WO2012060587A2 - Novel ruthenium-based dye and preparation method thereof - Google Patents

Novel ruthenium-based dye and preparation method thereof Download PDF

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WO2012060587A2
WO2012060587A2 PCT/KR2011/008175 KR2011008175W WO2012060587A2 WO 2012060587 A2 WO2012060587 A2 WO 2012060587A2 KR 2011008175 W KR2011008175 W KR 2011008175W WO 2012060587 A2 WO2012060587 A2 WO 2012060587A2
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formula
dye
compound
unsubstituted
group
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PCT/KR2011/008175
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French (fr)
Korean (ko)
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WO2012060587A3 (en
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이종찬
안현철
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주식회사 동진쎄미켐
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Priority to CN2011800526100A priority Critical patent/CN103189452A/en
Priority claimed from KR1020110111744A external-priority patent/KR101940491B1/en
Publication of WO2012060587A2 publication Critical patent/WO2012060587A2/en
Publication of WO2012060587A3 publication Critical patent/WO2012060587A3/en

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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 System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System 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
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • 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
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C09B23/0033—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being bound through a sulfur atom
    • 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
    • C09B23/0066—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of a carbocyclic ring,(e.g. benzene, naphtalene, cyclohexene, cyclobutenene-quadratic acid)
    • 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
    • C09B23/0075—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of an heterocyclic ring
    • 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
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
    • C09B23/083—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines five >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
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
    • C09B23/086—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines more than five >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
    • 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
    • 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 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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a novel ruthenium-based dye used as a dye in a dye-sensitized solar cell and a manufacturing method thereof.
  • Dye-sensitized solar cells have the potential to replace conventional amorphous silicon solar cells because their manufacturing cost is significantly lower than conventional silicon-based solar cells. Unlike silicon solar cells, dye-sensitized solar cells absorb visible light It is a photoelectrochemical solar cell whose main constituent material is a dye molecule capable of generating a hole pair and a transition metal oxide that transfers generated electrons.
  • Typical dyes used in dye-sensitized solar cells include the following compounds.
  • the present invention shows a remarkably improved photoelectric conversion efficiency than the conventional dye, enhances the bonding force with the oxide semiconductor fine particles, JSC (short circuit photocurrent density) and the molar extinction coefficient is excellent It is an object of the present invention to provide a dye and a method for producing the same that can greatly improve the efficiency of a solar cell.
  • the present invention exhibits a remarkably improved photoelectric conversion efficiency, including the dye, the bonding strength with the oxide semiconductor fine particles, the dye-sensitized photoelectric conversion element and excellent efficiency of the short circuit photocurrent density (Jsc) and the molar extinction coefficient is significantly improved It is an object to provide a solar cell.
  • the present invention provides a dye represented by the following formula (1).
  • Me is Ru or Os, and each of the a1 rings may not independently have a substituent or may have one or more substituents, and examples of the substituent include a halogen atom, an amide group, a cyano group, a hydroxyl group, a nitro group, and an acyl group.
  • substituents include a halogen atom, an amide group, a cyano group, a hydroxyl group, a nitro group, and an acyl group.
  • Y is hydrogen, Na, or TBA (tert-butyl alcohol)
  • X 1 , X 2 are each independently methyl or a compound represented by the formula (2), at least one of X 1 and X 2 is a compound represented by the formula (2),
  • A is , , And At least one selected from the group consisting of wherein X is each independently selected from the group consisting of O, S, Se, Si and NR 5 , R 1 to R 4 are each independently hydrogen, substituted or unsubstituted C 1-12 alkyl, substituted or unsubstituted C 6-30 aryl and substituted or unsubstituted C 6-20 heteroaryl, or may be linked to each other to form a ring, R 5 is hydrogen or Substituted or unsubstituted C 1-30 alkyl, n is an integer from 1 to 10,
  • B is a compound represented by the following formula (3) or a compound represented by the following formula (4),
  • Ar 1 and Ar 3 are each independently a substituted or unsubstituted C 6-50 aryl, substituted or unsubstituted selected from the consisting of unsubstituted C 6-20 heteroaryl group, or a ring are connected to each other It may form, * is a bonding moiety, in Formula 4 R 6 and R 7 are each independently substituted or unsubstituted C 1-30 alkyl, * is a bonding moiety.
  • the present invention provides a method for preparing a dye represented by the formula (1) characterized in that the compound of formula (5) is sequentially reacted with the compound of formula (6), formula (7) and formula (8).
  • X 1 , X 2 , and a1 are as defined above.
  • the present invention provides a dye-sensitized photoelectric conversion device comprising an oxide semiconductor fine particles supported by a compound represented by the formula (1).
  • the present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device.
  • novel ruthenium-based dyes of the present invention exhibit significantly improved photovoltaic conversion efficiency than conventional dyes, enhance bonding with oxide semiconductor fine particles, and have excellent short circuit photocurrent density (Jsc) and molar extinction coefficient to improve solar cell efficiency. It can greatly improve.
  • Jsc short-circuit photocurrent density
  • Jsc short-circuit photocurrent density
  • the inventors of the present invention have excellent durability by supporting the compound represented by Chemical Formula 1 on oxide semiconductor fine particles by strongly binding to oxide semiconductor fine particles, and having excellent durability, photoelectric conversion efficiency, short circuit photocurrent density (Jsc) and molar extinction coefficient. It was confirmed that the high efficiency than the existing dye-sensitized solar cell is high and completed the present invention.
  • the dye of the present invention is characterized by represented by the following formula (1).
  • Me is Ru or Os, and each of the a1 rings may not independently have a substituent or may have one or more substituents, and examples of the substituent include a halogen atom, an amide group, a cyano group, a hydroxyl group, a nitro group, and an acyl group.
  • substituents include a halogen atom, an amide group, a cyano group, a hydroxyl group, a nitro group, and an acyl group.
  • Y is hydrogen, Na, or TBA (tert-butyl alcohol)
  • X 1 , X 2 are each independently methyl or a compound represented by the formula (2), at least one of X 1 and X 2 is a compound represented by the formula (2),
  • A is , , And At least one selected from the group consisting of wherein X is each independently selected from the group consisting of O, S, Se, Si and NR 5 , R 1 to R 4 are each independently hydrogen, substituted or unsubstituted C 1-12 alkyl, substituted or unsubstituted C 6-30 aryl and substituted or unsubstituted C 6-20 heteroaryl, or may be linked to each other to form a ring, R 5 is hydrogen or Substituted or unsubstituted C 1-30 alkyl, n is an integer from 1 to 10,
  • B is a compound represented by the following formula (3) or a compound represented by the following formula (4),
  • Ar 1 and Ar 3 are each independently a substituted or unsubstituted C 6-50 aryl, substituted or unsubstituted selected from the consisting of unsubstituted C 6-20 heteroaryl group, or a ring are connected to each other It may be formed, * is a bonding moiety, in Formula 4 R 6 and R 7 are each independently substituted or unsubstituted C 1-30 alkyl, * is a bonding moiety, preferably R 6 and R 7 is a C 5-10 alkyl, including C 5-10 alkyl or sulfur.
  • the dye represented by Chemical Formula 1 may be one of the compounds represented by the following Chemical Formulas 1-1 to 1-48.
  • the present invention provides a method for preparing a dye represented by the formula (1) characterized in that the compound of formula (5) is sequentially reacted with the compound of formula (6), formula (7) and formula (8).
  • X 1 , X 2 , and a1 are as defined above.
  • the compounds used as starting materials for the preparation of the dye of Formula 1 may be prepared or purchased in a conventional manner.
  • the present invention provides a dye-sensitized photoelectric conversion device, the dye-sensitized photoelectric conversion device is characterized in that the dye represented by the formula (1) on the oxide semiconductor fine particles.
  • the present invention is a dye-sensitized photoelectric conversion device in addition to using the dye represented by the formula (1) can be applied to the method of manufacturing a dye-sensitized photoelectric conversion device for a solar cell using a conventional dye, of course, preferably the present invention
  • the dye-sensitized photoelectric conversion device may be prepared by fabricating a thin film of an oxide semiconductor on a substrate using oxide semiconductor fine particles, and then supporting the dye of the present invention on the thin film.
  • the surface is electroconductive as a board
  • conductive metal oxides such as tin oxide coated with indium, fluorine, and antimony on a surface of glass or a transparent polymer material such as polyethylene terephthalate or polyethersulfone, or a metal thin film such as steel, silver, or gold may be used.
  • the formed thing can be used.
  • the conductivity is usually preferably 1000 ⁇ or less, particularly preferably 100 ⁇ or less.
  • a metal oxide is preferable.
  • oxides such as titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum and vanadium can be used. Of these, oxides such as titanium, tin, zinc, niobium and indium are preferable, and among these, titanium oxide, zinc oxide, and tin oxide are more preferable, and titanium oxide is most preferable.
  • the oxide semiconductor may be used alone, or may be mixed or coated on the surface of the semiconductor.
  • the particle size of the fine particles of the oxide semiconductor is preferably 1-500 nm, more preferably 1-100 nm as the average particle diameter.
  • the fine particles of the oxide semiconductor may be mixed with a large particle size and a small particle size, or may be used as a multilayer.
  • the oxide semiconductor thin film is a method of forming oxide semiconductor fine particles into a thin film directly on a substrate by spray spraying, a method of electrically depositing a semiconductor fine particle thin film using a substrate as an electrode, a slurry of semiconductor fine particles or semiconductor fine particles such as a semiconductor alkoxide.
  • the paste containing the fine particles obtained by hydrolyzing the precursor onto the substrate it can be produced by a method of drying, curing or baking, and a method of applying the paste onto the substrate is preferable.
  • the slurry can be obtained by dispersing secondary agglomerated oxide semiconductor fine particles in a dispersion medium so as to have an average primary particle size of 1-200 nm.
  • the dispersion medium for dispersing the slurry can be used without particular limitation so long as it can disperse the semiconductor fine particles, and alcohols such as water and ethanol, ketones such as acetone and acetylacetone, or hydrocarbons such as hexane can be used, and these can be mixed and used. Among them, it is preferable to use water among them in order to reduce the viscosity change of the slurry. Moreover, a dispersion stabilizer can be used for the purpose of stabilizing the dispersion state of oxide semiconductor microparticles
  • acids such as acetic acid, hydrochloric acid, nitric acid, or acetylacetone, acrylic acid, polyethyleneglycol, polyvinyl alcohol, etc. are mentioned, for example.
  • the substrate coated with the slurry can be fired, and its firing temperature is at least 100 ° C, preferably at least 200 ° C, and the upper limit is generally below the melting point (softening point) of the substrate, and usually the upper limit is 900 ° C, preferably 600. It is below °C.
  • the firing time is not particularly limited, but is usually within 4 hours.
  • the thickness of the thin film on the substrate is preferably 1-200 ⁇ m, preferably 1-50 ⁇ m.
  • some thin layers of the oxide semiconductor fine particles are welded, but such welding is not particularly troubled for the present invention.
  • the oxide semiconductor thin film may be subjected to secondary treatment.
  • the performance of a semiconductor thin film may be improved by directly depositing a thin film for each substrate and drying or refiring it in a solution such as an alkoxide, chloride, nitride or sulfide of the same metal as the semiconductor.
  • the metal alkoxide include titanium ethoxide, titanium isopropoxide, titanium t-butoxide, n-dibutyl-diacetyl tin and the like, and an alcohol solution thereof can be used.
  • a chloride titanium tetrachloride, tin tetrachloride, zinc chloride, etc. are mentioned, for example, The aqueous solution can be used.
  • the oxide semiconductor thin film thus obtained is composed of fine particles of an oxide semiconductor.
  • the method of supporting the dye on the oxide semiconductor fine particles formed in the thin film phase in the present invention is not particularly limited, as a specific example by dispersing a solution obtained by dissolving the dye represented by the formula (1) in a solvent capable of dissolving, or dye
  • substrate with which the said oxide semiconductor thin film was provided in the obtained dispersion liquid is mentioned.
  • the concentration in the solution or dispersion can be appropriately determined by the dye.
  • the deposition time is usually from room temperature to the boiling point of the solvent, and the deposition time is about 1 minute to 48 hours.
  • the solvent that can be used to dissolve the dye include methanol, ethanol, acetonitrile, dimethyl sulfoxide, dimethylformamide, acetone, t-butanol and the like.
  • the dye concentration of the solution is usually preferably 1 ⁇ 10 ⁇ 6 M ⁇ 1 M, preferably 1 ⁇ 10 ⁇ 5 M ⁇ 1 ⁇ 10 ⁇ 1 M.
  • the dye represented by the formula (1) supported by the present invention may be one kind or may be mixed in several kinds.
  • only the dye of this invention can be used and other dye and metal complex dye can be mixed.
  • metal complex dyes that can be mixed are not particularly limited, but MK Nazeeruddin, A.Kay, I.Rodicio, R.Humphry-Baker, E.Muller, P.Liska, N.Vlachopoulos, M.Gratzel, J. Am . Chem. Soc., Vol. 115, pp. 6382 (1993).
