WO2007034976A1 - Composé, convertisseur photoélectrique et cellule photoélectrochimique - Google Patents

Composé, convertisseur photoélectrique et cellule photoélectrochimique Download PDF

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Publication number
WO2007034976A1
WO2007034976A1 PCT/JP2006/319096 JP2006319096W WO2007034976A1 WO 2007034976 A1 WO2007034976 A1 WO 2007034976A1 JP 2006319096 W JP2006319096 W JP 2006319096W WO 2007034976 A1 WO2007034976 A1 WO 2007034976A1
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group
carbon atoms
complex compound
compound
formula
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PCT/JP2006/319096
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English (en)
Japanese (ja)
Inventor
Toshiya Takahashi
Akio Tanaka
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Sumitomo Chemical Company, Limited
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Priority to DE112006002512T priority Critical patent/DE112006002512T5/de
Priority to US12/067,195 priority patent/US8124777B2/en
Publication of WO2007034976A1 publication Critical patent/WO2007034976A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • C07F15/0053—Ruthenium compounds without a metal-carbon linkage
    • 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
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
    • 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
    • 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

Definitions

  • the present invention relates to a compound, a photosensitizing dye containing the compound, a photoelectric conversion element containing the dye, and a photoelectrochemical cell such as a solar cell containing the photoelectric conversion element.
  • a photosensitizing dye containing the compound
  • a photoelectric conversion element containing the dye containing the dye
  • a photoelectrochemical cell such as a solar cell containing the photoelectric conversion element.
  • Easy photosensitizing dye It is made of bis (2,2'-bibilin fine particles.
  • the photoelectrochemical cell has a problem that the photoelectric conversion efficiency in the long wavelength region of 700 nm or more is not sufficient. Disclosure of the invention
  • An object of the present invention is to provide a compound that provides a photoelectric conversion element having high photoelectric conversion efficiency even in a long wavelength region of 700 nm or longer. That is, the present invention provides the following [1] to [20].
  • ⁇ 1 and ⁇ 2 each independently represent a group you containing an unsaturated hydrocarbon group and an aromatic ring
  • R 1 and R 2 each independently, salts of pro tons donating group or Represents at least one of R 1 and R 2 is a proton-donating group
  • R 3 and R 4 each independently represent a non-proton-donating group
  • R 3 and R 4 may be bonded to each other
  • a and B each independently represent a group containing an element of Groups 14, 15 or 16 of the periodic table
  • m and n are each independently 0 to 2
  • b, c and d each independently represents an integer of 0 to 2, and a + b ⁇ 1.
  • the central atom is a metal atom
  • one of the ligands is a coordination child represented by formula (II)
  • the other is represented by formula (III)
  • Complex compound (I) which is a ligand.
  • Y 1 and Y 2 each independently represent a group containing a hydrocarbon hydrocarbon group and an aromatic ring, and R 1 and R 2 each independently represent a salt of a prodon donating group. Or a plutone donating group, at least one of R 1 and R 2 is a proton donating group, and R 3 and R 4 each independently represent a hydrogen atom or a non-proton donating group.
  • R 3 and R 4 may be bonded to each other, and ⁇ and ⁇ each independently represent a group containing an element of Group 14, 15, or 16 of the periodic table, and m and n are each independently Represents an integer of 0 to 2, and a, b, c and d each independently represent an integer of 2 to 2, and a + b ⁇ 1. ].
  • R 1 and R 2 are at least one type of proton selected from the group consisting of a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a squaric acid group, a phosphoric acid group, a boric acid group, and a key acid group. It is a donating group or a salt thereof.
  • the complex compound (I) described in [1] or [2] is a donating group or a salt thereof.
  • R 3 and R 4 are hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, alkoxyalkyl groups having 2 to 20 carbon atoms, or 6 to 6 carbon atoms.
  • R 3 and R 4 is an alkoxy group having a carbon number of 1-2 0 [1] ⁇ .
  • Ar represents an aromatic group
  • p represents an integer of 1 to 3.
  • N — are each independently _ S-, 101, _ S ⁇ _, 1 S ⁇ 2- , 1 PR 5- , -NR 5- , —S i (R 5 ) (R 6 )
  • R 5 and R 6 are each independently a hydrogen atom or The complex compound (I) according to any one of [1] to I11], which represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.
  • R 1 _ Y 1 — and R 2 — Y 2 — are groups represented by the formula (V), and R 3 and R 4 are hydrogen atoms, or have 1 to 2 carbon atoms.
