WO2008054024A1 - Novel photosensitizer and photovoltaic device - Google Patents

Novel photosensitizer and photovoltaic device Download PDF

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Publication number
WO2008054024A1
WO2008054024A1 PCT/JP2007/071669 JP2007071669W WO2008054024A1 WO 2008054024 A1 WO2008054024 A1 WO 2008054024A1 JP 2007071669 W JP2007071669 W JP 2007071669W WO 2008054024 A1 WO2008054024 A1 WO 2008054024A1
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group
formula
carbon atoms
compound
photosensitizer
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PCT/JP2007/071669
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French (fr)
Japanese (ja)
Inventor
Masaki Minami
Noriyo Yamanaka
Yoshinori Nishikitani
Hideki Masuda
Yasuhiro Funahashi
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Nippon Oil Corporation
Nagoya Institute Of Technology
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Publication of WO2008054024A1 publication Critical patent/WO2008054024A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
    • C07D471/14—Ortho-condensed systems
    • 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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/331—Metal complexes comprising an iron-series metal, e.g. Fe, Co, Ni
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—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
    • 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
    • H10K85/361—Polynuclear complexes, i.e. complexes comprising two or more metal centers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • 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
    • H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a novel photosensitizer, and more particularly to a novel photosensitizer used for a dye-sensitized solar cell. Furthermore, the present invention relates to a photovoltaic device having a semiconductor layer adsorbing the photosensitizer.
  • the dye-sensitized solar cell element announced by Gretzell et al. In 11991 is a wet solar cell using a porous titanium oxide thin film spectrally sensitized by a ruthenium complex as a working electrode. It has been reported that performance equivalent to that of a battery can be obtained (see Non-Patent Document 1). Since this method can use an inexpensive oxide semiconductor such as titania without purifying it with high purity, it can provide an inexpensive dye-sensitized solar cell element, and the absorption of the dye is broad. It has the advantage of being able to convert light in almost all wavelengths of visible light into electricity, and is attracting attention.
  • ruthenium complex dye absorbs visible light but hardly absorbs infrared light having a wavelength longer than 70 nm, and therefore has a low photoelectric conversion ability in the infrared region. Therefore, in order to further increase the conversion efficiency, development of a dye having absorption in the infrared region as well as visible light has been desired.
  • the black die can absorb light up to 920 nm, but the absorption coefficient is small, so in order to obtain a high current value, the amount adsorbed on the porous titanium oxide thin film is increased. There was a need.
  • Non-Patent Document 2 There are various methods for increasing the amount of adsorption to the titanium oxide porous thin film, but in general, it is possible to increase the thickness of the thin film (see Non-Patent Document 2). If the thickness of the thin film is increased, the conversion efficiency cannot be increased greatly because the open-circuit voltage value and the FF decrease due to an increase in reverse electron transfer and a decrease in the electron density in the thin film.
  • Non-patent document 1 “Nature”, 1 991 1 year, 3 5 3 ⁇ , p. 7 3 7
  • Non-Patent Document 2 "Jouraal of American Chemical Society J, 2000, 1 year,
  • the present inventors have found a metal complex dye having absorption in the infrared region as well as in the infrared region and having a large extinction coefficient, and has reached the present invention.
  • the present invention relates to a photosensitizer containing a compound having structural units of the formula (I) and the formula (II).
  • M represents a transition metal selected from Ru, Os, Fe, Re, and Rh.
  • M ′ represents Ni, Co, Cu
  • Z represents a transition metal selected from n, Mn, P t and P d
  • 1 to! ⁇ 16 are a hydrogen atom, a group containing a carbo group, one PO ( OH) 2 -.
  • n (oR ) groups represented by n (n is an integer of 0 to 2, R represents represents an alkyl group or Ariru group having 1 to 20 carbon atoms), an alkyl group having a carbon number of 1-30, Alkenyl group having 2 to 30 carbon atoms, alkoxyalkyl group having 2 to 30 carbon atoms, aminoalkyl group having 1 to 30 carbon atoms, perfluoroalkyl group having 1 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms And an alkyl group, an alkenyl group, an aryl group or an aralkyl group having a aralkyl group having 7 to 30 carbon atoms or a carbo group-containing group.
  • each X independently represents a monodentate ligand selected from 1 NCS, halogen, 1 CN, 1 NC 0, 1 OH and 1 NCN 2 .
  • X may be bonded to each other or may be a bidentate ligand represented by the general formula (III a) or (Illb).
  • R 31 to R 33 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, an aminoalkyl group having 1 to 30 carbon atoms, carbon It represents a perfluoroalkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms.
  • R 34 and R 35 are each independently a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms. 15 represents an aryl group, and R 34 and R 35 may be bonded to form a ring.
  • the present invention also relates to the photosensitizer as described above, wherein the compound having the structural unit of the formula (I) and the formula (II) is a compound of the formula (IV) About.
  • the present invention also relates to the photosensitizer as described above, wherein the compound having the structural units of the formula (I) and the formula ( ⁇ ) is the compound of the formula (V).
  • the present invention relates to a photovoltaic device having a semiconductor layer adsorbing the photosensitizer described above. [The invention's effect]
  • novel sensitizer of the present invention absorbs not only the visible region but also the infrared region, the conversion efficiency of the photovoltaic device can be increased.
  • the novel photosensitizer of the present invention comprises a compound having structural units represented by general formulas (I) and (II) in one molecule.
  • M is a transition metal selected from Ru, Os, Fe, Re and Rh, and Ru is particularly preferred.
  • M ′ represents a transition metal selected from Ni, Co, Cu, Zn, Mn, Pt, and Pd. Among these, Ni, Co, and Zn are preferable. .
  • 1 ⁇ ! ⁇ 16 is a hydrogen atom, a group containing a carbonyl group, a group represented by one PO (OH) 2 — n (OR) n (n is an integer of 0-2, R is a carbon number of 1-30 An alkyl group or an aryl group.), An alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxy alkyl group having 2 to 30 carbon atoms, an aminoalkyl group having 1 to 30 carbon atoms,.
  • Examples of the group containing a carbonyl group include one (CH 2 ) p _COOH, one (CH 2 ) q — CHO, one (CH 2 ) r and one CO — R (wherein p, q and r are respectively Each represents an integer of 0 to 2, and R represents an alkyl group or aryl group having 1 to 30 carbon atoms.)
  • one COOH, one CHO, one CH 2 C 0 CH 3 , one CH 2 COC 2 H 5 , 1 C 0 CH 3 , 1 COC 2 H 5 and the like can be exemplified.
  • n (OR) n group represented by n (OR) n (wherein n represents an integer of 0 to 2, R represents an alkyl group having 1 to 30 carbon atoms or an aryl group)
  • n represents an integer of 0 to 2
  • R represents an alkyl group having 1 to 30 carbon atoms or an aryl group
  • the alkyl group having 1 to 30 carbon atoms may be linear or branched, and specifically includes a methyl group, an ethyl group, an i-propyl group, an n-propyl group, a butyl group, an s-butyl group, Examples include t-butyl group, hexyl group, octyl group, nonyl group, dodecyl group, icosyl group, docosyl group and the like.
  • Specific examples of the alkenyl group having 2 to 30 carbon atoms include a bur group and a allyl group.
  • alkoxyalkyl group having 2 to 30 carbon atoms include a methoxymethyl group, a methoxychelyl group, a methoxypropyl group, an ethoxymethyl group, an ethoxybutyl group, an ethoxyhexyl group, an ethoxynonyl group, a propoxymethyl group, and a butoxy group.
  • examples thereof include a methyl group, a hexyloxymethyl group, a nonoxymethyl group, and a dodecoxychichetyl group.
  • aminoalkyl group having 1 to 30 carbon atoms include aminomethyl group, dimethylaminomethyl group, aminoethyl group, dimethylaminomethyl group, dipropylaminomethyl group, dibutylaminomethyl group, diio Examples include octylaminomethyl group, dimethylaminoethyl group, dipropylaminoethyl group, dibutylaminoethyl group, dioctylaminoethyl group, and the like.
  • perfluoroalkyl group having 1 to 30 carbon atoms include 1 CF 3 , 1 C 2 F 5 , i 1 C 3 F 7, and the like.
  • aryl group having 6 to 30 carbon atoms include phenyl group and naphthyl group.
  • aralkyl group having 7 to 30 carbon atoms include benzyl group, phenethyl group, Examples thereof include a phenylbutyl group, a phenylnonyl group, and a naphthylnoel group.
  • examples of the alkyl group, alkenyl group, aryl group, and aralkyl group having a group containing a carbonyl group include a carboxymethyl group, a carbo group Examples thereof include a xichetyl group, a force no- oxybutyptinore group, a carboxybinole group, a 4-force noreoxy furyl group, and a 3-carboxyphenyl group.
  • an aromatic ring bonded by R n and R n + 1 (n is an integer of 1 to 15, except for 8, 10 and 12) may be formed.
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 9 and Any of R 10 , R 11 and R 12 , R 13 and R 14 , R 14 and R 15 , and R 15 and R 16 may be bonded to form an aromatic ring.
  • Examples of the case where Ri to R 12 form a ring include structures represented by the following general formulas (VIIa) to (Vllh).
  • Examples of the case where R 13 to R 16 form a ring include the structures represented by the following general formulas (Villa) to (VIII c).
  • Each ring is a group containing a carbonyl group, a group represented by one PO (OH) 2 _ n (OR) n (n is an integer of 0 to 2, R is an alkyl group having 1 to 30 carbon atoms) Or an aryl group), an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, an aminoalkyl group having 1 to 30 carbon atoms, or a carbon number of 1 To 30 perfluoroalkyl group, C 6-30 aralkyl group, C 7-30 aralkyl group, or alkenyl group, alkenyl group, allyl group or group having a carbonyl group. It may have a functional group represented by an aralkyl group.
  • Each X in formula (I) is independently a monodentate coordination selected from 1 NCS, halogen, _CN, 1 NC0, _ 0 H and _ NCN 2 A child.
  • X may be bonded to each other, and X is a diketone derivative represented by the general formula (Ilia) or a bidentate represented by a 1,2-dithiolene derivative represented by the general formula (III b). It may be a ligand. .
  • R 31 to R 33 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, or a perful having 1 to 30 carbon atoms.
  • the alkyl group having 1 to 30 carbon atoms may be linear or branched, and specifically includes a methyl group, an ethyl group, an i-propyl group, an n-propyl group, a butyl group, an s-butyl group, t-Butyl group, hexyl group, octyl group, Noel group, dodecyl group, ico Examples include syl group and docosyl group.
  • alkoxyalkyl group having 2 to 30 carbon atoms include a methoxymethyl group, a methoxyxyl group, a methoxypropyl group, an ethoxymethyl group, an ethoxybutyl group, an ethoxyhexyl group, an ethoxynonyl group, and a propoxymethyl group.
  • aryl group having 6 to 30 carbon atoms include a phenyl group and a naphthyl group.
  • aralkyl group having 7 to 30 carbon atoms include a benzyleno group, a phenethyl group, a ferro-quinole group, a phen-norenonyl group, and a naphthyl nonyl group. More specifically, the following functional groups can be mentioned.
  • R 34 and R 35 are preferably the same and may be different, and each independently represents a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, A perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and R 34 and R 35 may be bonded to form a ring.
  • the alkyl group having 1 to 30 carbon atoms may be linear or branched.
  • Specific examples of the perfluoroalkyl group having 1 to 20 carbon atoms include —CF 3 , —C 2 F 5 , and i-C 3 F 7 .
  • Specific examples of the aryl group having 6 to 15 carbon atoms include a phenyl group and a naphthyl group. More specifically, the following functional groups are listed.
  • the compound having the structural unit of the formula (I) and the formula (II) needs to have at least one COOH group in order to be adsorbed on the metal oxide semiconductor layer.
  • at least one of Uchi of 1 1 to 1 16 is a CO OH groups.
  • Examples of the structural unit represented by the general formula (I) include the following.