  • Ruthenium complexes, quaternary salts thereof, phthalocyanine, porphyrin, and the like are preferred, and organic dyes used for mixing are metal-free phthalocyanine, porphyrin, cyanine, merocyanine, oxo.
  • Methine dyes such as knol, triphenylmethane and acrylic acid dyes described in WO2002 / 011213, and dyes such as xanthene, azo, anthraquinone and perylene.
  • the dyes may be adsorbed onto the semiconductor thin film in sequence, or may be mixed and dissolved and adsorbed.
  • the dye when the dye is supported on the thin film of the oxide semiconductor fine particles in the present invention, it is preferable to support the dye in the presence of the inclusion compound in order to prevent the bonding of the dyes.
  • the inclusion compound include deoxycholic acid, dehydrodeoxycholic acid, kenodeoxycholic acid, cholic acid methyl ester, and cholic acid such as sodium cholate, steroid-based compounds such as polyethylene oxide and cholic acid, crown ether, cyclodextrin, and calix arene, Polyethylene oxide and the like can be used.
  • the semiconductor electrode surface can be treated with an amine compound such as 4-t-butyl pyridine or a compound having an acidic group such as acetic acid or propionic acid.
  • an amine compound such as 4-t-butyl pyridine
  • a compound having an acidic group such as acetic acid or propionic acid.
  • a treatment method for example, a method of dipping a substrate provided with a thin film of semiconductor fine particles in which a dye is supported in an amine ethanol solution may be used.
  • the present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device, using a dye-sensitized photoelectric conversion device using the oxide semiconductor fine particles carrying the dye represented by the formula (1)
  • conventional methods of manufacturing a solar cell using a conventional photoelectric conversion device may be applied, and, as a specific example, a photoelectric conversion device electrode (cathode) and a counter electrode in which the dye represented by Formula 1 is supported on the oxide semiconductor fine particles. (Anode), a redox electrolyte, a hole transport material, a p-type semiconductor, or the like.
  • the method includes coating a titanium oxide paste on a conductive transparent substrate, baking a substrate coated with a paste to form a titanium oxide thin film, and a titanium oxide thin film. Impregnating the formed substrate into a mixed solution in which the dye represented by Chemical Formula 1 is dissolved to form a titanium oxide film electrode on which the dye is adsorbed, and providing a second glass substrate having a counter electrode formed thereon, and a second glass.
  • thermoplastic polymer film between the counter electrode and the titanium oxide film electrode on which the dye is adsorbed, and performing a heat compression process to perform the counter electrode and the titanium oxide film. Bonding the electrodes to the thermoplastic polymer film between the counter electrode and the titanium oxide film electrode through the holes; It is good to prepare through the step of injecting an electrolyte and the step of sealing the thermoplastic polymer.
  • Examples of the forms of the redox electrolyte, the hole transport material, the p-type semiconductor, and the like include liquids, coagulated bodies (gels and gels), solids, and the like.
  • As liquids, redox electrolytes, dissolved salts, hole transport materials, p-type semiconductors, and the like are dissolved in a solvent, and room temperature dissolved salts, etc., are solid polymers (gels and gels). What was contained in etc. can be mentioned, respectively.
  • a redox electrolyte, a dissolution salt, a hole transport material, a p-type semiconductor, etc. can be used.
  • the hole transport material examples include amine-induced amines, conductive polymers such as polyacetylene, polyaniline, and polythiophene, and those using discotech liquid crystal phases such as triphenylene compounds.
  • conductive polymers such as polyacetylene, polyaniline, and polythiophene
  • discotech liquid crystal phases such as triphenylene compounds.
  • CuI, CuSCN, etc. can be used as a p-type semiconductor.
  • the counter electrode has conductivity and catalyzes the reduction reaction of the redox electrolyte.
  • platinum, carbon, rhodium, ruthenium, or the like deposited on glass or a polymer film, or coated with conductive fine particles can be used.
  • a halogen redox electrolyte composed of a halogen compound having a halogen ion as a large ion and a halogen molecule, a ferrocyanate-ferrocyanate, a ferrocene-ferricinium ion, a cobalt complex and the like
  • Metal redox-based electrolytes such as metal complexes, organic redox-based electrolytes such as alkylthiol-alkyldisulfides, viologen dyes, and hydroquinone-quinones, and the like, and halogen-redox electrolytes are preferable.
  • a halogen molecule in a halogen redox electrolyte composed of a halogen compound-halogen molecule an iodine molecule is preferable.
  • the halogen compound to a halogen ion as a counter ion LiI, NaI, KI, CaI 2, MgI 2, a halogenated metal salt such as CuI, or tetra-alkyl ammonium iodine, imidazolium iodine, the organic ammonium salt of halogen such as flutes Stadium iodine, Or I 2 can be used.
  • an electrochemically inert one may be used as the solvent.
  • an electrochemically inert one may be used as the solvent.
  • Specific examples include acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxy propionitrile, methoxy acetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butyrolactone, dimethoxyethane, dimethyl carbonate, 1,3-dioxolane, methylformate, 2-methyltetrahydrofuran, 3-methoxy-oxazolidin-2-one, sulfolane, tetrahydrofuran, water, and the like, in particular acetonitrile, Propylene carbonate, ethylene carbonate, 3-methoxy propionitrile, ethylene glycol, 3-methoxy-oxazolidin-2-one, butyrolactone and the like are preferable.
  • the solvents may be used alone or in combination.
  • a gel positive electrolyte one containing an electrolyte or an electrolyte solution in a matrix such as an oligomer and a polymer, or one containing an electrolyte or an electrolyte solution in the same manner as a starch gelling agent can be used.
  • the concentration of the redox electrolyte is preferably 0.01-99% by weight, more preferably 0.1-30% by weight.
  • a counter electrode anode
  • a photoelectric conversion element cathode
  • a solution containing a redox electrolyte is filled therebetween.
  • Ruthenium-based dye compound 4 was prepared according to the same reaction scheme as described below.
  • 4,4'-dibromo-2,2'-bipyridine (20 g, 63.70 mmol) was dissolved in 300 ml of THF, and n-Butyllithium (56.06 ml 2.5 M in Hexane, 140 mmol) was slowly added dropwise at -78 ° C. After stirring for minutes, DMF (10.24 g 140.14 mmol) was added thereto, and the mixture was stirred at 25 ° C. for 6 hours under nitrogen gas. After stirring, the mixture was extracted with ether 300 ml and the organic layer was extracted using water, and then separated by recrystallization under chloroform / methanol (1/10).
  • 2,2'-bipyridine-4,4'-dicarbaldehyde (15 g, 70.69 mmol), 2- (heptadecan-9-yl) thieno [3,2-b] thiophene (26.77 g, 70.69 mmol) and Trimethylamine (0.42 g, 7.07 mmol) was dissolved in 100 ml of Acetic anhydride and stirred under reflux. After stirring, the mixture was extracted with 300 ml of chloroform and the organic layer was extracted using water, and then separated by recrystallization under chloroform / methanol (1/10).
  • Ruthenium-based dye compound 7 was prepared according to the same reaction scheme as described below.
  • Compound 5 was synthesized using Thiophene instead of Thieno [3,2-b] thiophene in the method of preparing Compound 2 of Example 1.
  • a ruthenium-based dye compound 10 was prepared according to the same reaction scheme as described in Scheme 3 below.
  • Compound 8-1 was synthesized by using compound 8 instead of Thieno [3,2-b] thiophene in the method of preparing compound 2 of Example 1.
  • the dye compound of the present invention prepared in Example 1 is expected to exhibit a much higher absorbance than the comparative dyes to improve the efficiency of the solar cell.
  • the dye compounds of the present invention prepared in Examples 2 and 3 also exhibited absorbances comparable to those of the dye compounds prepared in Example 1.
  • a solar cell was manufactured by varying the thickness as described in Table 2 and FIGS. 2 to 3 using a TiO 2 transparent layer. And a TiO 2 paste (Solaronix, 13 nm paste) was screen-printed to prepare a TiO 2 transparent layer. This TiO 2 film was treated with 40 mM TiCl 4 solution and dried at 500 ° C. for 30 minutes. After the treated film was cooled to 60 ° C., the dye compound of the present invention prepared in Example 1 was impregnated into the dimethylformamide solution. As a reference, an ethanol solution of N719 was used.
  • a sealed sandwich cell was assembled by heating a hot melt film (Surlyn 1702, 25 ⁇ m thick) as a spacer between the dye-adsorbed TiO 2 electrode and the platinum-electrode.
  • a hot melt film As the electrolyte solution, a solution of 0.6 M 3-hexyl-1,2-dimethylimidazolium iodine, 0.04 MI 2 , 0.025 M GSCn and 0.28 M tert -butylpyridine was dissolved in acetonitrile. Scattering layer and AR coating was not.
  • Photoelectrochemical characteristics of the solar cell manufactured using the dye compound of the present invention and N719 were measured and are shown in FIGS. 2 (Example 1) to 3 (N719) and Table 2 below.
  • the photoelectrochemical characteristics of the solar cell were measured using a Keithley M 236 source measuring device, and a 300 W Xe lamp equipped with an AM 1.5 filter (Oriel) was used as the light source, and the electrode size was 0.4 ⁇ 0.4 cm 2 .
  • the intensity was 1 sun (100 mW / cm 2 ).
  • Light intensity was adjusted using a Si solar cell.
  • J sc represents a short-circuit photocurrent density
  • V oc represents an open circuit photovoltage
  • FF represents a fill factor
  • the dye compound of the present invention shows a very high photoelectric conversion efficiency compared to N719
  • the dye compounds prepared in Examples 2 and 3 are also not described in Table 2. Although it showed a photoelectric conversion efficiency similar to that of Example 1, it was confirmed that it can be usefully used as a dye compound of the dye-sensitized solar cell.
  • novel ruthenium-based dyes of the present invention exhibit significantly improved photovoltaic conversion efficiency than conventional dyes, enhance bonding with oxide semiconductor fine particles, and have excellent short circuit photocurrent density (Jsc) and molar extinction coefficient to improve solar cell efficiency. It can greatly improve.

Abstract

The present invention relates to novel ruthenium-based dyes and a preparation method thereof, and more specifically, to a dye which offers photoelectric conversion efficiency remarkably improved over that of conventional dyes by being used in dye-sensitized solar cells, reinforces the bonding force with titanium dioxide, and has superior Jsc(short circuit photocurrent density) and molar absorptivity, thereby remarkably improving the efficiency of the solar cells, and a preparation method thereof.

Description

신규한 루테늄계 염료 및 이의 제조방법Novel ruthenium-based dyes and preparation methods thereof
본 발명은 염료감응태양전지(Dye-Sensitized Solar Cell)에 염료로 사용되는 신규한 루테늄계 염료 및 이의 제조방법에 관한 것이다.The present invention relates to a novel ruthenium-based dye used as a dye in a dye-sensitized solar cell and a manufacturing method thereof.
1991년도 스위스 국립 로잔 고등기술원(EPFL)의 마이클 그라첼(Michael Gratzel) 연구팀에 의해 염료감응 나노입자 산화티타늄 태양전지가 개발된 이후 이 분야에 관한 많은 연구가 진행되고 있다. 염료감응태양전지는 기존의 실리콘계 태양전지에 비해 제조단가가 현저히 낮기 때문에 기존의 비정질 실리콘 태양전지를 대체할 수 있는 가능성을 가지고 있으며, 실리콘 태양전지와 달리 염료감응태양전지는 가시광선을 흡수하여 전자-홀 쌍을 생성할 수 있는 염료분자와, 생성된 전자를 전달하는 전이금속 산화물을 주 구성 재료로 하는 광전기화학적 태양전지이다.Since the development of the dye-sensitized nanoparticle titanium oxide solar cell by the team of Michael Gratzel of the Swiss National Lausanne Institute of Advanced Technology (EPFL) in 1991, much work has been done in this area. Dye-sensitized solar cells have the potential to replace conventional amorphous silicon solar cells because their manufacturing cost is significantly lower than conventional silicon-based solar cells. Unlike silicon solar cells, dye-sensitized solar cells absorb visible light It is a photoelectrochemical solar cell whose main constituent material is a dye molecule capable of generating a hole pair and a transition metal oxide that transfers generated electrons.
종래 염료감응태양전지에 사용되는 염료로는 대표적인 것으로는 하기 화합물들을 들 수 있다.Typical dyes used in dye-sensitized solar cells include the following compounds.
Figure PCTKR2011008175-appb-I000001
Figure PCTKR2011008175-appb-I000001
*TBA : tetrabutylammonium cation* TBA: tetrabutylammonium cation
그러나 아직도 상기 염료들과 비교하여 산화물 반도체 미립자와의 결합력, 광전기 변환효율, Jsc(short circuit photocurrent density) 및 몰 흡광계수를 높여 태양전지의 효율성 및 내구성을 더욱 높일 것이 요청되고 있으며, 새로운 염료에 대한 연구가 필요한 실정이다.However, it is still required to increase the efficiency and durability of the solar cell by increasing the bonding force with the oxide semiconductor fine particles, the photoelectric conversion efficiency, the short circuit photocurrent density (Jsc) and the molar extinction coefficient compared to the above dyes. Research is needed.
