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WO2008146975A1 - Novel organic dye containing n-arylcarbazole moiety and preparation thereof - Google Patents

Novel organic dye containing n-arylcarbazole moiety and preparation thereof Download PDF

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Publication number
WO2008146975A1
WO2008146975A1 PCT/KR2007/003206 KR2007003206W WO2008146975A1 WO 2008146975 A1 WO2008146975 A1 WO 2008146975A1 KR 2007003206 W KR2007003206 W KR 2007003206W WO 2008146975 A1 WO2008146975 A1 WO 2008146975A1
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WO
WIPO (PCT)
Prior art keywords
formula
compound
dye
following formula
prepare
Prior art date
Application number
PCT/KR2007/003206
Other languages
French (fr)
Inventor
Chong-Chan Lee
Ho-Gi Bae
Jae-Jung Ko
Jong-Hyub Baek
Duck-Hyun Kim
Original Assignee
Dongjin Semichem Co., Ltd
Korea University Industrial & Academic Collaboration Foundation
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Application filed by Dongjin Semichem Co., Ltd, Korea University Industrial & Academic Collaboration Foundation filed Critical Dongjin Semichem Co., Ltd
Publication of WO2008146975A1 publication Critical patent/WO2008146975A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B49/00—Sulfur dyes
    • 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
    • C09B49/00—Sulfur dyes
    • C09B49/12—Sulfur dyes from other compounds, e.g. other heterocyclic compounds
    • C09B49/124—Sulfur dyes from other compounds, e.g. other heterocyclic compounds from polycarbocyclic compounds
    • 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
    • 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
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • 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
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to novel organic dye containing N- arylcarbazole moiety, which is used for a dye-sensitized solar cell (DSSC), and a process for preparing the same.
  • DSSC dye-sensitized solar cell
  • the dye-sensitized solar cell is a photoelectrochemical solar cell essentially consisting of a dye molecule capable of absorbing a visible ray and generating electron-hole pair and a transition metal oxide for transmitting the generated electrons.
  • ruthenium complex As the dye for a dye-sensitized solar cell, ruthenium complex having high photoelectric conversion efficiency has been widely used. However, the ruthenium complex had a defect of high cost.
  • metal-free organic dye which has excellent properties in terms of an absorption efficiency, oxidation- reduction stability and charge-transfer(CT) absorption in a molecule, can be used as the dye for a solar cell instead of the expensive ruthenium complex.
  • CT charge-transfer
  • the organic dye has a structure consisting of an electron donor - electron acceptor moities which are linked by ⁇ -bond.
  • an amine derivative functions as an electron donor
  • 2- cyanoacrylic acid or rhodanine moiety functions as an electron acceptor
  • the two parts are linked by a ⁇ -bond system such as methaine unit or thiophene chain.
  • the structural change of electron donor amine causes a change in electron' s properties, for example, a blue-shifted absorption spectrum, and causes a change in the ⁇ -bond length thus controlling absorption spectrum and redox potential.
  • N-arylcarbazole based dye of the following Formula 1: [Formula 1]
  • X 9,9-dimethylfluorenyl or 4-(2,2-diphenylvinyl )phenyl
  • Y is cyanoacrylic acid or rhodanine-3-acetic acid moiety
  • n is an integer of 1 to 5
  • two or more thiophene units can be optionally linked by vinyl group.
  • the present invention provides a process for preparing N-carbazole based dye of the Formula Ia or Ib, comprising the steps of:
  • n is an integer of 1 to 5, and two or more thiophene units can be optionally linked by vinyl group.
  • the present invention provides a process for preparing N- arylcarbazole based dye of the Formula Ic, comprising the steps of:
  • n 1
  • the present invention provides a process for preparing N- arylcarbazole based dye of the Formula Id, comprising the steps of:
  • the present invention provides a dye-sensitized photoelectric conversion element comprising oxide semiconductor particles where the N- arylcarbazole based dye of the present invention is supported.
  • the present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion element of the present invention.
  • the novel dye containing N-arylcarbazole moiety of the present invention shows improved molar absorptivity, JscCshort circuit photocurrent density) and photoelectric conversion efficiency compared to dyes of the prior art, and thus it can greatly improve solar cell efficiency. And, it can dramatically decrease dye synthesis cost because the dye of the present invention can be purified without using expensive columns.
  • Fig. 1 (a) to (f) show absorption and emission spectrums of each of the dye compounds Ia-I, la-2, Ib-I, lb-2, Ic and Id of the present invention in ethanol, and emission spectrums of the dye compounds supported on TiO 2 layer.
  • Fig. 3 shows IPCEC incident photon-to-current conversion efficiency) spectrums of the solar cells respectively prepared using each of the dye compounds Ia-I, la-2, Ib-I, lb-2, Ic and Id of the present invention.
  • a dye-sensitized solar cell prepared by supporting, on oxide semiconductor particles, a compounds of the Formula 1, which has a novel organic dye structure of using fluorene and carbazole as an electron donor, introducing thiophene unit in the middle linking part for increasing molar absorptivity and stability of the element, and using rhodanine-3-acetic acid or cyanoacrylic acid which is closely connected with TiO 2 reforming and has the best electron transport capacity as an electron acceptor, has high photoelectric conversion efficiency, JscCshort circuit photocurrent density) and molar absorptivity, and thus has superior efficiency to the existing dye-sensitized solar cells, and completed the present invention.
  • the dye of the present invention is represented by the following Formula 1, and preferably one of the following Formulas Ia-I, la-2, Ib-I, lb-2, Ic or Id:
  • each X, Y and n has the same meaning as defined above.
  • the present invention provides processes for preparing dye of the Formula Ia or Ib, dye of the Formula Ic and dye of the Formula Id.
  • Stille coupling reaction means reacting under Sti lie reaction conditions using tetrakis(triphenylphosphine)pal ladium(O) , dimethylformamide and stanylthiophene;
  • Ullmann coupling means reacting under Ullmann reaction conditions using copper bronze, potassium carbonate and 18-crwon-6;
  • Horner-Emmons-Wittig coupling means reacting under Horner-Emmons-Wittig reaction conditions using potassium-ferf-butoxide in tetrahydrofurane.
  • the dye of the Formula Ia and Ib can be prepared according he following Reaction Formula 1. [Reaction Formula 1]
  • the dye of the Formula Ic and Id can be prepared according he following Reaction Formula 2. [Reaction Formula 2]
  • 3-iodocarbazole which is used for a starting material for preparing the dye of the Formula 1 can be obtained by common methods.
  • the present invention provides a dye-sensitized photoelectric conversion element, wherein the dye of the Formula 1 is supported on oxide semiconductor particles.
  • any processes for preparing a dye-sensitized photoelectric conversion element for solar cells of the prior art can be applied, except using the dye of the above
  • the dye-sensitized photoelectric conversion element of the present invention is prepared by forming an oxide semiconductor thin film on a substrate, using oxide semiconductor particles, and then supporting the dye of the present invention on the thin film.
  • a substrate having conductive surface is preferably used, but any commercially available substrates can be used.
  • a substrate wherein a thin film of metal such as copper, silver, gold, etc. or conductive metal oxide such as tin oxide coated with indium, fluorine, or antimony, etc. is formed on the surface of glass or transparent polymer such as polyethyleneterephthalate or polyethersulfone, etc. can be used.
  • the conductivity of the substrate is preferably 1000 ⁇ or less, and more preferably 100 ⁇ or less.
  • a metal oxide is preferably used as the oxide semiconductor particles.
  • oxides of titanium, tin, zinc, tungsten, zirconium, gallium, indium, itrium, niobium, tantalum, vanadium, etc. can be used.
  • an oxide of titanium, tin, zinc, niobium, or indium is preferable, titanium oxide, zinc oxide and tin oxide are more preferable, and titanium oxide is most preferable.
  • the oxide semiconductor can be used alone or in combination, and can be coated on the surface of the semiconductor.
  • the oxide semiconductor particles preferably have an average particle size of 1 ⁇ 500 run, and more preferably 1 ⁇ 100 nm.
  • oxide semiconductor particles having large particle size and those having small particle size can be mixed, or they can be used in multi-layers.
  • the oxide semiconductor thin film can be prepared by directly forming a thin film of oxide semiconductor particles by spraying, etc.; by electrically depositing semiconductor thin film using a substrate as an electrode; or by coating on a substrate a paste containing semiconductor particles which is obtained by hydrolyzing a precursor of semiconductor particles such as a slurry of semiconductor particles or semiconductor alkoxide, etc., and then drying, curing or calcining.
  • a process of coating a paste on a substrate wherein a slurry can be obtained by dispersing secondary condensed oxide semiconductor particles in a dispersion medium by a common method so that a first average particle size is 1 ⁇ 200 nm.
  • any dispersion medium capable of dispersing semiconductor particles can be used without limitation.
  • water, alcohol such as ethanol, etc., ketone such as acetone, acetylacetone, etc., or hydrocarbon such a hexane, etc. can be used. They can be used in combination, and water is preferable because it reduces viscosity change of the slurry.
  • a dispersion stabilizer can be used for stabilizing the dispersion state of the oxide semiconductor particles.
  • the dispersion stabilizer include acid such as acetic acid, hydrochloric acid, nitric acid, etc. acetylacetone, acrylic acid, polyethyleneglycol , polyvinylalcohol , etc.
  • the substrate coated with the slurry can be subjected to calcination.
  • the calcination temperature is 100 °C or more, preferably 200 °C or more, and the upper limit of the calcination temperature is a melting point(softening point) of the substrate or less, commonly 900 °C , preferably 600 °C or less.
  • the calcination time is not specifically limited, but preferably within 4 hours.
  • the thickness of the thin film on the substrate is suitably 1 - 200 ⁇ m, and preferably 1 ⁇ 50 ⁇ m.
  • a thin layer of the oxide semiconductor particles is partly welded, which does not specifically cause any troubles in the present invention.
  • the thin film can be immersed in a solution of alkoxide, chloride, nitride or sulfide of the same metal as the semiconductor, and dried or re-calcined, thereby improving the performance of the semiconductor thin film.
  • the metal alkoxide includes titanium ethoxide, titanium isoproepoxide, titanium t-butoxide, n-dibutyl-diacetyl tin, etc., and the alcohol solution thereof can be used.
  • the chloride includes titanium chloride, tin chloride, zinc chloride, etc., and the aqueous solution thereof can be used.
  • oxide semiconductor thin film consists of oxide semiconductor particles.
  • the method for supporting dye on the oxide semiconductor thin film is not specifically limited in the present invention.
  • a substrate on which the oxide semiconductor thin film is formed can be immersed in a solution obtained by dissolving the dye of the Formula 1 in a solvent capable of dissolving it, or in a dispersion obtained by dispersing the dye.
