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WO2012060587A2 - Nouveau colorant à base de ruthénium et son procédé de préparation - Google Patents

Nouveau colorant à base de ruthénium et son procédé de préparation Download PDF

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Publication number
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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English (en)
Korean (ko)
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WO2012060587A3 (fr
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이종찬
안현철
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주식회사 동진쎄미켐
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Priority to CN2011800526100A priority Critical patent/CN103189452A/zh
Priority claimed from KR1020110111744A external-priority patent/KR101940491B1/ko
Publication of WO2012060587A2 publication Critical patent/WO2012060587A2/fr
Publication of WO2012060587A3 publication Critical patent/WO2012060587A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • C07F15/0053—Ruthenium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0008—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, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • 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.

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Abstract

La présente invention concerne de nouveaux colorants à base de ruthénium et leur procédé de préparation, et plus particulièrement, un colorant qui offre une efficacité de conversion photoélectrique remarquablement améliorée par rapport aux colorants classiques lors de l'utilisation dans des cellules solaires à colorants, qui renforce la force de liaison au dioxyde de titane, et qui a un Jsc (densité de photocourant de court-circuit) supérieur et une absorptivité molaire supérieure, améliorant ainsi remarquablement l'efficacité des cellules solaires, et son procédé de préparation.
PCT/KR2011/008175 2010-11-01 2011-10-31 Nouveau colorant à base de ruthénium et son procédé de préparation WO2012060587A2 (fr)

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KR1020110111744A KR101940491B1 (ko) 2010-11-01 2011-10-31 신규한 루테늄계 염료 및 이의 제조방법

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999050358A1 (fr) * 1998-03-27 1999-10-07 Hahn-Meitner-Institut Berlin Gmbh Photosensibilisateur destine a des applications industrielles solaires, son procede de production et configuration correspondante
EP1176618A1 (fr) * 2000-07-25 2002-01-30 Fuji Photo Film Co., Ltd. Colorant de complexes métalliques, dispositif de conversion photoélectrique et cellule photoélectrochimique
EP1178084A1 (fr) * 2000-07-31 2002-02-06 Neomat S.A. Procédés de préparation de colorants et d'intermédiaires complexes du ruthénium avec des carboxylates et phosphonates de polypyridines

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999050358A1 (fr) * 1998-03-27 1999-10-07 Hahn-Meitner-Institut Berlin Gmbh Photosensibilisateur destine a des applications industrielles solaires, son procede de production et configuration correspondante
EP1176618A1 (fr) * 2000-07-25 2002-01-30 Fuji Photo Film Co., Ltd. Colorant de complexes métalliques, dispositif de conversion photoélectrique et cellule photoélectrochimique
EP1178084A1 (fr) * 2000-07-31 2002-02-06 Neomat S.A. Procédés de préparation de colorants et d'intermédiaires complexes du ruthénium avec des carboxylates et phosphonates de polypyridines

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