  • a photosensitizing dye comprising the complex compound (I) according to any one of [1] to [18].
  • a photoelectric conversion device comprising a semiconductor fine particle layer adsorbed with the photosensitizing dye according to [19]. [2 1].
  • a photoelectrochemical battery including the photoelectric conversion device according to [20], a charge transfer layer, and a counter electrode.
  • FIG. 1 is a schematic sectional view of the photoelectrochemical cell of the present invention.
  • the complex compound (I) of the present invention is represented by the coordination represented by the above formula (II) and the above formula (III) on a metal atom such as Fe, Ru or Os, preferably Ru. Obtained by coordinating ligands. ⁇
  • the central atom is a metal atom such as Fe, Ru or Os, preferably Ru, and one of the ligands is a compound represented by the formula (II). It is a ligand, and another one of the ligands is a ligand represented by the formula ( ⁇ ).
  • R 1 and R 2 each independently represents a salt of a proton donating group or a proton donating group, and at least one of R ′ and R 2 is a proton donating group.
  • the proton-donating group is a group containing active hydrogen (hydrogen that reacts with a Grignard reagent to generate a hydrocarbon), and specifically includes a phenolic hydroxyl group, a carboxyl group, and a sulfonic acid.
  • active hydrogen hydrogen that reacts with a Grignard reagent to generate a hydrocarbon
  • a phenolic hydroxyl group a carboxyl group
  • a sulfonic acid a containing active hydrogen (hydrogen that reacts with a Grignard reagent to generate a hydrocarbon)
  • phenolic hydroxyl group a carboxyl group
  • a sulfonic acid specifically includes a phenolic hydroxyl group, a carboxyl group, and a sulfonic acid.
  • squaric acid group phosphoric acid group, boric acid group, kaylic acid group and the like.
  • phenolic hydroxyl groups, carboxyl groups, and sulfonic acid groups are preferred because they are
  • At least one of R 1 and R 2 may form a salt, and examples of the salt include organic base salts, such as tetraalkylammonium salt, imidazolium salt, pyridinium salt. Quaternary salts such as
  • Y 1 and Y 2 are groups containing an unsaturated hydrocarbon group (olefin hydrocarbon group or acetylene hydrocarbon group) and an aromatic ring, and a group that plays a role in the pyridine ring in formula (II). Preferably there is.
  • Y 1 and Y 2 are preferably the same.
  • Specific examples of Y 1 and Y 2 include a group represented by the formula (IV) or the formula (IV), and a group represented by the formula (IV) is preferable.
  • ⁇ CH CH + Ar- (IV)
  • Ar represents an aromatic group, and ⁇ represents an integer of 1 to 3. * In the following examples is preferably a bond.
  • the binding site of Ar may be bonded to R 1 or R 2 or to the pyridine ring.
  • the site is preferably bound to R 1 or R 2 .
  • R 1 or R 2 Represents a binding site between R 1 or R 2 and Ar.
  • Ar containing a heteroatom usually a site close to the heteroatom (a sulfur atom or an oxygen atom is preferred over a nitrogen atom).
  • R 1 or R 2 it is bonded to R 1 or R 2 at the site having a hetero atom on both sides.
  • Y 1 and Y 2 are preferably both groups represented by the formula (IV), and in particular, Ar contained in the group represented by the formula (IV) is R ′ or R 2 .
  • Preferred is a bonded group, and in particular, it is preferred that Ar is thiophene and p is 1.
  • a and b in the formula (II) each independently represent an integer of 0 to 2, and a + b ⁇ l. That is, the formula (II) contains at least one: donor donating group.
  • R 3 and R 4 each independently represents a hydrogen atom or a proton non-donating group.
  • the non-prodon-donating group is a group that does not contain active hydrogen (hydrogen that reacts with a Grignard sample to generate a hydrocarbon), and specifically includes an alkyl group; an alkoxy group; Alkylalkyl group; aryloxyl group; aryloxyalkyl group; alkylthio group; alkylthioalkyl group; arylthio group; arylalkylthio group; arylthioalkyl group; alkylsulfonyl group; An arylsulfonyl group '; an amino group substituted with an alkyl group or an aryl group, and the like.
  • the alkyl group has 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms.
  • Specific examples include methyl groups, ethyl groups, n-pro'pyr groups, n-butyl groups, ' ⁇ -hexyl groups, ⁇ -anthyl groups, ⁇ -octyl groups, and ⁇ -nonyl groups.