  • the compound having the structural unit represented by the formula (I) and the formula (II) is usually a compound in which the formula (I) and the formula (II) are bonded directly or via an aromatic ring or an aromatic heterocyclic ring. is there.
  • Specific examples of such a linking group include the following.
  • R 17 represents the same group as Ri to R 16, and R 18 represents an alkyl group having 1 to 20 carbon atoms.
  • the alkyl group having 1 to 20 carbon atoms may be linear or branched, and specifically includes a methyl group, an ethyl group, an i-propyl group, an n-propyl group, a butyl group, an s-butyl group, t-Butyl group, hexyl group, octyl group, nonyl group, dodecyl group, icosyl group, docosyl group and the like. Specific examples of the general formula (V) are shown below, but the present invention is not limited thereto.
  • the photovoltaic device of the present invention has a semiconductor layer adsorbing the photosensitizer of the present invention described above.
  • FIG. 1 As an example of the photovoltaic element of the present invention, for example, an element having a cross section shown in FIG. 1 can be mentioned.
  • a semiconductor layer 3 on which a photosensitizer of the present invention acting as a light absorber is adsorbed is disposed on a transparent conductive substrate 1, and an electrolyte layer 4 is disposed between the semiconductor layer 3 and the counter electrode substrate 2.
  • the periphery is sealed with a sealing material 5.
  • the lead wire is connected to the conductive portions of the transparent conductive substrate 1 and the counter electrode substrate 2 so that electric power can be taken out.
  • a transparent conductive substrate is usually manufactured by laminating a transparent conductive film on a transparent substrate.
  • the transparent substrate is not particularly limited, and the material, thickness, dimensions, shape, and the like can be appropriately selected according to the purpose.
  • colorless or colored glass, meshed glass, glass block, etc. are used.
  • a colorless or colored resin having transparency may be used.
  • Specific examples of such resins include polyesters such as polyethylene terephthalate, polyamides, polysulfones, polyethersulfones, polyetheretherketones, polyphenylenesanolides, polycarbonates, polyimides, polymethylenomethacrylates, polystyrene, Examples thereof include cellulose trisuccinate and polymethylpentene.
  • the term “transparent” means having a transmittance of 10 to 100%, and the substrate in the present invention has a smooth surface at room temperature, and the surface is flat or It may be a curved surface or may be deformed by stress.
  • the transparent conductive film for forming the conductive layer of the electrode is not particularly limited as long as it fulfills the object of the present invention.
  • it is made of a metal thin film such as gold, silver, chromium, copper, tungsten, or metal oxide.
  • a conductive film e.g., gold, silver, chromium, copper, tungsten, or metal oxide.
  • metal oxides include Indium Tin Oxide (I TO (I n 2 0 3 : Sn)), Fluorine doped Tin Oxide (F TO (S n O 2: F)), aluminum doped Zinc Oxide (AZO (ZnO: A1)), etc. are preferably used.
  • the film thickness is usually from 10 nm to 10 ⁇ m, preferably from 100 nm to 2 ⁇ m.
  • the surface resistance (resistivity) is appropriately selected depending on the use of the substrate of the present invention. However, it is usually 0.5 to 500 ⁇ / sq, preferably 2 to 50 ⁇ / sq.
  • platinum, carbon electrode, or the like can be usually used.
  • the material of the substrate is not particularly limited, and the material, thickness, dimensions, shape, etc. can be appropriately selected according to the purpose. For example, colorless or colored glass, netted glass, glass block, etc. are used. A colorless or colored resin having transparency may be used.
  • polyester terephthalate such as polyethylene terephthalate, polyamide, polysenorephone, polyethersulfone, polyetherenoleetherketone, polyphenylenesanorefide, polycarbonate, polyimide, polymethylmethacrylate, polystyrene, cellulose triacetate, Examples include polymethylpentene. Also, a metal plate or the like can be used as the substrate.
  • the semiconductor layer used in the photovoltaic device of the present invention particularly limited, such bur, for example, T i ⁇ 2, Z n O, such as a layer consisting of S N_ ⁇ 2, N b 2 ⁇ 5 can be mentioned Of these, a layer composed of T i 0 2 and Z ⁇ ⁇ is preferable.
  • the semiconductor used in the present invention may be single crystal or polycrystalline.
  • As the crystal system anatase-ze type, rutile type, brookite type and the like are mainly used, but anatase type is preferred.
  • a known method can be used for forming the semiconductor layer.
  • the above-mentioned semiconductor nanoparticle dispersion, sol solution, and the like can be obtained by coating on a substrate by a known method.
  • the coating method in this case is not particularly limited, and examples thereof include a method of obtaining a thin film by a casting method, a spin coating method, a dip coating method, a bar coating method, and various printing methods including a screen printing method. Can do.
  • the thickness of the semiconductor layer is arbitrary, but is 0.5 m or more and 50 m or less, preferably 1 ⁇ m or more and 20 ix m or less.
  • the photosensitizer (dye) of the present invention for example, after applying a solution in which the photosensitizer is dissolved in a solvent to the semiconductor layer by spray coating, spin coating or the like. It can be formed by a drying method. In this case, the substrate may be heated to an appropriate temperature. Alternatively, a method in which a semiconductor layer is immersed in a solution and adsorbed can be used. The immersion time is not particularly limited as long as the photosensitizer is sufficiently adsorbed, but is preferably 10 minutes to 30 hours, more preferably 1 to 2 0 hours. Moreover, you may heat a solvent and a board
  • the concentration of the photosensitizer in the solution is about 0.01 to 10 Ommo1 ZL, preferably about 0.1 to 5 Ommo1 ZL.
  • solvent alcohols, ethers, nitriles, esters, hydrocarbons and the like can be used.
  • a colorless compound having properties as a surfactant may be added to the photosensitizer adsorbing solution and co-adsorbed on the semiconductor layer.
  • colorless compounds include steroids such as carboxylic acid having a carboxyl group or sulfo group, deoxycholic acid, chenodeoxycholic acid, taurodeoxycholic acid, and sulfonates.
  • the unadsorbed photosensitizer is preferably removed by washing immediately after the adsorption step. Cleaning is preferably performed using acetonitrile, alcohol solvent, etc. in a wet cleaning tank.
  • amines, quaternary ammonium salts, ureido compounds having at least one ureido group, silyl compounds having at least one silyl group, alkali metal salts, alkaline earth metal salts, etc. May be used to treat the surface of the semiconductor layer.
  • preferred amines include pyridine, 4 tert-butyl pyridine, polybutyl pyridine and the like.
  • preferable quaternary ammonium salts include tetraptyl ammonium salts, tetrahexyl ammonium salts and the like. These may be used by dissolving in an organic solvent, or may be used as they are in the case of a liquid.
  • the electrolyte used in the present invention is not particularly limited, and may be either a liquid system or a solid system, and preferably exhibits a reversible electrochemical redox characteristic.
  • reversible electrochemical redox characteristics means that an electrochemical redox reaction can occur reversibly in the potential region where the photoelectric conversion element acts.
  • Ionic conductivity of the electrolyte is usually at room temperature 1 X 1 0- 7 SZ cm or more, it is desirable that preferably 1 X 1 0- es Z cm or more, still more preferably 1 X 1 0- 5 S / cm or more .
  • the thickness of the electrolyte layer is not particularly limited, but is preferably 1 ⁇ or more, more preferably 10 ⁇ or more, and preferably 3 mm or less, more preferably 1 mm or less.
  • Such an electrolyte is not particularly limited as long as the above-described conditions are satisfied. Both liquid and solid electrolytes known in the art can be used.
  • Photosensitizer 1 was synthesized with reference to the method described in Reference A (Eur. J. Inorg. Chem., 2003, 1900-1910). That is, dichloro (p-cymene) ruthenium dimer (1.63 g; 12.7 mmol) and 2,2,1 bibiridine-1,4'-dicarboxylic acid (1.36 g; 5.6 mm) o 1) was dissolved in ethanol (100 ml) and then heated to reflux for 4 hours. After completion of the reaction, the mixture was filtered, then dispersed in toluene (.100 ml) and filtered to obtain 2.93 g (5.3 mmo 1) of Compound A.
  • Compound B Compound B (0.28 g; 6.9 mm o 1) and 3-formyl_4-hydroxybenzoic acid (0.3 g; 1.8 mm o 1) are mixed in ethanol After adding the acid ester, the mixture was heated to reflux for 2 hours. Zinc acetate (0.17 g; 0.9 mm o 1) was added, and the mixture was further heated to reflux for 10 hours. After completion of the reaction, Compound C was obtained by filtration.
  • Photosensitizer 2 was synthesized with reference to the method described in Reference B (Bull. Chem. Soc. Jpn., 76, 977-984 (2003)).
  • phenanthrolinediamine was synthesized by the method described in Reference C (Tetrahedron letters 38, 8159 (1997)).
  • Phenanthrolinediamine (0.21 g; 1. Omm o 1) and 3-honoleminole 4-hydroxyoxybenzoic acid (0.34 g; 2.0 mm o 1) were dissolved in ethanol and orthoformate was dissolved. Ester (0.1 ml) was added and heated to reflux for 3 hours. Subsequently, zinc acetate (0.2 g; l. 1 mmo 1) was added and heated to reflux for 10 hours. After completion of the reaction, 0, 39 g (0.7 mmo 1) of Compound D was obtained by filtration.
  • photosensitizer 3 and photosensitizer 4 were synthesized according to the synthesis method of photosensitizer 2.
  • photosensitizer 5 and photosensitizer 6 were synthesized according to the synthesis method of photosensitizer 2.
  • photosensitizer 7 and photosensitizer 8 were synthesized according to the synthesis method of photosensitizer 1.
  • a photovoltaic device based on sensitization of a titanium dioxide film supported on a conductive substrate was produced as follows.
  • Conductive glass (fluorine-doped S ⁇ 0 2, 1 0 ⁇ ) on the colloids form T i 0 2 particles (particle diameter:. 20 to 30 nm) was applied, 450 ° C, 30 minutes baking (thickness: 1 0 mu m), and therefore scattering light on T i 0 2 particles (particle diameter: 300 to 400 nm) is applied, 5 20 ° C, 1 hour baking (thickness: 6 ⁇ 8 ⁇ ⁇ ) was .
  • the film of two layers was immersed for 30 minutes T i C 1 4 solution was heated 450 ° C, 30 min.
  • the obtained film was immersed in the above photosensitizer / ethanol solution (3.0 X 10 0 4 mo 1 / L) for 15 hours to form a dye layer (photosensitizer layer).
  • the obtained substrate and the Pt surface of the glass with Pt thin film were put together, and a solution of 0.3 mmol / L lithium iodide and 0.03 mo 1 ZL of iodine was impregnated by capillary action.
  • the periphery was sealed with an epoxy adhesive. Note that lead wires were connected to the conductive layer portion of the transparent conductive substrate and the counter electrode.
  • a photovoltaic element using a ruthenium dye (Ru tenium5 35-bis TBA: manufactured by SOL ARON IX: black die), which is generally used as a dye for a photovoltaic element, is used. Produced. At a wavelength of 8 10 nm, I P C E is 0%.
  • Table 1 shows the results of measuring the incident photon-current conversion efficiency (I PCE) by irradiating the monochromatic light of pseudo sunlight 810 nm to the device thus obtained.
  • Fig. 1 is an example of a cross section of a photovoltaic device.
  • 1 transparent conductive substrate
  • 2 counter electrode substrate
  • 3 semiconductor layer
  • 4 electrolyte layer
  • novel sensitizer of the present invention absorbs not only the visible region but also the infrared region, the conversion efficiency of the photovoltaic device can be increased, and its industrial value is extremely high.

Abstract

Disclosed is a photosensitizer having high light absorption coefficient, which absorbs light over a wide range from visible light to infrared light and has high light absorption rate even in the form of an extremely thin film. The photosensitizer contains a compound having a specific structural unit (I) having a transition metal selected from Ru, Os, Fe, Re and Rh, and another specific structural unit (II) having a transition metal selected from Ni, Co, Cu, Zn, Mn, Pt and Pd.

