WO2009099302A2 - Colorant pour cellule solaire à colorant et cellule solaire le comprenant - Google Patents

Colorant pour cellule solaire à colorant et cellule solaire le comprenant Download PDF

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WO2009099302A2
WO2009099302A2 PCT/KR2009/000561 KR2009000561W WO2009099302A2 WO 2009099302 A2 WO2009099302 A2 WO 2009099302A2 KR 2009000561 W KR2009000561 W KR 2009000561W WO 2009099302 A2 WO2009099302 A2 WO 2009099302A2
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compound
dye
group
formula
mmol
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Korean (ko)
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WO2009099302A3 (fr
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Kwang-Yol Kay
Kang-Jin Kim
Jong-Hyung Kim
Young-Jin Kwon
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Solarsys Co Ltd
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Solarsys Co Ltd
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Priority claimed from KR1020080011757A external-priority patent/KR20080018238A/ko
Priority claimed from KR1020080012929A external-priority patent/KR20080019669A/ko
Priority claimed from KR1020080035194A external-priority patent/KR20080039863A/ko
Priority claimed from KR1020090008472A external-priority patent/KR101082086B1/ko
Application filed by Solarsys Co Ltd filed Critical Solarsys Co Ltd
Priority to US12/866,347 priority Critical patent/US8629269B2/en
Publication of WO2009099302A2 publication Critical patent/WO2009099302A2/fr
Publication of WO2009099302A3 publication Critical patent/WO2009099302A3/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
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
    • 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
    • C09B47/00—Porphines; Azaporphines
    • 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
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/361—Polynuclear complexes, i.e. complexes comprising two or more metal centers
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • H10K85/653—Aromatic compounds comprising a hetero atom comprising only oxygen as heteroatom
    • 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
    • H10K85/30—Coordination compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/311—Phthalocyanine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
    • 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
    • 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 a dye used in a dye-sensitized solar cell and a dye-sensitized solar cell using the same. More particularly, a novel dye having a high light absorption is prepared and applied to a light absorbing layer for a solar cell to improve photoelectric current conversion efficiency.
  • the present invention relates to a dye that can increase the open voltage.
  • Dye-sensitized solar cells instead of the electrical energy used in the organic electroluminescent display (OLED) driving mechanism, are a mechanism that absorbs the light energy of visible light and generates electron-hole pairs. It is a photoelectrochemical solar cell whose main component material is a transition metal oxide which transfers electrons.
  • a dye-sensitized solar cell using nanoparticle titanium oxide developed in 1991 by Michael Graetzel of the Swiss National Institute of Advanced Technology (EPFL), is a representative example of conventional dye-sensitized solar cells.
  • the dye-sensitized solar cells developed by them have the advantage that they can be applied to glass walls or glass greenhouses of buildings due to the transparent electrodes and are cheaper to manufacture than conventional silicon solar cells. .
  • the photoelectric current conversion efficiency is proportional to the amount of electrons generated by the absorption of sunlight.
  • the conventional method has a limitation in improving the photoelectric conversion efficiency of the solar cell, and therefore, the development of a new technology for improving the efficiency, in particular, the improvement of the photoelectric conversion efficiency through the development of a new dye having high light absorption and broad light absorption area. This situation is urgent required.
  • the present invention provides a compound having a structure of the following formula (1) or (2) and a dye for a dye-sensitized solar cell comprising the same.
  • X 1 and X 2 are independently a substituent consisting of a (C6-C60) aryl group, a (C3-C60) heteroaryl group, or a combination thereof, wherein at least one of X 1 and X 2 is a popinyl group, phenothia A vinyl group, a coumarinyl group, or a phthalocyanyl group;
  • Y 1 and Y 2 are independently a substituent consisting of a (C 6 -C 60) aromatic hydrocarbon group, a (C 3 -C 60) aromatic heterocyclic group, a combination thereof, or Y 3 and Y 4 are independently selected from a substituent consisting of a (C 6 -C 60) aryl group, a (C 3 -C 60) heteroaryl group, or a combination thereof, at least one of Y 1 to Y 4 is selected from A popinyl group, a phenothiazinyl group, a coumarinyl group, or a phthalocyanyl group;
  • Z 1 and Z 2 are independently a chemical bond or are selected from (C 6 -C 30) arylene, at least one (C 3 -C 30) heteroarylene, at least one vinylene, or a combination thereof;
  • a 1 and A 2 are acidic functional groups
  • the aryl, heteroaryl, arylene, heteroaryl or vinylene group is further substituted with one or more substituents selected from (C1-C20) alkyl, (C1-C20) alkoxy, halogen, amino, nitro and cyano (CN) groups. May be substituted.]