  • Examples include alkyl groups; branched alkyl groups such as i-propyl group, t-butyl group, and 2-ethyl-hexyl group; and alicyclic alkyl groups such as cyclopropyl group and cyclohexyl group. :
  • the aryl group has 6 to 20 carbon atoms, and specific examples include aromatic groups such as phenyl, naphthyl, and benzyl groups.
  • the carbon atom contained in the alkyl group or aryl group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom.
  • Examples of the amiso group disubstituted with an alkyl group or an aryl group include, for example, a straight chain such as a dimethylamino / group, a jetylamino group, a dibubutylamino group, a dimethylethylamino group, a methylhexylamino group, and a methyloctylamino group.
  • Dialkylamino groups containing a linear or branched alkyl group aromatic amino groups such as phenylamino group, naphthylamino group, benzylamino group; diaromatic amino groups such as diphenylamino group, dinaphthylamino group, dibenzylamino group, etc.
  • c and d each independently represents an integer of 0 to 2.
  • R 3 and R 4 include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 1 to An alkoxy group having 20 carbon atoms and an alkoxyalkyl group having 2 to 20 carbon atoms are preferable, and in particular, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms are preferable.
  • a and B each independently represent a group containing an element of Group 14, 15 or 16 of the periodic table.
  • R 5 and R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
  • alkyl group having 1 to 20 carbon atoms examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-pentyl group, an n-pentyl group, and an n_ Linear alkyl groups such as nonyl groups; i-propyl groups, t-butyl groups, branched alkyl groups such as 2 -ethyl-hexyl groups; alicyclic alkyl groups such as cyclopropyl groups and cyclohexyl groups Groups and the like.
  • aryl groups having 6 to 20 carbon atoms include aromatic groups such as phenyl, naphthyl, and benzyl groups.
  • a method for producing compound (II) for example, a 2-halogen-substituted pyridine derivative containing Y 1 and Y 2 is reacted with an appropriate phosphine ligand in the presence of a Ni catalyst or a Pd catalyst.
  • R 1 and R 2 are coupled with a protective group after introducing a protective group such as an ester (for example, methyl ester, ethyl ester, propyl ester, butyl ester), and then the protective group is removed.
  • a protective group such as an ester (for example, methyl ester, ethyl ester, propyl ester, butyl ester)
  • 2-Halogen-substituted pyridine derivatives containing Y 1 and Y 2 can be synthesized by reactions that insert olefins in the Wittig reaction, Suzuki reaction, etc.
  • Compound (III) is a 2-halogen-substituted pyridine derivative that does not contain Y 1 and Y 2 , and is one (B) n instead of (A) m —, and R instead of R 1 and R 2 except that the derivative is 3 and R 4 pro ton non-donating group is attached, it can be produced according to the reduction compound (II).
  • the complex compound (I) of the present invention has the above formula ( It is obtained by coordinating the ligand represented by II) and the ligand represented by the formula (III).
  • the central atom is a metal atom
  • one of the ligands is a ligand represented by the formula (II)
  • another one of the ligands is the above-mentioned It is a ligand represented by the formula (II I). .
  • the complex compound (I) may be coordinated with a ligand represented by the formula (II) and an auxiliary ligand other than the ligand represented by the formula (III).
  • [RuCl 2 (p-cymene)] 2 is replaced with non-prodon such as ⁇ , ⁇ -dimethylformamide. After dissolving the bidentate ligand and the tridentate ligand in a range of 40 to 180, mix with the salt that gives the auxiliary coordination defect if necessary. Examples of the method include recrystallization from the obtained reaction solution, purification by chromatography, and the like. '
  • Ru reagent divalent and trivalent Ru reagents are used, and specific examples include RuCI 3 and RuCI 2 (DMS0) 4 .
  • Specific examples of the complex compound (I) include compounds represented by the following formula and 'Table 3 (1-1) to (1-50), and compounds represented by the following formula and Table 4 (1- 51) to (1-100), and the compounds represented by the following formula and Table 5 (1-100) to (1-149). '
  • R 1 _ Y 1 — and R 2 — Y 2 — are groups represented by the formula (V), and R 3 and R 4 are hydrogen atoms, Carbon number 1-20 Coxy group, C2-C20 alkoxyalkyloxy group, carbon number?
  • Complex compounds in which B is —S—, which is a group consisting of 20 aryloxyalkyl groups of 20 to 20 (I)
  • the photosensitizing dye of the present invention is a dye containing the complex compound (I) of the present invention.