상기와 같은 종래기술의 문제점을 해결하고자, 본 발명은 종래의 염료보다 현저히 향상된 광전기변환효율을 나타내며, 산화물 반도체 미립자와의 결합력을 강화시키고, Jsc(short circuit photocurrent density)와 몰 흡광계수가 우수하여 태양전지의 효율을 크게 향상시킬 수 있는 염료 및 이의 제조방법을 제공하는 것을 목적으로 한다.In order to solve the problems of the prior art as described above, the present invention shows a remarkably improved photoelectric conversion efficiency than the conventional dye, enhances the bonding force with the oxide semiconductor fine particles, JSC (short circuit photocurrent density) and the molar extinction coefficient is excellent It is an object of the present invention to provide a dye and a method for producing the same that can greatly improve the efficiency of a solar cell.
또한 본 발명은 상기 염료를 포함하여 현저히 향상된 광전기 변환 효율을 나타내며, 산화물 반도체 미립자와의 결합력이 강화되고, Jsc(short circuit photocurrent density)와 몰 흡광계수가 우수한 염료증감 광전변환소자 및 효율이 현저히 향상된 태양전지를 제공하는 것을 목적으로 한다.In addition, the present invention exhibits a remarkably improved photoelectric conversion efficiency, including the dye, the bonding strength with the oxide semiconductor fine particles, the dye-sensitized photoelectric conversion element and excellent efficiency of the short circuit photocurrent density (Jsc) and the molar extinction coefficient is significantly improved It is an object to provide a solar cell.
상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1로 표시되는 염료를 제공한다.In order to achieve the above object, the present invention provides a dye represented by the following formula (1).
[화학식 1][Formula 1]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-11
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-11
상기 화학식 1에서 Me는 Ru 또는 Os이며, a1 환은 각각 독립적으로 치환기를 가지지 않거나 1개 이상의 치환기를 가질 수 있으며, 치환기로는 할로겐 원자, 아미드기, 시아노기, 히드록실기, 니트로기, 아실기, C1-30 알킬기 또는 C1-30 알콕시기 일 수 있으며, Y는 수소, Na, 또는 TBA(tert-butyl alcohol)이며, In Formula 1, Me is Ru or Os, and each of the a1 rings may not independently have a substituent or may have one or more substituents, and examples of the substituent include a halogen atom, an amide group, a cyano group, a hydroxyl group, a nitro group, and an acyl group. , C 1-30 alkyl group or C 1-30 alkoxy group, Y is hydrogen, Na, or TBA (tert-butyl alcohol),
또한 X1, X2는 각각 독립적으로 메틸 또는 하기 화학식 2로 표시되는 화합물이며, X1와 X2 중 적어도 하나는 화학식 2로 표시되는 화합물이며,In addition, X 1 , X 2 are each independently methyl or a compound represented by the formula (2), at least one of X 1 and X 2 is a compound represented by the formula (2),
[화학식 2][Formula 2]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-15
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-15
[규칙 제91조에 의한 정정 23.12.2011]　
상기 화학식 2에서 A는
Figure WO-DOC-FIGURE-16a
,
Figure WO-DOC-FIGURE-16b
,
Figure WO-DOC-FIGURE-16c
및
Figure WO-DOC-FIGURE-16d
로 이루어진 군에서 1종 이상 선택되며, 이때 X는 각각 독립적으로 O, S, Se, Si 및 NR5로 이루어진 군으로부터 선택되고, R1 내지 R4는 각각 독립적으로 수소, 치환 또는 비치환된 C1-12 알킬, 치환 또는 비치환된 C6-30 아릴 및 치환 또는 비치환된 C6-20 헤테로아릴로 이루어진 군에서 선택되거나, 또는 서로 연결되어 환을 형성할 수 있으며, R5는 수소 또는 치환 또는 비치환된 C1-30 알킬이고, n은 1 내지 10의 정수이며, [Revisions under Rule 91 23.12.2011]
In Formula 2, A is
Figure WO-DOC-FIGURE-16a
,
Figure WO-DOC-FIGURE-16b
,
Figure WO-DOC-FIGURE-16c
And
Figure WO-DOC-FIGURE-16d
At least one selected from the group consisting of wherein X is each independently selected from the group consisting of O, S, Se, Si and NR 5 , R 1 to R 4 are each independently hydrogen, substituted or unsubstituted C 1-12 alkyl, substituted or unsubstituted C 6-30 aryl and substituted or unsubstituted C 6-20 heteroaryl, or may be linked to each other to form a ring, R 5 is hydrogen or Substituted or unsubstituted C 1-30 alkyl, n is an integer from 1 to 10,
B는 하기 화학식 3으로 표시되는 화합물 또는 하기 화학식 4로 표시되는 화합물이며,B is a compound represented by the following formula (3) or a compound represented by the following formula (4),
[화학식 3][Formula 3]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-19
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-19
[화학식 4][Formula 4]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-21
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-21
상기 화학식 3에서 Ar1, Ar2 및 Ar3은 각각 독립적으로 치환 또는 비치환된 C6-50 아릴, 치환 또는 비치환된 C6-20 헤테로아릴로 이루어진 군에서 선택되거나, 또는 서로 연결되어 환을 형성할 수 있으며, *는 결합부분이며, 상기 화학식 4에서 R6 및 R7는 각각 독립적으로 치환 또는 비치환된 C1-30 알킬이며, *는 결합부분이다.In Formula 3 Ar 1, Ar 2 and Ar 3 are each independently a substituted or unsubstituted C 6-50 aryl, substituted or unsubstituted selected from the consisting of unsubstituted C 6-20 heteroaryl group, or a ring are connected to each other It may form, * is a bonding moiety, in Formula 4 R 6 and R 7 are each independently substituted or unsubstituted C 1-30 alkyl, * is a bonding moiety.
또한 본 발명은 하기 화학식 5의 화합물을 하기 화학식 6, 화학식 7 및 화학식 8의 화합물과 순차적으로 반응시키는 것을 특징으로 하는 화학식 1로 표시되는 염료의 제조방법을 제공한다.In another aspect, the present invention provides a method for preparing a dye represented by the formula (1) characterized in that the compound of formula (5) is sequentially reacted with the compound of formula (6), formula (7) and formula (8).
[화학식 5][Formula 5]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-25
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-25
[화학식 6][Formula 6]
[RuCl2(p-cymene)]2 RuCl 2 ( p -cymene) 2
[화학식 7][Formula 7]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-29
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-29
[화학식 8][Formula 8]
NH4NCSNH 4 NCS
상기 화학식 5, 6, 7 및 8에서 X1, X2, 및 a1는 상기에서 정의한 바와 같다.In Formulas 5, 6, 7 and 8, X 1 , X 2 , and a1 are as defined above.
또한 본 발명은 상기 화학식 1로 표시되는 화합물로 담지시킨 산화물 반도체 미립자를 포함하는 것을 특징으로 하는 염료증감 광전변환소자를 제공한다.In another aspect, the present invention provides a dye-sensitized photoelectric conversion device comprising an oxide semiconductor fine particles supported by a compound represented by the formula (1).
또한 본 발명은 상기 염료증감 광전변환소자를 포함하는 것을 특징으로 하는 염료감응태양전지를 제공한다.In another aspect, the present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device.
본 발명의 신규한 루테늄계 염료는 종래의 염료보다 현저히 향상된 광전기 변환 효율을 나타내며, 산화물 반도체 미립자와의 결합력을 강화시키고, Jsc(short circuit photocurrent density)와 몰 흡광계수가 우수하여 태양전지의 효율을 크게 향상시킬 수 있다.The novel ruthenium-based dyes of the present invention exhibit significantly improved photovoltaic conversion efficiency than conventional dyes, enhance bonding with oxide semiconductor fine particles, and have excellent short circuit photocurrent density (Jsc) and molar extinction coefficient to improve solar cell efficiency. It can greatly improve.
도 1은 실시예 1에서 제조된 본 발명의 염료 화합물 및 N719의 흡광 스펙트럼이고,1 is an absorption spectrum of the dye compound of the present invention prepared in Example 1 and N719,
도 2는 실시예 1에서 제조된 본 발명의 염료 화합물를 사용하여 제조한 염료감응태양전지로 측정한 단회로 광전류 밀도(short-circuit photocurrent density, Jsc) 그래프이고,2 is a graph of a short-circuit photocurrent density (Jsc) measured by a dye-sensitized solar cell prepared using the dye compound of the present invention prepared in Example 1,
도 3은 N719 염료 화합물를 사용하여 제조한 염료감응태양전지로 측정한 단회로 광전류 밀도(short-circuit photocurrent density, Jsc) 그래프이다.3 is a graph of a short-circuit photocurrent density (Jsc) measured by a dye-sensitized solar cell prepared using a N719 dye compound.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명자들은 화학식 1로 표시되는 화합물을 산화물 반도체 미립자에 담지시켜 염료감응태양전지를 제조할 경우 산화물 반도체 미립자에 강하게 결합하여 내구성이 뛰어나며, 광전기 변환효율, Jsc(short circuit photocurrent density) 및 몰 흡광계수가 높아 기존에 존재하였던 염료감응태양전지보다도 우수한 효율을 나타냄을 확인하고 본 발명을 완성하게 되었다.The inventors of the present invention have excellent durability by supporting the compound represented by Chemical Formula 1 on oxide semiconductor fine particles by strongly binding to oxide semiconductor fine particles, and having excellent durability, photoelectric conversion efficiency, short circuit photocurrent density (Jsc) and molar extinction coefficient. It was confirmed that the high efficiency than the existing dye-sensitized solar cell is high and completed the present invention.
본 발명의 염료는 하기 화학식 1로 표시되는 것을 특징으로 한다.The dye of the present invention is characterized by represented by the following formula (1).
[화학식 1][Formula 1]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-44
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-44
상기 화학식 1에서 Me는 Ru 또는 Os이며, a1 환은 각각 독립적으로 치환기를 가지지 않거나 1개 이상의 치환기를 가질 수 있으며, 치환기로는 할로겐 원자, 아미드기, 시아노기, 히드록실기, 니트로기, 아실기, C1-30 알킬기 또는 C1-30 알콕시기 일 수 있으며, Y는 수소, Na, 또는 TBA(tert-butyl alcohol)이며, In Formula 1, Me is Ru or Os, and each of the a1 rings may not independently have a substituent or may have one or more substituents, and examples of the substituent include a halogen atom, an amide group, a cyano group, a hydroxyl group, a nitro group, and an acyl group. , C 1-30 alkyl group or C 1-30 alkoxy group, Y is hydrogen, Na, or TBA (tert-butyl alcohol),
또한 X1, X2는 각각 독립적으로 메틸 또는 하기 화학식 2로 표시되는 화합물이며, X1와 X2 중 적어도 하나는 화학식 2로 표시되는 화합물이며,In addition, X 1 , X 2 are each independently methyl or a compound represented by the formula (2), at least one of X 1 and X 2 is a compound represented by the formula (2),
[화학식 2][Formula 2]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-48
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-48
[규칙 제91조에 의한 정정 23.12.2011]　
상기 화학식 2에서 A는
Figure WO-DOC-FIGURE-49a
,
Figure WO-DOC-FIGURE-49b
,
Figure WO-DOC-FIGURE-49c
및
Figure WO-DOC-FIGURE-49d
로 이루어진 군에서 1종 이상 선택되며, 이때 X는 각각 독립적으로 O, S, Se, Si 및 NR5로 이루어진 군으로부터 선택되고, R1 내지 R4는 각각 독립적으로 수소, 치환 또는 비치환된 C1-12 알킬, 치환 또는 비치환된 C6-30 아릴 및 치환 또는 비치환된 C6-20 헤테로아릴로 이루어진 군에서 선택되거나, 또는 서로 연결되어 환을 형성할 수 있으며, R5는 수소 또는 치환 또는 비치환된 C1-30 알킬이고, n은 1 내지 10의 정수이며, [Revisions under Rule 91 23.12.2011]
In Formula 2, A is
Figure WO-DOC-FIGURE-49a
,
Figure WO-DOC-FIGURE-49b
,
Figure WO-DOC-FIGURE-49c
And
Figure WO-DOC-FIGURE-49d
At least one selected from the group consisting of wherein X is each independently selected from the group consisting of O, S, Se, Si and NR 5 , R 1 to R 4 are each independently hydrogen, substituted or unsubstituted C 1-12 alkyl, substituted or unsubstituted C 6-30 aryl and substituted or unsubstituted C 6-20 heteroaryl, or may be linked to each other to form a ring, R 5 is hydrogen or Substituted or unsubstituted C 1-30 alkyl, n is an integer from 1 to 10,
B는 하기 화학식 3으로 표시되는 화합물 또는 하기 화학식 4로 표시되는 화합물이며,B is a compound represented by the following formula (3) or a compound represented by the following formula (4),
[화학식 3][Formula 3]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-52
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-52
[화학식 4][Formula 4]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-54
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-54
상기 화학식 3에서 Ar1, Ar2 및 Ar3은 각각 독립적으로 치환 또는 비치환된 C6-50 아릴, 치환 또는 비치환된 C6-20 헤테로아릴로 이루어진 군에서 선택되거나, 또는 서로 연결되어 환을 형성할 수 있으며, *는 결합부분이며, 상기 화학식 4에서 R6 및 R7는 각각 독립적으로 치환 또는 비치환된 C1-30 알킬이며, *는 결합부분이며, 바람직하기로 R6 및 R7는 C5-10 알킬 또는 황을 포함하는 C5-10 알킬이다.In Formula 3 Ar 1, Ar 2 and Ar 3 are each independently a substituted or unsubstituted C 6-50 aryl, substituted or unsubstituted selected from the consisting of unsubstituted C 6-20 heteroaryl group, or a ring are connected to each other It may be formed, * is a bonding moiety, in Formula 4 R 6 and R 7 are each independently substituted or unsubstituted C 1-30 alkyl, * is a bonding moiety, preferably R 6 and R 7 is a C 5-10 alkyl, including C 5-10 alkyl or sulfur.