Description

新規光増感剤および光起電力素子  Novel photosensitizer and photovoltaic device
[技術分野] [Technical field]
本発明は新規光增感剤、 詳しくは色素増感型太陽電池に用いる新規光増感剤に 関する。 さらに該光増感剤を吸着した半導体層を有する光起電力素子に関する。 明  The present invention relates to a novel photosensitizer, and more particularly to a novel photosensitizer used for a dye-sensitized solar cell. Furthermore, the present invention relates to a photovoltaic device having a semiconductor layer adsorbing the photosensitizer. Light
[背景技術]  [Background]
1 9 9 1年にグレッツエルらが発表した田色素増感型太陽電池素子は、 ルテユウ ム錯体によつて分光増感された酸化チタン多孔質薄膜を作用電極とする湿式太陽 電池であり、 シリコン太陽電池並みの性能が得られることが報告されている （非 特許文献 1参照）。 この方法は、チタニア等の安価な酸化物半導体を高純度に精製 することなく用いることができるため、 安価な色素増感型太陽電池素子を提供で き、 しかも色素の吸収がブロードであるため、 可視光線のほぼ全波長領域の光を 電気に変換できるという利点があり、 注目を集めている。 しかしながら、 公知の ルテニウム錯体色素は、 可視光は吸収するものの 7 0 0 n mより長波長の赤外光 はほとんど吸収しないため赤外域での光電変換能は低い。 したがって更に変換効 率を上げるためには可視光のみならず赤外域に吸収を有する色素の開発が望まれ ていた。 一方、 ブラックダイに関して、 9 2 0 n mまで光を吸収することができ るが、 吸光係数が、 小さいため、 高電流値を得るためには、 酸化チタン多孔質薄 膜に吸着する量を多くする必要があった。 酸化チタン多孔質薄膜への吸着量を増 加する方法は、 種々の方法があるが、 一般的には、 薄膜の厚みを増加することで 可能である （非特許文献 2参照）。 薄膜の厚みを増加すると、 逆電子移動の増加、 薄膜中の電子密度の減少などによって、 開放電圧値の減少、 F Fの低下などが生 ずるため、 変換効率は大きく増加することはできない。  1 9 9 The dye-sensitized solar cell element announced by Gretzell et al. In 11991 is a wet solar cell using a porous titanium oxide thin film spectrally sensitized by a ruthenium complex as a working electrode. It has been reported that performance equivalent to that of a battery can be obtained (see Non-Patent Document 1). Since this method can use an inexpensive oxide semiconductor such as titania without purifying it with high purity, it can provide an inexpensive dye-sensitized solar cell element, and the absorption of the dye is broad. It has the advantage of being able to convert light in almost all wavelengths of visible light into electricity, and is attracting attention. However, a known ruthenium complex dye absorbs visible light but hardly absorbs infrared light having a wavelength longer than 70 nm, and therefore has a low photoelectric conversion ability in the infrared region. Therefore, in order to further increase the conversion efficiency, development of a dye having absorption in the infrared region as well as visible light has been desired. On the other hand, the black die can absorb light up to 920 nm, but the absorption coefficient is small, so in order to obtain a high current value, the amount adsorbed on the porous titanium oxide thin film is increased. There was a need. There are various methods for increasing the amount of adsorption to the titanium oxide porous thin film, but in general, it is possible to increase the thickness of the thin film (see Non-Patent Document 2). If the thickness of the thin film is increased, the conversion efficiency cannot be increased greatly because the open-circuit voltage value and the FF decrease due to an increase in reverse electron transfer and a decrease in the electron density in the thin film.
( 1 ) 非特許文献 1 ： 「Nature」， 1 9 9 1年， 3 5 3卷， p . 7 3 7  (1) Non-patent document 1: “Nature”, 1 991 1 year, 3 5 3 卷, p. 7 3 7
( 2 ) 非特許文献 2 ：「Jouraal of American Chemical SocietyJ , 2 0 0 1年，  (2) Non-Patent Document 2: "Jouraal of American Chemical Society J, 2000, 1 year,
1 2 3卷， p . 1 6 1 3 [発明の開示] 1 2 3 卷, p. 1 6 1 3 [Disclosure of the Invention]
このため、 可視光から赤外光までの広い範囲で光を吸収し、 極薄い薄膜におい ても、 光吸収率が高くなる吸光係数の大きな色素が望まれていた。  For this reason, there has been a demand for a dye having a large extinction coefficient that absorbs light in a wide range from visible light to infrared light and has a high light absorption rate even in an extremely thin thin film.
本発明者らは、 前記課題について鋭意研究した結果、 可視光のみならず赤外域 にも吸収を有し、 吸光係数の大きな金属錯体色素を見出し、 本発明に到達したも のである。  As a result of diligent research on the above problems, the present inventors have found a metal complex dye having absorption in the infrared region as well as in the infrared region and having a large extinction coefficient, and has reached the present invention.
すなわち、 本発明は、 式 （ I ) および式 （II) の構造単位を有する化合物を含 む光增感剤に関する。  That is, the present invention relates to a photosensitizer containing a compound having structural units of the formula (I) and the formula (II).
Figure imgf000003_0001
Figure imgf000003_0001
(式 （ I) 中、 Mは、 Ru、 O s、 F e、 R eおよび R hから選ばれる遷移金属 を表し、 式 （II) 中、 M' は、 N i、 C o、 Cu、 Z n、 Mn、 P tおよび P d から選ばれる遷移金属を表す。 式 （I ) および式 （II) 中、 1〜!^16は、 水素 原子、カルボ-ル基を含有する基、 一 PO (OH) 2— n (OR) nで表される基（n は 0~2の整数、 Rは炭素数 1~20のアルキル基又はァリール基を表す。）、 炭 素数 1〜 30のアルキル基、 炭素数 2〜 30のアルケニル基、 炭素数 2〜30の アルコキシアルキル基、 炭素数 1〜30のアミノアルキル基、 炭素数 1〜30の パーフルォロアルキル基、 炭素数 6〜 30のァリール基、 炭素数 7〜30のァラ ルキル基、またはカルボ-ル基を含有する基を有するアルキル基、アルケニル基、 ァリール基若しくはァラルキル基を表す。 また、 R"と Rn + 1 (nは 1〜15の整 数、 ただし、 8、 1 0、 12を除く。） で結合した芳香環を形成しても良い。 ただ し、式（ I ) または式（II) 中に、少なくとも一つの COOH基を有する。 式（ I ) 中、 個々の Xは、 独立に、 一 NCS、 ハロゲン、 一 CN、 一 NC〇、 一 OHおよ び一 NCN2より選ばれる単座配位子を表す。 Xは、 X同士が結合していてもよ く、 一般式 （III a) または （Illb) で表される二座配位子でもよい。 式 （Ilia) 中、 R31〜R33は、 それぞれ独立に、 水素原子、 炭素数 1〜30のアルキル基、 炭素数 2〜 30のアルコキシアルキル基、 炭素数 1〜30のアミノアルキル基、 炭素数 1〜 30のパーフルォロアルキル基、 炭素数 6〜 30のァリール基、 また は炭素数 7〜30のァラルキル基を表す。 式 （Illb) 中、 R34および R35は、 それぞれ個別に、 水素原子、 シァノ基、 炭素数 1〜20のアルキル基、 炭素数 1 〜 20のパーフルォロアルキル基、 または炭素数 6〜 1 5のァリ一ル基を表し、 また R 34および R 35が結合して環を形成していても良い。） (In the formula (I), M represents a transition metal selected from Ru, Os, Fe, Re, and Rh. In the formula (II), M ′ represents Ni, Co, Cu, Z represents a transition metal selected from n, Mn, P t and P d In formulas (I) and (II), 1 to! ^ 16 are a hydrogen atom, a group containing a carbo group, one PO ( OH) 2 -. n (oR ) groups represented by n (n is an integer of 0 to 2, R represents represents an alkyl group or Ariru group having 1 to 20 carbon atoms), an alkyl group having a carbon number of 1-30, Alkenyl group having 2 to 30 carbon atoms, alkoxyalkyl group having 2 to 30 carbon atoms, aminoalkyl group having 1 to 30 carbon atoms, perfluoroalkyl group having 1 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms And an alkyl group, an alkenyl group, an aryl group or an aralkyl group having a aralkyl group having 7 to 30 carbon atoms or a carbo group-containing group. R "and R n + 1 (n is 1 ~ 15 adjustment , However, 8, 1 0, 12 excluding.) May combine to form a aromatic ring. Just And at least one COOH group in formula (I) or formula (II). In formula (I), each X independently represents a monodentate ligand selected from 1 NCS, halogen, 1 CN, 1 NC 0, 1 OH and 1 NCN 2 . X may be bonded to each other or may be a bidentate ligand represented by the general formula (III a) or (Illb). In the formula (Ilia), R 31 to R 33 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, an aminoalkyl group having 1 to 30 carbon atoms, carbon It represents a perfluoroalkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. In formula (Illb), R 34 and R 35 are each independently a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms. 15 represents an aryl group, and R 34 and R 35 may be bonded to form a ring. )
Figure imgf000004_0001
Figure imgf000004_0001
(III a ) (III b ) また本発明は、 式 （I) および式 （II) の構造単位を有する化合物が、 式 （IV) の化合物であることを特徴とする前記記載の光増感剤に関する。  (III a) (III b) The present invention also relates to the photosensitizer as described above, wherein the compound having the structural unit of the formula (I) and the formula (II) is a compound of the formula (IV) About.
Figure imgf000004_0002
また本発明は、 式 （I) および式 （Π) の構造単位を有する化合物が、 式 （V) の化合物であることを特徴とする前記記載の光増感剤に関する。
Figure imgf000004_0002
The present invention also relates to the photosensitizer as described above, wherein the compound having the structural units of the formula (I) and the formula (Π) is the compound of the formula (V).
Figure imgf000005_0001
Figure imgf000005_0001
(式 （V). 中、 R17は 1〜!^16と同様な基を表し、 R18は炭素数 1〜20のァ ルキル基を表す。） また本発明は、 式 （I) およぴ式 （Π) の構造単位を有する化合物が、 式 （VI) の化合物であることを特徴とする前記記載の光増感剤に関する。 (In the formula (V)., R 17 represents a group similar to 1 to! ^ 16, and R 18 represents an alkyl group having 1 to 20 carbon atoms.) The compound having the structural unit represented by formula (Π) is the compound represented by formula (VI):
Figure imgf000005_0002
さらに本発明は、 前記記載の光増感剤を吸着した半導体層を有する光起電力素 子に関する。 [発明の効果]
Figure imgf000005_0002
Furthermore, the present invention relates to a photovoltaic device having a semiconductor layer adsorbing the photosensitizer described above. [The invention's effect]
本発明の新規増感剤は、 可視領域のみならず、 赤外領域も吸収するため、 光起 電力素子の変換効率を上げることができる。  Since the novel sensitizer of the present invention absorbs not only the visible region but also the infrared region, the conversion efficiency of the photovoltaic device can be increased.
[発明を実施するための最良の形態] [Best Mode for Carrying Out the Invention]
以下、 本発明について詳細に説明する。  Hereinafter, the present invention will be described in detail.
本発明の新規光増感剤は、 1分子中に一般式 （I) および （II) で表される構 造単位を有する化合物からなる。  The novel photosensitizer of the present invention comprises a compound having structural units represented by general formulas (I) and (II) in one molecule.
Figure imgf000006_0001
Figure imgf000006_0001
—般式 （I) において、 Mは、 Ru、 O s、 F e、 R eおよび Rhから選ばれ る遷移金属であり、 なかでも Ruが好ましい。 —In the general formula (I), M is a transition metal selected from Ru, Os, Fe, Re and Rh, and Ru is particularly preferred.
一般式 （II) において、 M' は、 N i、 C o、 C u、 Z n、 Mn、 P tおよび P dから選ばれる遷移金属を表し、 なかでも N i、 C o、 Z nが好ましい。  In the general formula (II), M ′ represents a transition metal selected from Ni, Co, Cu, Zn, Mn, Pt, and Pd. Among these, Ni, Co, and Zn are preferable. .