  • the dye may be one kind of complex compound (I) or a mixture of different kinds of complex compounds (I), and a different dye and complex compound (I) from the complex compound (I) It may be a mixture. '
  • Examples of the dye that may be mixed with the complex compound (I) include gold-metal complexes and organic dyes having absorption at a wavelength of about 300 to 700 nm.
  • metal complex examples include metal phthalocyanines such as copper phthalocyanine, titanyl fluorite, chlorophyll, hemin, and Japanese Patent Application Laid-Open No. 1_2 2 0 3 8 0
  • metal phthalocyanines such as copper phthalocyanine, titanyl fluorite, chlorophyll, hemin
  • examples include the ruthenium, osmium, iron, and zinc complexes described in No. 3.
  • ruthenium complexes include bis (isothiocyanate) bis (2,2'-bibilidyl-4,4'-dicarboxyl) -ruthenium (II) bis-tetrabutylammonium, bis (isothione). Oscrite) bis (2; 2'-bibilidyl-4,4'-dicarboxylate) -ruthenium (11), ..
  • organic dyes examples include metal-free phthalocyanine, cyanine dyes, merocyanine dyes, xanthene dyes, triphenylmethane dyes, indoline organic dyes, squalium dyes, and the like.
  • cyanine dyes include NK 1 19 4 and NK 3 4 2 2 (both manufactured by Nippon Sensitive Dye Research Laboratories).
  • merocyanine dyes include NK 2 4 2 6 and 'NK 2 5 0 1 (both manufactured by Nippon Sensitive Dye Research Laboratories).
  • xanthene dyes examples include uranin, eosin, rose bengal, rhodamine B, dibromofluorescein and the like.
  • triphenylmethane dye examples include malachite green and Chris Yuba Leo.
  • Examples of coumarin dyes include compounds containing the following structural sites such as NKX-2 6 7 7 (manufactured by Hayashibara Biochemical Laboratories).
  • organic dyes such as indoline compounds include compounds containing the structural sites shown below.
  • squary dyes include compounds containing the structural moieties shown below.
  • the photoelectric conversion device of the present invention is a device comprising a semiconductor fine particle layer adsorbed with a photosensitizing dye containing the complex compound (I) of the present invention and a conductive substrate, and the adsorbed photosensitizing dye is 70.degree. Light energy with a long wavelength of 0 nm or more can also be absorbed.
  • the photoelectric conversion element is used for, for example, a photosensor sensitive to a wavelength of 700 nm or more, which is an absorption wavelength of a photosensitizing dye containing the complex compound (I) of the present invention, and a photoelectrochemical cell described later. be able to.
  • the primary particle size of the semiconductor fine particles used in the photoelectric conversion element of the present invention is usually about 1 to 500 nm, preferably about 5 to 300 nm.
  • semiconductor particles having different primary particle sizes may be mixed. Tubes and hollow fine particles may be used.
  • semiconductor fine particles include titanium oxide, tin oxide, zinc oxide, iron oxide, tungsten oxide, zirconium oxide, hafnium oxide, strontium oxide, indium oxide, cerium oxide, yttrium oxide, lanthanum oxide, vanadium oxide, niobium oxide. Tantalum oxide, gallium oxide, nickel oxide, strontium titanate, barium titanate, potassium niobate, sodium tantalate Metal oxides such as lithium;
  • Metal halides such as silver iodide, silver bromide, sodium iodide, copper bromide;
  • Gold scrap sulfides such as zinc sulfide, titanium sulfide, indium sulfide, bismuth sulfide, gadmium sulfide, zirconium sulfide, tantalum sulfide, molybdenum sulfide, silver sulfide, copper sulfide, tin sulfide, tungsten sulfide, antimony sulfide;
  • Metal selenides such as cadmium selenide, zirconium selenide, zinc selenide, titanium selenide, indium selenide, tungsten selenide, molybdenum selenide, bismuth selenide, lead selenide;
  • Metal tellurides such as cadmium telluride, tungsten telluride, molybdenum telluride, zinc telluride, bismuth telluride;
  • Metal phosphides such as zinc phosphide, gallium phosphide, phosphide cadmium, cadmium phosphide;
  • Examples include gallium arsenide, copper-indium-selenide, copper-indium-sulfide, silicon, and germanium.