또한 바람직하기로는 상기 화학식 1로 표시되는 염료는 하기 화학식 1-1 내지 1-48로 표시되는 화합물 중 하나인 것이 좋다.Also preferably, the dye represented by Chemical Formula 1 may be one of the compounds represented by the following Chemical Formulas 1-1 to 1-48.
[화학식 1-1][Formula 1-1]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-58
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-58
[화학식 1-2][Formula 1-2]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-60
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-60
[화학식 1-3][Formula 1-3]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-62
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-62
[화학식 1-4][Formula 1-4]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-64
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-64
[화학식 1-5][Formula 1-5]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-66
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-66
[화학식 1-6][Formula 1-6]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-68
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-68
[화학식 1-7][Formula 1-7]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-70
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-70
[화학식 1-8][Formula 1-8]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-72
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-72
[화학식 1-9][Formula 1-9]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-74
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-74
[화학식 1-10][Formula 1-10]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-76
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-76
[화학식 1-11][Formula 1-11]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-78
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-78
[화학식 1-12][Formula 1-12]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-80
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-80
[화학식 1-13][Formula 1-13]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-82
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-82
[화학식 1-14][Formula 1-14]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-84
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-84
[화학식 1-15][Formula 1-15]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-86
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-86
[화학식 1-16][Formula 1-16]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-88
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-88
[화학식 1-17][Formula 1-17]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-90
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-90
[화학식 1-18][Formula 1-18]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-92
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-92
[화학식 1-19][Formula 1-19]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-94
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-94
[화학식 1-20][Formula 1-20]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-96
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-96
[화학식 1-21][Formula 1-21]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-98
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-98
[화학식 1-22][Formula 1-22]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-100
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-100
[화학식 1-23][Formula 1-23]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-102
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-102
[화학식 1-24][Formula 1-24]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-104
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-104
[화학식 1-25][Formula 1-25]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-106
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-106
[화학식 1-26][Formula 1-26]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-108
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-108
[화학식 1-27][Formula 1-27]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-110
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-110
[화학식 1-28][Formula 1-28]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-112
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-112
[화학식 1-29][Formula 1-29]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-114
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-114
[화학식 1-30][Formula 1-30]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-116
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-116
[화학식 1-31][Formula 1-31]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-118
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-118
[화학식 1-32][Formula 1-32]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-120
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-120
[화학식 1-33][Formula 1-33]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-122
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-122
[화학식 1-34][Formula 1-34]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-124
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-124
[화학식 1-35][Formula 1-35]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-126
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-126
[화학식 1-36][Formula 1-36]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-128
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-128
[화학식 1-37][Formula 1-37]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-130
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-130
[화학식 1-38][Formula 1-38]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-132
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-132
[화학식 1-39][Formula 1-39]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-134
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-134
[화학식 1-40][Formula 1-40]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-136
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-136
[화학식 1-41][Formula 1-41]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-138
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-138
[화학식 1-42][Formula 1-42]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-140
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-140
[화학식 1-43][Formula 1-43]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-143
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-143
[화학식 1-44][Formula 1-44]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-145
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-145
[화학식 1-45][Formula 1-45]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-147
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-147
[화학식 1-46][Formula 1-46]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-149
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-149
[화학식 1-47][Formula 1-47]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-151
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-151
[화학식 1-48][Formula 1-48]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-153
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-153
또한 본 발명은 하기 화학식 5의 화합물을 하기 화학식 6, 화학식 7 및 화학식 8의 화합물과 순차적으로 반응시키는 것을 특징으로 하는 화학식 1로 표시되는 염료의 제조방법을 제공한다.In another aspect, the present invention provides a method for preparing a dye represented by the formula (1) characterized in that the compound of formula (5) is sequentially reacted with the compound of formula (6), formula (7) and formula (8).
[화학식 5][Formula 5]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-158
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-158
[화학식 6][Formula 6]
[RuCl2(p-cymene)]2 RuCl 2 ( p -cymene) 2
[화학식 7][Formula 7]
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-165
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-165
[화학식 8][Formula 8]
NH4NCSNH 4 NCS
상기 화학식 5, 6, 7 및 8에서 X1, X2, 및 a1는 상기에서 정의한 바와 같다.In Formulas 5, 6, 7 and 8, X 1 , X 2 , and a1 are as defined above.
본 발명에 있어서 화학식 1의 염료의 제조에 출발물질로서 사용되는 화합물들은 통상적인 방법으로 제조하거나 구입하여 사용할 수 있다. In the present invention, the compounds used as starting materials for the preparation of the dye of Formula 1 may be prepared or purchased in a conventional manner.
또한 본 발명은 염료증감 광전변환소자를 제공하는 바, 상기 염료증감 광전변환소자는 산화물 반도체 미립자에 상기 화학식 1로 표시되는 염료를 담지시킨 것을 특징으로 한다. 본 발명은 염료증감 광전변환소자는 상기 화학식 1로 표시되는 염료를 사용하는 것 이외에 종래 염료를 이용하여 태양전지용 염료증감 광전변환소자를 제조하는 방법들이 적용될 수 있음은 물론이며, 바람직하기로는 본 발명의 염료증감 광전변환소자는 산화물 반도체 미립자를 이용해서 기판상에 산화물 반도체의 박막을 제조하고, 이어서 상기 박막에 본 발명의 염료를 담지시킨 것이 좋다.In addition, the present invention provides a dye-sensitized photoelectric conversion device, the dye-sensitized photoelectric conversion device is characterized in that the dye represented by the formula (1) on the oxide semiconductor fine particles. The present invention is a dye-sensitized photoelectric conversion device in addition to using the dye represented by the formula (1) can be applied to the method of manufacturing a dye-sensitized photoelectric conversion device for a solar cell using a conventional dye, of course, preferably the present invention The dye-sensitized photoelectric conversion device may be prepared by fabricating a thin film of an oxide semiconductor on a substrate using oxide semiconductor fine particles, and then supporting the dye of the present invention on the thin film.
본 발명에서 산화물 반도체의 박막을 설치하는 기판으로서는 그 표면이 도전성인 것이 바람직하며, 시중에서 판매되는 것을 사용할 수도 있다. 구체적인 일예로 글라스의 표면 또는 폴리에틸렌테레프탈레이트 혹은 폴리에테르설폰 등의 투명성이 있는 고분자 재료의 표면에 인듐, 불소, 안티몬을 도포한 산화주석 등의 도전성 금속산화물이나 강, 은, 금 등의 금속 박막을 형성한 것을 이용할 수 있다. 이 때 도전성은 보통 1000 Ω 이하가 바람직하며, 특히 100 Ω 이하의 것이 바람직하다. In this invention, it is preferable that the surface is electroconductive as a board | substrate which provides the thin film of an oxide semiconductor, and what is marketed can also be used. As a specific example, conductive metal oxides such as tin oxide coated with indium, fluorine, and antimony on a surface of glass or a transparent polymer material such as polyethylene terephthalate or polyethersulfone, or a metal thin film such as steel, silver, or gold may be used. The formed thing can be used. In this case, the conductivity is usually preferably 1000 Ω or less, particularly preferably 100 Ω or less.
또한 산화물 반도체의 미립자로서는 금속산화물이 바람직하다. 구체적인 예로서는 티탄, 주석, 아연, 텅스텐, 지르코늄, 갈륨, 인듐, 이트륨, 니오브, 탄탈, 바나듐 등의 산화물을 사용할 수 있다. 이들 중 티탄, 주석, 아연, 니오브, 인듐 등의 산화물이 바람직하고, 이들 중 산화티탄, 산화아연, 산화주석이 더욱 바람직하며, 산화티탄인 것이 가장 바람직하다. 상기 산화물 반도체는 단독으로 사용할 수도 있지만, 혼합하거나 반도체의 표면에 코팅시켜서 사용할 수도 있다.  As the fine particles of the oxide semiconductor, a metal oxide is preferable. As specific examples, oxides such as titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum and vanadium can be used. Of these, oxides such as titanium, tin, zinc, niobium and indium are preferable, and among these, titanium oxide, zinc oxide, and tin oxide are more preferable, and titanium oxide is most preferable. The oxide semiconductor may be used alone, or may be mixed or coated on the surface of the semiconductor.
또한 상기 산화물 반도체의 미립자의 입경은 평균 입경으로서 1-500 nm인 것이 좋으며, 더욱 바람직하게는 1-100 nm인 것이 좋다. 또한 이 산화물 반도체의 미립자는 큰 입경의 것과 작은 입경의 것을 혼합하거나, 다층으로 하여 이용할 수도 있다. In addition, the particle size of the fine particles of the oxide semiconductor is preferably 1-500 nm, more preferably 1-100 nm as the average particle diameter. In addition, the fine particles of the oxide semiconductor may be mixed with a large particle size and a small particle size, or may be used as a multilayer.
상기 산화물 반도체 박막은 산화물 반도체 미립자를 스프레이 분무 등으로 직접 기판상에 박막으로 형성하는 방법, 기판을 전극으로 하여 전기적으로 반도체 미립자 박막을 석출시키는 방법, 반도체 미립자의 슬러리 또는 반도체 알콕사이드 등의 반도체 미립자의 전구체를 가수분해함으로써 얻을 수 있은 미립자를 함유하는 페이스트를 기판상에 도포한 후, 건조, 경화 혹은 소성하는 방법 등에 의해 제조할 수 있으며, 페이스트를 기판상에 도포하는 방법이 바람직하다. 이 방법의 경우, 슬러리는 2차 응집하고 있는 산화물 반도체 미립자를 통상의 방법에 의해 분산매 중에 평균 1차 입경이 1-200 nm이 되도록 분산시킴으로써 얻을 수 있다. The oxide semiconductor thin film is a method of forming oxide semiconductor fine particles into a thin film directly on a substrate by spray spraying, a method of electrically depositing a semiconductor fine particle thin film using a substrate as an electrode, a slurry of semiconductor fine particles or semiconductor fine particles such as a semiconductor alkoxide. After applying the paste containing the fine particles obtained by hydrolyzing the precursor onto the substrate, it can be produced by a method of drying, curing or baking, and a method of applying the paste onto the substrate is preferable. In the case of this method, the slurry can be obtained by dispersing secondary agglomerated oxide semiconductor fine particles in a dispersion medium so as to have an average primary particle size of 1-200 nm.
슬러리를 분산시키는 분산매로서는 반도체 미립자를 분산시킬 수 있는 것이면 특별히 제한 없이 사용할 수 있으며, 물, 에탄올 등의 알코올, 아세톤, 아세틸아세톤 등의 케톤 또는 헥산 등의 탄화수소를 이용할 수 있고, 이것들은 혼합해서 사용할 수 있고, 이 중 물을 이용하는 것이 슬러리의 점도변화를 적게 한다는 점에서 바람직하다. 또한 산화물 반도체 미립자의 분산 상태를 안정화시킬 목적으로 분산 안정제를 사용할 수 있다. 사용할 수 있는 분산 안정제의 구체적인 예로서는 예를 들면 초산, 염산, 질산 등의 산, 또는 아세틸아세톤, 아크릴산, 폴리에틸렌글리콜, 폴리비닐알코올 등을 들 수 있다. The dispersion medium for dispersing the slurry can be used without particular limitation so long as it can disperse the semiconductor fine particles, and alcohols such as water and ethanol, ketones such as acetone and acetylacetone, or hydrocarbons such as hexane can be used, and these can be mixed and used. Among them, it is preferable to use water among them in order to reduce the viscosity change of the slurry. Moreover, a dispersion stabilizer can be used for the purpose of stabilizing the dispersion state of oxide semiconductor microparticles | fine-particles. As a specific example of the dispersion stabilizer which can be used, acids, such as acetic acid, hydrochloric acid, nitric acid, or acetylacetone, acrylic acid, polyethyleneglycol, polyvinyl alcohol, etc. are mentioned, for example.