一般式 （ I) およぴ一般式 （Π) において、 1〜！^16は、 水素原子、 カルボ 二ル基を含有する基、 一 PO (OH) 2— n (OR) nで表される基 （nは 0〜2の 整数、 Rは炭素数 1〜30のアルキル基又はァリール基を表す。）、 炭素数 1〜3 0のアルキル基、 炭素数 2〜 30のアルケニル基、 炭素数 2〜 30のアルコキシ アルキル基、 炭素数 1〜30のアミノアルキル基、.炭素数 1〜30のパーフルォ 口アルキル基、 炭素数 6〜30のァリール基、 炭素数 7〜 30のァラルキル基、 あるいはまたカルボ-ル基を含有する基を有するアルキル基、 ァルケエル基、 ァ リール基若しくはァラルキル基を表す。 In general formula (I) and general formula (Π), 1 ~! ^ 16 is a hydrogen atom, a group containing a carbonyl group, a group represented by one PO (OH) 2 — n (OR) n (n is an integer of 0-2, R is a carbon number of 1-30 An alkyl group or an aryl group.), An alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxy alkyl group having 2 to 30 carbon atoms, an aminoalkyl group having 1 to 30 carbon atoms,. A perfluorinated alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or an alkyl group having a group containing a carbo group, an alkell group, an Represents a reel group or an aralkyl group.
カルボュル基を含有する基としては、 一 （CH2) p_COOH、 一 (CH2) q — CHO、 一 (CH2) r一 CO— Rが挙げられ （式中、 p、 q、 rはそれぞれ個 別に 0〜 2の整数を示し、 Rは炭素数 1〜30のアルキル基又はァリール基を表 す。）、 具体的には、 一 COOH、 一 CHO、 一 CH2C〇CH3、 一CH2COC2 H5、 一 C〇CH3、 一 COC2H5などを例示することができる。 Examples of the group containing a carbonyl group include one (CH 2 ) p _COOH, one (CH 2 ) q — CHO, one (CH 2 ) r and one CO — R (wherein p, q and r are respectively Each represents an integer of 0 to 2, and R represents an alkyl group or aryl group having 1 to 30 carbon atoms.) Specifically, one COOH, one CHO, one CH 2 C 0 CH 3 , one CH 2 COC 2 H 5 , 1 C 0 CH 3 , 1 COC 2 H 5 and the like can be exemplified.
-PO (OH) 2— n (OR) nで表される基 （式中、 nは 0〜2の整数を示し、 Rは炭素数 1〜 30のアルキル基又はァリール基を表す。） とは、 具体的には、 一 PO (OH) 2、 -PO (OR) (OH), -PO (OR) 2などを例示することが できる。 -PO (OH) 2 — group represented by n (OR) n (wherein n represents an integer of 0 to 2, R represents an alkyl group having 1 to 30 carbon atoms or an aryl group) Specifically, one PO (OH) 2 , -PO (OR) (OH), -PO (OR) 2 and the like can be exemplified.
炭素数 1〜30のアルキル基としては、 直鎖状でも分岐状でもよく、 具体的に は、 メチル基、 ェチル基、 i一プロピル基、 n—プロピル基、 ブチル基、 s—ブ チル基、 t—ブチル基、 へキシル基、 ォクチル基、 ノニル基、 ドデシル基、 ィコ シル基、ドコシル基などが挙げられる。炭素数 2〜30のアルケル-基としては、 具体的には、 ビュル基、 ァリル基などが挙げられる。 炭素数 2〜30のアルコキ シアルキル基としては、 具体的には、 メ トキシメチル基、 メ トキシェチル基、 メ トキシプロピル基、ェトキシメチル基、ェトキシブチル基、ェトキシへキシル基、 エトキシノニル基、 プロポキシメチル基、 ブトキシメチル基、 へキシロキシメチ ル基、 ノ-ロキシメチル基、 ドデシ口キシェチル基などが挙げられる。 炭素数 1 〜30のアミノアルキル基としては、 具体的には、 アミノメチル基、 ジメチルァ ミノメチル基、 アミノエチル基、 ジメチルァミノメチル基、 ジプロピルアミノメ チル基、 ジブチルァミノメチル基、 ジォクチルァミノメチル基、 ジメチルァミノ ェチル基、 ジプロピルアミノエチル基、 ジブチルアミノエチル基、 ジォクチルァ ミノエチル基などが挙げられる。 炭素数 1〜30のパーフルォロアルキル基とし ては、 具体的には、 一 CF3、 一 C2F5、 i一 C3F7などが挙げられる。 炭素数 6〜 30のァリール基としては、 具体的には、 フエニル基、 ナフチル基などが挙 げられ、 炭素数 7〜30のァラルキル基としては、 具体的には、 ベンジル基、 フ エネチル基、 フエニルブチル基、 フエニルノニル基、 ナフチルノエル基などが挙 げられる。さらにカルボ二ル基を含有する基を有するアルキル基、ァルケ-ル基、 ァリール基、 ァラルキル基としては、 具体的には、 カルボキシメチル基、 カルボ キシェチル基、 力ノレボキシプチノレ基、 カルボキシビ二ノレ基、 4—力ノレボキシフエ ュル基、 3—カルボキシフエニル基などが挙げられる。 The alkyl group having 1 to 30 carbon atoms may be linear or branched, and specifically includes a methyl group, an ethyl group, an i-propyl group, an n-propyl group, a butyl group, an s-butyl group, Examples include t-butyl group, hexyl group, octyl group, nonyl group, dodecyl group, icosyl group, docosyl group and the like. Specific examples of the alkenyl group having 2 to 30 carbon atoms include a bur group and a allyl group. Specific examples of the alkoxyalkyl group having 2 to 30 carbon atoms include a methoxymethyl group, a methoxychelyl group, a methoxypropyl group, an ethoxymethyl group, an ethoxybutyl group, an ethoxyhexyl group, an ethoxynonyl group, a propoxymethyl group, and a butoxy group. Examples thereof include a methyl group, a hexyloxymethyl group, a nonoxymethyl group, and a dodecoxychichetyl group. Specific examples of the aminoalkyl group having 1 to 30 carbon atoms include aminomethyl group, dimethylaminomethyl group, aminoethyl group, dimethylaminomethyl group, dipropylaminomethyl group, dibutylaminomethyl group, diio Examples include octylaminomethyl group, dimethylaminoethyl group, dipropylaminoethyl group, dibutylaminoethyl group, dioctylaminoethyl group, and the like. Specific examples of the perfluoroalkyl group having 1 to 30 carbon atoms include 1 CF 3 , 1 C 2 F 5 , i 1 C 3 F 7, and the like. Specific examples of the aryl group having 6 to 30 carbon atoms include phenyl group and naphthyl group. Specific examples of the aralkyl group having 7 to 30 carbon atoms include benzyl group, phenethyl group, Examples thereof include a phenylbutyl group, a phenylnonyl group, and a naphthylnoel group. Furthermore, examples of the alkyl group, alkenyl group, aryl group, and aralkyl group having a group containing a carbonyl group include a carboxymethyl group, a carbo group Examples thereof include a xichetyl group, a force no- oxybutyptinore group, a carboxybinole group, a 4-force noreoxy furyl group, and a 3-carboxyphenyl group.
また、 Rnと Rn+1 (nは 1〜1 5の整数、 ただし、 8、 1 0、 1 2を除く。） で結合した芳香環を形成していても良い。 具体的には、 R1と R2、 R2と R3、 R 3と R4、 R4と R5、 R5と R6、 R6と R7、 R7と R8、 R9と R10、 R11と R12、 R13と R14、 R14と R15、 R15と R16のいずれかが結合して芳香環を形成して も良い。 Ri〜R12が環を形成する場合の例としては、 例えば、 下記一般式 （VII a) 〜 （Vllh) で表される構造が挙げられる。 また R13〜R16が環を形成する 場合の例としては、 例えば、 下記一般式 （Villa) 〜 （VIII c) で表される構造 が挙げられる。 In addition, an aromatic ring bonded by R n and R n + 1 (n is an integer of 1 to 15, except for 8, 10 and 12) may be formed. Specifically, R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 9 and Any of R 10 , R 11 and R 12 , R 13 and R 14 , R 14 and R 15 , and R 15 and R 16 may be bonded to form an aromatic ring. Examples of the case where Ri to R 12 form a ring include structures represented by the following general formulas (VIIa) to (Vllh). Examples of the case where R 13 to R 16 form a ring include the structures represented by the following general formulas (Villa) to (VIII c).
それぞれの環は、 カルボ二ル基を含有する基、 一 PO (OH) 2_n (OR) n で表される基 （nは 0〜2の整数、 Rは炭素数 1〜30のアルキル基又はァリー ル基を表す。）、 炭素数 1〜30のアルキル基、 炭素数 2〜30のアルケニル基、 炭素数 2〜 30のアルコキシアルキル基、 炭素数 1〜30のアミノアルキル基、 炭素数 1〜 30のパーフルォロアルキル基、 炭素数 6〜 30のァリール基、 炭素 数 7〜30のァラルキル基、 あるいはまたカルボ二ル基を含有する基を有するァ ルキル基、 アルケニル基、 ァリール基若しくはァラルキル基で表される官能基を 有していても良い。 Each ring is a group containing a carbonyl group, a group represented by one PO (OH) 2 _ n (OR) n (n is an integer of 0 to 2, R is an alkyl group having 1 to 30 carbon atoms) Or an aryl group), an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, an aminoalkyl group having 1 to 30 carbon atoms, or a carbon number of 1 To 30 perfluoroalkyl group, C 6-30 aralkyl group, C 7-30 aralkyl group, or alkenyl group, alkenyl group, allyl group or group having a carbonyl group. It may have a functional group represented by an aralkyl group.
Figure imgf000008_0001
Figure imgf000008_0001
(Vila) (VTIb)
Figure imgf000009_0001
(Vila) (VTIb)
Figure imgf000009_0001
Figure imgf000010_0001
Figure imgf000010_0001
(VIII a ) (VIII b ) (VIII c ) 式 （ I) 中の個々の Xは、 独立に、 一 NCS、 ハロゲン、 _CN、 一 NC〇、 _ 0 Hおよび _ N C N 2より選ばれる単座配位子である。 (VIII a) (VIII b) (VIII c) Each X in formula (I) is independently a monodentate coordination selected from 1 NCS, halogen, _CN, 1 NC0, _ 0 H and _ NCN 2 A child.
または Xは、 X同士が結合していてもよく、 一般式 （Ilia) で表されるジケト ン誘導体、 あるいは一般式 （III b) で表される 1, 2—ジチオレン誘導体で表さ れるニ座配位子でもよい。 .  Or X may be bonded to each other, and X is a diketone derivative represented by the general formula (Ilia) or a bidentate represented by a 1,2-dithiolene derivative represented by the general formula (III b). It may be a ligand. .
Figure imgf000010_0002
一般式 （Ilia) の場合、 R31〜R33は、 それぞれ独立に、 水素原子、 炭素数 1〜30のアルキル基、 炭素数 2〜 30のアルコキシアルキル基、 炭素数 1〜3 0のパーフルォロアルキル基、 炭素数 6〜 30のァリール基、 炭素数 7〜30の ァラルキル基を表す。
Figure imgf000010_0002
In the case of the general formula (Ilia), R 31 to R 33 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, or a perful having 1 to 30 carbon atoms. An o-alkyl group, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms.