  • titanium oxide canonized tin, zinc oxide, iron oxide, tungsten oxide, zirconium oxide, hafnium oxide, strontium oxide, indium oxide, cerium oxide, yttrium oxide, lanthanum oxide, vanadium oxide, oxide
  • Metal oxides such as niobium, tantalum oxide, gallium oxide, nickel oxide, strontium titanate, barium titanate, potassium niobate, sodium tantalate, zinc oxide, tin oxide, tin oxide, and titanium oxide are relatively inexpensive. Titanium oxide is preferred for ⁇ because it is easy to obtain and is easy to be dyed. ':
  • a conductive substance itself or a substrate in which a conductive substance is superimposed can be used as the conductive substrate (8 and 9 in FIG. 1) used in the photoelectric conversion element of the present invention.
  • Examples of conductive materials include platinum, gold, silver, copper, aluminum, rhodium, indium, titanium, palladium, iron, and other metals, alloys of these metals, or indium mutin complex oxides, and tin oxide doped with fluorine.
  • Conductive metal oxides such as carbon, conductive polymers such as carbon, polyethylenedioxythiophene (PEDOT), polyaniline, and the like.
  • the conductive polymer may be doped with para-toluenesulfonic acid or the like.
  • the conductive layer (2, 6 in FIG. 1) should have a lower resistance, and preferably has a high transmittance (on the longer wavelength side than 3550 ⁇ m, the transmittance is 80% or more).
  • the conductive substrate (8 and 9 in FIG. 1) is preferably a glass or plastic coated with a conductive metal oxide.
  • conductive glass in which conductive layers made of tin dioxide doped with fluorine are laminated is particularly preferable.
  • plastic substrates cyclic polyolefins (COP) such as Arton (registered trademark of JSR), Zeonor (registered trademark of Nippon Zeon), Abel (registered trademark of Mitsui Chemicals), Topas (registered trademark of Ticona), etc. ), Polyethylene terephthalate (PET), Polyethylene naphthalate (PEN), Polyphenylene Solefide (PPS), Polycarbonate (PC), Polypropylene.
  • COP cyclic polyolefins
  • Pp Polyimide
  • TAC Triacetyl cellulose
  • SPS Syndiotactic polystyrene
  • PAR Polyarylate
  • PES Polyethersulfone
  • PE I Polyether imide
  • PSF polysulfone
  • PA polyamide
  • conductive PET on which a conductive layer made of indium-tin composite oxide is deposited is particularly preferable because of its low resistance, good permeability, and low availability.
  • Examples of the method of precipitation a method of producing a slurry by applying a slurry of semiconductor fine particles on a conductive substrate, followed by drying, curing or firing.
  • a method of applying a slurry of semiconductor fine particles onto a conductive substrate! For example, doctor blade, squeegee, small spin coat, dip coating and screen printing. .
  • the average particle size in the dispersed state of the semiconductor fine particles in the slurry is
  • the dispersion medium for dispersing the slurry is not limited as long as it can disperse the semiconductor fine particles, such as water, alcohol solvents such as ethanol, isopropanol, t-butanol and terbinol; ketone ketones of aceton ⁇ , etc.
  • Organic solvents are mentioned. These water and organic solvent may be a mixture.
  • the dispersion contains a polymer such as polyethylene lenglycol; a surfactant such as Triton-X; an organic acid or inorganic acid such as acetic acid, formic acid, nitric acid or hydrochloric acid; and a chelating agent such as acetylylacetone. Also good.
  • the conductive substrate coated with the slurry is fired, but the firing temperature is lower than the melting point (or softening point) of the base material such as a thermoplastic resin.
  • the upper limit of the firing temperature is 900 ° C. It is below 600 ° C.
  • the firing time is usually within 10 hours.
  • the thickness of the semiconductor fine particle layer on the conductive substrate is usually 1 to 200 ⁇ , preferably 5 to 50 m.
  • a hydrothermal method in which a porous semiconductor fine particle layer is formed by performing a hydrothermal treatment (a dye-sensitized photoelectrochemical cell for practical application, 2 (Hideki Kajiura) 63-65, published by NTS (2 003)), Electrodeposition method (T. Miyasaka et al., Chem.
  • the surface of the semiconductor fine particle layer may be subjected to chemical plating using a titanium tetrachloride aqueous solution or electrochemical plating using a titanium trichloride aqueous solution. This increases the surface area of the semiconductor fine particles, increases the purity in the vicinity of the semiconductor fine particles, masks impurities such as iron existing on the surface of the semiconductor fine particles, or improves the connectivity and bonding of the semiconductor fine particles. can do.
  • the semiconductor fine particles preferably have a large surface area so that many photoelectric conversion element dyes can be adsorbed.