  • the first step in driving a solar cell in a dye-sensitized solar cell is the process of generating a photo charge from the light energy.
  • a dye material is used to generate a photo charge, and the dye material is excited by absorbing light transmitted through the conductive transparent substrate.
  • Metal complexes are widely used as the dye material, and mono, bis, or tris (substituted 2,2'-bipyridine) complex salts of ruthenium are generally used among the metal complexes.
  • they have relatively high efficiencies with the advantage that both metallization and absorption by the ligand and the metal to ligand charge transfer (MLCT) can be used.
  • MLCT metal to ligand charge transfer
  • they have a problem in that the efficiency of the electrons excited by light in the bottom state of the metal composite falls back to the ground state is relatively high, resulting in low efficiency.
  • many cases have been reported in which various electron transfer materials are introduced into a metal complex through covalent bonds.
  • the introduction of electron transfer materials through covalent bonds has a problem that the process is very complicated and difficult to introduce various electron transfer materials.
  • the larger the light absorbing area and the higher the light absorbency is advantageous, but the conventional ruthenium composite has a problem of low light absorbance.
  • a new dye having high light absorbency was synthesized by providing a compound or ruthenium complex in which a popinyl group, phenothiazinyl group, coumarinyl group, and phthalocyanyl group were introduced into an aniline structure as a dye for a solar cell.
  • a popinyl group, phenothiazinyl group, coumarinyl group, and phthalocyanyl group were introduced into an aniline structure as a dye for a solar cell.
  • the dye for a dye-sensitized solar cell according to the present invention is selected from the compounds of Formula 1 or Formula 2.
  • the aryl is an aromatic hydrocarbon group selected from the group consisting of phenyl group, naphthyl group, anthracenyl group, fluorenyl group, biphenyl group, and combinations thereof, and has a carbocycle aromatic compound having 6 to 30 carbon atoms. (carbocyclic aromatic compound) is preferred.
  • the heteroaryl is an aromatic heterocyclic group containing a hetero element such as nitrogen (N), sulfur (S), oxygen (O) to form an aromatic ring, pyran, pyrrole, thiophene, carbazole and combinations thereof It is preferable to select from the substituent which consists of.
  • Z 1 and Z 2 is a chemical bond or in the form of a radical capable of bonding at both ends, and is selected from arylene, heteroarylene, vinylene and combinations thereof, specifically vinylene, polyvinylene, phenyl Ethylene, naphthylene, anthracenylene, fluorenylene, biphenylene, pyranylene, pyrrolene, thiophenylene, carbazoylene group or a combination thereof.
  • the A 1 and A 2 is an acidic functional group, specifically, selected from a substituent consisting of a carboxyl group, a phosphorous acid group, a sulfonic acid group, a phosphinic acid group, a hydroxy group, an oxycarboxylic acid, an acid amide, and a combination thereof, and more preferably.
  • Carboxyl group is an acidic functional group, specifically, selected from a substituent consisting of a carboxyl group, a phosphorous acid group, a sulfonic acid group, a phosphinic acid group, a hydroxy group, an oxycarboxylic acid, an acid amide, and a combination thereof, and more preferably.
  • Carboxyl group is an acidic functional group, specifically, selected from a substituent consisting of a carboxyl group, a phosphorous acid group, a sulfonic acid group, a phosphinic acid group, a hydroxy group, an oxycarboxylic
  • the dye includes at least one functional group selected from a popinyl group, a phenothiazinyl group, a coumarinyl group, or a phthalocyanyl group in the compound, and a popinyl group, phenothiazinyl group, and coumarinyl group in one compound. Or more preferably two or more functional groups selected from phthalocyanyl groups.
  • the compound of Formula 1 is more specifically selected from the compound of Formula 3, the compound of Formula 2 is more specifically selected from the compound of Formula 4 or Formula 5.
