boronic acid was used.
  • the obtained coupling product was dissolved in an appropriate amount of dichloromethane, and an excess amount of trifluoroacetic acid was added to perform Boc deprotection to obtain LD-2-16b.
  • a ligand LD-2-16 was synthesized by the same method as the above-described reaction for synthesizing the ligand LD-1-25 from LD-1-25c. Subsequently, using the obtained ligand LD-2-16, a metal complex dye Dye-1-24 was synthesized in the same manner as in the synthesis of the metal complex dye Dye-1-5.
  • the ligand LD- 9 was synthesized in the same manner as the synthesis of the ligand LD-1-9 except that LD-3-1a was used instead of LD-1-9b. 3-1 was synthesized. Subsequently, using the obtained ligand LD-3-1, a metal complex dye Dye-1-26 was synthesized in the same manner as the synthesis of the metal complex dye Dye-1-5.
  • the ligand LD-2-16 In the synthesis of the ligand LD-2-16, except that 2- (methylthio) phenylboronic acid was used instead of N- (tert-butoxycarbonyl) -2-methylindole, the ligand LD-2-16 Similarly to the synthesis, LD-6-13c was synthesized from LD-2-16a. 20 g of the obtained LD-6-13c was dissolved in 200 mL of hexamethylphosphoric triamide (HMPA) under a nitrogen atmosphere, 3.5 g of sodium methanethiolate was added, and the mixture was stirred at 140 ° C. for 12 hours.
  • HMPA hexamethylphosphoric triamide
  • LD-9-16a was synthesized according to the method described in Japanese Patent No. 4338192, and this was synthesized by the same reaction as that for synthesizing LD-1-25 from the above-mentioned LD-1-25c. Converted to 16b. Under a nitrogen atmosphere, 15.4 g of LD-9-16b was dissolved in 300 mL of DMSO (dimethyl sulfoxide), 2.5 g of sodium cyanide was added, and the mixture was stirred at 120 ° C. for 2 hours. The solution after stirring was cooled to room temperature, 1500 mL of water was added, the precipitated solid was filtered, and the filtrate was washed with water to obtain a crude product of LD-9-16c.
  • DMSO dimethyl sulfoxide
  • the crude product of LD-9-16c was dissolved in 300 mL of ethanol, 15 mL of 1N aqueous potassium hydroxide solution was added, and the mixture was heated to reflux for 13 hours. After the refluxed solution was cooled to room temperature, 500 mL of water and 500 mL of ethyl acetate were added for liquid separation.
  • the crude product obtained by concentrating the organic phase was purified by silica gel column chromatography to obtain 7.6 g of a ligand LD-9-16. Subsequently, using the obtained ligand LD-9-16, a metal complex dye Dye-1-41 was synthesized in the same manner as the synthesis of the metal complex dye Dye-1-5.
  • Dye-2-2a was synthesized according to the following scheme as a precursor of metal complex dye Dye-2-2.
  • LA-2-6a Am. Chem. Soc. , 130, 11013 (2008).
  • LA-2-6b is described in J. Am. Chem. Soc. , 134, 7488 (2012).
  • 3.4 g of LA-2-6a was dissolved in 40 mL of metaxylene, 4.4 g of LA-2-6b and 1.2 g of tetrakis (triphenylphosphine) palladium were added, and the mixture was stirred at 120 ° C. for 20 minutes. Stir for hours. After the stirred solution was cooled to room temperature, 2N aqueous sodium hydroxide solution (50 mL) and toluene (40 mL) were added thereto for liquid separation.
  • LA-2-6c The crude product obtained by concentrating the organic phase was purified by silica gel column chromatography to obtain 2.6 g of LA-2-6c. Subsequently, 2.6 g of LA-2-6c was dissolved in 100 mL of THF (tetrahydrofuran) under a nitrogen atmosphere, and 20 mL of water, 1.6 g of 2,4,6-trimethylbenzeneboronic acid, and potassium carbonate 8. 6 g and 0.7 g of tetrakis (triphenylphosphine) palladium were added and heated to reflux for 10 hours. After the refluxed solution was returned to room temperature, 100 mL of 1N dilute hydrochloric acid and 100 mL of ethyl acetate were added thereto for liquid separation.