炭素数 1〜30のアルキル基としては、 直鎖状でも分岐状でもよく、 具体的に は、 メチル基、 ェチル基、 i一プロピル基、 n—プロピル基、 ブチル基、 s—ブ チル基、 t一ブチル基、 へキシル基、 ォクチル基、 ノエル基、 ドデシル基、 ィコ シル基、 ドコシル基などが挙げられる。 炭素数 2〜 3 0のアルコキシアルキル基 としては、 具体的には、 メ トキシメチル基、 メ トキシェチル基、 メ トキシプロピ ル基、 エトキシメチル基、 エトキシブチル基、 エトキシへキシル基、 エトキシノ ニル基、 プロポキシメチル基、 ブトキシメチル基、 へキシロキシメチル基、 ノ- ロキシメチル基、 ドデシ口キシェチル基などが挙げられる。 炭素数 1〜3 0のパ 一フルォロアルキル基としては、 具体的には、 一 C F 3、 _ C 2 F 5、 i— C 3 F 7 などが挙げられる。 炭素数 6〜 3 0のァリール基としては、 具体的には、 フエ二 ル基、 ナフチル基が挙げられる。 炭素数 7〜 3 0のァラルキル基としては、 具体 的にはべンジノレ基、 フエネチル基、 フエ-ルプチノレ基、 フエ-ノレノニル基、 ナフ チルノニル基などが挙げられる。 さらに具体的には、 以下に示す官能基が挙げら れる。 The alkyl group having 1 to 30 carbon atoms may be linear or branched, and specifically includes a methyl group, an ethyl group, an i-propyl group, an n-propyl group, a butyl group, an s-butyl group, t-Butyl group, hexyl group, octyl group, Noel group, dodecyl group, ico Examples include syl group and docosyl group. Specific examples of the alkoxyalkyl group having 2 to 30 carbon atoms include a methoxymethyl group, a methoxyxyl group, a methoxypropyl group, an ethoxymethyl group, an ethoxybutyl group, an ethoxyhexyl group, an ethoxynonyl group, and a propoxymethyl group. Group, butoxymethyl group, hexyloxymethyl group, noroxymethyl group, dodecoxychichetyl group and the like. The path one Furuoroarukiru group having a carbon number of 1-3 0, specifically, one CF 3, _ C 2 F 5 , etc. i-C 3 F 7 and the like. Specific examples of the aryl group having 6 to 30 carbon atoms include a phenyl group and a naphthyl group. Specific examples of the aralkyl group having 7 to 30 carbon atoms include a benzyleno group, a phenethyl group, a ferro-quinole group, a phen-norenonyl group, and a naphthyl nonyl group. More specifically, the following functional groups can be mentioned.
Figure imgf000011_0001
Figure imgf000011_0001
Figure imgf000011_0002
—般式 （Illb) の場合、 R 34および R 35は、 同一であることが好ましく、 ま た異なっていても良く、 それぞれ個別に、 水素原子、 シァノ基、 炭素数 1〜20 のアルキル基、 炭素数 1〜 20のパーフルォロアルキル基、 または炭素数 6〜1 5のァリ一ル基を表し、また R 34および R 35が結合して環を形成していても良レ、。 炭素数 1〜30のアルキル基としては、 直鎖状でも分岐状でもよく、 具体的に は、 メチル基、 ェチル基、 i—プロピル基、 n—プロピル基、 プチル基、 s—ブ チル基、 t一ブチル基、 へキシル基、 ォクチル基、 ノニル基、 ドデシル基などが 挙げられる。 炭素数 1〜20のパーフルォロアルキル基としては、 具体的には、 — CF3、 _C2F5、 i一 C3F 7などが挙げられる。 炭素数 6〜： 1 5のァリール 基としては、 具体的には、 フエニル基、 ナフチル基などが挙げられる。 さらに具 体的には、 以下に示す官能基が挙げられる。
Figure imgf000011_0002
—In the general formula (Illb), R 34 and R 35 are preferably the same and may be different, and each independently represents a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, A perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and R 34 and R 35 may be bonded to form a ring. The alkyl group having 1 to 30 carbon atoms may be linear or branched. Specifically, a methyl group, an ethyl group, an i-propyl group, an n-propyl group, a butyl group, an s-butyl group, t-Butyl group, hexyl group, octyl group, nonyl group, dodecyl group and the like. Specific examples of the perfluoroalkyl group having 1 to 20 carbon atoms include —CF 3 , —C 2 F 5 , and i-C 3 F 7 . Specific examples of the aryl group having 6 to 15 carbon atoms include a phenyl group and a naphthyl group. More specifically, the following functional groups are listed.
Figure imgf000012_0001
Figure imgf000012_0001
R 34および R 35が結合して環を形成する場合、具体的には以下に示す官能基が 挙げられる。 ' When R 34 and R 35 are bonded to form a ring, specific examples include the functional groups shown below. '
Figure imgf000012_0002
Figure imgf000012_0002
式 （I) および式 （II) の構造単位を有する化合物中に、 金属酸化物半導体層 に吸着するために、少なくとも一つの COOH基を有していることが必要である。 従って、 1 1〜1 16のぅちの少なくとも一つは CO OH基である。 The compound having the structural unit of the formula (I) and the formula (II) needs to have at least one COOH group in order to be adsorbed on the metal oxide semiconductor layer. Thus, at least one of Uchi of 1 1 to 1 16 is a CO OH groups.
以下に一般式 （ I) で示される構造単位および一般式 （Π) で示される構造単 位の具体例を示すが、 本発明はこれらに限定されるものではない。  Specific examples of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (Π) are shown below, but the present invention is not limited thereto.
一般式 （I) で示される構造単位としては以下のものが挙げられる。
Figure imgf000013_0001
Examples of the structural unit represented by the general formula (I) include the following.
Figure imgf000013_0001
/ν O/-0/-00ί&1£ 301soM7 / ν O / -0 / -00ί & 1 £ 301soM7
Figure imgf000014_0001
Figure imgf000014_0001
。io寸 . io dimension
Figure imgf000015_0001
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000017_0001
 また式 （ I ) と式 （II) で示される構造単位を有する化合物は、 通常、 式 （ I ) と式 （II) が直接、 または芳香環若しくは芳香族複素環を介して結合されたもの である。 かかる結合基の具体例としては以下のものを例示することができる。  In addition, the compound having the structural unit represented by the formula (I) and the formula (II) is usually a compound in which the formula (I) and the formula (II) are bonded directly or via an aromatic ring or an aromatic heterocyclic ring. is there. Specific examples of such a linking group include the following.
Figure imgf000018_0001
本発明の式 （I ) と式 （II) で示される構造単位を有する化合物としては、 下 記一般式 （IV) で示される化合物が好ましい。
Figure imgf000018_0001
As the compound having the structural unit represented by the formula (I) or the formula (II) of the present invention, a compound represented by the following general formula (IV) is preferable.
Figure imgf000018_0002
Figure imgf000018_0002
(式 （IV) 中、 1 17は1 1〜1 16と同様な基を表す。） 以下に一般式 （IV) の具体例を示すが、 '本発明はこれらに限定されるものでは ない。 Specific examples of the general formula (IV) to (formula (IV), 1 17 1 1 represents a ~ 1 16 a similar group.) Hereinafter, 'the present invention is not limited thereto.
Figure imgf000019_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000020_0001
Figure imgf000020_0002
Figure imgf000020_0002
Figure imgf000021_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000022_0002
Figure imgf000022_0001
Figure imgf000022_0002
Figure imgf000022_0003
Figure imgf000022_0003
Figure imgf000023_0001
Figure imgf000023_0001
Figure imgf000023_0002
Figure imgf000024_0001
Figure imgf000024_0002
Figure imgf000024_0003
Figure imgf000025_0001
Figure imgf000023_0002
Figure imgf000024_0001
Figure imgf000024_0002
Figure imgf000024_0003
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000028_0001
Figure imgf000028_0002
Figure imgf000028_0002
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000030_0002
Figure imgf000030_0003
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000030_0002
Figure imgf000030_0003
Figure imgf000031_0001
本発明の式 （ I) と式 （II) で示される構造単位を有する化合物としては、 下 記一般式 （V) で示される化合物が好ましい。
Figure imgf000031_0001
As the compound having the structural unit represented by the formula (I) and the formula (II) of the present invention, a compound represented by the following general formula (V) is preferable.
Figure imgf000032_0001
式 （V) 中、 R17は Ri〜R16と同様な基を表し、 R18は炭素数 1〜20のァ ルキル基を表す。 炭素数 1〜20のアルキル基としては、 直鎖状でも分岐状でも よく、 具体的には、 メチル基、 ェチル基、 i—プロピル基、 n—プロピル基、 ブ チル基、 s—プチル基、 t一ブチル基、 へキシル基、 ォクチル基、 ノニル基、 ド デシル基、 ィコシル基、 ドコシル基などが挙げられる。 以下に一般式 （V) の具体例を示すが、 本発明はこれらに限定されるものでは ない。
Figure imgf000032_0001
In the formula (V), R 17 represents the same group as Ri to R 16, and R 18 represents an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be linear or branched, and specifically includes a methyl group, an ethyl group, an i-propyl group, an n-propyl group, a butyl group, an s-butyl group, t-Butyl group, hexyl group, octyl group, nonyl group, dodecyl group, icosyl group, docosyl group and the like. Specific examples of the general formula (V) are shown below, but the present invention is not limited thereto.
Figure imgf000033_0001
Figure imgf000033_0001
Figure imgf000033_0002
Figure imgf000033_0002
xooo xoo
Figure imgf000034_0001
xooo xoo
Figure imgf000034_0001
Figure imgf000034_0002
Figure imgf000035_0001
Figure imgf000034_0002
Figure imgf000035_0001
本発明の式 （I ) と式 （Π) で示される構造単位を有する化合物としては、 下 記一般式 （VI) で示される化合物が好ましい。 As the compound having a structural unit represented by the formula (I) and the formula (Π) of the present invention, a compound represented by the following general formula (VI) is preferable.
Figure imgf000036_0001
以下に一般式 （VI) の具体例を示すが、 本発明はこれらに限定されるものでは なレ、。
Figure imgf000036_0001
Specific examples of the general formula (VI) are shown below, but the present invention is not limited thereto.
Figure imgf000037_0001
Figure imgf000037_0001
Figure imgf000037_0002
Figure imgf000037_0002
Figure imgf000038_0001
Figure imgf000038_0002
Figure imgf000038_0001
Figure imgf000038_0002
Figure imgf000038_0003
Figure imgf000038_0003
Figure imgf000039_0001
Figure imgf000039_0002
Figure imgf000039_0003
Figure imgf000039_0001
Figure imgf000039_0002
Figure imgf000039_0003
6S 6S
Figure imgf000040_0001
Figure imgf000040_0001
1^0 800Z OAV 1 ^ 0 800Z OAV
699 0函 df/l d Of 699 0 box df / ld Of
Figure imgf000041_0001
Figure imgf000041_0001
699l.0/.00Zdf/X3d 1?Z0l7S0/800Z OAV If 699l.0 / .00Zdf / X3d 1? Z0l7S0 / 800Z OAV If
Figure imgf000042_0001
Figure imgf000042_0001
699U0/L00Zdr/∑Jd 1?Z0l7S0/800Z OAV 699U0 / L00Zdr / ∑Jd 1? Z0l7S0 / 800Z OAV
Figure imgf000043_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000045_0002
Figure imgf000045_0003
Figure imgf000045_0001
Figure imgf000045_0002
Figure imgf000045_0003
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000048_0002
Figure imgf000048_0003
ooo oo
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000048_0002
Figure imgf000048_0003
ooo oo
ooo  ooo
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Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000050_0002
Figure imgf000050_0003
次に、 本発明の光起電力素子について説明する。 ¾ood) ooo
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000050_0002
Figure imgf000050_0003
Next, the photovoltaic element of the present invention will be described.
本発明の光起電力素子は、 前記した本発明の光增感剤を吸着した半導体層を有 することを特徴とする。  The photovoltaic device of the present invention has a semiconductor layer adsorbing the photosensitizer of the present invention described above.