  • [X 11 and Y 11 to Y 13 in Chemical Formulas 3 to 5 may be independently selected from the following structures:
  • X 12 is selected from the structure
  • Z 11 and Z 12 are independently Is selected from,
  • Z 21 to Z 24 are independently Is selected from,
  • n is an integer from 0 to 4
  • j is an integer from 0 to 2
  • k is an integer from 0 to 4
  • p is an integer of 0-2
  • q is an integer of 0-4.
  • R 11 to R 22 and R 30 to R 31 are independently hydrogen or selected from (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, halogen element, amino group, nitro group or cyano group (CN).]
  • the compound of Formula 3 to Formula 5 is specifically selected from compounds of the following structure, in the compound of the structure 11 To R 22 , R 31 To R 32 And R 40 Is independently selected from hydrogen or (C1-C20) alkyl, n is an integer from 0 to 4, a is 0 or 1, b is an integer from 0 to 2, c is 0 or 1, d is 0 It is an integer of 2 to.
  • the present invention provides a solar cell containing at least one of the dye materials according to the present invention in a light absorption layer.
  • FIG. 1 The vertical structure of the solar cell containing the dye material according to the present invention is shown in FIG. 1.
  • the titanium alkoxide solution is coated on an FTO glass substrate and then dried, followed by coating, drying, and heat treating a titania sol to form a titania film.
  • the substrate on which the titania film is formed is immersed in a dye-containing solution and dried to adsorb the dye onto the titania film made of titania particles.
  • a substrate having a dye layer and a substrate having an electrode layer were bonded to each other to manufacture a solar cell having a structure as shown in FIG. 1.
  • FIG. 1 is a schematic cross-sectional view of a dye-sensitized solar cell device according to an embodiment of the present invention.
  • 13 is a current-voltage curve of a solar cell prepared using compounds 102 and 103,
  • 17 is a current-voltage curve of a solar cell prepared using compound 108,
  • 19 is a current-voltage curve of a solar cell prepared using Compound 110.
  • Compound 11 Compound 10 (4.50 g, 16.46 mmol) is added to glacial acetic acid (50 ml), and the temperature is raised to 70 ° C. After confirming that the reactants are completely dissolved, KI (5.46g, 32.87mmol), KIO 3 (10.56 g, 49.33 mmol) was added and then stirred for 3 hours. After cooling the reaction solution, the resulting solids are filtered and washed several times with water. The product was dissolved in dichloromethane, washed with dilute ammonia solution (pH ⁇ 8), and then NaHSO 3 Wash several times with saturated solution and water.
  • Compound 14 Compound 13 (3.0 g, 13.80 mmol), DMF (3.2 ml, 38.4 mmol) and POCl 3 (3.9 ml, 38.4 mmol) were added to 1,2-dichloroethane (20 ml). Next, the mixture is stirred at room temperature for 1 hour and then refluxed for 1 hour. The reaction solution is cooled to room temperature, poured slowly into a saturated aqueous sodium acetate solution, and then stirred for 10 minutes. Extracted with dichloromethane, the organic layer was separated and dried over MgSO 4 .
  • Compound 16 Compound 15 (0.15 g, 0.68 mmol), Compound 11 (0.15 g, 0.28 mmol), Pd (OAc) 2 (3 mg, 0.014 mmol), K 2 CO 3 (0.14g, 0.14mmol), Bu 4 NBr (0.18 g, 0.57 mmol) was added to DMF (5 ml), then the temperature was raised to 95 ° C. and stirred for 16 h. After cooling the reaction solution, water (50ml) is added and extracted with dichloromethane.
  • Compound 18 Compound 17 (6.10 g, 9.79 mmol), 2-thiophenebronic acid (0.42 g, 3.26 mmol), Pd (PPh) 4 (0.15 g, 0.13 mmol), K 2 CO 3 (1.18 g, 9.79 mmol) was added to DMF (5 ml), then the temperature was raised to 60 ° C. and stirred for 2 hours. After cooling the reaction solution, water (50ml) is added and extracted with dichloromethane.
  • Compound 20 Compound 15 (0.41 g, 1.68 mmol), Compound 19 (0.28 g, 0.46 mmol), Pd (OAc) 2 (5mg, 0.023mmol), K 2 CO 3 (0.22g, 1.84mmol), Bu 4 NBr (0.30 g, 0.92 mmol) was added to DMF (5 ml), then the temperature was 95 Raise to C and stir for 6 hours. After cooling the reaction solution, water (50ml) was added and extracted with dichloromethane. The organic layer was separated and then MgSO 4 After drying under reduced pressure, the solvent was removed under reduced pressure, and the liquid was chromatographed with dichloromethane as a developing solvent. (0.36 g, 100%).