슬러리를 도포한 기판은 소성할 수 있고, 그 소성온도는 100 ℃ 이상, 바람직하게는 200 ℃ 이상이고, 또 상한은 대체로 기재의 융점(연화점) 이하로서 통상 상한은 900 ℃이며, 바람직하게는 600 ℃ 이하이다. 본 발명에서 소성시간에는 특별하게 한정되지 않지만, 대체로 4시간 이내가 바람직하다.  The substrate coated with the slurry can be fired, and its firing temperature is at least 100 ° C, preferably at least 200 ° C, and the upper limit is generally below the melting point (softening point) of the substrate, and usually the upper limit is 900 ° C, preferably 600. It is below ℃. In the present invention, the firing time is not particularly limited, but is usually within 4 hours.
본원발명에서 기판상의 박막의 두께는 1-200 ㎛인 것이 좋으며, 바람직하게는 1-50 ㎛이다. 소성을 실시하는 경우에는 산화물 반도체 미립자의 박층은 일부 용착하지만, 그러한 용착은 본 발명을 위해서는 특별하게 지장은 없다. In the present invention, the thickness of the thin film on the substrate is preferably 1-200 μm, preferably 1-50 μm. In the case of firing, some thin layers of the oxide semiconductor fine particles are welded, but such welding is not particularly troubled for the present invention.
또한 상기 산화물 반도체 박막에 2차 처리를 실시할 수도 있다. 일 예로 반도체와 동일한 금속의 알콕사이드, 염화물, 질소화물, 황화물 등의 용액에 직접, 기판별로 박막을 침적시켜서 건조 혹은 재소성 함으로써 반도체 박막의 성능을 향상시킬 수도 있다. 금속 알콕사이드로서는 티탄에톡사이드, 티탄니움이소프로에폭사이드, 티탄 t-부톡사이드, n-디부틸-디아세틸 주석 등을 들 수 있고, 그것들의 알코올 용액을 이용할 수 있다. 염화물로서는 예를 들면 4염화 티탄, 사염화주석, 염화아연 등을 들 수 있고, 그 수용액을 이용할 수 있다. 이렇게 하여 수득된 산화물 반도체 박막은 산화물 반도체의 미립자로 이루어져 있다. In addition, the oxide semiconductor thin film may be subjected to secondary treatment. For example, the performance of a semiconductor thin film may be improved by directly depositing a thin film for each substrate and drying or refiring it in a solution such as an alkoxide, chloride, nitride or sulfide of the same metal as the semiconductor. Examples of the metal alkoxide include titanium ethoxide, titanium isopropoxide, titanium t-butoxide, n-dibutyl-diacetyl tin and the like, and an alcohol solution thereof can be used. As a chloride, titanium tetrachloride, tin tetrachloride, zinc chloride, etc. are mentioned, for example, The aqueous solution can be used. The oxide semiconductor thin film thus obtained is composed of fine particles of an oxide semiconductor.
또한 본 발명에서 박막 상으로 형성된 산화물 반도체 미립자에 염료를 담지시키는 방법은 특별히 한정되지 않으며, 구체적인 예로서 상기 화학식 1로 표시되는 염료를 용해할 수 있는 용매로 용해해서 얻은 용액, 또는 염료를 분산시켜서 얻은 분산액에 상기 산화물 반도체 박막이 설치된 기판을 침지시키는 방법을 들 수 있다. 용액 또는 분산액 중의 농도는 염료에 의해 적당하게 결정할 수 있다. 침적시간은 대체로 상온에서 용매의 비점까지이고, 또 침적시간은 1분에서 48시간 정도이다. 염료를 용해시키는데 사용할 수 있는 용매의 구체적인 예로서, 예를 들면 메탄올, 에탄올, 아세토니트릴, 디메틸설폭사이드, 디메틸포름아미드, 아세톤, t-부탄올 등을 들 수 있다. 용액의 염료 농도는 보통 1× 10-6 M - 1 M이 좋고, 바람직하게는 1× 10-5 M - 1× 10-1 M인 것이 좋다. 이렇게 해서 염료로 증감된 박막 상의 산화물 반도체 미립자를 가진 본 발명의 광전변환소자를 얻을 수 있다.In addition, the method of supporting the dye on the oxide semiconductor fine particles formed in the thin film phase in the present invention is not particularly limited, as a specific example by dispersing a solution obtained by dissolving the dye represented by the formula (1) in a solvent capable of dissolving, or dye The method of immersing the board | substrate with which the said oxide semiconductor thin film was provided in the obtained dispersion liquid is mentioned. The concentration in the solution or dispersion can be appropriately determined by the dye. The deposition time is usually from room temperature to the boiling point of the solvent, and the deposition time is about 1 minute to 48 hours. Specific examples of the solvent that can be used to dissolve the dye include methanol, ethanol, acetonitrile, dimethyl sulfoxide, dimethylformamide, acetone, t-butanol and the like. The dye concentration of the solution is usually preferably 1 × 10 −6 M −1 M, preferably 1 × 10 −5 M −1 × 10 −1 M. In this way, the photoelectric conversion element of this invention which has oxide semiconductor microparticles | fine-particles on the thin film sensitized with dye can be obtained.
본 발명에서 담지하는 화학식 1의 표시되는 염료는 1종류일 수도 있고, 수 종류 혼합할 수도 있다. 또한 혼합하는 경우에는 본 발명의 염료만을 사용할 수 있고, 다른 염료나 금속 착체 염료를 혼합할 수 있다. 혼합할 수 있는 금속 착체 염료의 예로서는 특별하게 제한은 없지만 M.K.Nazeeruddin, A.Kay, I.Rodicio, R.Humphry-Baker, E.Muller, P.Liska, N.Vlachopoulos, M.Gratzel, J. Am. Chem. Soc., 제115권, 6382쪽(1993년)에 나타나 있다 루테늄 착체나 그 4급염, 프탈로시아닌, 포르피린 등이 바람직하고, 혼합 이용하는 유기염료로서는 무금속의 프탈로시아닌, 포르피린이나 시아닌, 메로시아닌, 옥소놀, 트리페닐메탄계, WO2002/011213호에 제시되는 아크릴산계 염료 등의 메틴계 염료나, 크산텐계, 아조계, 안트라퀴논계, 페릴렌계 등의 염료를 들 수 있다. 염료를 2종 이상 이용하는 경우에는 염료를 반도체 박막에 차례로 흡착시킬 수도, 혼합 용해해서 흡착시킬 수도 있다.The dye represented by the formula (1) supported by the present invention may be one kind or may be mixed in several kinds. In addition, when mixing, only the dye of this invention can be used and other dye and metal complex dye can be mixed. Examples of metal complex dyes that can be mixed are not particularly limited, but MK Nazeeruddin, A.Kay, I.Rodicio, R.Humphry-Baker, E.Muller, P.Liska, N.Vlachopoulos, M.Gratzel, J. Am . Chem. Soc., Vol. 115, pp. 6382 (1993). Ruthenium complexes, quaternary salts thereof, phthalocyanine, porphyrin, and the like are preferred, and organic dyes used for mixing are metal-free phthalocyanine, porphyrin, cyanine, merocyanine, oxo. Methine dyes such as knol, triphenylmethane and acrylic acid dyes described in WO2002 / 011213, and dyes such as xanthene, azo, anthraquinone and perylene. In the case of using two or more kinds of dyes, the dyes may be adsorbed onto the semiconductor thin film in sequence, or may be mixed and dissolved and adsorbed.
또한 본 발명에서 산화물 반도체 미립자의 박막에 염료를 담지할 때, 염료끼리의 결합을 방지하기 위해서 포섭 화합물의 존재하에서 염료를 담지하는 것이 좋다. 상기 포섭화합물로서는 데옥시콜산, 데히드로데옥시콜산, 케노데옥시콜산, 콜산메틸에스테르, 콜산나트륨 등의 콜산류, 폴리에틸렌옥사이드, 콜산 등의 스테로이드계 화합물, 크라운에테르, 사이클로덱스트린, 캘릭스아렌, 폴리에틸렌옥사이드 등을 사용할 수 있다. In addition, when the dye is supported on the thin film of the oxide semiconductor fine particles in the present invention, it is preferable to support the dye in the presence of the inclusion compound in order to prevent the bonding of the dyes. Examples of the inclusion compound include deoxycholic acid, dehydrodeoxycholic acid, kenodeoxycholic acid, cholic acid methyl ester, and cholic acid such as sodium cholate, steroid-based compounds such as polyethylene oxide and cholic acid, crown ether, cyclodextrin, and calix arene, Polyethylene oxide and the like can be used.
또한, 염료를 담지시킨 후, 4-t-부틸 피리딘 등의 아민 화합물이나 초산, 프로피온산 등의 산성기를 가지는 화합물 등으로 반도체 전극표면을 처리할 수 있다. 처리방법은 예를 들면 아민의 에탄올 용액에 염료를 담지한 반도체 미립자 박막이 설치된 기판을 담그는 방법 등이 사용될 수 있다.After the dye is supported, the semiconductor electrode surface can be treated with an amine compound such as 4-t-butyl pyridine or a compound having an acidic group such as acetic acid or propionic acid. As a treatment method, for example, a method of dipping a substrate provided with a thin film of semiconductor fine particles in which a dye is supported in an amine ethanol solution may be used.
또한 본 발명은 상기 염료감응 광전변환소자를 포함하는 것을 특징으로 하는 염료감응태양전지를 제공하는 바, 상기 화학식 1로 표시되는 염료를 담지시킨 산화물 반도체 미립자를 이용한 염료증감 광전변환소자를 사용하는 것 이외에 종래 광전변환소자를 사용하여 태양전지를 제조하는 통상의 방법들이 적용될 수 있음은 물론이며, 구체적인 예로 상기 산화물 반도체 미립자에 화학식 1로 표시되는 염료를 담지시킨 광전변환소자 전극(음극), 대전극(양극), 레독스 전해질, 정공수송 재료 또는 p형 반도체 등으로 구성될 수 있다.In another aspect, the present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device, using a dye-sensitized photoelectric conversion device using the oxide semiconductor fine particles carrying the dye represented by the formula (1) In addition, conventional methods of manufacturing a solar cell using a conventional photoelectric conversion device may be applied, and, as a specific example, a photoelectric conversion device electrode (cathode) and a counter electrode in which the dye represented by Formula 1 is supported on the oxide semiconductor fine particles. (Anode), a redox electrolyte, a hole transport material, a p-type semiconductor, or the like.
바람직하기로는 본 발명의 염료감응태양전지의 구체적인 제조방법의 일예로는 전도성 투명 기판 위에 산화티타늄 페이스트를 코팅하는 단계, 페이스트가 코팅된 기판을 소성하여 산화티타늄 박막을 형성하는 단계, 산화티타늄 박막이 형성된 기판을 화학식 1로 표시되는 염료가 용해된 혼합용액에 함침시켜 염료가 흡착된 산화티타늄 필름 전극을 형성하는 단계, 그 상부에 대전극이 형성된 제2의 유리기판을 구비하는 단계, 제2 유리기판 및 대전극을 관통하는 홀(hole)을 형성하는 단계, 상기 대전극 및 상기 염료가 흡착된 산화티타늄 필름 전극 사이에 열가소성 고분자 필름을 두고, 가열 압착 공정을 실시하여 상기 대전극 및 산화티타늄 필름전극을 접합시키는 단계, 상기 홀을 통하여 대전극과 산화티타늄 필름 전극 사이의 열가소성 고분자 필름에 전해질을 주입하는 단계 및 상기 열가소성 고분자를 실링하는 단계를 통하여 제조되는 것이 좋다.Preferably, as an example of a specific method of manufacturing a dye-sensitized solar cell of the present invention, the method includes coating a titanium oxide paste on a conductive transparent substrate, baking a substrate coated with a paste to form a titanium oxide thin film, and a titanium oxide thin film. Impregnating the formed substrate into a mixed solution in which the dye represented by Chemical Formula 1 is dissolved to form a titanium oxide film electrode on which the dye is adsorbed, and providing a second glass substrate having a counter electrode formed thereon, and a second glass. Forming a hole penetrating the substrate and the counter electrode, placing a thermoplastic polymer film between the counter electrode and the titanium oxide film electrode on which the dye is adsorbed, and performing a heat compression process to perform the counter electrode and the titanium oxide film. Bonding the electrodes to the thermoplastic polymer film between the counter electrode and the titanium oxide film electrode through the holes; It is good to prepare through the step of injecting an electrolyte and the step of sealing the thermoplastic polymer.
레독스 전해질, 정공수송 재료, p형 반도체 등의 형태는 액체, 응고체(겔 및 겔상), 고체 등을 들 수 있다. 액상의 것으로서는 레독스 전해질, 용해염, 정공수송재료, p형 반도체 등을 각각 용매에 용해시킨 것이나 상온 용해염 등이, 응고체(겔 및 겔상)의 경우에는 이것들을 폴리머 매트릭스나 저분자 겔화제 등에 함유시킨 것 등을 각각 들 수 있다. 고체의 것으로서는 레독스 전해질, 용해염, 정공수송재료, p형 반도체 등을 사용할 수 있다. Examples of the forms of the redox electrolyte, the hole transport material, the p-type semiconductor, and the like include liquids, coagulated bodies (gels and gels), solids, and the like. As liquids, redox electrolytes, dissolved salts, hole transport materials, p-type semiconductors, and the like are dissolved in a solvent, and room temperature dissolved salts, etc., are solid polymers (gels and gels). What was contained in etc. can be mentioned, respectively. As a solid thing, a redox electrolyte, a dissolution salt, a hole transport material, a p-type semiconductor, etc. can be used.