  • concentration of the dye in the solution or dispersion can be appropriately determined according to the dye.
  • the immersion temperature is generally from a room temperature to a boiling point of the solvent, and the immersion time is from about 1 minute to 48 hours.
  • the solvent for dissolving the dye includes methanol, ethanol, acetonitri Ie, dimethylsulfoxide, dimethylformamide, acetone, t-butanol, etc.
  • the concentration of the dye in the solution is suitably Ix 10 "6 M ⁇ 1 M, and preferably 1 x 10 "5 M ⁇ 1 x 10 "1 M.
  • the dye-sensitized photoelectric conversion element of the present invention comprising oxide semiconductor particles in the form of a thin film can be obtained.
  • One kind of the dye of the Formula 1 can be supported, or some kinds of the dyes can be mixed and supported. And, the dye of the present invention can be mixed with other dyes or metal complex dyes.
  • the examples of the metal complex dyes which can be mixed with the dye of the present invention are not specifically limited, but ruthenium complex or the quaternary salt thereof, phthalocyanine, or porphyrin is preferable.
  • the examples of the organic dyes which can be mixed with the dye of the present invention include metal-free phthalocyanine, porphyrin or cyanine, merocyanine, oxonol , triphenylmethane-based dyes, methyne-based dyes such as acrylic acid based dyes described in W02002/011213, xanthene-based, azo ⁇ based, anthraquinone-based, or perylene-based dyes (see the literature [M.K.Nazeeruddin, A.Kay, I.Rodicio, R.Humphry-Baker, E.Muller, P.Liska, N.Vlachopoulos, M.Gratzel, J .Am.Chem.Soc. , ro/ii5,p6382(1993)]).
  • the dyes can be sequentially absorbed to the semiconductor thin film, or they can be mixed, dissolved and absorbed.
  • the dye when the dye is supported on the thin film of the oxide semiconductor particles, it is preferable to support the dye in the presence of an inclusion compound in order to prevent bonding between the dyes.
  • an inclusion compound cholic acid such as deoxycholic acid, dehydrodeoxychol ic acid, kenodeoxycholic acid, cholic acid methyl ester, sodium cholic acid, etc., steroid-based compound, crown ether, cyclodextrin, calix arene, polyethylene oxide, etc. can be used.
  • the electrode surface of the semiconductor can be treated with amine compound such as 4-t-butyl pyridine, etc., or compounds having an acid group such as acetic acid, propionic acid, etc.
  • amine compound such as 4-t-butyl pyridine, etc.
  • compounds having an acid group such as acetic acid, propionic acid, etc.
  • a substrate on which a dye-supported semiconductor thin film is formed can be immersed in an ethanol solution of amine.
  • the present invention also provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion element of the present invention.
  • a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion element of the present invention.
  • the dye-sensitized solar cell may consist of a photoelectric conversion element electrode (anode), a counter electrode (cathode), redox electrolyte, hole transport material or p-type semiconductor, etc.
  • the dye-sensitized solar cell of the present invention can be prepared by a process comprising the steps of coating a titanium oxide on a transparent conductive substrate! subjecting the coated substrate to calcination so as to form a titanium oxide thin film; impregnating the titanium oxide thin film with a mixed solution in which the dye of the Formula 1 is dissolved, so as to form a dye-absorbed titanium oxide film electrode; providing a second glass substrate on which a counter electrode is formed; forming a hole through the second glass substrate and the counter electrode; placing a thermoplastic polymer film between the counter electrode and the dye-absorbed titanium oxide film electrode, and conducting heat pressing, so as to join the counter electrode and the titanium oxide film electrode; injecting an electrolyte in the thermoplastic polymer film placed between the counter electrode and the titanium oxide film electrode through the hole; and, sealing the thermoplastic polymer.
  • the redox electrolyte, hole transport material, p-type semiconductor, etc. can be of a liquid, condensed (gel and gel-type), or solid type.
  • the liquid type includes those prepared by dissolving redox electrolyte, dissolved salt, hole transport material, or p-type semiconductor in a solvent, or a room temperature dissolved salt.
  • the condensed type includes those containing redox electrolyte, dissolved salt, hole transport material, or p-type semiconductor in a polymer matrix or low molecule gelling agent.
  • the solid type includes redox electrolyte, dissolved salt, hole transport material, or p-type semiconductor.
  • the hole transport material those using discotic liquid crystal phase such as amine derivatives, conductive polymer such as polyacetylene, polyaniline, polythiophene, etc., or triphenylene-based compounds can be used.
  • conductive polymer such as polyacetylene, polyaniline, polythiophene, etc.
  • triphenylene-based compounds can be used.
  • the p-type semiconductor CuI, CuSCN, etc. can be used.
  • the counter electrode preferably has conductivity, and functions as a catalyst for the reduction of redox electrolyte.
  • those prepared by depositing platinum, carbon, rhodium, ruthenium, etc. on a glass or polymer film, or by coating conductive particles on a glass or polymer film can be used.
  • halogen redox electrolyte consisting of a halogen compound with halogen ions as a counter ion and a halogen molecule, metal redox electrolyte such as ferrocyanide-ferricyanide, ferrocene-ferricinium ion, metal complex such as cobalt complex, etc., organic redox electrolyte such as alkylthiol-alkyldisulfide, vologen dye, hydroquinone-quinone, etc. can be used. Specifically, halogen redox electrolyte is preferable.
  • halogen molecule for the halogen redox electrolyte iodine molecule is preferably used.
  • halogen compound halogenated metal salt such as LiI, NaI, KI, CaI 2 , MgI 2 , CuI, etc., or organic ammonium salt of halogen such as tetraalkylammonium iodide, imidazolium iodide, pyridium iodide, etc. or I 2 can be used.
  • an electrochemical Iy inert solvent can be used.
  • acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitri Ie, methoxyacetonitri Ie, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol , butyrolactone, dimethoxyethane, dimethylcarbonate, 1,3- dioxolane, methylformate, 2-methyl tetrahydrofurane, 3-methoxy-oxazolidin- 2-on, sulfolane, tetrahydrofurance, water, etc. can be used.
  • acetonitrile, propylene carbonate, ethylene carbonate, 3- methoxypropionitri Ie, ethylene glycol, 3-methoxy-oxazol idin-2-on, or butyrolactone is preferable.
  • One kind of solvent can be used or some kinds of solvents can be mixed and used.
  • As a gel-type positive electrolyte those containing electrolyte or electrolyte solution in a matrix of oligomer or polymer, or those containing an electrolyte or an electrolyte solution in a starch gelling agent can be used.
  • the concentration of the redox electrolyte is preferably 0.01 - 99 wt%, and more preferably 0.1-30 wt%.
  • the solar cell of the present invention can be obtained by placing on a substrate, a photoelectric conversion element (anode) where the dye of the Formula 1 is supported on the oxide semiconductor particles and a counter electrode (cathode), and filling a solution comprising a redox electrolyte therebetween.
  • a 3-electrode system consisting of a gold disc, a working electrode and a platinum wire electrode was used.
  • the redox potential of dye on Ti ⁇ 2 was measured at a scan ratio of 5OmVs "1 (vs.Fc/Fc + ) using 0.1M (TT-C 4 Hg) 4 N-PF 6 in CH 3 CN.
  • I) 3-(thiophen-2-yl)carbazole (compound 3, n l)
  • Example 2 Preparation of a dye-sensitized solar cell
  • a solar cell was prepared using 13+10 ⁇ m TiO 2 transparent layer.
  • the washed FTO(Pi lkington, 8 ⁇ sq ⁇ x ) glass substrate was impregnated with 4OmM TiCl 4 aqueous solution.
  • a TiO 2 paste(Solaronix, 13nm anatase) was screen printed to prepare a first TiO 2 layer having a thickness of 13 ⁇ m, and a second TiO 2 layer having a thickness of lO ⁇ m was prepared using another paste(CCIC, HWP-400) for light diffusion.
  • the TiO 2 electrode was impregnated with each solution of the dye compounds Ia-I, la-2, Ib-I, lb-2, Ic and Id of the present invention prepared in the above steps VII) to X), XIII) and XVI) (0,3 mM dye in ethanol containing 1OmM 3a,7a-dihydroxy-5b-chloic acid), and allowed to stand at room temperature for 18 hours.
  • An H 2 PtCl 6 solution (2mg Pt IN ImL ethanol) was coated on FTO substrate to prepare a counter electrode.
  • an electrolyte prepared by dissolving 0.6 M 3- hexyl-l,2-dimethylimidazolium iodide, 0.04 M I 2 , 0.025 M LiI, 0.05 M guanidium thiocyanate and 0.28 M tert-hnty ⁇ pyridine in acetonitrile was injected in the cell.
  • the photocell performance of the solar cell was measured using IOOOW xenone light source.
  • the IPCE spectrum of the solar cell was measured using IPCE measurement system (PV measurement).
  • the graphs as shown in Fig. 1 indicate that the absorption spectrums become red-shifted as ⁇ -bond system increases. And, the graphs as shown in Fig. 1 indicate that N-substituted carbazole unit inhibits condensation by molecular adhesion, thus inducing a non-planar structure, and condensation inhibition capacity decreases as the bonded dye increases.
  • Fig. 2 the geometrical structures of the compounds Ia-I, la-2, Ib-I, lb-2, Ic and Id (molecular orbital of HOMO and LUMO, TD-DFT computation at B3LYP/3-21G) were shown in Fig. 2.
  • the structures as shown in Fig. 2 indicate that HOMO-LUMO excitation moves electron distribution from carbazole unit to cyanoacrylic acid, and that light-induced electron transfer from dye to Ti ⁇ 2 electrode is efficiently conducted by HOMO-LUMO transition.
  • ⁇ is an absorption coefficiency
  • E 0x is an oxidation potential
  • E 0 - O is a voltage at the intersection of absorption and emission spectrums.
  • a means that an absorption spectrum is measured in ethanol
  • b means that an absorption spectrum is measured on TiO 2 film
  • c means that an emission spectrum is measured in ethanol solution
  • d means that the redox potential of the dye on TiO 2 is measured at a scan ratio of 50 mV s ' Hvs.
  • N719 is a ruthenium based catalyst used for dye- sensitized solar cell of the prior art, having the following Formula:
  • J sc is a short-circuit photocurrent density
  • V 00 is an open circuit photovoltage
  • ff is a fill factor
  • i ⁇ is a total photoconversion efficiency.
  • the performances of the dye- sensitized solar cell were measured on the working area of 0.18cm 2 .