  • Compound 21 Compound 17 (3.20 g, 5.13 mmol), 2,2'-bithiophene-5-bronic acid pinacol ester (0.50 g, 1.71 mmol), Pd ( PPh) 4 (79mg, 0.068mmol), K 2 CO 3 (0.62 g, 5.13 mmol) was added to DMF (5 ml), and then the temperature was 60 Raise to C and stir for 2 hours. After cooling the reaction solution, water (50ml) was added and extracted with dichloromethane.
  • Compound 23 Compound 15 (0.20 g, 0.82 mmol), Compound 22 (0.24 g, 0.35 mmol), Pd (OAc) 2 (4mg, 0.017mmol), K 2 CO 3 (0.17g, 1.40mmol), Bu 4 NBr (0.22 g, 0.70 mmol) was added to DMF (5 ml), then the temperature was 95 Raise to C and stir for 16 h. After cooling the reaction solution, water (50ml) was added and extracted with dichloromethane.
  • Compound 25 Compound 24 (1.0 g, 1.59 mmol), DMF (1.3 ml, 15.87 mmol), POCl in 1,2-Dichloroethane (20 ml) 3 (1.6ml, 15.87mmol) was added thereto, stirred at room temperature for 10 minutes, and refluxed for 16 hours. The reaction solution is cooled to room temperature, poured slowly into a saturated aqueous sodium acetate solution, and then stirred for 10 minutes. Extract with dichloromethane, separate organic layer, MgSO 4 To dry. The solvent was removed by distillation under reduced pressure, and liquid chromatography was carried out using dichloromethane as a developing solvent to obtain a red solid compound (0.86 g, 81.1%).
  • Compound 26 Compound 25 (0.48 g, 2.19 mmol), Compound 15 (0.48 g, 0.73 mmol), Pd (OAc) 2 (8mg, 0.036mmol), K 2 CO 3 (0.35g, 2.92mmol), Bu 4 NBr (0.47 g, 1.46 mmol) was added to DMF (5 ml), then the temperature was raised to 95 ° C. and stirred for 16 h. After cooling the reaction solution, water (50ml) was added and extracted with dichloromethane.
  • Absorption of the ultraviolet-visible region of the compound 104 was measured at 2 * 10 -5 M concentration using 2-methoxyethanol as a solvent, as shown in FIG. 5, and the absorbance of 58000 dm 3 mol -1 cm -1 was measured. Indicated.
  • Compound 28 Compound 27 in Glacial acetic acid (10 ml) (1.0 g, 3.32 mmol) was added and the temperature was raised to 70 ° C. After confirming that the reactants are all dissolved, KI (0.55g, 3.32mmol), KIO 3 (1.07 g, 4.98 mmol) is added and then stirred for 16 hours. After cooling the reaction solution, the resulting solids are filtered and washed several times with water. The product was dissolved in dichloromethane, washed with dilute ammonia solution (pH ⁇ 8), and then NaHSO 3 Wash several times with saturated solution and water. MgSO organic layer 4 To a light yellow solid which is then dried under reduced pressure to remove the solvent.
  • Compound 29 Compound 28 (0.34 g, 1.55 mmol), Compound 15 (0.66 g, 1.55 mmol), Pd (OAc) 2 (17mg, 0.077mmol), K 2 CO 3 (0.56g, 4.65mmol), Bu 4 NBr (0.75 g, 2.33 mmol) was added to DMF (5 ml), then the temperature was 95 Raise to C and stir for 4 h. After cooling the reaction solution, water (50ml) is added and extracted with dichloromethane.
  • the absorbance of the ultraviolet-visible region at 2.5 * 10 -5 M concentration using 2-methoxyethanol as a solvent for the compound 105 was shown in FIG. 6, and the absorbance of 67000 dm 3 mol -1 cm -1 was measured. Indicated.