  • THF tetrahydrofuran
  • the crude product obtained by concentrating the organic phase was purified by silica gel column chromatography to obtain 2.5 g of LA-2-6d. Further, under a nitrogen atmosphere, 1 L of ethanol and 1.3 g of ruthenium (III) chloride hydrate were added to 2.5 g of LA-2-6d, and the mixture was heated to reflux for 10 hours. After the refluxed solution was cooled to room temperature, the produced crystals were filtered and washed with ethanol to obtain 3.5 g of a precursor Dye-2-2a. Using the precursor Dye-2-2a synthesized as described above, a metal complex dye Dye-2-2 was synthesized in the same manner as the synthesis of the metal complex dye Dye-1-5.
  • Dye-3-2a which is an intermediate of the metal complex dye Dye-3-2
  • 3.2 g of potassium iodide were added to 15 mL of diglyme, and the mixture was stirred at 110 ° C. for 2 hours.
  • the stirred solution was cooled to room temperature, water (15 mL) and ethyl acetate (30 mL) were added, and the reaction product was extracted into ethyl acetate. After liquid separation, the organic phase was concentrated, and the obtained black solid was purified by silica gel column chromatography to obtain 214 mg of Dye-3-3a. This was hydrolyzed with an ester site in the same manner as in the synthesis of the metal complex dye Dye-3-2, to obtain the target metal complex dye Dye-3-3.
  • Example 2 [Dye-sensitized solar cell] A dye-sensitized solar cell was produced by the following procedure. A photoelectrode having the same configuration as that of the photoelectrode 12 shown in FIG. 5 described in Japanese Patent Laid-Open No. 2002-289274 is manufactured, and this photoelectrode is replaced with the photoelectrode shown in FIG. A dye-sensitized solar cell of 10 mm ⁇ 10 mm scale having the same configuration as the dye-sensitized solar cell 20 of FIG. 3 except that the photoelectrode was used was produced. The specific configuration is shown in FIG. In FIG.
  • 41 is a transparent electrode
  • 42 is a semiconductor electrode
  • 43 is a transparent conductive film
  • 44 is a substrate
  • 45 is a semiconductor layer
  • 46 is a light scattering layer
  • 40 is a photoelectrode
  • 20 is a dye-sensitized solar cell
  • CE is The counter electrode
  • E is an electrolyte
  • S is a spacer.
  • Paste A A titania slurry was prepared by placing spherical TiO 2 particles (anatase, average particle size; 25 nm, hereinafter referred to as spherical TiO 2 particles A) in a nitric acid solution and stirring. Next, a cellulosic binder was added to the titania slurry as a thickener and kneaded to prepare paste A.
  • a titania slurry was prepared by stirring spherical TiO 2 particles A and spherical TiO 2 particles (anatase, average particle size: 200 nm, hereinafter referred to as spherical TiO 2 particles B) in a nitric acid solution. .
  • rod-like TiO 2 particles C anatase, diameter: 100 nm, aspect ratio: 5, hereinafter referred to as rod-like TiO 2 particles C
  • a transparent electrode 41 (conductive support) in which a fluorine-doped SnO 2 conductive film (transparent conductive film 43, film thickness: 500 nm) was formed on a glass substrate (substrate 44) was prepared. Then, the paste 1 was screen-printed on the SnO 2 conductive film and then dried. Then, it baked on the conditions of 450 degreeC in the air. Furthermore, by repeating screen printing and baking using the paste 2, a semiconductor electrode having the same configuration as the semiconductor electrode 42 shown in FIG. 2 (light receiving surface area; 10 mm ⁇ 10 mm, layer thickness) is formed on the SnO 2 conductive film.
  • the dye was adsorbed to the photoelectrode (semiconductor electrode) containing no dye as follows. First, anhydrous ethanol dehydrated with magnesium ethoxide was used as a solvent, and the metal complex dyes listed in Table 2 below were dissolved therein so as to have a concentration of 3 ⁇ 10 ⁇ 4 mol / L. Each dye solution was prepared by adding 20 mol of an equimolar mixture of chenodeoxycholic acid and cholic acid to 1 mol of the metal complex dye. The water content of this dye solution was measured by Karl Fischer titration and found to be less than 0.01% by mass. Next, the semiconductor electrode was dipped in this solution, pulled up and dried at 50 ° C. to complete a photoelectrode in which the dye was adsorbed by about 1.5 ⁇ 10 ⁇ 7 mol / cm 2 on the semiconductor electrode.