  • IPCE graphs of the dye compounds(Ia-I: bar line, la ⁇ 2: dotted line, Ib- l: bar line-dotted line, lb-2: bar line-dotted line-dotted line, Ic: short bar line, Id: short dotted line, N719: solid line) as shown in Fig. 3 indicate that the IPCE maximums of the compounds Ia-I and la-2 are especially high and the conversion efficiencies thereof are also excellent. [Industrial Applicability]
  • the novel dye containing N-arylcarbazole moiety of the present invention shows improved molar absorptivity, Jsc (short circuit photocurrent density) and photoelectric conversion efficiency, compared to the metal complex dye of the prior art, and thus can largely improve the efficiency of a solar cell. And, it can dramatically decrease dye synthesis cost because it can be purified without using expensive columns.

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Abstract

The present invention relates to novel dye containing N- arylcarbazole moiety and preparation thereof. The dye compound of the present invention which comprises fluorene and carbazole as an electron donor, a thiophene unit as a middle linking part, and rhodanine-3-acetic acid or cyanoacrylic acid as an electron acceptor can be used for a dye- sensitized solar cell (DSSC). The dye of the present invention shows improved molar absorptivity, Jsc(short circuit photocurrent density) and photoelectric conversion efficiency, compared to dyes of the prior art, and thus it can greatly improve solar cell efficiency. And, it can dramatically decrease dye synthesis cost because the dye of the present invention can be purified without using expensive columns.

Description

NOVEL ORGANIC DYE CONTAINING N-ARYLCARBAZOLE MOIETY AND PREPARATION
THEREOF
[Technical Field] The present invention relates to novel organic dye containing N- arylcarbazole moiety, which is used for a dye-sensitized solar cell (DSSC), and a process for preparing the same. [Background Art]
Many studies regarding a dye-sensitized nanoparticle titanium oxide solar cell have been progressed since it was developed by Swiss Federal
Institute of Technology Lausanne (EPFL), Michael Gratzel et al. on the year
1991. Because a dye-sensitized solar cell has higher efficiency and lower manufacture cost than the existing si 1 icone-based solar cell, it can replace the existing amorphous si 1 icone-based solar cell. And, differently from the si 1 icone-based solar cell, the dye-sensitized solar cell is a photoelectrochemical solar cell essentially consisting of a dye molecule capable of absorbing a visible ray and generating electron-hole pair and a transition metal oxide for transmitting the generated electrons.
As the dye for a dye-sensitized solar cell, ruthenium complex having high photoelectric conversion efficiency has been widely used. However, the ruthenium complex had a defect of high cost.
Recently, it has been discovered that metal-free organic dye, which has excellent properties in terms of an absorption efficiency, oxidation- reduction stability and charge-transfer(CT) absorption in a molecule, can be used as the dye for a solar cell instead of the expensive ruthenium complex. Thus, studies focus on the metal-free organic dye.
In general, the organic dye has a structure consisting of an electron donor - electron acceptor moities which are linked by π-bond. For most organic dyes, an amine derivative functions as an electron donor, 2- cyanoacrylic acid or rhodanine moiety functions as an electron acceptor, and the two parts are linked by a π-bond system such as methaine unit or thiophene chain.
In general, the structural change of electron donor amine causes a change in electron' s properties, for example, a blue-shifted absorption spectrum, and causes a change in the π-bond length thus controlling absorption spectrum and redox potential.
However, most organic dyes so far known show lower conversion efficiencies and lower working stability compared to ruthenium complex dyes, which was found to be caused by the fact that dyes are condensed on the surface of semiconductor and unstable radical species are generated during oxidation-reduction cycle.
Accordingly, there have been continued efforts to develop novel dyes showing improved molar absorptivity and high photoelectric conversion efficiency compared to the existing organic dye compounds, by changing the kinds of electron donor and acceptor or the length of π-bond. [Disclosure] [Technical Problem]
Accordingly, it is an object of the present invention to provide organic dyes showing improved molar absorptivity and photoelectric conversion efficiency compared to metal complex dyes of the prior art, thus capable of largely improving the efficiency of solar cell, and a process for preparing the same.
It is another object of the present invention to provide a dye- sensitized photoelectric conversion element comprising the dye of the present invention thus showing remarkably improved photoelectric conversion efficiency and having excellent Jsc(short circuit photocurrent density)and molar absorptivity, and a solar cell having remarkably improved efficiency. [Technical Solution!
In order to achieve the above objects of the invention, the present invention provides N-arylcarbazole based dye of the following Formula 1: [Formula 1]
Figure imgf000005_0001
wherein, X is 9,9-dimethylfluorenyl or 4-(2,2-diphenylvinyl )phenyl , Y is cyanoacrylic acid or rhodanine-3-acetic acid moiety, n is an integer of 1 to 5, and two or more thiophene units can be optionally linked by vinyl group.
And, the present invention provides a process for preparing N-carbazole based dye of the Formula Ia or Ib, comprising the steps of:
(1) subjecting 3-iodocarbazole to Stille coupling reaction with a compound of the following Formula 2 to prepare a compound of the following Formula 3;
(2) subjecting the compound of the Formula 3 to Ul lmann coupling reaction with 2-iodo-9,9-dimethylfluorene to prepare a compound of the following Formula 4; (3) lithiating the compound of the Formula 4 with n-butyl 1 ithium, and then continuously cooling it with dimethylformamide (DMF) to prepare a compound of the following Formula 5; and
(4) reacting the compound of the Formula 5 with cyanoacetic acid in CH3CN in the presence of piperidine, or with rhodanine-3-acetic acid and ammonium acetate in acetic acid:
[Formula Ia]
Figure imgf000006_0001
[Formula Ib]
Figure imgf000007_0001
[Formula 2]
Figure imgf000007_0002
[Formula 3]
Figure imgf000007_0003
[Formula 4]
Figure imgf000008_0001
[Formula 5]
Figure imgf000008_0002
wherein, n is an integer of 1 to 5, and two or more thiophene units can be optionally linked by vinyl group.
And, the present invention provides a process for preparing N- arylcarbazole based dye of the Formula Ic, comprising the steps of:
(1) subjecting 3-iodocarbazole to Stille coupling reaction with a compound of the following Formula 2 to prepare a compound of the following Formula 3;
(2) subjecting the compound of the Formula 3 to Ullmann coupling reaction with l-(2-(4-bromophenyl )-l-phenylvinyl)benzene to prepare a compound of the following Formula 6;
(3) formylating the compound of the Formula 6 with n-butyl lithium to prepare a compound of the Formula 7; and
(4) reacting the compound of the Formula 7 with cyanoacetic acid in CH3CN in the presence of piperidine:
[Formula Ic]
Figure imgf000009_0001
[Formul a 2]
/SVV-SΠBLL
[Formula 3]
Figure imgf000009_0002
Figure imgf000010_0001
[Formula 7]
Figure imgf000010_0002
wherein, n is 1.
And, the present invention provides a process for preparing N- arylcarbazole based dye of the Formula Id, comprising the steps of:
(1) subjecting 3-iodocarbazole to Stϊ 1 Ie coupling reaction with a compound of the following Formula 2 to prepare a compound of the following Formula 3;
(2) subjecting the compound of the Formula 3 to Ullmann coupling reaction with 2-iodo-9,9-dimethylfluorene to prepare a compound of the following Formula 4; (3) lithiating the compound of the Formula 4 with n-butyl 1 ithium, and then continuously cooling it with dimethylformamide (DMF) to prepare a compound of the following Formula 5;
(4) subjecting the compound of the Formula 5 to Horner-Emmons-Wittig coupling reaction with (2-thienylmethyl)triphenylphosphinium bromide to prepare a compound of the following Formula 8;
(5) formylating the compound of the Formula 8 with n-butyl 1 ithium to prepare a compound of the following Formula 9; and
(6) reacting the compound of the Formula 9 with cyanoacetic acid in CH3CN in the presence of piperidine:
[Formula Id]
Figure imgf000011_0001
[Formula 2]
Figure imgf000011_0002
[Formul a 3]
Figure imgf000012_0001
[Formula 4]
Figure imgf000012_0002
[Formula 5]
Figure imgf000012_0003
[Formula 8]
Figure imgf000013_0001
[Formula 9]
Figure imgf000013_0002
wherein, n is 1. And, the present invention provides a dye-sensitized photoelectric conversion element comprising oxide semiconductor particles where the N- arylcarbazole based dye of the present invention is supported.
And, the present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion element of the present invention.
[Advantageous Effects]
The novel dye containing N-arylcarbazole moiety of the present invention shows improved molar absorptivity, JscCshort circuit photocurrent density) and photoelectric conversion efficiency compared to dyes of the prior art, and thus it can greatly improve solar cell efficiency. And, it can dramatically decrease dye synthesis cost because the dye of the present invention can be purified without using expensive columns. [Description Drawings] Fig. 1 (a) to (f) show absorption and emission spectrums of each of the dye compounds Ia-I, la-2, Ib-I, lb-2, Ic and Id of the present invention in ethanol, and emission spectrums of the dye compounds supported on TiO2 layer. Fig. 2 (a) to (f) are diagrams respectively showing the geometrical structure of each of the dye compounds Ia-I, la-2, Ib-I, lb-2, Ic and Id of the present invention (HOMO and LUMO molecular orbital, TD-DFT computation at B3LYP/3-21G) .
Fig. 3 shows IPCEC incident photon-to-current conversion efficiency) spectrums of the solar cells respectively prepared using each of the dye compounds Ia-I, la-2, Ib-I, lb-2, Ic and Id of the present invention. [Mode for Invention]
The present invention will now be explained in detail.
The present inventors have discovered that a dye-sensitized solar cell prepared by supporting, on oxide semiconductor particles, a compounds of the Formula 1, which has a novel organic dye structure of using fluorene and carbazole as an electron donor, introducing thiophene unit in the middle linking part for increasing molar absorptivity and stability of the element, and using rhodanine-3-acetic acid or cyanoacrylic acid which is closely connected with TiO2 reforming and has the best electron transport capacity as an electron acceptor, has high photoelectric conversion efficiency, JscCshort circuit photocurrent density) and molar absorptivity, and thus has superior efficiency to the existing dye-sensitized solar cells, and completed the present invention.
The dye of the present invention is represented by the following Formula 1, and preferably one of the following Formulas Ia-I, la-2, Ib-I, lb-2, Ic or Id:
[Formula 1]
Figure imgf000015_0001
[Formula Ia-I]
Figure imgf000015_0002
[Formula la-2]
Figure imgf000016_0001
[Formula Ib-I]
Figure imgf000016_0002
[Formula lb-2]
Figure imgf000016_0003
[Formula Ic]
Figure imgf000017_0001
[Formula Id]
Figure imgf000017_0002
wherein, each X, Y and n has the same meaning as defined above. And, the present invention provides processes for preparing dye of the Formula Ia or Ib, dye of the Formula Ic and dye of the Formula Id.