  • Compound 32 Compound 31 (3.0 g, 13.56 mmol) was added to Isopropyl alcohol (100 ml), and a solution of NaSH (6.03 g, 108.48 mmol) dissolved in water (5 ml) was added thereto, followed by reflux for 16 hours. do. After cooling the reaction solution, the solvent is removed under reduced pressure and washed with excess water. Ethyl acetate is added to completely dissolve the resulting solids, and then poured into water (100 ml) and stirred for 10 minutes.
  • Compound 36 Compound 32 in o-Xylene (20 ml) (0.25 g, 1.21 mmol), Compound 35 (1.09g, 3.0mmol), Pd (OAc) 2 (11 mg, 0.05 mmol), P ( t Bu) 3 (0.03ml), NaO t Bu (0.35 g, 1.63 mmol) is added and then refluxed for 16 h. After cooling the reaction solution, the catalyst and by-products are removed by filtration, and then the solvent is removed under reduced pressure.
  • Compound 37 Compound 36 in THF (150 ml), water (50 ml) (0.39g, 0.51mmol), CF 3 COOH (10 ml) is added and then stirred for 1 hour. NaHCO 3 The reaction solution is neutralized with an aqueous solution and then extracted with dichloromethane. The organic layer was separated and then MgSO 4 After drying under reduced pressure, the solvent was removed under reduced pressure, and the liquid was chromatographed with dichloromethane as a developing solvent. (0.24 g, 68.6%).
  • Compound 38 Compound 34 (7.07 g, 24.94 mmol), DMF (5.82 ml, 74.83 mmol), and POCl 3 (6.98 ml, 74.83 mmol) were added to 1,2-dichloroethane (30 ml). Next, the mixture is stirred at room temperature for 1 hour and then refluxed for 2 hours. The reaction solution is cooled to room temperature, poured slowly into a saturated aqueous sodium acetate solution, and then stirred for 10 minutes. Extracted with dichloromethane, the organic layer was separated and dried over MgSO 4 .
  • Compound 40 Compound 11 (0.19 g, 0.36 mmol) prepared in Synthesis Example 1, compound 39 (0.27 g, 0.87 mmol), Pd (OAc) 2 (4mg, 0.018mmol), K 2 CO 3 (0.17g, 1.44mmol), Bu 4 NBr (0.23 g, 0.72 mmol) was added to DMF (5 ml), and then the temperature was 95 Raise to C and stir for 6 hours. After cooling the reaction solution, water (50ml) was added and extracted with dichloromethane.
  • the absorption wavelength of the ultraviolet-visible wide region of the compound 107 is shown in FIG. 8. Under 1.5 * 10 -5 M condition using 2-methoxyethanol as a solvent, the absorbance is 70,000 dm 3 mol -1 cm -1 or more, which is significantly higher than that of conventional dyes.
  • Triethylamine (4.67ml, 33.5mmol) is added and stirred for 30 minutes before terminating the reaction.
  • TLC dichloromethane
  • Compound 45 Compound 11 (120 mg, 0.19 mmol) and Compound 44 (40 mg, 0.077 mmol) prepared in Synthesis Example 1 were added to the purified dimethylformamide (3 ml) after blocking light under a nitrogen stream, followed by stirring. do.
  • Palladium (II) acetate (8 mg, 0.039 mmol), tetrabutylammonium bromide (TBAB, 62 mg, 0.19 mmol), anhydrous potassium carbonate anhydrous (K 2 CO 3 , 56 mg, 0.462 ) Is added and stirred at 95 ° C. for 15 hours. Extract using dichloromethane.
  • Compound 52 Compound 51 in Absolute ethanol (80 ml) (1.0 g, 4.09 mmol) was added, the mixture was stirred for 10 minutes, and concentrated sulfuric acid (1 ml) was added to the reaction solution, followed by reflux for 80 hours. After the temperature was lowered to room temperature and distilled water (80 ml) was added, the solution was neutralized with 1M aqueous sodium hydroxide solution. The resulting solid is filtered and dried to give a white solid compound (1.18g, 95.0%) is obtained. M.p.
  • Compound 53 Compound 52 in Absolute ethanol (70 ml) (1.1 g, 3.66 mmol) and sodium borohydride (2.77 g, 73.2 mmol) are added, and the reaction solution is refluxed for 3 hours. Lower the temperature to room temperature, and add a solution of ammonium chloride solution (3.8g, 75.0mmol) in distilled water (75ml) to the reaction solution. The white solid product is filtered off and then depressurized to remove the solvent. Ethyl acetate was added to completely dissolve the produced solids, and then the organic layer was separated and then MgSO 4 After drying under reduced pressure, the solvent is removed to give a pale pink solid compound. (0.69 g, 87.5%). M.p.