정공수송 재료로서는 아민 유도에나 폴리아세티틸렌, 폴리아닐린, 폴리티오펜 등의 도전성 고분자, 트리페닐렌계 화합물 등의 디스코테크 액정상을 이용하는 물건 등을 사용할 수 있다. 또한 p형 반도체로서는 CuI, CuSCN 등을 사용할 수 있다. 대전극으로는 도전성을 가지고 있으며, 레독스 전해질의 환원 반응을 촉매적으로 작용하는 것이 바람직하다. 예를 들면, 글라스 또는 고분자 필름에 백금, 카본, 로듐, 루테늄 등을 증착하거나, 도전성 미립자를 도포한 것을 사용할 수 있다.Examples of the hole transport material include amine-induced amines, conductive polymers such as polyacetylene, polyaniline, and polythiophene, and those using discotech liquid crystal phases such as triphenylene compounds. Moreover, CuI, CuSCN, etc. can be used as a p-type semiconductor. It is preferable that the counter electrode has conductivity and catalyzes the reduction reaction of the redox electrolyte. For example, platinum, carbon, rhodium, ruthenium, or the like deposited on glass or a polymer film, or coated with conductive fine particles can be used.
본 발명의 태양전지에 이용하는 레독스 전해질로서는 할로겐 이온을 대이온으로 하는 할로겐 화합물 및 할로겐 분자로 구성되는 할로겐 산화 환원계 전해질, 페로시안산염-페로시안산염이나 페로센-페리시늄 이온, 코발트 착체 등의 금속착체 등의 금속산화 환원계 전해질, 알킬티올-알킬디설피드, 비올로겐 염료, 하이드로퀴논-퀴논 등의 유기산화 환원계 전해질 등을 사용할 수 있으며, 할로겐 산화 환원계 전해질이 바람직하다. 할로겐 화합물-할로겐 분자로 구성되는 할로겐 산화 환원계 전해질에 있어서의 할로겐 분자로서는 요오드 분자가 바람직하다. 또한 할로겐 이온을 대이온으로 하는 할로겐 화합물로서는 LiI, NaI, KI, CaI2, MgI2, CuI 등의 할로겐화 금속염, 또는 테트라알킬암모늄요오드, 이미다졸리움요오드, 피리디움요오드 등의 할로겐의 유기 암모늄염, 또는 I2를 사용할 수 있다.As a redox electrolyte used in the solar cell of the present invention, a halogen redox electrolyte composed of a halogen compound having a halogen ion as a large ion and a halogen molecule, a ferrocyanate-ferrocyanate, a ferrocene-ferricinium ion, a cobalt complex and the like Metal redox-based electrolytes such as metal complexes, organic redox-based electrolytes such as alkylthiol-alkyldisulfides, viologen dyes, and hydroquinone-quinones, and the like, and halogen-redox electrolytes are preferable. As a halogen molecule in a halogen redox electrolyte composed of a halogen compound-halogen molecule, an iodine molecule is preferable. In addition, the halogen compound to a halogen ion as a counter ion LiI, NaI, KI, CaI 2, MgI 2, a halogenated metal salt such as CuI, or tetra-alkyl ammonium iodine, imidazolium iodine, the organic ammonium salt of halogen such as flutes Stadium iodine, Or I 2 can be used.
또한 레독스 전해질은 이를 포함하는 용액의 형태로 구성되어 있는 경우, 그 용매로는 전기 화학적으로 불활성인 것을 사용할 수 있다. 구체적인 예로서 아세토니트릴, 프로필렌카보네이트, 에틸렌카보네이트, 3-메톡시프로피오니트릴, 메톡시아세토니트릴, 에틸렌글리콜, 프로필렌글리콜, 디에틸렌글리콜, 트리에틸렌글리콜, 부틸로락톤, 디메톡시에탄, 디메틸카보네이트, 1,3-디옥소란, 메틸포르메이트, 2-메틸테트라하이드로퓨란, 3-메톡시-옥사졸리딘-2-온, 설포란, 테트라하이드로퓨란, 물 등을 들 수 있으며, 특히 아세토니트릴, 프로필렌카보네이트, 에틸렌카보네이트, 3-메톡시프로피오니트릴, 에틸렌글리콜, 3-메톡시-옥사졸리딘-2-온, 부틸로락톤 등이 바람직하다. 상기 용매들은 1종 또는 혼합해서 사용할 수 있다. 겔상 양전해질의 경우에는 올리고머 및 폴리머 등의 매트릭스에 전해질 또는 전해질 용액을 함유시킨 것이나, 전분자 겔화제 등에 동일하게 전해질 또는 전해질 용액을 함유시킨 것을 사용할 수 있다. 레독스 전해질의 농도는 0.01-99 중량%인 것이 좋으며, 0.1-30 중량%인 것이 더욱 바람직하다.In addition, when the redox electrolyte is configured in the form of a solution containing the same, an electrochemically inert one may be used as the solvent. Specific examples include acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxy propionitrile, methoxy acetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butyrolactone, dimethoxyethane, dimethyl carbonate, 1,3-dioxolane, methylformate, 2-methyltetrahydrofuran, 3-methoxy-oxazolidin-2-one, sulfolane, tetrahydrofuran, water, and the like, in particular acetonitrile, Propylene carbonate, ethylene carbonate, 3-methoxy propionitrile, ethylene glycol, 3-methoxy-oxazolidin-2-one, butyrolactone and the like are preferable. The solvents may be used alone or in combination. In the case of a gel positive electrolyte, one containing an electrolyte or an electrolyte solution in a matrix such as an oligomer and a polymer, or one containing an electrolyte or an electrolyte solution in the same manner as a starch gelling agent can be used. The concentration of the redox electrolyte is preferably 0.01-99% by weight, more preferably 0.1-30% by weight.
본 발명의 태양전지는 기판상의 산화물 반도체 미립자에 염료를 담지한 광전변환소자(음극)에 그것과 대치하도록 대전극(양극)을 배치하고 그 사이에 레독스 전해질을 함유하는 용액을 충전하는 것에 의하여 얻어질 수 있다.In the solar cell of the present invention, a counter electrode (anode) is disposed in a photoelectric conversion element (cathode) on which a dye is supported on oxide semiconductor fine particles on a substrate so as to face it, and a solution containing a redox electrolyte is filled therebetween. Can be obtained.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.
[실시예]EXAMPLE
염료의 합성에 관련된 반응은 아르곤 분위기에서 진행되었고, 용매는 시그마-알드리치(Sigma-Adrich)사에서 구입한 적합한 시약으로 증류되었다.The reaction involved in the synthesis of the dye proceeded in an argon atmosphere and the solvent was distilled off with a suitable reagent purchased from Sigma-Adrich.
실시예 1 염료의 합성Example 1 Synthesis of Dye
하기 기재된 반응식 1과 같은 반응에 따라 루테늄계 염료 화합물 4를 제조하였다.Ruthenium-based dye compound 4 was prepared according to the same reaction scheme as described below.
[반응식 1]Scheme 1
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-200
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-200
(1) 화합물 1의 제조(1) Preparation of Compound 1
4,4'-dibromo-2,2'-bipyridine(20 g, 63.70 mmol)을 THF 300 ml에 녹인 후 n-Butyllithium(56.06 ml 2.5 M in Hexane, 140 mmol)을 -78 ℃에서 천천히 적가하고 30분간 교반시킨 후 DMF(10.24 g 140.14 mmol)를 넣고 질소 가스 상태 하에서 6시간 동안 25 ℃에서 교반하였다. 교반이 끝난 후 ether 300 ml로 추출 후 water를 사용하여 유기층을 추출하여 chloroform / methanol (1/10) 하에서 재결정으로 분리하였다.4,4'-dibromo-2,2'-bipyridine (20 g, 63.70 mmol) was dissolved in 300 ml of THF, and n-Butyllithium (56.06 ml 2.5 M in Hexane, 140 mmol) was slowly added dropwise at -78 ° C. After stirring for minutes, DMF (10.24 g 140.14 mmol) was added thereto, and the mixture was stirred at 25 ° C. for 6 hours under nitrogen gas. After stirring, the mixture was extracted with ether 300 ml and the organic layer was extracted using water, and then separated by recrystallization under chloroform / methanol (1/10).
(2) 화합물 2의 제조(2) Preparation of Compound 2
Thieno[3,2-b]thiophene(10 g, 71.31 mmol)을 THF 200 ml에 녹인 후 n-Butyllithium(28.52 ml 2.5 M in Hexane, 71.31 mmol)을 -78 ℃에서 천천히 적가하고 30분간 교반시킨 후 9-bromoheptadecane(22.77 g 71.31 mmol)를 넣고 질소 가스 상태 하에서 6시간 동안 25 ℃에서 교반하였다. 교반이 끝난 후 chloroform 200 ml로 추출 후 water를 사용하여 유기층을 추출하여 컬럼 정제(Chloroform/Hexane = 1:1) 후 chloroform / methanol (1/20) 하에서 재결정으로 분리하였다.Thieno [3,2-b] thiophene (10 g, 71.31 mmol) was dissolved in 200 ml of THF, and n-Butyllithium (28.52 ml 2.5 M in Hexane, 71.31 mmol) was slowly added dropwise at -78 ° C and stirred for 30 minutes. 9-bromoheptadecane (22.77 g 71.31 mmol) was added thereto, and the mixture was stirred at 25 ° C. for 6 hours under nitrogen gas. After stirring, the mixture was extracted with 200 ml of chloroform and the organic layer was extracted using water, and then purified by column (Chloroform / Hexane = 1: 1), and then separated by recrystallization under chloroform / methanol (1/20).
(3) 화합물 3의 제조(3) Preparation of Compound 3
2,2'-bipyridine-4,4'-dicarbaldehyde(15 g, 70.69 mmol), 2-(heptadecan-9-yl)thieno[3,2-b]thiophene(26.77 g, 70.69 mmol)와 Trimethylamine(0.42 g, 7.07 mmol)을 Acetic anhydride 100 ml에 녹인 후 reflux하에 교반하였다. 교반이 끝난 후 chloroform 300 ml로 추출 후 water를 사용하여 유기층을 추출하여 chloroform / methanol (1/10) 하에서 재결정으로 분리하였다.2,2'-bipyridine-4,4'-dicarbaldehyde (15 g, 70.69 mmol), 2- (heptadecan-9-yl) thieno [3,2-b] thiophene (26.77 g, 70.69 mmol) and Trimethylamine (0.42 g, 7.07 mmol) was dissolved in 100 ml of Acetic anhydride and stirred under reflux. After stirring, the mixture was extracted with 300 ml of chloroform and the organic layer was extracted using water, and then separated by recrystallization under chloroform / methanol (1/10).
(4) 화합물 4의 제조(4) Preparation of Compound 4
상기 제조된 화합물 3을 이용하여 기존 문헌(Chem. Mater. 2006, 18, 5604-5608)의 합성 방법을 따라 상기 반응식 1과 같이 5번 화합물을 합성하였다.Using compound 3, Compound 5 was synthesized as in Scheme 1 according to the synthesis method of the existing document (Chem. Mater. 2006, 18, 5604-5608).
실시예 2 염료의 합성Example 2 Synthesis of Dye
하기 기재된 반응식 2와 같은 반응에 따라 루테늄계 염료 화합물 7을 제조하였다.Ruthenium-based dye compound 7 was prepared according to the same reaction scheme as described below.
[반응식 2]Scheme 2
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-214
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-214
(1) 화합물 5의 제조(1) Preparation of Compound 5
상기 실시예 1의 화합물 2의 제조방법에서 Thieno[3,2-b]thiophene 대신에 Thiophene을 이용하여 화합물 5를 합성하였다.Compound 5 was synthesized using Thiophene instead of Thieno [3,2-b] thiophene in the method of preparing Compound 2 of Example 1.
(2) 화합물 6의 제조(2) Preparation of Compound 6
상기 실시예 1의 화합물 3의 제조방법에서 2-(heptadecan-9-yl)thieno[3,2-b]thiophene 대신에 화합물 5을 이용하여 화합물 6을 합성하였다. Compound 6 was synthesized by using compound 5 instead of 2- (heptadecan-9-yl) thieno [3,2-b] thiophene in the method of preparing compound 3 of Example 1.
(3) 화합물 7의 제조(3) Preparation of Compound 7
상기 실시예 1의 화합물 4의 제조방법에서 화합물 3 대신에 화합물 6을 이용하여 합성하였다. Compound 6 in place of compound 3 in the method for preparing compound 4 of Example 1 was synthesized.