  • the surface area in a state where the semiconductor fine particle layer is applied on the substrate is preferably 10 times or more, more preferably 100 times or more the projected area. This upper limit is usually about 100000 times.
  • the semiconductor fine particle layer is not limited to a single fine particle layer, and a plurality of layers having different particle diameters may be stacked.
  • Examples of the method for adsorbing the photosensitizing dye of the present invention to the semiconductor fine particles include a method in which the finely dried semiconductor fine particles are immersed in the solution of the photosensitizing dye of the present invention for about 1 minute to 24 hours. .
  • Adsorption of the photosensitizing dye may be performed at room temperature or under heating and reflux. Adsorption of the photosensitizing dye may be performed before or after the application of the semiconductor fine particles. Alternatively, the semiconductor fine particles and the photosensitizing dye may be applied and adsorbed at the same time.
  • the photosensitizing dye adsorption is preferably performed after the heat treatment, and a method of quickly adsorbing the photosensitizing dye after the heat treatment and before water is adsorbed on the surface of the fine particle layer is particularly preferable.
  • the photosensitizing dye to be adsorbed may be one kind or a mixture of several kinds.
  • a photosensitizing dye it is preferable to select a photosensitizing dye to be mixed so that the wavelength range of photoelectric conversion of irradiation light such as sunlight is as wide as possible.
  • the adsorption amount of the light-sensitive dye to the semiconductor fine particles is preferably 0.1 to 1 millimole per 1 g of the semiconductor fine particles. With such a dye amount, a sufficient sensitizing effect on the semiconductor fine particles can be obtained, and the reduction of the sensitizing effect due to floating of the photosensitizing dye not attached to the semiconductor fine particles tends to be suppressed. To preferred.
  • a colorless compound may be co-adsorbed for the purpose of suppressing interactions such as association and aggregation between photosensitizing dyes.
  • the hydrophobic compound to be co-adsorbed include sterol compounds having a carboxy group (for example, kenodeoxycholic acid).
  • the surface of the semiconductor fine particles may be treated with amines after adsorbing the photosensitizing dye.
  • Preferable amines include pyridine, 4_tert-butylpyridine, polyvinyl pyridine and the like. When these are liquids, they may be used as they are, or when they are solids, they may be dissolved in an organic solvent.
  • the photoelectrochemical cell of the present invention includes a photoelectric conversion element, a charge transfer layer, and a counter electrode, and can convert light into electricity.
  • a photoelectrochemical cell usually, a photoelectric conversion element, a charge transfer layer, and a counter electrode are sequentially stacked, and the conductive substrate of the photoelectric conversion element and the counter electrode are connected to move the electric charge, thereby generating power.
  • photoelectrochemical cells include, for example, a photoelectrochemical cell comprising a plurality of stacked portions composed of photoelectric conversion elements and charge transfer layers and one counter electrode, a plurality of photoelectric conversion elements, one charge transfer layer, and one Examples thereof include a photoelectrochemical cell in which a counter electrode is laminated.
  • Photoelectrochemical cells are roughly classified into wet photoelectrochemical cells and dry photoelectrochemical cells.
  • the wet photoelectrochemical cell is a layer in which the charge transfer layer included is composed of an electrolytic solution, and the charge transfer layer is usually filled with an electrolytic solution between the photoelectric conversion element and the counter electrode.
  • Examples of the dry photoelectrochemical cell include a battery in which the charge transfer layer between the photoelectric conversion element and the counter electrode is a solid hole transport material.
  • the conductive substrate 8 includes a substrate 1 and a conductive layer 2 in order from the top.
  • the counter electrode 9 is composed of a substrate 7 and a conductive layer 6 in order from the bottom.
  • examples of the electrolyte used for the electrolyte contained in the charge transfer include a combination of I 2 and various iodides, a combination of Br 2 and various bromides, Ferrocyanate-ferricyanate metal complex, combination of pheucene-felicinium ion metal complex, argyl thiol-alkyl disulfide thio compound combination, alkyl viologen and its Examples include combinations of reductants, and combinations of polyhydroxybenzenes and their oxidants. '.
  • metal iodides such as Li I, Na I, KI,. C s I and C a I 2 ; I —propyl-3-methylimidazolium iodium 1, iodine salt of tetravalent imidazolium compound such as 1-propyl-1,2,3-dimethyl imidazolium idide; iodine salt of tetravalent pyridinium compound; iodine salt of tetraalkylammonium compound Be
  • the bromide may be combined with B r 2, for example, L i B r, N a B r, KB r, C s B r and C a B r 2, etc. of the metal bromide; tetraalkyl ammonium Niu Mubu Roma I Doyapiri Examples include bromine salts of tetravalent ammonium compounds such as zinc bromide.
