WO2008146975A1 - Nouveau colorant organique contenant un fragment n-arylcarbazole et sa préparation - Google Patents

Nouveau colorant organique contenant un fragment n-arylcarbazole et sa préparation 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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Prior art keywords
formula
compound
dye
following formula
prepare
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PCT/KR2007/003206
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English (en)
Inventor
Chong-Chan Lee
Ho-Gi Bae
Jae-Jung Ko
Jong-Hyub Baek
Duck-Hyun Kim
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Dongjin Semichem Co., Ltd
Korea University Industrial & Academic Collaboration Foundation
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Publication of WO2008146975A1 publication Critical patent/WO2008146975A1/fr

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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

La présente invention concerne un nouveau colorant contenant un fragment N-arylcarbazole et sa préparation. Le composé colorant de la présente invention qui comprend du fluorène et du carbazole en tant que donneurs d'électrons, une unité thiophène en tant que partie de liaison intermédiaire, et de l'acide rhodanine-3-acétique ou de l'acide cyanoacrylique en tant qu'accepteurs d'électrons peut être utilisé pour une cellule solaire sensibilisée par colorant (DSSC). Le colorant de la présente invention présente une capacité d'absorption molaire améliorée, une meilleure Jsc (densité de photocourant de court-circuit) et une plus grande efficacité de conversion photoélectrique, par comparaison avec des colorants de l'art antérieur, et peut ainsi améliorer de manière considérable l'efficacité de la cellule solaire. Le colorant de l'invention peut également réduire de manière notable les coûts de synthèse de colorant étant donné qu'il peut être purifié sans utiliser de colonnes présentant un coût élevé.
PCT/KR2007/003206 2007-05-25 2007-07-03 Nouveau colorant organique contenant un fragment n-arylcarbazole et sa préparation WO2008146975A1 (fr)

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JP2011162644A (ja) * 2010-02-09 2011-08-25 Hodogaya Chem Co Ltd 光電変換用増感色素及びそれを用いた光電変換素子及び色素増感太陽電池
CN102604412A (zh) * 2012-01-17 2012-07-25 北京师范大学 用于染料敏化太阳能电池的含双并咔唑基团的染料及制备
WO2012078005A3 (fr) * 2010-12-10 2012-08-23 고려대학교 산학협력단 Composés dotés de la propriété de conduction par trous, corps co-adsorbant en contenant et photopile sensibilisée par un colorant intégrant ledit corps co-adsorbant
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JP2012214671A (ja) * 2011-03-31 2012-11-08 Fujifilm Corp 色素、光電変換素子及び光電気化学電池
KR101290406B1 (ko) 2010-06-29 2013-07-26 고려대학교 산학협력단 정공전도성을 갖는 화합물, 그의 공흡착체로서의 용도, 및 그를 포함하는 염료감응 태양전지
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WO2011081357A2 (fr) * 2009-12-30 2011-07-07 주식회사 동진쎄미켐 Nouveau colorant organique et son procédé de préparation
KR101882394B1 (ko) * 2009-12-31 2018-07-26 주식회사 동진쎄미켐 신규한 유기염료 및 이의 제조방법
CN102167913B (zh) * 2011-02-25 2013-09-25 中国科学院上海有机化学研究所 含多联咔唑的有机染料及其制备方法和应用
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WO2014003405A1 (fr) * 2012-06-26 2014-01-03 주식회사 제이앤드제이 캐미칼 Nouveau composé et dispositif émettant de la lumière le comprenant
KR101465454B1 (ko) * 2012-11-13 2014-12-02 재단법인대구경북과학기술원 염료감응 태양전지용 유기염료 및 이를 포함하는 염료감응 태양전지
KR101749379B1 (ko) 2014-06-12 2017-06-20 주식회사 엘지화학 공중합체, 이의 제조방법 및 상기 공중합체를 포함하는 유기 태양 전지
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CN102695759A (zh) * 2009-12-30 2012-09-26 株式会社东进世美肯 新的有机染料及其制造方法
CN103525116A (zh) * 2009-12-30 2014-01-22 株式会社东进世美肯 新的有机染料及其制造方法
JP2011162644A (ja) * 2010-02-09 2011-08-25 Hodogaya Chem Co Ltd 光電変換用増感色素及びそれを用いた光電変換素子及び色素増感太陽電池
KR101290406B1 (ko) 2010-06-29 2013-07-26 고려대학교 산학협력단 정공전도성을 갖는 화합물, 그의 공흡착체로서의 용도, 및 그를 포함하는 염료감응 태양전지
KR101311584B1 (ko) 2010-06-29 2013-09-26 고려대학교 산학협력단 정공전도성을 갖는 화합물, 그의 공흡착체로서의 용도, 및 그를 포함하는 염료감응 태양전지
WO2012078005A3 (fr) * 2010-12-10 2012-08-23 고려대학교 산학협력단 Composés dotés de la propriété de conduction par trous, corps co-adsorbant en contenant et photopile sensibilisée par un colorant intégrant ledit corps co-adsorbant
JP2012214671A (ja) * 2011-03-31 2012-11-08 Fujifilm Corp 色素、光電変換素子及び光電気化学電池
CN102604412A (zh) * 2012-01-17 2012-07-25 北京师范大学 用于染料敏化太阳能电池的含双并咔唑基团的染料及制备
CN105934497A (zh) * 2013-12-03 2016-09-07 东进世美肯株式会社 新型发光化合物以及包含其的有机发光元件
CN105934497B (zh) * 2013-12-03 2018-07-17 东进世美肯株式会社 新型发光化合物以及包含其的有机发光元件
CN110372719A (zh) * 2019-08-09 2019-10-25 浙江工业大学 N-芴基苯并咔唑类化合物、制备方法及其应用
CN110372719B (zh) * 2019-08-09 2020-08-11 浙江工业大学 N-芴基苯并咔唑类化合物、制备方法及其应用

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