The term "Stille coupling" reaction means reacting under Sti lie reaction conditions using tetrakis(triphenylphosphine)pal ladium(O) , dimethylformamide and stanylthiophene; "Ullmann coupling" reaction means reacting under Ullmann reaction conditions using copper bronze, potassium carbonate and 18-crwon-6; and, "Horner-Emmons-Wittig coupling" reaction means reacting under Horner-Emmons-Wittig reaction conditions using potassium-ferf-butoxide in tetrahydrofurane.
Preferably, the dye of the Formula Ia and Ib can be prepared according he following Reaction Formula 1. [Reaction Formula 1]
Figure imgf000018_0001
Preferably, the dye of the Formula Ic and Id can be prepared according he following Reaction Formula 2. [Reaction Formula 2]
Figure imgf000019_0001
CH1CN
Figure imgf000019_0003
Figure imgf000019_0002
1<l
In the above Reaction Formula, 3-iodocarbazole which is used for a starting material for preparing the dye of the Formula 1 can be obtained by common methods.
And, the present invention provides a dye-sensitized photoelectric conversion element, wherein the dye of the Formula 1 is supported on oxide semiconductor particles. For the preparation of the dye-sensitized photoelectric conversion element of the present invention, any processes for preparing a dye-sensitized photoelectric conversion element for solar cells of the prior art can be applied, except using the dye of the above
Formula 1. Preferably, the dye-sensitized photoelectric conversion element of the present invention is prepared by forming an oxide semiconductor thin film on a substrate, using oxide semiconductor particles, and then supporting the dye of the present invention on the thin film.
As the substrate on which the oxide semiconductor thin film is formed, a substrate having conductive surface is preferably used, but any commercially available substrates can be used. For examples, a substrate wherein a thin film of metal such as copper, silver, gold, etc. or conductive metal oxide such as tin oxide coated with indium, fluorine, or antimony, etc. is formed on the surface of glass or transparent polymer such as polyethyleneterephthalate or polyethersulfone, etc. can be used. The conductivity of the substrate is preferably 1000 Ω or less, and more preferably 100 Ω or less.
As the oxide semiconductor particles, a metal oxide is preferably used. For examples, oxides of titanium, tin, zinc, tungsten, zirconium, gallium, indium, itrium, niobium, tantalum, vanadium, etc. can be used. Specifically, an oxide of titanium, tin, zinc, niobium, or indium is preferable, titanium oxide, zinc oxide and tin oxide are more preferable, and titanium oxide is most preferable. The oxide semiconductor can be used alone or in combination, and can be coated on the surface of the semiconductor.
And, the oxide semiconductor particles preferably have an average particle size of 1 ~ 500 run, and more preferably 1 ~ 100 nm. And, oxide semiconductor particles having large particle size and those having small particle size can be mixed, or they can be used in multi-layers. The oxide semiconductor thin film can be prepared by directly forming a thin film of oxide semiconductor particles by spraying, etc.; by electrically depositing semiconductor thin film using a substrate as an electrode; or by coating on a substrate a paste containing semiconductor particles which is obtained by hydrolyzing a precursor of semiconductor particles such as a slurry of semiconductor particles or semiconductor alkoxide, etc., and then drying, curing or calcining. Preferably, a process of coating a paste on a substrate is used, wherein a slurry can be obtained by dispersing secondary condensed oxide semiconductor particles in a dispersion medium by a common method so that a first average particle size is 1 ~ 200 nm.
As the dispersion medium for dispersing the slurry, any dispersion medium capable of dispersing semiconductor particles can be used without limitation. For examples, water, alcohol such as ethanol, etc., ketone such as acetone, acetylacetone, etc., or hydrocarbon such a hexane, etc. can be used. They can be used in combination, and water is preferable because it reduces viscosity change of the slurry. And, a dispersion stabilizer can be used for stabilizing the dispersion state of the oxide semiconductor particles. Examples of the dispersion stabilizer include acid such as acetic acid, hydrochloric acid, nitric acid, etc. acetylacetone, acrylic acid, polyethyleneglycol , polyvinylalcohol , etc.
The substrate coated with the slurry can be subjected to calcination. The calcination temperature is 100 °C or more, preferably 200 °C or more, and the upper limit of the calcination temperature is a melting point(softening point) of the substrate or less, commonly 900 °C , preferably 600 °C or less. In the present invention, the calcination time is not specifically limited, but preferably within 4 hours.
In the present invention, the thickness of the thin film on the substrate is suitably 1 - 200 μm, and preferably 1 ~ 50 μm. When subjected to calcination, a thin layer of the oxide semiconductor particles is partly welded, which does not specifically cause any troubles in the present invention.
And, a secondary treatment can be conducted on the oxide semiconductor thin film. For example, the thin film can be immersed in a solution of alkoxide, chloride, nitride or sulfide of the same metal as the semiconductor, and dried or re-calcined, thereby improving the performance of the semiconductor thin film. The metal alkoxide includes titanium ethoxide, titanium isoproepoxide, titanium t-butoxide, n-dibutyl-diacetyl tin, etc., and the alcohol solution thereof can be used. The chloride includes titanium chloride, tin chloride, zinc chloride, etc., and the aqueous solution thereof can be used. Thus obtained oxide semiconductor thin film consists of oxide semiconductor particles.
And, the method for supporting dye on the oxide semiconductor thin film is not specifically limited in the present invention. For example, a substrate on which the oxide semiconductor thin film is formed can be immersed in a solution obtained by dissolving the dye of the Formula 1 in a solvent capable of dissolving it, or in a dispersion obtained by dispersing the dye. The concentration of the dye in the solution or dispersion can be appropriately determined according to the dye. The immersion temperature is generally from a room temperature to a boiling point of the solvent, and the immersion time is from about 1 minute to 48 hours. The solvent for dissolving the dye includes methanol, ethanol, acetonitri Ie, dimethylsulfoxide, dimethylformamide, acetone, t-butanol, etc. The concentration of the dye in the solution is suitably Ix 10"6M ~ 1 M, and preferably 1 x 10"5M ~ 1 x 10"1M. Thus, the dye-sensitized photoelectric conversion element of the present invention comprising oxide semiconductor particles in the form of a thin film can be obtained.
One kind of the dye of the Formula 1 can be supported, or some kinds of the dyes can be mixed and supported. And, the dye of the present invention can be mixed with other dyes or metal complex dyes. The examples of the metal complex dyes which can be mixed with the dye of the present invention are not specifically limited, but ruthenium complex or the quaternary salt thereof, phthalocyanine, or porphyrin is preferable. And, the examples of the organic dyes which can be mixed with the dye of the present invention include metal-free phthalocyanine, porphyrin or cyanine, merocyanine, oxonol , triphenylmethane-based dyes, methyne-based dyes such as acrylic acid based dyes described in W02002/011213, xanthene-based, azo~based, anthraquinone-based, or perylene-based dyes (see the literature [M.K.Nazeeruddin, A.Kay, I.Rodicio, R.Humphry-Baker, E.Muller, P.Liska, N.Vlachopoulos, M.Gratzel, J .Am.Chem.Soc. , ro/ii5,p6382(1993)]). In case two or more kinds of dyes are used, the dyes can be sequentially absorbed to the semiconductor thin film, or they can be mixed, dissolved and absorbed.
And, when the dye is supported on the thin film of the oxide semiconductor particles, it is preferable to support the dye in the presence of an inclusion compound in order to prevent bonding between the dyes. As the inclusion compound, cholic acid such as deoxycholic acid, dehydrodeoxychol ic acid, kenodeoxycholic acid, cholic acid methyl ester, sodium cholic acid, etc., steroid-based compound, crown ether, cyclodextrin, calix arene, polyethylene oxide, etc. can be used.
After the dye is supported, the electrode surface of the semiconductor can be treated with amine compound such as 4-t-butyl pyridine, etc., or compounds having an acid group such as acetic acid, propionic acid, etc. For example, a substrate on which a dye-supported semiconductor thin film is formed can be immersed in an ethanol solution of amine.
The present invention also provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion element of the present invention. For the manufacture of the dye-sensitized solar cell, commonly used methods for preparing a solar cell using a photoelectric conversion element of the prior art can be applied, except using the dye- sensitized photoelectric conversion element comprising oxide semiconductor particles on which the dye of the Formula 1 is supported. For example, the dye-sensitized solar cell may consist of a photoelectric conversion element electrode (anode), a counter electrode (cathode), redox electrolyte, hole transport material or p-type semiconductor, etc.
Preferably, the dye-sensitized solar cell of the present invention can be prepared by a process comprising the steps of coating a titanium oxide on a transparent conductive substrate! subjecting the coated substrate to calcination so as to form a titanium oxide thin film; impregnating the titanium oxide thin film with a mixed solution in which the dye of the Formula 1 is dissolved, so as to form a dye-absorbed titanium oxide film electrode; providing a second glass substrate on which a counter electrode is formed; forming a hole through the second glass substrate and the counter electrode; placing a thermoplastic polymer film between the counter electrode and the dye-absorbed titanium oxide film electrode, and conducting heat pressing, so as to join the counter electrode and the titanium oxide film electrode; injecting an electrolyte in the thermoplastic polymer film placed between the counter electrode and the titanium oxide film electrode through the hole; and, sealing the thermoplastic polymer.
The redox electrolyte, hole transport material, p-type semiconductor, etc. can be of a liquid, condensed (gel and gel-type), or solid type. The liquid type includes those prepared by dissolving redox electrolyte, dissolved salt, hole transport material, or p-type semiconductor in a solvent, or a room temperature dissolved salt. The condensed type (gel and gel-type) includes those containing redox electrolyte, dissolved salt, hole transport material, or p-type semiconductor in a polymer matrix or low molecule gelling agent. The solid type includes redox electrolyte, dissolved salt, hole transport material, or p-type semiconductor.
As the hole transport material, those using discotic liquid crystal phase such as amine derivatives, conductive polymer such as polyacetylene, polyaniline, polythiophene, etc., or triphenylene-based compounds can be used. As the p-type semiconductor, CuI, CuSCN, etc. can be used. The counter electrode preferably has conductivity, and functions as a catalyst for the reduction of redox electrolyte. For example, those prepared by depositing platinum, carbon, rhodium, ruthenium, etc. on a glass or polymer film, or by coating conductive particles on a glass or polymer film can be used.