  • Alkyl viologens include, for example, methyl viologen chloride, hexyl viologen bromide, benzyl viologen tetrafluoroborate and the like.
  • Polyhydroxybenzenes include, for example, hydride quinone. Nyafthide mouth quinone.
  • At least one iodine selected from the group consisting of metal iodides, tetravalent imidazolium compound iodine salts, tetravalent pyridinium compound iodine salts, and tetraalkylammonium compound iodine salts.
  • the combination of the compound and I 2 is preferred.
  • organic solvent used in the above electrolyte examples include nitrile solvents such as acetonitrile, methoxyacetyl diaryl and propionitrile; carbonate solvents such as ethylene carbonate propylene carbonate; 1 monomethyl 1-propylimidazole 1-methyl-3-methyl imidazolium dye; 1-ethyl 3-methylimidazolium bismuth (trifluoromethane sulfonic acid) ionic liquid; aptilolactone, etc. Lactone solvents; amide solvents such as N, N-dimethylformamide and the like. These solvents include polyacrylonitrile, polyvinylidene fluoride, and poly-4-vinyl.
  • nitrile solvents such as acetonitrile, methoxyacetyl diaryl and propionitrile
  • carbonate solvents such as ethylene carbonate propylene carbonate
  • 1 monomethyl 1-propylimidazole 1-methyl-3-methyl imidazolium dye 1-ethyl 3-
  • the solid hole transport material used for the charge transfer layer is a p-type inorganic semiconductor containing monovalent copper such as Cu I or Cu SCN; Aromatic, amines as shown by Me tal, 89, 2 1 5- (1 997) and Nature, 395, 583 (1 998); polythiophene and its derivatives; polypyrrole and its derivatives; 'polyaniline and its Derivatives; poly (p-phenylene) and its conductors; conductive polymers such as poly (p-phenylene vinylene) and its derivatives.
  • the counter electrode constituting the photoelectrochemical cell of the present invention is a conductive electrode, and a substrate similar to the conductive substrate may be used in order to maintain strength and improve hermeticity. ',
  • the conductive substrate and the counter electrode Since the light reaches the semiconductor fine particle layer on which the dye for the photoelectric conversion element is adsorbed, at least one of the conductive substrate and the counter electrode is usually substantially transparent.
  • the conductive substrate having the semiconductor fine particle layer is transparent and the irradiation light is incident from the conductive substrate side.
  • the counter electrode 9 has a property of reflecting light.
  • the counter electrode 9 of the photoelectrochemical cell for example, glass or plastic on which metal, carbon, conductive oxide or the like is deposited can be used.
  • the conductive layer can be formed by a method such as vapor deposition or sputtering so as to have a thickness of 1 mm or less, preferably in the range of 5 nm to 100 m.
  • sealing may be performed using a sealing material.
  • sealing material examples include: ionomer resin such as Himiran (Mitsui DuPont Polychemical); glass frit; hot melt adhesive such as SX 1 1700 (manufactured by Solaroni X); Amo si 14 (S o Adhesives such as 1 aronix); B ⁇ L (DuPont) can be used.
  • ionomer resin such as Himiran (Mitsui DuPont Polychemical)
  • glass frit hot melt adhesive such as SX 1 1700 (manufactured by Solaroni X); Amo si 14 (S o Adhesives such as 1 aronix); B ⁇ L (DuPont)
  • SX 1 1700 manufactured by Solaroni X
  • Amo si 14 S o Adhesives such as 1 aronix
  • B ⁇ L DuPont
  • T i -N anoxide T / SP a titanium oxide dispersion, on the conductive surface of a conductive glass with a tin oxide film doped with fluorine (made by Nippon Sheet Glass, 10 ⁇ / port).
  • fluorine made by Nippon Sheet Glass, 10 ⁇ / port.
  • an electrolytic solution (solvent is acetonitrile); the concentration of iodine in the solvent is 0.05 mol Z-litre, also lithium iodide concentration is 0.1 mol-litre, also 4—t-butylpyridine concentration is 0.5 mol-northol, also 1-propyl—2, 3— Dimethyl imidazolium iodide concentration was 0.6 mol / liter).