本発明の光起電力素子の例としては、 例えば、 図 1に示す断面を有する素子を 挙げることができる。 この素子は、 透明導電性基板 1上に光吸収剤として働く本 発明の光増感剤を吸着させた半導体層 3が配置され、 半導体層 3と対向電極基板 2の間に電解質層 4が配置され、 周辺がシール材 5で密封されている。 なお、 リ 一ド線は透明導電性基板 1と対向電極基板 2の導電部分に接続され、 電力を取り 出すことができる。  As an example of the photovoltaic element of the present invention, for example, an element having a cross section shown in FIG. 1 can be mentioned. In this element, a semiconductor layer 3 on which a photosensitizer of the present invention acting as a light absorber is adsorbed is disposed on a transparent conductive substrate 1, and an electrolyte layer 4 is disposed between the semiconductor layer 3 and the counter electrode substrate 2. The periphery is sealed with a sealing material 5. The lead wire is connected to the conductive portions of the transparent conductive substrate 1 and the counter electrode substrate 2 so that electric power can be taken out.
透明導電性基板は、 通常、 透明基板上に透明導電膜を積層させて製造される。 透明基板としては、 特に限定されず、 材質、 厚さ、 寸法、 形状等は目的に応じて 適宜選択することができ、 例えば無色あるいは有色ガラス、 網入りガラス、 ガラ スブロック等が用いられる他、無色あるいは有色の透明性を有する樹脂でも良い。 かかる樹脂としては、 具体的には、 ポリエチレンテレフタレートなどのポリエス テル、 ポリアミ ド、 ポリ スルホン、 ポリエーテルサルホン、 ポリエーテルエーテ ルケ トン、 ポリフエ二レンサノレフアイ ド、 ポリカーボネート、 ポリイミ ド、 ポリ メチノレメタタリ レート、 ポリスチレン、 トリ酉乍酸セルロース、 ポリメチルペンテ ンなどが挙げられる。 なお、 本発明における透明とは、 1 0〜1 0 0 %の透過率 を有することであり、 また、 本発明における基板とは、 常温において平滑な面を 有するものであり、 その面は平面あるいは曲面であってもよく、 また応力によつ て変形するものであってもよい。  A transparent conductive substrate is usually manufactured by laminating a transparent conductive film on a transparent substrate. The transparent substrate is not particularly limited, and the material, thickness, dimensions, shape, and the like can be appropriately selected according to the purpose. For example, colorless or colored glass, meshed glass, glass block, etc. are used. A colorless or colored resin having transparency may be used. Specific examples of such resins include polyesters such as polyethylene terephthalate, polyamides, polysulfones, polyethersulfones, polyetheretherketones, polyphenylenesanolides, polycarbonates, polyimides, polymethylenomethacrylates, polystyrene, Examples thereof include cellulose trisuccinate and polymethylpentene. In the present invention, the term “transparent” means having a transmittance of 10 to 100%, and the substrate in the present invention has a smooth surface at room temperature, and the surface is flat or It may be a curved surface or may be deformed by stress.
また、 電極の導電層を形成する透明導電膜としては、 本発明の目的を果たすも のである限り特に限定されなく、 例えば、 金、 銀、 クロム、 銅、 タングステンな どの金属薄膜、 金属酸化物からなる導電膜などが挙げられる。 金属酸化物として は、 例えば、 酸化錫や酸化亜鉛に、 他の金属元素を微量ドープした Indium Tin Oxide ( I TO ( I n 2〇3 : S n))、 Fluorine doped Tin Oxide (F TO ( S n O 2 ： F))、 Aluminum doped Zinc Oxide (AZ O (Z n O : A 1 )) などが好適 なものとして用いられる。 Further, the transparent conductive film for forming the conductive layer of the electrode is not particularly limited as long as it fulfills the object of the present invention. For example, it is made of a metal thin film such as gold, silver, chromium, copper, tungsten, or metal oxide. And a conductive film. Examples of metal oxides include Indium Tin Oxide (I TO (I n 2 0 3 : Sn)), Fluorine doped Tin Oxide (F TO (S n O 2: F)), aluminum doped Zinc Oxide (AZO (ZnO: A1)), etc. are preferably used.
膜厚は通常、 1 0 nm〜 1 0 μ m、 好ましくは 1 0 0 nm〜 2 μ mである。 ま た、 表面抵抗 （抵抗率） は、 本発明の基板の用途により適宜選択されるところで あるが、 通常、 0 . 5〜5 0 0 Ωノ s q、 好ましくは 2〜5 0 Ω / s qである。 対向電極は通常、 白金、 カーボン電極などを用いることができる。 基板の材質 は、 特に限定されず、 材質、 厚さ、 寸法、 形状等は目的に応じて適宜選択するこ とができ、 例えば無色あるいは有色ガラス、 網入りガラス、 ガラスブロック等が 用いられる他、 無色あるいは有色の透明性を有する樹脂でも良い。 具体的には、 ポリエチレンテレフタレートなどのポリエステノレ、 ポリアミ ド、 ポリスノレホン、 ポリエーテルサルホン、 ポリエーテノレエーテルケトン、 ポリフエ二レンサノレファ ィ ド、 ポリカーボネート、 ポリイミ ド、 ポリメチルメタクリレート、 ポリスチレ ン、 トリ酢酸セルロース、 ポリメチルペンテンなどが挙げられる。 また、 金属プ レートなどを基板として用いることもできる。 The film thickness is usually from 10 nm to 10 μm, preferably from 100 nm to 2 μm. Further, the surface resistance (resistivity) is appropriately selected depending on the use of the substrate of the present invention. However, it is usually 0.5 to 500 Ω / sq, preferably 2 to 50 Ω / sq. As the counter electrode, platinum, carbon electrode, or the like can be usually used. The material of the substrate is not particularly limited, and the material, thickness, dimensions, shape, etc. can be appropriately selected according to the purpose. For example, colorless or colored glass, netted glass, glass block, etc. are used. A colorless or colored resin having transparency may be used. Specifically, polyester terephthalate such as polyethylene terephthalate, polyamide, polysenorephone, polyethersulfone, polyetherenoleetherketone, polyphenylenesanorefide, polycarbonate, polyimide, polymethylmethacrylate, polystyrene, cellulose triacetate, Examples include polymethylpentene. Also, a metal plate or the like can be used as the substrate.
本発明の光起電力素子において用いられる半導体層としては、 特に限定されな いが、 例えば、 T i 〇2、 Z n O、 S n〇2、 N b 2〇 5からなる層等が挙げられ、 なかでも T i 〇2、 Z η θからなる層が好ましい。 The semiconductor layer used in the photovoltaic device of the present invention, particularly limited, such bur, for example, T i 〇 2, Z n O, such as a layer consisting of S N_〇 2, N b 2 〇 5 can be mentioned Of these, a layer composed of T i 0 2 and Z η θ is preferable.
本発明に用いられる半導体は単結晶でも多結晶でも良い。 結晶系としては、 ァ ナタ〜ゼ型、 ルチル型、 ブルッカイ ト型などが主に用いられるが、 好ましくはァ ナターゼ型である。  The semiconductor used in the present invention may be single crystal or polycrystalline. As the crystal system, anatase-ze type, rutile type, brookite type and the like are mainly used, but anatase type is preferred.
半導体層の形成には公知の方法を用レ、ることができる。 半導体層の形成方法と しては、 上記半導体のナノ粒子分散液、 ゾル溶液等を、 公知の方法により基板上 に塗布することで得ることが出来る。 この場合の塗布方法としては特に限定され ずキャス ト法による薄膜状態で得る方法、 スピンコート法、 ディップコート法、 バーコート法のほか、 スクリーン印刷法を初めとした各種の印刷方法を挙げるこ とができる。  A known method can be used for forming the semiconductor layer. As a method for forming the semiconductor layer, the above-mentioned semiconductor nanoparticle dispersion, sol solution, and the like can be obtained by coating on a substrate by a known method. The coating method in this case is not particularly limited, and examples thereof include a method of obtaining a thin film by a casting method, a spin coating method, a dip coating method, a bar coating method, and various printing methods including a screen printing method. Can do.
半導体層の厚みは任意であるが 0 . 5 m以上、 5 0 m以下、 好ましくは 1 μ m以上 2 0 ix m以下である。  The thickness of the semiconductor layer is arbitrary, but is 0.5 m or more and 50 m or less, preferably 1 μm or more and 20 ix m or less.
本発明の光増感剤 （色素） を半導体層に吸着させる方法としては、 例えば、 溶 媒に光増感剤を溶解させた溶液を、 半導体層上にスプレーコートゃスピンコート などにより塗布した後、 乾燥する方法により形成することができる。 この場合、 適当な温度に基板を加熱しても良い。 または半導体層を溶液に浸漬して吸着させ る方法を用いることもできる。 浸漬する時間は光増感剤が十分に吸着すれば特に 制限されることはないが、 好ま.しくは 1 0分〜 3 0時間、 より好ましくは 1〜2 0時間である。 また、 必要に応じて浸漬する際に溶媒や基板を加熱しても良い。 溶液にする場合の光増感剤の濃度としては、 0 . 0 1 〜 1 0 O mm o 1 Z L、 好 ましくは 0 . 1 〜 5 O mm o 1 Z L程度である。 As a method for adsorbing the photosensitizer (dye) of the present invention to the semiconductor layer, for example, after applying a solution in which the photosensitizer is dissolved in a solvent to the semiconductor layer by spray coating, spin coating or the like. It can be formed by a drying method. In this case, the substrate may be heated to an appropriate temperature. Alternatively, a method in which a semiconductor layer is immersed in a solution and adsorbed can be used. The immersion time is not particularly limited as long as the photosensitizer is sufficiently adsorbed, but is preferably 10 minutes to 30 hours, more preferably 1 to 2 0 hours. Moreover, you may heat a solvent and a board | substrate when immersing as needed. The concentration of the photosensitizer in the solution is about 0.01 to 10 Ommo1 ZL, preferably about 0.1 to 5 Ommo1 ZL.
溶媒としては、 アルコール類、 エーテル類、 二トリル類、 エステル類、 炭化水 素など用いることができる。  As the solvent, alcohols, ethers, nitriles, esters, hydrocarbons and the like can be used.
光増感剤間の凝集等の相互作用を低減するために、 界面活性剤としての性質を 持つ無色の化合物を光増感剤吸着液に添加し、 半導体層に共吸着させてもよい。 このような無色の化合物の例としては、 カルボキシル基やスルホ基を有するコー ル酸、 デォキシコール酸、 ケノデォキシコール酸、 タウロデオキシコール酸等の ステロイ ド化合物ゃスルホン酸塩類等が挙げられる。  In order to reduce the interaction such as aggregation between the photosensitizers, a colorless compound having properties as a surfactant may be added to the photosensitizer adsorbing solution and co-adsorbed on the semiconductor layer. Examples of such colorless compounds include steroids such as carboxylic acid having a carboxyl group or sulfo group, deoxycholic acid, chenodeoxycholic acid, taurodeoxycholic acid, and sulfonates.
未吸着の光増感剤は、吸着工程後、速やかに洗浄により除去するのが好ましい。 洗浄は湿式洗浄槽中でァセトニトリル、 アルコール系溶媒等を用いて行うのが好 ましい。  The unadsorbed photosensitizer is preferably removed by washing immediately after the adsorption step. Cleaning is preferably performed using acetonitrile, alcohol solvent, etc. in a wet cleaning tank.
光増感剤を吸着させた後、 アミン類、 4級アンモニゥム塩、 少なくとも 1つの ゥレイ ド基を有するゥレイ ド化合物、 少なくとも 1つのシリル基を有するシリル 化合物、 アルカリ金属塩、 アルカリ土類金属塩等を用いて、 半導体層の表面を処 理してもよい。 好ましいァミン類の例としては、 ピリジン、 4一 t一ブチルピリ ジン、 ポリビュルピリジン等が挙げられる。 好ましい 4級アンモニゥム塩の例と しては、 テトラプチルアンモニゥムョージド、 テトラへキシルアンモ-ゥムョー ジド等が挙げられる。 これらは有機溶媒に溶解して用いてもよく、 液体の場合は そのまま用いてもよい。  After adsorbing the photosensitizer, amines, quaternary ammonium salts, ureido compounds having at least one ureido group, silyl compounds having at least one silyl group, alkali metal salts, alkaline earth metal salts, etc. May be used to treat the surface of the semiconductor layer. Examples of preferred amines include pyridine, 4 tert-butyl pyridine, polybutyl pyridine and the like. Examples of preferable quaternary ammonium salts include tetraptyl ammonium salts, tetrahexyl ammonium salts and the like. These may be used by dissolving in an organic solvent, or may be used as they are in the case of a liquid.