As the redox electrolyte used for the solar cell of the present invention, halogen redox electrolyte consisting of a halogen compound with halogen ions as a counter ion and a halogen molecule, metal redox electrolyte such as ferrocyanide-ferricyanide, ferrocene-ferricinium ion, metal complex such as cobalt complex, etc., organic redox electrolyte such as alkylthiol-alkyldisulfide, vologen dye, hydroquinone-quinone, etc. can be used. Specifically, halogen redox electrolyte is preferable. As the halogen molecule for the halogen redox electrolyte, iodine molecule is preferably used. And, as the halogen compound, halogenated metal salt such as LiI, NaI, KI, CaI2, MgI2, CuI, etc., or organic ammonium salt of halogen such as tetraalkylammonium iodide, imidazolium iodide, pyridium iodide, etc. or I2 can be used.
In case the redox electrolyte is a solution comprising the same, an electrochemical Iy inert solvent can be used. For examples, acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitri Ie, methoxyacetonitri Ie, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol , butyrolactone, dimethoxyethane, dimethylcarbonate, 1,3- dioxolane, methylformate, 2-methyl tetrahydrofurane, 3-methoxy-oxazolidin- 2-on, sulfolane, tetrahydrofurance, water, etc. can be used. Specifically, acetonitrile, propylene carbonate, ethylene carbonate, 3- methoxypropionitri Ie, ethylene glycol, 3-methoxy-oxazol idin-2-on, or butyrolactone is preferable. One kind of solvent can be used or some kinds of solvents can be mixed and used. As a gel-type positive electrolyte, those containing electrolyte or electrolyte solution in a matrix of oligomer or polymer, or those containing an electrolyte or an electrolyte solution in a starch gelling agent can be used. The concentration of the redox electrolyte is preferably 0.01 - 99 wt%, and more preferably 0.1-30 wt%. The solar cell of the present invention can be obtained by placing on a substrate, a photoelectric conversion element (anode) where the dye of the Formula 1 is supported on the oxide semiconductor particles and a counter electrode (cathode), and filling a solution comprising a redox electrolyte therebetween. The present invention will be explained with reference to the following examples. However, these examples are only intended to illustrate the present invention and the scope of the present invention is not limited thereto.
[Example]
[Example 1] Synthesis of dye
All the reactions were conducted under argon atmosphere, and a solvent was distilled with suitable agent purchased from Sigma-Aldrich Company. IH and 13C NMR spectrums were measured by Varian Mercury 300 spectrometer, elementary analysis was measured by Carlo Elba Instruments CHNS-O EA 1108 spectrometer, and mass spectrum was measured by JEOL JMS-SX102A apparatus. Absorption and emission spectrums were respectively measured by Perkin- Elmer Lambda 2S UV-visible spectrometer and Perkin LS fluorescence spectrometer. < Cyclic voltammetry > BAS 100B(Bioanalytical Systems, Inc.) was used as a cyclic voltammeter. A 3-electrode system consisting of a gold disc, a working electrode and a platinum wire electrode was used. The redox potential of dye on Tiθ2 was measured at a scan ratio of 5OmVs"1(vs.Fc/Fc+) using 0.1M (TT-C4Hg)4N-PF6 in CH3CN. I) 3-(thiophen-2-yl)carbazole (compound 3, n=l)
3-iodocarbazole(1.0g, 3.41mmol) , tributyl(thiophen-2-yl)stannane(1.27g,
3.41mmol) and Pd(PPh3)4(0.197g, 0.17mmol) were stirred and heated in dimethylformamide(30ml) at 100°C for 12 hours. After the mixed solution was cooled, water(50ml) was added thereto, and the solution was extracted with dichloromethan(50 X 5) . An organic layer was separated and dried with magnesium sulfate. After the solvent was removed under vacuum, the obtained solid was subjected to silica gel chromatography(developer
MC:Hx=l:2, R/=0A) to obtain white solid title compound (yield 82%). Mp: 197°C. IH NMR (acetone-d6) : δ 10.45 (br, IH), 8.43 (s, IH),
8.20 (d, IH, J=8.1 Hz), 7.72 (d, IH, J=8.1 Hz), 7.55 (d, IH, J=8.1 Hz),
7.53 (d, IH, J=8.1 Hz), 7.44 (d, IH, J=3.6 Hz), 7.41 (t, IH, J=8.1 Hz), 7.38 (d, IH, J=5.1 Hz), 7.21 (t, IH, J=8.1 Hz), 7.12 (dd, IH, J=3.6, 5.1 Hz). 13C{1H} NMR (CDCl3/acetone-d6) : δ 145.8, 140.4, 139.4, 127.8, 125.9, 125.8, 124.2, 123.6, 123.0, 121.9, 120.2, 119.6, 119.1, 117.5, 111.1, 110.9. MS: m/z 249 [M+]. Anal. Calcd for Ci6H11NS: C, 77.07; H, 4.45. Found: C, 76.88; H, 4.28.
II) 3-(5-(thiophen-2-yl)thiophen-2-yl)carbazole (compound 3, n=2) The same process as the above step I) was conducted to obtain white solid title compound (yield 78%).
Mp: 201TC. IH NMR (acetone-d6) : δ 10.47 (br, IH), 8.46 (s, IH),
8.23 (d, IH, J=7.2 Hz), 7.74 (d, IH, J=8.1 Hz), 7.59 (d, IH, J=7.2 Hz),
7.54 (d, IH, J=8.1 Hz), 7.43 (d, IH, J=3.6 Hz), 7.42 (t, IH, J=7.5 Hz), 7.41 (d, IH, J=3.6 Hz), 7.32 (d, IH, J=5.1 Hz), 7.27 (d, IH, J=3.6 Hz), 7.22 (t , IH, J=7.5 Hz) , 7. 10 (dd, IH, J=5.1, 3.6 Hz) . 13CUH} NMR (acetone- d6) : δ 145.6, 141.6, 140.7, 138.3, 135.9, 128.9, 126.9, 126. 1 , 125.7, 125.3, 124.6, 124.2, 123.8, 123.7, 121.3, 120.9, 118.4, 118.0, 112.3, 112.0. MS: m/z 359 [M+] . Anal . Calcd for C20Hi3NS2: C, 72.47; H, 3.95. Found: C, 72. 18; H, 3.85.
Ill) 9-(9,9-dimethylf luoren-2-yl )-3-(thiophen-2-yl )-carbazole (compound 4, n=l)
The compound 3 prepared in the above step I) (n=l)(1.40g, 5.61mmol), 2- iodo~9,9-dimethylfluorene(1.97g, 6.17mmol), anhydrous potassium carbonate powder(1.55g, 11.22mmol), copper bronze(0.36g, 5.61mmol) and 18-crown- 6(0.22g, 0.84mmol) were refluxed in l,2-dochlorobenzene(50ml) for 48 hours. After the reaction solution was cooled, insoluble inorganic material was filtered under inhalation to collect dark brown filtrate. The insoluble material was washed with dichloromethane (3 X 3OmL). The mixed filtrate and organic layers were washed with aqueous ammonia and water and dried with magnesium sulfate. After the solvent was removed under vacuum, the obtained solid was subjected to silica gel chromatography(developer MC:Hx=l:3, #/=0.4) to obtain the title compound(1.96g) (yield 79%). Mp: 207°C. IH NMR (CDCl3): δ 8.39 (s, IH), 8.21 (d, IH, J=7.5 Hz), 7.94 (d, IH, J=8.1 Hz), 7.82 (s, IH, J=8.1 Hz), 7.71 (d, IH, J=8.4 Hz), 7.64 (s, IH), 7.55 (d, IH, J=8.1 Hz), 7.50 (t, IH, J=7.5 Hz), 7.48 (d, IH, J=8.4 Hz), 7.46 (d, IH, J=8.1 Hz), 7.42 (d, IH, J=8.1 Hz), 7.41 (t, IH, J=7.5 Hz), 7.39 (t, IH, J=7.5 Hz), 7.38 (d, IH, J=3.6 Hz), 7.33 (t, IH, J=7.5 Hz), 7.28 (d, IH, J=5.1 Hz), 7.13 (dd, IH1 J=5.1, 3.6 Hz), 1.58 (s, 6H). 13CUH} NMR (CDCl3): δ 155.6, 153.9, 145.7, 141.6, 140.7, 138.7, 138.5, 136.5, 131.2, 130.9, 130.0, 128.1, 127.8, 127.4, 126.9, 126.4, 126.9, 124.7, 123.9, 123.4, 122.9, 122.4, 121.5, 121.3, 120.6, 120.3, 117.9, 110.3, 47.3, 27.3. MS: m/z 441 [M+]. Anal. Calcd for C3IH23NS: C, 84.32; H, 5.25. Found: C, 84.04; H, 5.14.
IV) 9-(9,9-dimethylfluoren-2-yl)-3-(5-(thiophen-2-yl)-thiophen-2- yDcarbazole (compound 4, n=2)
The same process as the above step III) was conducted to obtain white solid title compound (yield 76%).
Mp: 2irC. IH NMR (CDCl3): δ 8.38 (s, IH), 8.21 (d, IH, J=7.5 Hz), 7.94 (d, IH, J=8.1 Hz), 7.81 (d, IH, J=8.1 Hz), 7.69 (d, IH, J=8.7 Hz), 7.63 (s, IH), 7.54 (d, IH, J=8.1 Hz), 7.52 (t, IH, J=7.5 Hz), 7.48 (d, IH, J=8.4 Hz), 7.45 (d, IH, J=8.7 Hz), 7.41 (t, IH, J=7.5 Hz), 7.39 (t, IH, J=7.5 Hz) , 7.35 (d, IH, J=8.4 Hz) , 7.33 (t , IH, J=7.5 Hz) , 7.28 (d, IH, J=3.9 Hz) , 7.23 (d, IH, J=3.9 Hz) , 7.22 (d , IH, J=5.1 Hz) , 7.20 (d, IH, J=3.6 Hz) , 7.05 (dd, IH, J=3.6, 5.1 Hz) , 1.57 (s , 6H) . 13C{1H} NMR (CDCl3) : δ 155.6, 153.9, 144.6, 141.7, 140.7, 138.8, 138.5, 137.9, 136.5, 135.8, 127.9, 127.8, 127.4, 126.5, 125.9, 124.8, 124.4, 124.2 , 124.1 , 124.0, 123.5, 123.4, 122.9, 122.8, 121.5 , 121.3 , 120.7, 120.4, 120.3 , 117.6 , 110.4, 110.2, 47.3 , 27.3. MS: m/z 523 [M+] . Anal . Calcd for C35H25NS2: C, 80.27; H, 4.81. Found: C, 79.96; H, 4.73.