  • a platinum-deposited glass as a counter electrode is stacked, and a conductive substrate, a semiconductor fine particle layer adsorbing a photosensitizing dye, and a counter electrode of the conductive substrate are stacked, and the conductive substrate and the counter electrode are stacked.
  • a photoelectrochemical cell in which the electrolyte was impregnated was obtained.
  • IPCE incident photon-to-current efficiency measuring device (manufactured by Spectrometer).
  • Table 6 shows I P C E of the photoelectric conversion element obtained in Example 1.
  • Production Example 2 Production Example of Compound (1-4)>
  • Compound (1-4) was obtained in the same manner as in Production Example 1, except that compound (III-9) was used instead of compound ( ⁇ -3).
  • the obtained solid was confirmed by ESI-MS to be the target compound (1-4, molecular weight 926).
  • the obtained solid was confirmed by ESI-MS to be the target compound (1-19, molecular weight 1045). .,.
  • a photoelectrochemical cell was obtained in the same manner as in Example 1 except that the compound (1-19) was used in place of the compound (1-2) as the photosensitizing dye.
  • I P C E was measured in the same manner as in Example 1. The results are summarized in Table 6.
  • the obtained solid was confirmed to be the target compound (1-17, molecular weight 894) by ESI-MS. confirmed.
  • Example 5 A photoelectrochemical cell was obtained in the same manner as in Example 1 except that the compound (1-17) was used instead of the compound (1-2) as the photosensitizing dye. Next, I P C E was measured in the same manner as in Example 1. The results are summarized in Table 6.
  • Example 1 As a photosensitizing dye, a compound (1-4 ′) in which one of the carboxyl groups forms a tetra-n-butyl ammonium salt is used instead of the compound (1-4).
  • Example A photoelectrochemical cell was obtained in the same manner as ⁇ .
  • I PCE was measured in the same manner as in Example 1. The results are summarized in Table 6. Comparative Example 1
  • the complex compound (I) of the present invention is excellent in photoelectric conversion not only in the visible light but also in the near-infrared region, and is suitably used as a photosensitizing dye.
  • the photoelectric conversion element containing the compound is excellent in photoelectric conversion efficiency, it can be used for a solar cell by sunlight, a photoelectrochemical cell by artificial light in a tunnel or indoor.
  • the photoelectric conversion element can be used as an optical sensor because current flows when irradiated with light.

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  • Crystallography & Structural Chemistry (AREA)
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  • Photovoltaic Devices (AREA)

Abstract

Cette invention concerne un composé complexe (I) obtenu par coordination d’un premier ligand (II) et d’un second ligand (III) à un atome de métal. Cette invention concerne également un colorant photosensibilisant qui contient le composé complexe (I), un convertisseur photoélectrique comprenant une couche de fines particules semi-conductrices sur laquelle le colorant est adsorbé, et une cellule photoélectrochimique comprenant le convertisseur photoélectrique, une couche de transport de charge et une électrode auxiliaire.
PCT/JP2006/319096 2005-09-22 2006-09-20 Composé, convertisseur photoélectrique et cellule photoélectrochimique WO2007034976A1 (fr)

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DE112006002512T DE112006002512T5 (de) 2005-09-22 2006-09-20 Verbindung, photoelektrischer Wandler und photoelektrochemische Zelle
US12/067,195 US8124777B2 (en) 2005-09-22 2006-09-20 Compound, photoelectric converter and photoelectrochemical cell

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008075756A1 (fr) * 2006-12-18 2008-06-26 Sumitomo Chemical Company, Limited Composé, convertisseur photoélectrique et cellule photoélectrochimique
US20120024338A1 (en) * 2010-07-21 2012-02-02 Addepalli Pratima V Back Contact Formation

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004296170A (ja) * 2003-03-26 2004-10-21 Mitsui Chemicals Inc 光電変換素子用材料、光電変換素子ならびにルテニウム錯体化合物

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CH674596A5 (fr) 1988-02-12 1990-06-15 Sulzer Ag
GB9217811D0 (en) 1992-08-21 1992-10-07 Graetzel Michael Organic compounds

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004296170A (ja) * 2003-03-26 2004-10-21 Mitsui Chemicals Inc 光電変換素子用材料、光電変換素子ならびにルテニウム錯体化合物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008075756A1 (fr) * 2006-12-18 2008-06-26 Sumitomo Chemical Company, Limited Composé, convertisseur photoélectrique et cellule photoélectrochimique
US20120024338A1 (en) * 2010-07-21 2012-02-02 Addepalli Pratima V Back Contact Formation

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