本発明において用いられる電解質としては、 特に限定されず、 液体系でも固体 系のいずれでもよく、 可逆な電気化学的酸化還元特性を示すものが望ましい。 こ こで、 可逆な電気化学的酸化還元特性を示すということは、 光電変換素子の作用 する電位領域において、 可逆的に電気化学的酸化還元反応を起こし得ることをい う。典型的には、通常、水素基準電極（N H E ) に対して〜 1〜十 2 V V s N H Eの電位領域で可逆的であることが望ましい。  The electrolyte used in the present invention is not particularly limited, and may be either a liquid system or a solid system, and preferably exhibits a reversible electrochemical redox characteristic. Here, reversible electrochemical redox characteristics means that an electrochemical redox reaction can occur reversibly in the potential region where the photoelectric conversion element acts. Typically, it is usually desirable to be reversible in the potential region of ˜1 to 12 V Vs N H E relative to the hydrogen reference electrode (N H E).
電解質のイオン伝導度は、 通常室温で 1 X 1 0— 7 S Z c m以上、 好ましくは 1 X 1 0— e s Z c m以上、さらに好ましくは 1 X 1 0— 5 S / c m以上であることが 望ましい。 電解質層の厚さは、 特に制限されないが、 1 μπι以上であることが好ましく、 より好ましくは 1 0 μπι以上であり、 また、 3 mm以下が好ましく、 より好まし くは 1 mm以下である。 Ionic conductivity of the electrolyte is usually at room temperature 1 X 1 0- 7 SZ cm or more, it is desirable that preferably 1 X 1 0- es Z cm or more, still more preferably 1 X 1 0- 5 S / cm or more . The thickness of the electrolyte layer is not particularly limited, but is preferably 1 μπι or more, more preferably 10 μπι or more, and preferably 3 mm or less, more preferably 1 mm or less.
かかる電解質としては、 上記の条件を満足すれば特に制限されるものでなく、 液体系および固体系とも、 本技術分野で公知のものを使用することができる。  Such an electrolyte is not particularly limited as long as the above-described conditions are satisfied. Both liquid and solid electrolytes known in the art can be used.
[実施例] [Example]
以下に実施例を挙げ、 本発明を具体的に説明するが、 本発明はこの実施例に限 定されるものではない。  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
(光增感剤 1の合成） (Synthesis of photosensitizer 1)
文献 A (Eur. J. Inorg. Chem. , 2003, 1900-1910) 記載の方法を参考に光増 感剤 1の合成を行った。すなわち、ジクロロ（p—シメン）ルテニウム二量体（ 1. 6 3 g ； 1 2. 7mmo l ) と 2, 2， 一ビビリジン一 4, 4' ージカルボン酸 (1. 3 6 g ； 5. 6 mm o 1 ) をエタノール （1 00m l ) に溶解した後、 4 時間加熱還流を行った。 反応終了後、 ろ過し、 続いて、 トルエン （.1 00m l ) に分散し、 ろ過することで化合物 Aを 2. 9 3 g (5. 3mmo 1 ) 得た。  Photosensitizer 1 was synthesized with reference to the method described in Reference A (Eur. J. Inorg. Chem., 2003, 1900-1910). That is, dichloro (p-cymene) ruthenium dimer (1.63 g; 12.7 mmol) and 2,2,1 bibiridine-1,4'-dicarboxylic acid (1.36 g; 5.6 mm) o 1) was dissolved in ethanol (100 ml) and then heated to reflux for 4 hours. After completion of the reaction, the mixture was filtered, then dispersed in toluene (.100 ml) and filtered to obtain 2.93 g (5.3 mmo 1) of Compound A.
Figure imgf000054_0001
化合物 A
Figure imgf000054_0001
Compound A
次に、 1 , 1 0—フエナント口リン一 5， 6—ジオン （0. 27 g ; l . 3m m o 1 ) と 1 , 2—ジァミノ一 4 , 5—ジュト口べンゼン （ 0. 27 g ； 1. 3 mmo 1 ) をメタノールに溶解し、 1 0時間加熱還流した。 反応後ろ過にてジニ トロ体を 0. 3 3 g (0. 9 mm o 1 ) 得た。 得られたジニトロ体 （0. 33 g ； 0. 9mmo 1 ) を常法にて、 接触水素還 元を行い、 目的のジァミノ体（化合物 B) 0. 28 g (0. 9mmo l ) を得た。 Next, 1, 1 0—Phenant Mouth Ring 5, 6-dione (0.27 g; l .3m mo 1) and 1, 2—Diamino 1,4—5-Jut Mouth Bensen (0.27 g; 1. 3 mmo 1) was dissolved in methanol and heated to reflux for 10 hours. After the reaction, 0.33 g (0.9 mm o 1) of dinitro compound was obtained by filtration. The obtained dinitro compound (0.33 g; 0.9 mmo 1) was subjected to catalytic hydrogen reduction by a conventional method to obtain 0.28 g (0.9 mmol) of the desired diamino compound (compound B). .
Figure imgf000055_0001
Figure imgf000055_0001
化合物 B 化合物 B (0. 28 g ； 6. 9 mm o 1 ) と 3—ホルミル _ 4—ヒ ドロキシ安 息香酸 （0. 3 g ； 1. 8 mm o 1 ) をエタノール中混合し、 オルトギ酸エステ ルを添加した後、 2時間過熱還流した。 酢酸亜鉛 （0. 1 7 g ； 0. 9 mm o 1 ) を添加し、 さらに 1 0時間過熱還流を行った。 反応終了後、 ろ過にて化合物 Cを 得た。  Compound B Compound B (0.28 g; 6.9 mm o 1) and 3-formyl_4-hydroxybenzoic acid (0.3 g; 1.8 mm o 1) are mixed in ethanol After adding the acid ester, the mixture was heated to reflux for 2 hours. Zinc acetate (0.17 g; 0.9 mm o 1) was added, and the mixture was further heated to reflux for 10 hours. After completion of the reaction, Compound C was obtained by filtration.
ィ匕合物 C ( 0. 3 2 g ； 0. 5 mm o 1 ) と化合物 A (0. 28 g , 0. 5 m m o 1 ) を DMF 20 m 1に溶解し、 4時間加熱攪拌した。 アンモニゥムチオシ ァネート （1. 2 g) を添加し、 さらに 4時間加熱攪拌した。 反応終了後、 減圧 濃縮し、 水 （200m l.) に分散し、 ろ過にて、 目的物 （化合物 1 ；光増感剤 1) を得た。 得られた化合物 1をカラムクロマトグラフィー （充填剤： S e p h a d e x LH— 20、 溶離液 DMF) にて精製し、 3 20mg (0. 28 mm o 1 ) を得た。  Compound C (0.32 g; 0.5 mm o 1) and compound A (0.28 g, 0.5 mm o 1) were dissolved in DMF 20 ml and stirred with heating for 4 hours. Ammonium thiocyanate (1.2 g) was added, and the mixture was further heated and stirred for 4 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, dispersed in water (200 ml), and filtered to obtain the desired product (compound 1; photosensitizer 1). The obtained compound 1 was purified by column chromatography (filler: Sephadex LH-20, eluent DMF) to obtain 320 mg (0.28 mm o 1).
計算値 C : 50. 87、 H : 2. 3 1、 N： 1 2. 36  Calculated value C: 50. 87, H: 2. 3 1, N: 1 2. 36
実験値 C : 50. 72、 H： 2. 47、 N ： 1 1. 991  Experimental value C: 50.72, H: 2.47, N: 1 1.991
MS (E S I /MS) m/ z : 1 1 3 1 (M— H)) MS (ESI / MS) m / z: 1 1 3 1 (M— H))
Figure imgf000056_0001
Figure imgf000056_0001
(光増感剤 2の合成) (Synthesis of photosensitizer 2)
文献 B (Bull. Chem. Soc. Jpn. , 76， 977 - 984 (2003) )記載の方法を参考にし て光増感剤 2の合成を行った。  Photosensitizer 2 was synthesized with reference to the method described in Reference B (Bull. Chem. Soc. Jpn., 76, 977-984 (2003)).
まず文献 C (Tetrahedron letters 38, 8159 (1997)) 記載の方法にてフエナン トロリンジァミンを合成した。  First, phenanthrolinediamine was synthesized by the method described in Reference C (Tetrahedron letters 38, 8159 (1997)).
フエナントロリンジァミン （0. 2 1 g ； 1. Omm o 1 ) と 3—ホノレミノレー 4ーヒ ドロキシ安息香酸（0. 34 g ; 2. 0 mm o 1 ) をエタノールに溶解し、 オルトギ酸エステル （0. 1 m l ) を添加し、 3時間加熱還流を行った。続いて、 酢酸亜鉛 （0. 2 g ; l. 1 mmo 1 ) を添加し、 1 0時間加熱還流を行った。 反応終了後、 ろ過にて、 化合物 Dを 0, 39 g (0. 7mmo 1 ) 得た。 Phenanthrolinediamine (0.21 g; 1. Omm o 1) and 3-honoleminole 4-hydroxyoxybenzoic acid (0.34 g; 2.0 mm o 1) were dissolved in ethanol and orthoformate was dissolved. Ester (0.1 ml) was added and heated to reflux for 3 hours. Subsequently, zinc acetate (0.2 g; l. 1 mmo 1) was added and heated to reflux for 10 hours. After completion of the reaction, 0, 39 g (0.7 mmo 1) of Compound D was obtained by filtration.
Figure imgf000057_0001
Figure imgf000057_0001
COOH COOH
化合物 D 化合物 A (0. 28 g ； 0. 5 mm o 1 ) と化合物 D (0. 28 g ； 0. 5 m mo 1 ) を DMF 20m 1中に添加し、 4時間過熱攪拌を行った。 続いて、 アン モニゥムチオシァネート （1. 2 g) を添加し、 4時間加熱還流を行った。  Compound D Compound A (0.28 g; 0.5 mm o 1) and Compound D (0.28 g; 0.5 mm o 1) were added to DMF 20 ml 1 and superheated for 4 hours. Subsequently, ammonium thiocyanate (1.2 g) was added and heated under reflux for 4 hours.
反応終了後、 減圧濃縮し、 水に分散し、 ろ過した、 得られた固形物をカラムク 口マトグラフィー （充填剤： S e p h a d e x LH— 20、 溶離液 DM F ) に て精製し、 目的物 （化合物 2 ；光増感剤 2) を 0. 3 g (0. 3mmo 1 ) 得た。  After completion of the reaction, the reaction mixture was concentrated under reduced pressure, dispersed in water, and filtered. The resulting solid was purified by column chromatography (filler: Sephadex LH-20, eluent DM F) to obtain the desired product (compound 2; 0.3 g (0.3 mmo 1) of photosensitizer 2) was obtained.
計算値 C : 48. 9 1、 H : 2. 3 5、 N： 10. 87  Calculated value C: 48. 9 1, H: 2. 3 5, N: 10. 87
実験値 C : 48. 65、 H : 2. 25、 N： 1 0. 7 1  Experimental value C: 48. 65, H: 2.25, N: 1 0. 7 1
MS (E S I /MS) mZ z ： 1 030  MS (E S I / MS) mZ z: 1 030
Figure imgf000057_0002
Figure imgf000057_0002
化合物 A 化合物 D 光増感剤 2 (光増感剤 3 , 4の合成） Compound A Compound D Photosensitizer 2 (Synthesis of photosensitizers 3 and 4)
下記の光増感剤 3および光増感剤 4を、光増感剤 2の合成法に準じて合成した。  The following photosensitizer 3 and photosensitizer 4 were synthesized according to the synthesis method of photosensitizer 2.