  • a platinum electrode thinness of Pt thin film; 100 nm
  • an iodine redox solution containing iodine and lithium iodide as the electrolyte E were prepared.
  • a DuPont spacer S (trade name: “Surlin”) having a shape corresponding to the size of the semiconductor electrode is prepared, as shown in FIG. 3 described in Japanese Patent Application Laid-Open No. 2002-289274.
  • the dye-sensitized solar cell (sample No.) using the photoelectrode is formed by making the photoelectrode, the counter electrode CE and the spacer S face each other and filling the above electrolyte (by forming a charge transfer layer). 1-13 and c1-c3) were completed. The performance of each dye-sensitized solar cell thus prepared was evaluated.
  • IPCE quantitative sensitivity characteristics at wavelengths of 800 nm and 850 nm> IPCE (quantum yield) at a wavelength of 300 to 1000 nm was measured with an IPCE measuring device manufactured by Pexel. Among these, IPCE at 800 nm and 850 nm was evaluated according to the following criteria.
  • IPCE is 1.1 times or more than IPCE of Comparative Compound (1)
  • Evaluation Criteria AAA Thermal degradation rate is 1.1 times or more with respect to thermal degradation rate of comparative compound (1)
  • AA Thermal degradation rate is 1.06 times or more with respect to thermal degradation rate of comparative compound (1) Less than 1 time
  • D Thermal degradation rate of Comparative Compound (1) Less than 1.00 times the rate Table 2 shows the durability.
  • the comparative compounds (1) to (3) are metal complex dyes described below. Comparative compound (1): Patent Document 2 Comparative compound (2): Non-patent document 1 Comparative compound (3): Patent Document 1
  • the ligand LD used with the tridentate ligand LA is a nitrogen atom coordinated to the metal ion M via a lone pair and has a strong electron withdrawing property.
  • both of the spectral sensitivity characteristics at 800 nm and 850 nm were measured with sample No.
  • Each of the dye-sensitized solar cells 1 to 13 showed good photoelectric conversion efficiency with respect to each of the dye-sensitized solar cells using the comparative compounds.
  • the evaluation (durability) of the thermal deterioration of the dye-sensitized solar cell evaluated by the above heat resistance test is good for each dye-sensitized solar cell using the comparative compound, and the sensitivity characteristics in the long wavelength region Succeeded in achieving both durability.
  • the durability of the metal complex dye and the photoelectric conversion element is achieved by exerting a balance between strengthening the binding force between the metal ion M and the nitrogen-containing aromatic ring and suppressing the thermal dissociation of the ligand LX. It is thought that the sex can be improved.

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Abstract

Un colorant de complexe métallique utilisé dans un élément de conversion photoélectrique de la présente invention est représenté par la formule suivante (I) : M(LD)(LA)(LX)·(Y)n … formule (I) Dans la formule (I), M représente un ion métallique, LD représente un ligand bidentate représenté par n'importe laquelle des formules (2L-1) à (2L-3), LA représente un ligand tridentate représenté par la formule (AL-1) ou la formule (AL-2), LX représente un ligand monodentate, Y représente un contre-ion nécessaire pour neutraliser la charge et n représente un entier de 0 à 4. Le colorant de complexe métallique de la présente invention est équipé d'un tel ligand bidentate spécifique, ce qui permet de rendre possible d'améliorer à la fois la caractéristique de sensibilité spectrale et la durabilité de l'élément de conversion photoélectrique dans une région de longueur d'onde longue.
PCT/JP2014/060250 2013-04-12 2014-04-09 Elément de conversion photoélectrique, cellule à pigment photosensible, colorant de complexe métallique, solution de colorant, électrode à colorant adsorbé et procédé de fabrication de cellule à pigment photosensible WO2014168163A1 (fr)

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