V) 9-(9,9-dimethylf luoren-2-yl )carbazol-6-yl )-thiophene-2-carbaldehyde (compound 5, n=l) The compound 4 prepared in the above step III) (n=l)(0.26g, 0.59mmol) was dissolved in tetrahydrofurane (2OmL), and then cooled to -78°C under N2. Then, n-butyllithium(0.92mL, 1.6M solution in hexane, 1.47mmol) was added dropwise thereto with vigorously stirring over 10 minutes. After the solution was allowed to reach 0°C for 1 hour, it was allowed to stand at the same temperature for additional 1 hour. The solution was cooled to - 78°C again, and anhydrous dimethylformamide(ImL) was added immediately. The obtained solution was allowed to reach room temperature, and then stirred overnight. HCl(ImL) diluted in 2OmL water was added to the reaction solution to complete the reaction, and then the reaction solution was extracted with diethylether(3 X 2OmL). The mixed organic extracts were dried with anhydrous magnesium sulfate and filtered. The filtrate was subjected to silica gel chromatography(developer MC:Hx=l:2,
Figure imgf000031_0001
to obtain the title compound (yield 89%). Mp: 226°C. IH NMR (CDCl3): δ 9.95 (s, IH), 8.74 (s, IH), 8.38 (d, IH, J=7.5 Hz), 8.14 (d, IH, J=7.5 Hz), 7.99 (d, IH, J=3.9 Hz), 7.96 (d, IH, J=8.1 Hz), 7.90 (d, IH, J=8.4 Hz), 7.86 (s, IH), 7.74 (d, IH, J=4.5 Hz), 7.64 (d, IH, J=8.1 Hz), 7.63 (t, IH, J=7.5 Hz), 7.55 (d, IH, J=8.4 Hz), 7.49 (t, IH, J=7.5 Hz), 7.43 (d, IH, J=6.9 Hz), 7.42 (t, IH, J=7.5 Hz), 7.38 (d, IH, J=6.9 Hz), 7.35 (t, IH, J=7.5 Hz), 1.61 (s, 6H). 13C{1H} NMR (CDCl3): δ 182.7, 156.1, 155.7, 153.9, 141.8, 141.7, 141.6, 139.1, 138.4, 137.9, 136.1, 127.9, 127.4, 126.9, 125.9, 125.3, 124.8, 124.1, 123.2, 123.0, 122.9, 121.4, 121.3, 120.7, 120.6, 120.4, 118.6, 110.6, 110.4, 47.3, 27.2. MS: m/z 469 [M+]. Anal. Calcd for C32H23NOS: C, 81.85; H, 4.94. Found: C, 81.58; H, 4.79. VI) 5-(5-(9-(9,9-dimethylfluoren-2-yl)carbazol-6-yl)-thiophen-2- yl)thiophene-2-carbaldehyde (compovind 5, n=2)
The same process as the above step V) was conducted to obtain yellow solid title compound (yield 86%).
Mp: 2340C. IH NMR (CDCl3): δ 9.84 (s, IH)1 8.37 (s, IH), 8.21 (d, IH, J=7.8 Hz), 7.92 (d, IH, J=8.1 Hz), 7.81 (d, IH, J=8.1 Hz), 7.66 (d, IH, J=8.4 Hz), 7.63 (d, IH, J=3.9 Hz), 7.62 (s, IH), 7.51 (d, IH, J=8.1 Hz), 7.50 (t, IH, J=7.5 Hz), 7.47 (d, IH, J=8.1 Hz), 7.46 (t, IH, J=7.5 Hz), 7.42 (d, IH, J=8.4 Hz), 7.41 (t, IH, J=7.5 Hz), 7.36 (d, IH, J=8.1 Hz), 7.34 (t, IH, J=7.5 Hz), 7.34 (d, IH, J=3.6 Hz), 7.29 (d, IH, J=3.6 Hz), 7.23 (d, IH, J=3.9 Hz), 1.58 (s, 6H). 13C{1H} NMR (CDCl3): δ 182.5, 155.6, 153.9, 147.7, 141.7, 141.2, 141.0, 138.9, 138.4, 137.7, 136.2, 134.0, 127.8, 127.4, 127.3, 126.7, 125.8, 125.7, 124.3, 124.0, 123.9, 123.7, 123.3, 123.2, 122.9, 121.4, 121.3, 120.6, 120.5, 120.3, 117.8, 110.5, 110.3, 47.3, 27.2. MS: m/z 551 [M+]. Anal. Calcd for C36H25NOS2: C, 78.27; H, 4.57. Found: C, 78.01; H, 4.51.
VII) 2-cyano-3-(5-(9-(9,9-dimethylfluoren-2-yl)carbazol-6-yl)thiophen-2- yOacrylic acid (compound Ia-I)
A mixture of the compound 5 prepared in the above step V) (n=l)(0.3g,
0.64mmol) and cyanoacetic acid(0.082g, 0.96mmol) was vacuum dried, and then added to acetonitrile(20mL) and piperidine(0.063mL) , and the mixed solution was refluxed for 6 hours. The reaction solution was cooled, and an organic layer was removed under vacuum, and then the obtained solid was subjected to silica gel chromatographyCdeveloper EA:Me0H=10: 1, R/=0.2) to obtain the title compound(0.19g) (yield 89%).
Mp: 251°C. IH NMR (DMSO-cfc): δ 8.77 (s, IH), 8.49 (s, IH), 8.43 (d, IH, J=7.8 Hz), 8.13 (d, IH, J=8.1 Hz), 8.04 (d, IH, J=3.9 Hz), 7.96 (d, IH, J=8.1 Hz), 7.90 (s, IH), 7.89 (d, IH, J=8.7 Hz), 7.84 (d, IH, J=3.9 Hz), 7.62 (d, IH, J=8.1 Hz), 7.61 (d, IH, J=7.8 Hz), 7.52 (t, IH, J=7.5 Hz), 7.51 (d, IH, J=8.7 Hz), 7.47 (t, IH, J=7.5 Hz), 7.41 (t, IH, J=7.8 Hz), 7.40 (d, IH, J=8.7 Hz), 7.36 (t, IH, J=7.5 Hz), 1.54 (s, 6H). 13C{1H} NMR (DMSO-cfe): δ 163.8, 155.4, 154.5, 153.7, 146.5, 141.6, 141.0, 138.3, 137.7, 135.3, 134.1, 133.7, 127.8, 127.3, 127.1, 125.6, 125.1, 124.6, 124.1, 123.5, 122.9, 122.5, 121.6, 121.4, 121.2, 120.6, 120.5, 119.1, 118.6, 116.8, 110.8,
110.1, 46.9, 26.6. MS: m/z 536 [M+]. Anal. Calcd for C35H24N2O2S: C, 78.33; H, 4.51. Found: C, 78.05; H, 4.44.
VI11) 2-cyano-3-(5-(5-(9-(9,9-dimethylfluoren-2-yl)carbazol-6- yl)thiophen-2-yl)-thiophen-2-yl)acrylic acid (compound la-2)
The same process as in the above step VII) was conducted to obtain red solid title compound (yield 86%).
Mp: 258°C. IH NMR (DMSCHfc): δ 8.66 (s, IH), 8.40 (d, IH, J=8.1 Hz), 8.11 (d, IH, J=7.8 Hz), 8.07 (s, IH), 7.94 (d, IH, J=8.1 Hz), 7.88 (s, IH), 7.81 (d, IH, J=7.8 Hz), 7.66 (d, IH, J=3.9 Hz), 7.61 (m, 3H), 7.53 (d, IH, J=3.9 Hz), 7.49-7.32 (m, 7H), 1.53 (s, 6H). 13C{1H} NMR (DMSO-dfe): δ 162.8, 155.4, 154.5, 153.7, 145.2, 141.2, 140.8, 140.0, 139.9, 138.1, 137.8, 136.5,
136.2, 135.7, 135.6, 133.7, 127.8, 127.3, 127.1, 126.9, 125.9, 125.5, 125.4, 124.2, 124.0, 123.4, 122.9, 122.7, 121.6, 121.3, 121.11, 120.5, 119.5, 117.6, 110.5, 110.0, 49.9, 26.7. MS: m/z 618 [M+]. Anal. Calcd for C39H26N2O2S2: C, 75.70; H, 4.24. Found: C, 75.42; H, 4.13.
IX) 2-(5-((5-(9-(9,9-dimethylfluoren-2-yl)carbazol-6-yl)thiophen-2- yl)methylene)-4-oxo-2-thioxothiazolidin-3-yl)acetic acid (compound Ib-I)
The compound 5 prepared in the above step V)Cn=I)(O.3g, 0.64mmol) was dissolved in acetic acid(30mL), and rhodanine-3-acetic acid(0.13g, 0.67mmol) and ammonium acetate(0.02g, 0.26mmol) were added thereto with stirring. The mixture was heated to 120°C, and then reacted for 2 hours. The reaction solution was cooled to room temperature, and then filtered and the collected solid was washed with water. After the solid was dried in the air, a crude product was subjected to silica gel chromatography (developer CH2Cl2:MeOH=10:1) to obtain black solid title compound (yield 74%).
Mp: 261°C. IH NMR (DMSO-^) : δ 8.78 (s, IH), 8.45 (d, IH, J=7.5 Hz), 8.13 (d, IH, J=8.1 Hz), 8.06 (s, IH), 7.95 (d, IH, J=8.1 Hz), 7.92 (d, IH, J=7.5 Hz), 7.90 (s, IH), 7.82 (m, 2H), 7.62 (d, IH, J=8.1 Hz), 7.61 (d, IH, J=8.4 Hz), 7.52-7.33 (m, 6H), 4.34 (s, 2H), 1.54 (s, 6H). 13CUH} NMR (DMSO-αk): δ 191.9, 175.2, 167.1, 166.6, 155.4, 153.7, 153.1, 140.9, 140.6, 138.2, 137.8, 137.6, 135.6, 135.4, 127.8, 127.3, 127.0, 125.5, 124.9, 124.6, 124.5 , 123.5, 122.9 , 122.6 , 121.6 , 121.3 , 121.2 , 120.6 , 120.5 , 119. 1 , 118.2 , 110.6 , 110. 1 , 46.9 , 26.7 , 23.5. MS: m/z 642 [M+] . Anal . Cal cd for C41H28N2O3S4: C , 67.93 ; H , 3.89. Found : C , 68.90 ; H , 3.80.
X) 2-(5-( (5-(5-(9-(9,9-dimethyl f luoren-2-yl )carbazol-6-yl )thiophen-2- yl )thiophen-2-yl )methylene)-4-oxo-2-thioxothiazol idin-3-yl )acet ic acid (compound lb-2)
The same process prepared in the above step IX) was conducted to obtain black solid title compound (yield 71%).