실시예 3 염료의 합성Example 3 Synthesis of Dye
하기 기재된 반응식 3과 같은 반응에 따라 루테늄계 염료 화합물 10을 제조하였다.A ruthenium-based dye compound 10 was prepared according to the same reaction scheme as described in Scheme 3 below.
[반응식 3] Scheme 3
[규칙 제91조에 의한 정정 23.12.2011]　
Figure WO-DOC-FIGURE-226
[Revisions under Rule 91 23.12.2011]
Figure WO-DOC-FIGURE-226
(1) 화합물 8-1의 제조(1) Preparation of Compound 8-1
상기 실시예 1의 화합물 2의 제조방법에서 Thieno[3,2-b]thiophene 대신에 화합물 8을 이용하여 화합물 8-1을 합성하였다. Compound 8-1 was synthesized by using compound 8 instead of Thieno [3,2-b] thiophene in the method of preparing compound 2 of Example 1.
(2) 화합물 9의 제조 (2) Preparation of Compound 9
상기 실시예 1의 화합물 3의 제조방법에서 2-(heptadecan-9-yl)thieno[3,2-b]thiophene 대신에 화합물 8-1을 이용하여 화합물 9를 합성하였다. Compound 9 was synthesized by using compound 8-1 instead of 2- (heptadecan-9-yl) thieno [3,2-b] thiophene in the method for preparing compound 3 of Example 1.
(3) 화합물 10의 제조(3) Preparation of Compound 10
상기 실시예 1의 화합물 4의 제조방법에서 화합물 3 대신에 화합물 9를 이용하여 합성하였다.In the method for preparing compound 4 of Example 1, compound 9 was used instead of compound 3.
실시예 4 : 제조된 염료의 물성 측정Example 4 Measurement of Physical Properties of Prepared Dyes
상기 실시예 1에서 제조된 본 발명의 염료 화합물의 흡광 스펙트럼을 하기 표 1 및 도 1에 나타내었다. 비교염료로는 종래 염료감응태양전지의 염료로 사용되는 N719를 사용하였다.Absorbance spectra of the dye compounds of the present invention prepared in Example 1 are shown in Table 1 and FIG. 1. As a comparative dye, N719 used as a dye of a conventional dye-sensitized solar cell was used.
표 1
λmax(nm) ε(M-1cm-1) λedge(nm) HOMO(eV) LUMO(eV)
실시예 1 609 11700 840 -5.55 -3.95
N719 515 14000 731 -5.50 -3.80
Table 1
λ max (nm) ε (M -1 cm -1 ) λ edge (nm) HOMO (eV) LUMO (eV)
Example 1 609 11700 840 -5.55 -3.95
N719 515 14000 731 -5.50 -3.80
상기 표 1 및 도 1의 결과로부터 알 수 있듯이, 실시예 1에서 제조된 본 발명의 염료 화합물은 비교염료에 비해 훨씬 높은 흡광도를 나타내어 태양전지의 효율을 향상시킬 것으로 예상된다.As can be seen from the results of Table 1 and Figure 1, the dye compound of the present invention prepared in Example 1 is expected to exhibit a much higher absorbance than the comparative dyes to improve the efficiency of the solar cell.
상기 표 1에 기재되지는 않았지만 실시예 2 및 3에서 제조된 본 발명의 염료 화합물도 상기 실시예 1에서 제조된 염료화합물과 대등한 흡광도를 나타내었다.Although not listed in Table 1, the dye compounds of the present invention prepared in Examples 2 and 3 also exhibited absorbances comparable to those of the dye compounds prepared in Example 1.
실시예 5 : 염료감응태양전지의 제조 및 물성 측정Example 5 Preparation and Measurement of Dye-Sensitized Solar Cell
염료 화합물의 전류-전압 특성을 평가하기 위해, TiO2 투명층을 이용하여 하기 표 2 및 도 2 내지 3에 기재된 바와 같이 두께를 달리하여 태양전지를 제조하였다. TiO2 페이스트(Solaronix, 13 nm 페이스트)를 스크린 프린팅하여 TiO2 투명층을 제조하였다. 이 TiO2 필름을 40 mM TiCl4 용액으로 처리하고 500 ℃에서 30분간 건조하였다. 처리된 필름을 60 ℃로 냉각한 후, 상기 실시예 1에서 제조된 본 발명의 염료 화합물을 디메틸포름아미드 용액에 함침시켰다. 참조(Reference)로서 N719의 에탄올 용액을 사용하였다. 염료-흡착된 TiO2 전극과 백금-대전극 사이에 스페이서로서 고온용융 필름(Surlyn 1702, 25㎛ 두께)을 놓고 가열하여 밀봉된 샌드위치 전지를 조합하였다. 전해질 용액으로는 아세토니트릴 중에 0.6 M 3-헥실-1,2-디메틸이미다졸리움 요오드, 0.04 M I2, 0.025 M GSCn 및 0.28 M tert-부틸피리딘을 용해시킨 것을 사용하였다. Scattering layer 및 AR 코팅은 하지 않았다.In order to evaluate the current-voltage characteristics of the dye compound, a solar cell was manufactured by varying the thickness as described in Table 2 and FIGS. 2 to 3 using a TiO 2 transparent layer. And a TiO 2 paste (Solaronix, 13 nm paste) was screen-printed to prepare a TiO 2 transparent layer. This TiO 2 film was treated with 40 mM TiCl 4 solution and dried at 500 ° C. for 30 minutes. After the treated film was cooled to 60 ° C., the dye compound of the present invention prepared in Example 1 was impregnated into the dimethylformamide solution. As a reference, an ethanol solution of N719 was used. A sealed sandwich cell was assembled by heating a hot melt film (Surlyn 1702, 25 μm thick) as a spacer between the dye-adsorbed TiO 2 electrode and the platinum-electrode. As the electrolyte solution, a solution of 0.6 M 3-hexyl-1,2-dimethylimidazolium iodine, 0.04 MI 2 , 0.025 M GSCn and 0.28 M tert -butylpyridine was dissolved in acetonitrile. Scattering layer and AR coating was not.
본 발명의 염료 화합물과 N719를 사용하여 제조된 태양전지의 광전자화학특성(photoelectrochemical characteristics)을 측정하여 도 2(실시예 1) 내지 3(N719) 및 하기 표 2에 나타내었다. 태양전지의 광전자화학특성은 Keithley M 236 소스 측정 장치를 이용하여 측정하였으며, 광원으로는 AM 1.5 필터(Oriel)가 구비된 300 W Xe 램프를 이용하였고, 전극크기는 0.4 × 0.4 cm2, 빛의 세기는 1 sun(100 mW/cm2)으로 하였다. 빛의 세기는 Si 태양전지를 이용하여 조정하였다.Photoelectrochemical characteristics of the solar cell manufactured using the dye compound of the present invention and N719 were measured and are shown in FIGS. 2 (Example 1) to 3 (N719) and Table 2 below. The photoelectrochemical characteristics of the solar cell were measured using a Keithley M 236 source measuring device, and a 300 W Xe lamp equipped with an AM 1.5 filter (Oriel) was used as the light source, and the electrode size was 0.4 × 0.4 cm 2 . The intensity was 1 sun (100 mW / cm 2 ). Light intensity was adjusted using a Si solar cell.
표 2
Voc(V) Jsc(mA/cm2) FF(%) η(%) Area(cm2) 두께(um)
N719 0.866 6.83 76.64 4.53 0.162 3.93
0.818 11.12 74.31 6.76 0.165 7.58
0.801 12.74 73.21 7.47 0.187 11.81
실시예 1 0.800 11.03 73.86 6.52 0.177 3.92
0.757 14.63 73.10 8.10 0.163 7.92
0.747 15.81 73.07 8.64 0.193 12.17
TABLE 2
V oc (V) J sc (mA / cm 2 ) FF (%) η (%) Area (cm 2 ) Thickness (um)
N719 0.866 6.83 76.64 4.53 0.162 3.93
0.818 11.12 74.31 6.76 0.165 7.58
0.801 12.74 73.21 7.47 0.187 11.81
Example 1 0.800 11.03 73.86 6.52 0.177 3.92
0.757 14.63 73.10 8.10 0.163 7.92
0.747 15.81 73.07 8.64 0.193 12.17
상기 표 2에서, Jsc는 단회로 광전류 밀도(short-circuit photocurrent density), Voc는 오픈 회로 광전압(open circuit photovoltage), FF는 충전 인자(fill factor)를 나타낸다.In Table 2, J sc represents a short-circuit photocurrent density, V oc represents an open circuit photovoltage, and FF represents a fill factor.
상기 표 2 및 도 2 내지 3에 나타난 바와 같이 본 발명의 염료화합물은 N719와 비교하여 매우 높은 광전변환 효율을 나타냄을 확인할 수 있었으며, 실시예 2 및 3에서 제조한 염료화합물도 표 2에는 기재되지 않았지만 실시예 1과 대등한 광전변환 효율을 나타내어 염료감응태양전지의 염료화합물로 유용하게 사용할 수 있음을 확인하였다.As shown in Table 2 and Figures 2 to 3 it was confirmed that the dye compound of the present invention shows a very high photoelectric conversion efficiency compared to N719, the dye compounds prepared in Examples 2 and 3 are also not described in Table 2. Although it showed a photoelectric conversion efficiency similar to that of Example 1, it was confirmed that it can be usefully used as a dye compound of the dye-sensitized solar cell.
본 발명의 신규한 루테늄계 염료는 종래의 염료보다 현저히 향상된 광전기 변환 효율을 나타내며, 산화물 반도체 미립자와의 결합력을 강화시키고, Jsc(short circuit photocurrent density)와 몰 흡광계수가 우수하여 태양전지의 효율을 크게 향상시킬 수 있다.The novel ruthenium-based dyes of the present invention exhibit significantly improved photovoltaic conversion efficiency than conventional dyes, enhance bonding with oxide semiconductor fine particles, and have excellent short circuit photocurrent density (Jsc) and molar extinction coefficient to improve solar cell efficiency. It can greatly improve.

Claims (7)

  1. [규칙 제91조에 의한 정정 23.12.2011]
    하기 화학식 1로 표시되는 염료:
    [화학식 1]
    Figure WO-DOC-FIGURE-c1
    상기 화학식 1에서 Me는 Ru 또는 Os이며, a1 환은 각각 독립적으로 치환기를 가지지 않거나 1개 이상의 치환기를 가질 수 있으며, 치환기로는 할로겐 원자, 아미드기, 시아노기, 히드록실기, 니트로기, 아실기, C1-30 알킬기 또는 C1-30 알콕시기 일 수 있으며, Y는 수소, Na, 또는 TBA(tert-butyl alcohol)이며,
    또한 X1, X2는 각각 독립적으로 메틸 또는 하기 화학식 2로 표시되는 화합물이며, X1와 X2 중 적어도 하나는 화학식 2로 표시되는 화합물이며,
    [화학식 2]
    Figure WO-DOC-FIGURE-c2a
    상기 화학식 2에서 A는 , , 및 로 이루어진 군에서 1종 이상 선택되며, 이때 X는 각각 독립적으로 O, S, Se, Si 및 NR5로 이루어진 군으로부터 선택되고, R1 내지 R4는 각각 독립적으로 수소, 치환 또는 비치환된 C1-12 알킬, 치환 또는 비치환된 C6-30 아릴 및 치환 또는 비치환된 C6-20 헤테로아릴로 이루어진 군에서 선택되거나, 또는 서로 연결되어 환을 형성할 수 있으며, R5는 수소 또는 치환 또는 비치환된 C1-30 알킬이고, n은 1 내지 10의 정수이며,
    Figure WO-DOC-FIGURE-c2b
    Figure WO-DOC-FIGURE-c2c
    Figure WO-DOC-FIGURE-c2d
    Figure WO-DOC-FIGURE-c2e
    B는 하기 화학식 3으로 표시되는 화합물 또는 하기 화학식 4로 표시되는 화합물이며,
    [화학식 3]
    Figure WO-DOC-FIGURE-c3
    [화학식 4]
    Figure WO-DOC-FIGURE-c4
    상기 화학식 3에서 Ar1, Ar2 및 Ar3은 각각 독립적으로 치환 또는 비치환된 C6-50 아릴, 치환 또는 비치환된 C6-20 헤테로아릴로 이루어진 군에서 선택되거나, 또는 서로 연결되어 환을 형성할 수 있으며, *는 결합부분이며, 상기 화학식 4에서 R6 및 R7는 각각 독립적으로 치환 또는 비치환된 C1-30 알킬이며, *는 결합부분이다.