Figure imgf000058_0001
Figure imgf000058_0001
光増感剤 3 光増感剤 4  Photosensitizer 3 Photosensitizer 4
(光増感剤 5 , 6の合成） (Synthesis of photosensitizers 5 and 6)
下記の光増感剤 5および光増感剤 6を、光増感剤 2の合成法に準じて合成した。  The following photosensitizer 5 and photosensitizer 6 were synthesized according to the synthesis method of photosensitizer 2.
Figure imgf000058_0002
Figure imgf000058_0002
(光増感剤 7 , 8の合成） (Synthesis of photosensitizers 7 and 8)
下記の光増感剤 7および光増感剤 8を、光増感剤 1の合成法に準じて合成した。
Figure imgf000059_0001
The following photosensitizer 7 and photosensitizer 8 were synthesized according to the synthesis method of photosensitizer 1.
Figure imgf000059_0001
<光起電力素子の作製および変換効率の測定 > <Production of photovoltaic elements and measurement of conversion efficiency>
導電性基板上に支持された二酸化チタン膜の増感に基づく光起電力素子を以下 のように作製した。  A photovoltaic device based on sensitization of a titanium dioxide film supported on a conductive substrate was produced as follows.
導電性ガラス（フッ素ドープ S η02， 1 0 Ω)上にコロイ ド状 T i 02粒子（粒 径： 20〜 30 n m) を塗布し、 450 °C、 30分間焼成 （膜厚： 1 0 μ m) し、 その上に光を散乱させるため T i 02粒子 （粒径： 300〜 400 n m) を塗布 し、 5 20°C、 1時間焼成 （膜厚： 6〜8 μπι) した。 これら 2層の膜を、 30 分間 T i C 14溶液に浸漬した後、 450°C、 30分間加熱した。 Conductive glass (fluorine-doped S η0 2, 1 0 Ω) on the colloids form T i 0 2 particles (particle diameter:. 20 to 30 nm) was applied, 450 ° C, 30 minutes baking (thickness: 1 0 mu m), and therefore scattering light on T i 0 2 particles (particle diameter: 300 to 400 nm) is applied, 5 20 ° C, 1 hour baking (thickness: 6~8 μ πι) was . The film of two layers was immersed for 30 minutes T i C 1 4 solution was heated 450 ° C, 30 min.
得られた膜を、 上記光増感剤/エタノール溶液 （3. 0 X 1 0一4 mo 1 /L) に 1 5時間浸し、 色素層 （光増感剤層） を形成した。 得られた基板と P t薄膜の ついたガラスの P t面を合わせ、 0. 3mo 1 /Lのヨウ化リチウムと 0. 0 3 m o 1 ZLのョゥ素を含むァセトニトリル溶液を毛細管現象によって染み込ませ、 周辺をエポキシ接着剤で封止した。 なお、 透明導電基板の導電層部分と対向電極 にはリード線を接続した。 The obtained film was immersed in the above photosensitizer / ethanol solution (3.0 X 10 0 4 mo 1 / L) for 15 hours to form a dye layer (photosensitizer layer). The obtained substrate and the Pt surface of the glass with Pt thin film were put together, and a solution of 0.3 mmol / L lithium iodide and 0.03 mo 1 ZL of iodine was impregnated by capillary action. The periphery was sealed with an epoxy adhesive. Note that lead wires were connected to the conductive layer portion of the transparent conductive substrate and the counter electrode.
なお、 比較のために、 色素として一般的に光起電力素子に用いられるルテユウ ム色素 （Ru t e n i um5 3 5— b i s TBA : S OL ARON I X社製：ブ ラックダイ） を用いた光起電力素子を作製した。 8 1 0 nmの波長において、 I P C Eは 0 %である。  For comparison, a photovoltaic element using a ruthenium dye (Ru tenium5 35-bis TBA: manufactured by SOL ARON IX: black die), which is generally used as a dye for a photovoltaic element, is used. Produced. At a wavelength of 8 10 nm, I P C E is 0%.
このようにして得た素子に疑似太陽光 8 1 0 nmの単色光を照射し、 入射フォ トン〜電流変換効率 （I PCE) を測定した結果を表 1に示した。  Table 1 shows the results of measuring the incident photon-current conversion efficiency (I PCE) by irradiating the monochromatic light of pseudo sunlight 810 nm to the device thus obtained.
表 1より、 従来のルテニウム色素を用いた場合は、 赤外領域である 8 1 0 nm において、 吸収を示さなかったが、 本発明の光増感剤 1〜8を用いた場合 （実施 例 1〜8 )、 同領域において明らかな吸収を示した。 また、 吸光係数 （ m a x ) も、 表 1に示すように、 本発明の光增感剤は、 ブラックダイに比較して大きかつ た。 表 1 From Table 1, when using a conventional ruthenium dye, the infrared region is 8 10 nm. However, when the photosensitizers 1 to 8 of the present invention were used (Examples 1 to 8), clear absorption was observed in the same region. Also, as shown in Table 1, the photosensitizer of the present invention was also larger than the black die, as shown in Table 1. table 1
Figure imgf000060_0001
Figure imgf000060_0001
[図面の簡単な説明] [Brief description of drawings]
図 1は、 光起電力素子の断面の例である。  Fig. 1 is an example of a cross section of a photovoltaic device.
(符号の説明）  (Explanation of symbols)
1 ：透明導電基板、 2 ：対向電極基板、 3 ：半導体層、 4 ：電解質層、  1: transparent conductive substrate, 2: counter electrode substrate, 3: semiconductor layer, 4: electrolyte layer,
5 ： シーノレ材  5: Sinore wood
[産業上の利用可能性] [Industrial applicability]
本発明の新規増感剤は、 可視領域のみならず、 赤外領域も吸収するため、 光起 電力素子の変換効率を上げることができ、 産業上の価値はきわめて大きい。  Since the novel sensitizer of the present invention absorbs not only the visible region but also the infrared region, the conversion efficiency of the photovoltaic device can be increased, and its industrial value is extremely high.

Claims

式 （I) および式 （II) の構造単位を有する化合物を含む光増感剤。  A photosensitizer comprising a compound having the structural unit of formula (I) and formula (II).
Figure imgf000061_0001
Figure imgf000061_0001
(I) (II) (I) (II)
(式 （ I) 中、 Mは、 Ru、 O s、 F e、 R eおよび R hから選ばれる遷移金属 を表し、 式 （II) 中、 M' は、 N i、 C 0、 C u、 Z n、 Mn、 P tおよび P d から選ばれる遷移金属を表す。 式 （ I ) および式 （Π) 中、 ！^1〜！^16は、 水素 原子、 カルボ二ル基を含有する基、 一 PO (OH) 2— n (OR) nで表される基（n は 0〜2の整数、 Rは炭素数 1〜30のアルキル基又はァリール基を表す。）、 炭 素数：！〜 30のアルキル基、 炭素数 2〜 30のァルケ-ル基、 炭素数 2〜 30の アルコキシアルキル基、 炭素数 1〜 30のアミノアルキル基、 炭素数 1〜30の パーフルォロアルキル基、 炭素数 6〜 30のァリール基、 炭素数 7〜 30のァラ ルキル基、またはカルボ二ル基を含有する基を有するアルキル基、ァルケ-ル基、 ァリール基若しくはァラルキル基を表す。 また、 Rnと Rn + 1 (nは 1〜15の整 数、 ただし、 8、 10、 1 2を除く。） で結合した芳香環を形成しても良い。 ただ し、 式（ I ) または式（II) 中に、少なくとも一つの COOH基を有する。 式（ I ) 中、 個々の Xは.、 独立に、 一 NCS、 ハロゲン、 一 CN、 一 NCO、 _〇Hおよ び一 NCN2より選ばれる単座配位子を表す。 Xは、 X同士が結合していてもよ く、 一般式 （Ilia) または （Illb) で表される二座配位子でもよい。 式 （Ilia) 中、 R31〜R33は、 それぞれ独立に、 水素原子、 炭素数 1〜30のアルキル基、 炭素数 2〜30のアルコキシアルキル基、 炭素数 1〜30のアミノアルキル基、 炭素数 1〜 30のパーフルォロアルキル基、 炭素数 6〜 30のァリール基、 また は炭素数 7〜 30のァラルキル基を表す。 式 （Illb) 中、 R 34および R 35は、 それぞれ個別に、 水素原子、 シァノ基、 炭素数 1〜20のアルキル基、 炭素数 1 〜20のパーフルォロアルキル基、 または炭素数 6〜1 5のァリール基を表し、 また R 34および R 35が結合して環を形成していても良い。） (In the formula (I), M represents a transition metal selected from Ru, Os, F e, R e and R h. In the formula (II), M ′ represents Ni, C 0, Cu, Represents a transition metal selected from Z n, Mn, P t and P d In formula (I) and formula (Π),! ^ 1 to! ^ 16 are a group containing a hydrogen atom, a carbonyl group, ! one PO (OH) 2 - n ( oR) groups represented by n (. n is an integer of 0 to 2, R represents represents an alkyl group or Ariru group having 1 to 30 carbon atoms), carbon number: ~ 30 An alkyl group having 2 to 30 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, an aminoalkyl group having 1 to 30 carbon atoms, a perfluoroalkyl group having 1 to 30 carbon atoms, a carbon number Represents an alkyl group having 6 to 30 aryl groups, an alkyl group having 7 to 30 carbon atoms, or a group containing a carbonyl group, an alkyl group, an aryl group or an aralkyl group, and R n R n + 1 (n is an integer of 1 to 15, except 8, 10, 12). However, at least in formula (I) or formula (II), In the formula (I), each X is independently a monodentate ligand selected from 1 NCS, halogen, 1 CN, 1 NCO, __H and 1 NCN 2. X may be bonded to each other and may be a bidentate ligand represented by the general formula (Ilia) or (Illb) In the formula (Ilia), R 31 to R 33 are Each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, An alkoxyalkyl group having 2 to 30 carbon atoms, an aminoalkyl group having 1 to 30 carbon atoms, a perfluoroalkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a 7 to 30 carbon atom Represents an aralkyl group. In formula (Illb), R 34 and R 35 are each independently a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms. 15 represents an aryl group, and R 34 and R 35 may combine to form a ring. )
Figure imgf000062_0001
Figure imgf000062_0001
2. 式 （I) および式 （Π) の構造単位を有する化合物が、 式 （IV) のィ匕 合物であることを特徴とする請求項 1に記載の光増感剤。 2. The photosensitizer according to claim 1, wherein the compound having the structural unit of the formula (I) and the formula (IV) is a compound of the formula (IV).
Figure imgf000062_0002
Figure imgf000062_0002
(式 （IV) 中、 R17は 1〜!^16と同様な基を表す。) (In formula (IV), R 17 represents the same group as 1 to! ^ 16. )
3. 式 （I ) および式 （Π) の構造単位を有する化合物が、 式 （V) の化 合物であることを特徴とする請求項 1に記載の光増感剤。 3. The photosensitizer according to claim 1, wherein the compound having the structural units of the formula (I) and the formula (Π) is a compound of the formula (V).
Figure imgf000063_0001
Figure imgf000063_0001
(式 （V) 中、 R17は！^1〜!^16と同様な基を表し、 R18は炭素数 1〜20のァ ノレキノレ基を表す。） (In the formula (V), R 17 represents a group similar to! ^ 1 to! ^ 16, and R 18 represents an arenoquinole group having 1 to 20 carbon atoms.)
4. 式 （ I) および式 （II) の構造単位を有する化合物が、 式 （VI) の化 合物であることを特徴とする請求項 1に記載の光増感剤。 4. The photosensitizer according to claim 1, wherein the compound having the structural units of the formula (I) and the formula (II) is a compound of the formula (VI).
Figure imgf000063_0002
Figure imgf000063_0002
5. 請求項 1〜 4のいずれかに記載の光増感剤を吸着した半導体層を有す る光起電力素子,。 5. A photovoltaic device having a semiconductor layer adsorbing the photosensitizer according to any one of claims 1 to 4.
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