Mp: 305°C. IH NMR (DMSO-d6) ■ δ 8.64 (s, IH), 8.38 (d, IH, J=7.8 Hz), 8.09 (d, IH, J=8.1 Hz), 8.02 (s, IH), 7.94 (d, IH, J=8.1 Hz), 7.87 (s, IH), 7.79 (d, IH, J=8.7 Hz), 7.73 (d, IH, J=3.9 Hz), 7.53 (d, IH, J=3.9 Hz), 7.63-7.30 (m, 10H), 4.37 (s, 2H), 1.52 (s, 6H). 13C{1H} NMR (DMSO-^): δ 191.6, 189.5, 179.1, 176.1, 171.5, 166.5, 160.0, 156.4, 155.4, 153.7, 145.8, 144.6, 143.7, 140.9, 140.1, 138.1, 137.8, 135.8, 135.5, 133.3, 125.5, 125.3, 124.2, 123.9, 123.4, 122.9, 122.6, 122.5, 121.6, 121.2, 120.5, 119.6, 115.1,
112.4, 110.5, 110.3, 105.1, 46.9, 26.6, 23.8. MS: m/z 724 [M+]. Anal. Calcd for C37H26N2O3S3: C, 69.13; H, 4.08. Found: C, 69.01; H, 4.02.
XI) 9-(4-(2,2-diphenylvinyl)phenyl)-3-(thiophen-2-yl)carbazole (compound 6)
The same process as the above step III) was conducted to obtain white solid title compound (yield 68%).
Mp: 214°C. IH NMR (CDCl3): δ 8.45 (s, IH), 8.24 (d, IH, J=7.5 Hz),
7.74 (d, IH, J=8.4 Hz), 7.54-7.32 (m, 20H), 7.19 (dd, IH, J=5.1, 3.9 Hz), 7.15 (s, IH). 13CUH} NMR (CDCl3): δ 145.9, 145.3, 143.9, 143.2, 142.5,
141.5, 141.0, 140.2, 137.2, 135.5, 131.2, 130.4, 130.1, 129.0, 128.5, 128.2, 127.8, 127.5, 127.0, 126.7, 126.4, 125.8, 125.4, 124.5, 123.7, 123.6, 123.2, 122.3, 120.6, 120.1, 119.6, 118.0, 111.4, 110.8. MS: m/z 503 [M+]. Anal. Calcd for C36H25NS: C, 85.85; H, 5.00. Found: C, 85.64; H, 4.86. XII) 5-(9-(4-(2,2-diphenylvinyl)phenyl)carbazol-6-yl)thiophene-2- carbaldehyde (compound 7)
The same process as the above step V) was conducted to obtain yellow solid title compound (yield 82%). Mp: 222°C. IH NMR (CDCl3): δ 9.89 (s, IH), 8.41 (s, IH), 8.15 (d, IH, J=7.5 Hz), 7.75 (d, IH, J=3.6 Hz), 7.69 (d, IH, J=8.4 Hz), 7.44 (d, IH, J=3.9 Hz), 7.42-7.27 (m, 17H), 7.25 (d, IH, J=3.9 Hz), 7.08 (s, IH). 13CUH} NMR (CDCl3): δ 182.7, 156.1, 143.9, 143.2, 141.6, 141.5, 141.4, 141.0, 140.2, 139.2, 137.9, 137.1, 136.7, 135.5, 131.1, 130.4, 129.0, 128.5, 128.0, 127.9, 127.8, 127.0, 126.8, 126.4, 125.9, 125.3, 124.7, 124.5, 124.1, 123.2, 120.8, 120.6, 118.5, 110.6, 110.4. MS: m/z 531 [M+]. Anal. Calcd for C37H25NOS: C, 83.59; H, 4.74. Found: C, 83.36; H, 4.66.
XIII) 2-cyano-3-(5-(9-(4-(2,2-diphenylvinyl)ρhenyl)carbazol-6- yl)thiophen-2-yl)-acrylic acid (compound Ic)
The same process as the above step VII) was conducted to obtain red solid title compound (yield 78%).
Mp: 255°C. IH NMR (DMSO-d6) : δ 8.62 (s, IH), 8.34 (d, IH, J=7.5 Hz),
8.13 (s, IH), 7.75 (d, IH, J=7.5 Hz), 7.73 (d, IH, J=3.9 Hz), 7.66 (d, IH, J=3.9 Hz) , 7.51-7.24 (m, 19H) . 13C{1H} NMR ( DMSO- c&) : δ 163.9, 152.5, 150.3,
149.8, 145.9, 143.7, 142.6, 142.4, 140.8, 140.6, 140.1, 139.8, 136.6, 136.4,
135.8, 135.3, 134.9, 130.9, 129.7 , 129.2 , 128.5, 127.9 , 127.8 , 127.2, 126.9,
126.8, 126. 1, 125.4, 124.6, 123.5, 122.6, 121. 1 , 120.6 , 119.3, 118.0, 110.5,
109.9, 108.3. MS: m/z 598 [M+] . Anal . Calcd for C40H26N2O2S: C, 80.24; H, 4.38. Found: C, 79.94; H, 4.27. XIV) 9-(9,9-dimethylfluoren-2-yl)-3-(5-(2-(thiophen-2-yl)vinylHhiophen- 2-yl)carbazole (compound 8)
(2-thienylmethyl )triphenylphosphonium bromide(0.65g, 1.48mmol) was suspended in THF(20mL) at room temperature under N2 atmosphere, and then tBu0K (0.17 g, 1.49 mmol) was added thereto. After the mixed solution was cooled to O0C, a solution of the compound 5(n=l) in THF(O.7g, 1.48mmol) was added dropwise. The mixture was stirred at 0°C for 1 hour, and then additionally stirred at room temperature for 8 hours. The reaction solution was diluted with CH2Cl2 and washed with water twice, and then dried with anhydrous sodium sulfate. After the solvent was removed under vacuum, the obtained solid was subjected to silica gel chromatography (developer CH2Cl2:Hx=I:3) to obtain white solid title compound (yield 73%).
Mp: 238°C. IH NMR (CDCl3): δ 8.44 (s, IH), 8.26 (d, IH, J=7.8 Hz), 7.95 (d, IH, J=8.4 Hz) , 7.84 (d, IH, J=7.2 Hz) , 7.73 (d, IH, J=8.7 Hz) , 7.68 (s, IH) , 7.57-7.33 (m, 9H) , 7.29 (d, IH, J=3.9 Hz) , 7.23 (d, IH, J=15.9 Hz) , 7.22 (d, IH, J=5. 1 Hz) , 7. 13 (d, IH, J=3.9 Hz) , 7. 11 (d, IH, J=15.9 Hz) , 7.05 (dd, IH, J=3.9, 5.1 Hz) , 1.62 (s , 6H) . 13C{1H} NMR (CDCl3) : δ 155.7, 154.0, 144.5, 142.9, 141.7, 141.0, 140.8 , 138.9, 138.6, 136.5, 128.3 , 127.9, 127.5, 127.0, 126.8 , 126.6, 126.3 , 126.1 , 125.9 , 124.5, 124.4, 124.1 , 123.5, 122.9, 122.5, 122.0, 121.5, 121.4, 121.0, 120.8, 120.5, 117.7, 110.5, 110.3, 47.4, 27.4. MS: m/z 549 [M+] . Anal . Calcd for C37H27NS2: C, 80.84; H, 4.95. Found: C, 80.59; H, 4.85.
XV) 5-(2-(5-(9-(9,9-dimethylf luoren-2-yl )carbazol-6-yl )thiophen-2- yl)vinyl)thiophene-2-carbaldehyde (compound 9)
The same process as the step V) was conducted to obtain yellow solid title compound (yield 73%).
Mp: 247°C. IH NMR (CDCl3): δ 9.82 (s, IH), 8.38 (s, IH), 8.20 (d, IH, J=7.5 Hz), 7.92 (d, IH, J=8.1 Hz), 7.81 (d, IH, J=7.8 Hz), 7.67 (d, IH, J=8.7 Hz), 7.63 (s, IH), 7.60 (d, IH, J=3.9 Hz), 7.53-7.33 (m, 8H), 7.28 (d, IH, J=3.9 Hz), 7.23 (d, IH, J=15.9 Hz), 7.11 (d, IH, J=3.9 Hz), 7.07 (d, IH, J=3.3 Hz), 6.99 (d, IH, J=15.9 Hz), 1.58 (s, 6H). 13C{1H} NMR (CDCl3): δ
182.4, 155.7, 154.0, 152.4, 146.7, 141.7, 141.3, 141.0, 139.7, 138.9, 138.4, 137.4, 136.3, 129.9, 127.8, 127.4, 126.6, 126.2, 125.9, 124.4, 124.0, 123.3,
123.2, 123.0, 122.9, 121.4, 121.3, 120.7, 120.6, 120.5, 120.3, 119.4, 117.8,
110.5, 110.3, 47.3, 27.2. MS: m/z 577 [M+]. Anal. Calcd for C38H27NOS2: C, 79.00; H, 4.71. Found: C, 78.78; H, 4.57.
XVI) 2-cyano-3-(5-(2-(5-(9-(9,9-dimethylfluoren-2-yl)carbazol-6- yl)thiophen-2-yl)vinyl)thiophen-2-yl)acryl ic acid (compound Id)
The same process as the step X) was conducted to obtain red solid title compound (yield 85%).
Mp: 284°C . IH NMR (DMSO-d6) : δ 8.61 (s, IH), 8.36 (d, IH, J=7.8 Hz), 8.12 (d, IH, J=8.1 Hz), 8.07 (s, IH), 7.95 (d, IH, J=7.8 Hz), 7.88 (s, IH), 7.77 (t, IH, J=8.4 Hz), 7.68 (d, IH, J=7.5 Hz), 7.63-7.31 (m, 12H), 7.19 (d, IH, J=15.9 Hz), 1.54 (s, 6H). 13C{1H} NMR (DMSO-<fc): δ 163.3, 162.6, 161.4, 159.4, 155.3, 153.7, 149.7, 146.9, 144.6, 141.2, 140.8, 140.0, 139.8, 138.1, 137.7, 135.7, 135.6, 132.2, 129.9, 127.7, 127.2, 126.8, 125.8, 125.5, 124.2, 123.9, 123.6, 123.3, 122.8, 122.6, 121.5, 121.2, 120.9, 120.4, 119.2, 117.3, 110.5, 109.9 , 46.8, 26.6. MS: m/z 644 [M+] . Anal . Calcd for C4IH28N2O2S2: C, 76.37 ; H , 4.38. Found : C , 76. 14; H , 4.21.