    [Revisions under Rule 91 23.12.2011]
    Dye represented by the following formula (1):
    [Formula 1]
    Figure WO-DOC-FIGURE-c1
    In Formula 1, Me is Ru or Os, and each of the a1 rings may independently have a substituent or may have one or more substituents, and examples of the substituent include a halogen atom, an amide group, a cyano group, a hydroxyl group, a nitro group, and an acyl group. , C 1-30 alkyl group or C 1-30 alkoxy group, Y is hydrogen, Na, or TBA (tert-butyl alcohol),
    In addition, X 1 , X 2 are each independently methyl or a compound represented by the formula (2), at least one of X 1 and X 2 is a compound represented by the formula (2),
    [Formula 2]
    Figure WO-DOC-FIGURE-c2a
    In Formula 2, A is selected from one or more selected from the group consisting of, wherein X is each independently selected from the group consisting of O, S, Se, Si and NR 5 , and R 1 to R 4 are each independently Hydrogen, substituted or unsubstituted C 1-12 alkyl, substituted or unsubstituted C 6-30 aryl and substituted or unsubstituted C 6-20 heteroaryl, or are linked to each other to form a ring R 5 is hydrogen or substituted or unsubstituted C 1-30 alkyl, n is an integer from 1 to 10,
    Figure WO-DOC-FIGURE-c2b
    Figure WO-DOC-FIGURE-c2c
    Figure WO-DOC-FIGURE-c2d
    Figure WO-DOC-FIGURE-c2e
    B is a compound represented by the following formula (3) or a compound represented by the following formula (4),
    [Formula 3]
    Figure WO-DOC-FIGURE-c3
    [Formula 4]
    Figure WO-DOC-FIGURE-c4
    In Formula 3 Ar 1, Ar 2 and Ar 3 are each independently a substituted or unsubstituted C 6-50 aryl, substituted or unsubstituted selected from the consisting of unsubstituted C 6-20 heteroaryl group, or a ring are connected to each other It may form, * is a bonding moiety, in Formula 4 R 6 and R 7 are each independently substituted or unsubstituted C 1-30 alkyl, * is a bonding moiety.
  2. [규칙 제91조에 의한 정정 23.12.2011]
    제1항에 있어서,
    상기 염료는 하기 화학식 1-1 내지 1-48로 표시되는 것들 중 하나인 루테늄(Ru)계 염료:
    [화학식 1-1]
    Figure WO-DOC-FIGURE-c11
    [화학식 1-2]
    Figure WO-DOC-FIGURE-c12
    [화학식 1-3]
    Figure WO-DOC-FIGURE-c13
    [화학식 1-4]
    Figure WO-DOC-FIGURE-c14
    [화학식 1-5]
    Figure WO-DOC-FIGURE-c15
    [화학식 1-6]
    Figure WO-DOC-FIGURE-c16
    [화학식 1-7]
    Figure WO-DOC-FIGURE-c17
    [화학식 1-8]
    Figure WO-DOC-FIGURE-c18
    [화학식 1-9]
    Figure WO-DOC-FIGURE-c19
    [화학식 1-10]
    Figure WO-DOC-FIGURE-c110
    [화학식 1-11]
    Figure WO-DOC-FIGURE-c111
    [화학식 1-12]
    Figure WO-DOC-FIGURE-c112
    [화학식 1-13]
    Figure WO-DOC-FIGURE-c113
    [화학식 1-14]
    Figure WO-DOC-FIGURE-c114
    [화학식 1-15]
    Figure WO-DOC-FIGURE-c115
    [화학식 1-16]
    Figure WO-DOC-FIGURE-c116
    [화학식 1-17]
    Figure WO-DOC-FIGURE-c117
    [화학식 1-18]
    Figure WO-DOC-FIGURE-c118
    [화학식 1-19]
    Figure WO-DOC-FIGURE-c119
    [화학식 1-20]
    Figure PCTKR2011008175-appb-I000100
    [화학식 1-21]
    Figure PCTKR2011008175-appb-I000101
    [화학식 1-22]
    Figure WO-DOC-FIGURE-c122
    [화학식 1-23]
    Figure WO-DOC-FIGURE-c123
    [화학식 1-24]
    Figure WO-DOC-FIGURE-c124
    [화학식 1-25]
    Figure WO-DOC-FIGURE-c125
    [화학식 1-26]
    Figure WO-DOC-FIGURE-c126
    [화학식 1-27]
    Figure WO-DOC-FIGURE-c127
    [화학식 1-28]
    Figure WO-DOC-FIGURE-c128
    [화학식 1-29]
    Figure WO-DOC-FIGURE-c129
    [화학식 1-30]
    Figure WO-DOC-FIGURE-c130
    [화학식 1-31]
    Figure WO-DOC-FIGURE-c131
    [화학식 1-32]
    Figure WO-DOC-FIGURE-c132
    [화학식 1-33]
    Figure WO-DOC-FIGURE-c133
    [화학식 1-34]
    Figure WO-DOC-FIGURE-c134
    [화학식 1-35]
    Figure WO-DOC-FIGURE-c135
    [화학식 1-36]
    Figure WO-DOC-FIGURE-c136
    [화학식 1-37]
    Figure WO-DOC-FIGURE-c137
    [화학식 1-38]
    Figure WO-DOC-FIGURE-c138
    [화학식 1-39]
    Figure WO-DOC-FIGURE-c139
    [화학식 1-40]
    Figure WO-DOC-FIGURE-c140
    [화학식 1-41]
    Figure WO-DOC-FIGURE-c141
    [화학식 1-42]
    Figure WO-DOC-FIGURE-c142
    [화학식 1-43]
    Figure WO-DOC-FIGURE-c143
    [화학식 1-44]
    Figure WO-DOC-FIGURE-c144
    [화학식 1-45]
    Figure WO-DOC-FIGURE-c145
    [화학식 1-46]
    Figure WO-DOC-FIGURE-c146
    [화학식 1-47]
    Figure WO-DOC-FIGURE-c147
    [화학식 1-48]
    Figure WO-DOC-FIGURE-c148
    [Revisions under Rule 91 23.12.2011]
    The method of claim 1,
    The dye is a ruthenium (Ru) -based dye which is one of those represented by the formula 1-1 to 1-48:
    [Formula 1-1]
    Figure WO-DOC-FIGURE-c11
    [Formula 1-2]
    Figure WO-DOC-FIGURE-c12
    [Formula 1-3]
    Figure WO-DOC-FIGURE-c13
    [Formula 1-4]
    Figure WO-DOC-FIGURE-c14
    [Formula 1-5]
    Figure WO-DOC-FIGURE-c15
    [Formula 1-6]
    Figure WO-DOC-FIGURE-c16
    [Formula 1-7]
    Figure WO-DOC-FIGURE-c17
    [Formula 1-8]
    Figure WO-DOC-FIGURE-c18
    [Formula 1-9]
    Figure WO-DOC-FIGURE-c19
    [Formula 1-10]
    Figure WO-DOC-FIGURE-c110
    [Formula 1-11]
    Figure WO-DOC-FIGURE-c111
    [Formula 1-12]
    Figure WO-DOC-FIGURE-c112
    [Formula 1-13]
    Figure WO-DOC-FIGURE-c113
    [Formula 1-14]
    Figure WO-DOC-FIGURE-c114
    [Formula 1-15]
    Figure WO-DOC-FIGURE-c115
    [Formula 1-16]
    Figure WO-DOC-FIGURE-c116
    [Formula 1-17]
    Figure WO-DOC-FIGURE-c117
    [Formula 1-18]
    Figure WO-DOC-FIGURE-c118
    [Formula 1-19]
    Figure WO-DOC-FIGURE-c119
    [Formula 1-20]
    Figure PCTKR2011008175-appb-I000100
    [Formula 1-21]
    Figure PCTKR2011008175-appb-I000101
    [Formula 1-22]
    Figure WO-DOC-FIGURE-c122
    [Formula 1-23]
    Figure WO-DOC-FIGURE-c123
    [Formula 1-24]
    Figure WO-DOC-FIGURE-c124
    [Formula 1-25]
    Figure WO-DOC-FIGURE-c125
    [Formula 1-26]
    Figure WO-DOC-FIGURE-c126
    [Formula 1-27]
    Figure WO-DOC-FIGURE-c127
    [Formula 1-28]
    Figure WO-DOC-FIGURE-c128
    [Formula 1-29]
    Figure WO-DOC-FIGURE-c129
    [Formula 1-30]
    Figure WO-DOC-FIGURE-c130
    [Formula 1-31]
    Figure WO-DOC-FIGURE-c131
    [Formula 1-32]
    Figure WO-DOC-FIGURE-c132
    [Formula 1-33]
    Figure WO-DOC-FIGURE-c133
    [Formula 1-34]
    Figure WO-DOC-FIGURE-c134
    [Formula 1-35]
    Figure WO-DOC-FIGURE-c135
    [Formula 1-36]
    Figure WO-DOC-FIGURE-c136
    [Formula 1-37]
    Figure WO-DOC-FIGURE-c137
    [Formula 1-38]
    Figure WO-DOC-FIGURE-c138
    [Formula 1-39]
    Figure WO-DOC-FIGURE-c139
    [Formula 1-40]
    Figure WO-DOC-FIGURE-c140
    [Formula 1-41]
    Figure WO-DOC-FIGURE-c141
    [Formula 1-42]
    Figure WO-DOC-FIGURE-c142
    [Formula 1-43]
    Figure WO-DOC-FIGURE-c143
    [Formula 1-44]
    Figure WO-DOC-FIGURE-c144
    [Formula 1-45]
    Figure WO-DOC-FIGURE-c145
    [Formula 1-46]
    Figure WO-DOC-FIGURE-c146
    [Formula 1-47]
    Figure WO-DOC-FIGURE-c147
    [Formula 1-48]
    Figure WO-DOC-FIGURE-c148
  3. [규칙 제91조에 의한 정정 23.12.2011]
    하기 화학식 5의 화합물을 하기 화학식 6, 화학식 7 및 화학식 8의 화합물과 순차적으로 반응시키는 것을 특징으로 하는 화학식 1로 표시되는 염료의 제조방법:
    [화학식 5]
    Figure WO-DOC-FIGURE-c5
    [화학식 6]
    [RuCl2(p-cymene)]2
    [화학식 7]
    Figure WO-DOC-FIGURE-c7
    [화학식 8]
    NH4NCS
    상기 화학식 5, 6, 7 및 8에서 X1, X2, 및 a1는 제1항에서 정의한 바와 같다.
    [Revisions under Rule 91 23.12.2011]
    A method for preparing a dye represented by Formula 1, comprising sequentially reacting a compound of Formula 5 with a compound of Formula 6, Formula 7, and Formula 8:
    [Formula 5]
    Figure WO-DOC-FIGURE-c5
    [Formula 6]
    RuCl 2 ( p -cymene) 2
    [Formula 7]
    Figure WO-DOC-FIGURE-c7
    [Formula 8]
    NH 4 NCS
    In Formulas 5, 6, 7, and 8, X 1 , X 2 , and a1 are the same as defined in claim 1.
  4. 제1항 기재의 염료로 담지시킨 산화물 반도체 미립자를 포함하는 것을 특징으로 하는 염료증감 광전변환소자.A dye-sensitized photoelectric conversion element comprising oxide semiconductor fine particles supported by the dye of claim 1.
  5. 제4항에 있어서,The method of claim 4, wherein
    상기 염료증감 광전변환소자는 산화물 반도체 미립자에 포섭화합물의 존재하에 염료를 담지시킨 것을 특징으로 하는 염료증감 광전변환소자.The dye-sensitized photoelectric conversion device is a dye-sensitized photoelectric conversion device characterized in that the dye is carried on the oxide semiconductor fine particles in the presence of the inclusion compound.
  6. 제4항에 있어서,The method of claim 4, wherein
    상기 산화물 반도체 미립자가 평균 입경이 1-500 nm인 이산화티탄을 필수성분으로 포함하는 것을 특징으로 하는 염료증감 광전변환소자.The dye-sensitized photoelectric conversion device, characterized in that the oxide semiconductor fine particles contain titanium dioxide having an average particle diameter of 1-500 nm as an essential component.
  7. 제4항 기재의 염료증감 광전변환소자를 포함하는 것을 특징으로 하는 염료감응태양전지.A dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device according to claim 4.
PCT/KR2011/008175 2010-11-01 2011-10-31 Novel ruthenium-based dye and preparation method thereof WO2012060587A2 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999050358A1 (en) * 1998-03-27 1999-10-07 Hahn-Meitner-Institut Berlin Gmbh Photosensitizer for applications in solar technology, method for the production thereof and configuration to implement the method
EP1176618A1 (en) * 2000-07-25 2002-01-30 Fuji Photo Film Co., Ltd. Metal complex dye, photoelectric conversion device and photoelectric cell
EP1178084A1 (en) * 2000-07-31 2002-02-06 Neomat S.A. Processes for the preparation of carboxylate and phosphonate ruthenium polypyridine dyes and intermediates

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999050358A1 (en) * 1998-03-27 1999-10-07 Hahn-Meitner-Institut Berlin Gmbh Photosensitizer for applications in solar technology, method for the production thereof and configuration to implement the method
EP1176618A1 (en) * 2000-07-25 2002-01-30 Fuji Photo Film Co., Ltd. Metal complex dye, photoelectric conversion device and photoelectric cell
EP1178084A1 (en) * 2000-07-31 2002-02-06 Neomat S.A. Processes for the preparation of carboxylate and phosphonate ruthenium polypyridine dyes and intermediates

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