  • Compound 54 Compound 53 (0.69 g, 3.16 mmol) is dissolved in 48% HBr (15.5 ml) and concentrated sulfuric acid (5.1 ml) and refluxed for 6 hours. After cooling the reaction solution, distilled water (30 ml) is added. After neutralizing with 1M sodium hydroxide solution, the pale pink solid product was filtered and dissolved in chloroform. The organic layer was separated and then MgSO 4 After drying under reduced pressure, the solvent is removed to give a pale pink solid compound. (0.83 g, 76.0%) is obtained. M.p.
  • Compound 56 Compound 55 (0.40 g, 0.88 mmol) and 95% NaH (64 mg, 2.62 mmol) were added to THF (10 ml), followed by stirring for 30 minutes, followed by compound 14 (0.46 g, 2.10 mmol) prepared in Synthesis Example 1. Add and stir for 16 hours. Water (50 ml) was added to the reaction solution, followed by extraction with chloroform. The organic layer was separated and then MgSO. 4 To dry. Solvent is removed under reduced pressure, and the solid formed by methanol is washed (0.25 g, 48.1%).
  • Compound 109 has an absorption up to about 740 nm (band edge), shows an absorption wavelength of coumarin structure at 465 nm and a metal to ligand charge transfer (MLCT) band at 557 nm, and a molar extinction coefficient ( ⁇ , M -1 cm -1 ) are calculated as 54,000 (465 nm) and 23,000 (557 nm), respectively.
  • MLCT metal to ligand charge transfer
  • the MLCT band was moved to a long wavelength of about 43 nm while having a much higher absorbance than N719.
  • Such high absorbance allows light to be absorbed more efficiently when applied to solar cells, thus further improving the photoelectric conversion efficiency of the solar cell.
  • Compound 57 Compound 55 (0.20 g, 0.44 mmol) and 95% NaH (32 mg, 1.31 mmol) prepared in Synthesis Example 9 were added to THF (5 ml), and stirred for 1 hour, followed by compound 38 prepared in Synthesis Example 7. (0.33 g, 1.05 mmol) was added and stirred for 16 hours. Water (50 ml) was added to the reaction solution, followed by extraction with chloroform. The organic layer was separated and then MgSO. 4 To dry. Remove the solvent by depressurizing and wash the solid produced with methanol. (0.24 g, 70.6%).
  • Compound 110 had absorption up to about 740 nm (band edge), showed maximum absorption wavelength at 307 nm, absorption wavelength of phenothiazine structure at 434 nm, and metal to ligand charge transfer (MLCT) band at 545 nm.
  • the molar extinction coefficients ( ⁇ , M -1 cm -1 ) are calculated as 100,000 (307 nm), 59,000 (434 nm) and 28,000 (545 nm), respectively.
  • the MLCT band was moved to a long wavelength at about 30 nm while having a much higher absorbance than N719. Such high absorbance allows light to be absorbed more efficiently when applied to solar cells, thus further improving the photoelectric conversion efficiency of the solar cell.
  • the dyes for dye-sensitized solar cells of Synthesis Examples 1 to 10 have a high absorbance of 5 times or more than conventional dyes (N719), and thus can be improved in photoelectric conversion efficiency when applied to dye-sensitized solar cells.
  • Dysol titania (TiO 2 ) is coated on the FTO glass by the doctor blade method.
  • the coated film is dried in an oven at 100 ° C. for 10 minutes and then heat treated at 450 ° C. for 30 minutes to obtain a 10 micrometer thick TiO 2 film.
  • the TiO 2 film is immersed in an anhydrous ethanol solution of the synthesized dye at a concentration of 0.5 mM for 24 hours to adsorb the dye (when the dye is not dissolved in anhydrous ethanol, a solvent that can be dissolved is dissolved. use).
  • the dye that has not been adsorbed with anhydrous ethanol is thoroughly washed and dried. The dye-adsorbed film is scraped off, leaving only the size of 4 mm x 4 mm.