[Example 2] Preparation of a dye-sensitized solar cell In order to evaluate current-voltage properties of a dye compound, a solar cell was prepared using 13+10 μm TiO2 transparent layer. The washed FTO(Pi lkington, 8Ωsq~x) glass substrate was impregnated with 4OmM TiCl4 aqueous solution. A TiO2 paste(Solaronix, 13nm anatase) was screen printed to prepare a first TiO2 layer having a thickness of 13μm, and a second TiO2 layer having a thickness of lOμm was prepared using another paste(CCIC, HWP-400) for light diffusion. The TiO2 electrode was impregnated with each solution of the dye compounds Ia-I, la-2, Ib-I, lb-2, Ic and Id of the present invention prepared in the above steps VII) to X), XIII) and XVI) (0,3 mM dye in ethanol containing 1OmM 3a,7a-dihydroxy-5b-chloic acid), and allowed to stand at room temperature for 18 hours. An H2PtCl6 solution (2mg Pt IN ImL ethanol) was coated on FTO substrate to prepare a counter electrode. Subsequently, an electrolyte prepared by dissolving 0.6 M 3- hexyl-l,2-dimethylimidazolium iodide, 0.04 M I2, 0.025 M LiI, 0.05 M guanidium thiocyanate and 0.28 M tert-hnty\pyridine in acetonitrile was injected in the cell. The photocell performance of the solar cell was measured using IOOOW xenone light source. The IPCE spectrum of the solar cell was measured using IPCE measurement system (PV measurement).
[Example 3] Measurement of properties of the prepared dye and dye- sensitized solar cell Absorption spectrums (bar line) and emission spectrums (solid line) of each of the dye compounds Ia-I, la-2, Ib-I, lb-2, Ic and Id prepared in the above steps VII) to X), XIII) and XVI) in ethanol, and absorption spectrums (solid line) of the dye compounds supported on TiC^ were shown in Fig. 1 ((a): Ia-I, (b): la-2, (c): Ib-I, (d): lb-2, (e): Ic, (f): Id).
The graphs as shown in Fig. 1 indicate that the absorption spectrums become red-shifted as π-bond system increases. And, the graphs as shown in Fig. 1 indicate that N-substituted carbazole unit inhibits condensation by molecular adhesion, thus inducing a non-planar structure, and condensation inhibition capacity decreases as the bonded dye increases.
And, the geometrical structures of the compounds Ia-I, la-2, Ib-I, lb-2, Ic and Id (molecular orbital of HOMO and LUMO, TD-DFT computation at B3LYP/3-21G) were shown in Fig. 2. The structures as shown in Fig. 2 indicate that HOMO-LUMO excitation moves electron distribution from carbazole unit to cyanoacrylic acid, and that light-induced electron transfer from dye to Tiθ2 electrode is efficiently conducted by HOMO-LUMO transition.
Optical performances and electrochemical performances of each of the dye compounds Ia-I, la-2, Ib-I, lb~2, Ic and Id of the present invention were shown in the following Table 1, and photoelectrochemical characteristics of the solar cells prepared using each of the dye compounds were shown in the following Tables 2 and 3. [Table 1]
Figure imgf000041_0001
In the above Table 1, ε is an absorption coefficiency, E0x is an oxidation potential, E0-O is a voltage at the intersection of absorption and emission spectrums. And, a means that an absorption spectrum is measured in ethanol, b means that an absorption spectrum is measured on TiO2 film, c means that an emission spectrum is measured in ethanol solution, d means that the redox potential of the dye on TiO2 is measured at a scan ratio of 50 mV s'Hvs. Fc/Fc+) using 0.1M (/7-C4Hg)4N-PF6 in CH3CN, e means that E0-O is determined at the intersection of absorption and emission spectrums in ethanol, and f means that Euw is calculated by E0x-Eo-O-
[Table 2]
Figure imgf000041_0002
Figure imgf000042_0002
In the above Table 2, N719 is a ruthenium based catalyst used for dye- sensitized solar cell of the prior art, having the following Formula:
Figure imgf000042_0001
In the above Table 2, Jsc is a short-circuit photocurrent density, V00 is an open circuit photovoltage, ff is a fill factor, and iχ is a total photoconversion efficiency. Wherein, the performances of the dye- sensitized solar cell were measured on the working area of 0.18cm2. IPCE graphs of the dye compounds(Ia-I: bar line, la~2: dotted line, Ib- l: bar line-dotted line, lb-2: bar line-dotted line-dotted line, Ic: short bar line, Id: short dotted line, N719: solid line) as shown in Fig. 3 indicate that the IPCE maximums of the compounds Ia-I and la-2 are especially high and the conversion efficiencies thereof are also excellent. [Industrial Applicability]
The novel dye containing N-arylcarbazole moiety of the present invention shows improved molar absorptivity, Jsc (short circuit photocurrent density) and photoelectric conversion efficiency, compared to the metal complex dye of the prior art, and thus can largely improve the efficiency of a solar cell. And, it can dramatically decrease dye synthesis cost because it can be purified without using expensive columns.

Claims

[CLAIMS] [Claim 1] N-arylcarbazole based dye of the following Formula l:
[Formula 1]
Figure imgf000044_0001
wherein, X is 9,9-dimethylfluorenyl or 4-(2,2-diphenylvinyl )phenyl ,
Y is cyanoacrylic acid or rhodanine-3-acetic acid moiety, n is an integer of 1 to 5, and two or more thiophene units can be optionally linked by vinyl group. [Claim 2]
The N-arylcarbazole based dye according to claim 1, wherein the dye is represented by one of the following Formulas Ia-I, la-2, Ib-I, lb-2, Ic or Id:
[Formula Ia-I]
Figure imgf000045_0001
[Formula la-2]
Figure imgf000045_0002
[Formula Ib-I]
Figure imgf000045_0003
[Formula lb-2]
Figure imgf000046_0001
[Formula Ic]
Figure imgf000046_0002
[Formula Id]
Figure imgf000046_0003
[Claim 3]
A process for preparing N-carbazole based dye of the following Formula Ia or Ib, comprising the steps of: (1) subjecting 3-iodocarbazole to Stille coupling reaction with a compound of the following Formula 2 to prepare a compound of the following Formula 3;
(2) subjecting the compound of the Formula 3 to Ullmann coupling reaction with 2-iodo-9,9-dimethylfluorene to prepare a compound of the following Formula 4;
(3) lithiating the compound of the Formula 4 with n-butyl lithium, and then continuously cooling it with dimethylformamide (DMF) to prepare a compound of the following Formula 5; and (4) reacting the compound of the Formula 5 with cyanoacetic acid in CH3CN in the presence of piperidine, or with rhodanine-3-acetic acid and ammonium acetate in acetic acid: [Formula Ia]
Figure imgf000047_0001
[Formula Ib]
Figure imgf000048_0001
[Formula 2]
Figure imgf000048_0002
[Formula 3]
Figure imgf000048_0003
[Formula 4]
Figure imgf000049_0001
[Formula 5]
Figure imgf000049_0002
wherein, n is an integer of 1 to 5, and two or more thiophene units can be optionally linked by vinyl group. [Claim 4]
A process for preparing N-arylcarbazole based dye of the following Formula Ic, comprising the steps of:
(1) subjecting 3-iodocarbazole to Stille coupling reaction with a compound of the following Formula 2 to prepare a compound of the following Formula 3;
(2) subjecting the compound of the Formula 3 to Ullmann coupling reaction with l-(2-(4-bromophenyl )-l-phenylvinyl )benzene to prepare a compound of the following Formula 6;
(3) formylating the compound of the Formula 6 with n-butyl 1 ithium to prepare a compound of the Formula 7; and
(4) reacting the compound of the Formula 7 with cyanoacetic acid in CH3CN in the presence of piperidine:
[Formula Ic]
Figure imgf000050_0001
[Formul a 2]
Figure imgf000050_0002
[Formul a 3]
Figure imgf000050_0003
[Formula 6]
Figure imgf000051_0001
[Formula 7]
Figure imgf000051_0002
wherein, n is 1. [Claim 5]
A process for preparing N-carbazole based dye of the following Formula Id, comprising the steps of:
(1) subjecting 3-iodocarbazole to Stille coupling reaction with a compound of the following Formula 2 to prepare a compound of the following Formula 3;
(2) subjecting the compound of the Formula 3 to Ullmann coupling reaction with 2-iodo-9,9-dimethylfluorene to prepare a compound of the following Formula 4; (3) lithiating the compound of the Formula 4 with n-butyl 1 ithium, and then continuously cooling it with dimethylformamide (DMF) to prepare a compound of the following Formula 5;
(4) subjecting the compound of the Formula 5 to Horner-Emmons-Wittig coupling reaction with (2-thienhylmethyl)triphenylphosphinium bromide to prepare a compound of the following Formula 8;
(5) formylating the compound of the Formula 8 with n-butyl 1 ithium to prepare a compound of the following Formula 9; and
(6) reacting the compound of the Formula 9 with cyanoacetic acid in CH3CN in the presence of piperidine:
[Formula Id]
Figure imgf000052_0001
[Formul a 2]
Figure imgf000052_0002
[Formula 3]
Figure imgf000053_0001
[Formula 4]
Figure imgf000053_0002
[Formula 5]
Figure imgf000053_0003
[Formula 8]
Figure imgf000054_0001
[Formula 9]
Figure imgf000054_0002
wherein, n is 1. [Claim 6]
A dye-sensitized photoelectric conversion element comprising oxide semiconductor particles where the N-arylcarbazole based dye as described in claim 1 is supported. [Claim 7]
The dye-sensitized photoelectric conversion element according to claim 6, wherein the N-arylcarbazole based dye is supported on the oxide semiconductor particles in the presence of an inclusion compound. [Claim 8] The dye-sensitized photoelectric conversion element according to claim 6, wherein the oxide semiconductor particles comprise titanium dioxide as an essential element.
[Claim 9] The dye-sensitized photoelectric conversion element according to claim 6, wherein the oxide semiconductor particles have an average particle size of 1 ~ 500 nm. [Claim 10]
A dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion element as described in claim 6 as an electrode. [Claim 11]
The dye-sensitized solar cell according to claim 10, wherein the dye- sensitized solar cell is prepared by a process comprising the steps of: coating a titanium oxide on a transparent conductive substrate; subjecting the coated substrate to calcination so as to form a titanium oxide thin film; impregnating the titanium oxide thin film with a mixed solution in which the dye of the Formula 1 is dissolved, so as to form a dye-absorbed titanium oxide film electrode; providing a second glass substrate on which a counter electrode is formed; forming a hole through the second glass substrate and the counter electrode; placing a thermoplastic polymer film between the counter electrode and the dye-absorbed titanium oxide film electrode, and conducting heat pressing, so as to join the counter electrode and the titanium oxide film electrode; injecting an electrolyte in the thermoplastic polymer film placed between the counter electrode and the titanium oxide film electrode through the hole; and sealing the thermoplastic polymer.
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