  • the electrolyte solution was 0.1 M LiI, 0.05 MI 2 , 0.6 M 1-hexyl-2,3-dimethylimidazolium iodide and 0.5 M 4-t-butylpyridine. (4- tert- butylpyridine) was prepared using 3-methoxypropionitrile solvent.
  • the M236 source measure unit SMU, Keithley was used to obtain the current-voltage curve.
  • the electric potential ranged from -0.8 V to 0.2 V, and the light intensity was 100 mW / cm 2 .
  • the solar cell device was manufactured by the method described above, and its characteristics were checked. Opening voltages (V oc ) and short circuits measured from the used dye and the manufactured solar cell device were measured.
  • the current (J sc ), fill factor (FF), and photoelectric conversion efficiency (%) are shown in Table 3 below.
  • the efficiency according to the following examples is based on device structure, size of titanium oxide, and concentration of co-adsorbant. And type, concentration and type of electrolyte, and the like, and are therefore not limited to the following values.
  • the dye according to the present invention exhibits high light absorption, and the dye-sensitized solar cell including the dye has excellent photoelectric conversion efficiency.

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Abstract

La présente invention concerne un colorant pour une cellule solaire à colorant. Le colorant selon la présente invention présente un degré élevé d'absorbance de la lumière et peut améliorer le rendement de conversion du courant photoélectrique lorsqu'il est utilisé dans une couche d'absorption de lumière pour une cellule solaire.
PCT/KR2009/000561 2008-02-05 2009-02-05 Colorant pour cellule solaire à colorant et cellule solaire le comprenant Ceased WO2009099302A2 (fr)

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US12/866,347 US8629269B2 (en) 2008-02-05 2009-02-05 Dye for a dye-sensitised solar cell, and a solar cell comprising the same

Applications Claiming Priority (8)

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KR1020080011757A KR20080018238A (ko) 2008-02-05 2008-02-05 쿠마린 함유 염료 감응 태양전지용 염료
KR10-2008-0011757 2008-02-05
KR10-2008-0012929 2008-02-13
KR1020080012929A KR20080019669A (ko) 2008-02-13 2008-02-13 페노티아진 함유 염료 감응 태양전지용 염료
KR1020080035194A KR20080039863A (ko) 2008-04-16 2008-04-16 포피린 함유 염료 감응 태양전지용 염료
KR10-2008-0035194 2008-04-16
KR1020090008472A KR101082086B1 (ko) 2008-02-05 2009-02-03 염료 감응 태양전지용 염료 및 이를 함유하는 태양전지
KR10-2009-0008472 2009-02-03

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102093740A (zh) * 2011-01-21 2011-06-15 电子科技大学 一种用于染料敏化太阳能电池的有机染料及其制备方法
US20110155237A1 (en) * 2009-12-24 2011-06-30 Noh-Jin Myung Dye-sensitized solar cell
CN111100099A (zh) * 2019-12-03 2020-05-05 西安近代化学研究所 一种苯基为末端桥链的三苯胺共敏剂及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3001877A1 (de) * 1980-01-19 1981-07-23 Bayer Ag, 5090 Leverkusen Lichtsammelsysteme und die verwendung von cumarinderivaten als energiewandler in ihnen
JPH11144773A (ja) * 1997-09-05 1999-05-28 Fuji Photo Film Co Ltd 光電変換素子および光再生型光電気化学電池
US7332599B2 (en) * 2003-06-06 2008-02-19 North Carolina State University Methods and intermediates for the synthesis of dipyrrin-substituted porphyrinic macrocycles
JP2008021496A (ja) * 2006-07-12 2008-01-31 Nippon Kayaku Co Ltd 色素増感光電変換素子

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110155237A1 (en) * 2009-12-24 2011-06-30 Noh-Jin Myung Dye-sensitized solar cell
CN102093740A (zh) * 2011-01-21 2011-06-15 电子科技大学 一种用于染料敏化太阳能电池的有机染料及其制备方法
CN102093740B (zh) * 2011-01-21 2013-06-12 电子科技大学 一种用于染料敏化太阳能电池的有机染料及其制备方法
CN111100099A (zh) * 2019-12-03 2020-05-05 西安近代化学研究所 一种苯基为末端桥链的三苯胺共敏剂及其制备方法
CN111100099B (zh) * 2019-12-03 2023-04-18 西安近代化学研究所 一种苯基为末端桥链的三苯胺共敏剂及其制备方法

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