WO2011040680A2 - Dye-sensitized/ligand-to-metal charge-transfer hybrid solar cell comprising a working electrode including nano-oxide layer composed of nano-oxide particles adsorbed with dyes and ligands and method of manufacturing the same - Google Patents

Dye-sensitized/ligand-to-metal charge-transfer hybrid solar cell comprising a working electrode including nano-oxide layer composed of nano-oxide particles adsorbed with dyes and ligands and method of manufacturing the same Download PDF

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WO2011040680A2
WO2011040680A2 PCT/KR2009/007376 KR2009007376W WO2011040680A2 WO 2011040680 A2 WO2011040680 A2 WO 2011040680A2 KR 2009007376 W KR2009007376 W KR 2009007376W WO 2011040680 A2 WO2011040680 A2 WO 2011040680A2
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group
carbon atoms
substituted
acid
dye
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PCT/KR2009/007376
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French (fr)
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WO2011040680A3 (en
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Chi Hwan Han
Kyung Hoon Yoon
Hak Soo Lee
Tae Yeon Cho
Sang Hoon Bae
Semina Jeon
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Korea Institute Of Energy Research
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Publication of WO2011040680A3 publication Critical patent/WO2011040680A3/en

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    • 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
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a dye-sensit i zed/1 igand-to-metal charge-transfer hybrid solar cell comprising a working electrode including a nano-oxide layer adsorbed with dyes and ligands, and to a method of manufacturing the same.
  • the present invention relates to a dye-sensit i zed/1 igand-to-metal charge-transfer hybrid solar cell comprising a working electrode including a nano-oxide layer composed of nano-oxide particles adsorbed with dyes and ligands, the photoelectric conversion efficiency of which is improved compared to that of a conventional dye- sensitized solar cell adsorbed with only dyes because the adsorbed dyes and ligands simultaneously generate electric current, and to a method of manufacturing the same.
  • a solar cell is a device for directly converting solar energy into electric energy, and is expected to be an energy source which can solve future energy problems because it produces hardly any pollution, uses an unlimited resource and has a semipermanent lifespan.
  • Such solar cells are largely classified into inorganic solar cells, dye-sensitized solar cells and organic solar cells according to the kind of material .
  • a monocrystal 1 ine silicon solar cell is one of such inorganic solar cells, and is advantageous in that it can be manufactured into a thin-film solar cell, but is problematic in that its manufacturing costs are high and its stabi 1 ity is low.
  • a dye-sensitized solar cell is a photoelectric chemical solar cell which is essentially composed of photosensitive dye molecules for forming electron-hole pairs by absorbing visible light and transition metal oxides for transferring the formed electrons.
  • a dye-sensitized solar cell is advantageous in that it can withstand exposure to heat and light for a long period of time and can easily produce energy at low cost, compared to conventional silicon-based solar cells.
  • the dye-sensitized solar cell includes a semiconductor electrode made of titanium dioxide (T1O2) nanopart icles coated with dye molecules, a counter electrode coated with platinum or carbon, and an electrolyte solution charged between these electrodes.
  • T1O2 titanium dioxide
  • Such a photoelectric chemical solar cell has attracted considerable attention because its manufacturing cost per watt is lower than that of a conventional silicon solar cell.
  • This dye-sensitized solar cell developed by Gratzel, shows the fact that it can become a cheap alternative to an expensive silicon solar cell.
  • such a dye-sensitized solar cell compared to a conventional solar cell, is advantageous in that its manufacturing cost is low and it can be applied to the window glass of outer walls of buildings, glass greenhouses or the like, but is problematic in that its photoelectric conversion efficiency is low, and thus its practical use is limited.
  • the photoelectric conversion efficiency of a solar cell is proportionate to the amount of electrons generated by the absorption of solar light. Therefore, in order to increase the photoelectric conversion efficiency thereof, the amount of produced electrons may be increased by accelerating the absorption of solar light or increasing the adsorbed amount of dye, or the extinction of produced electrons resulting from the recombination of excited electrons and holes may be prevented.
  • a method of forming oxide semiconductor particles at a level of nanometer so as to increase the adsorbed amount of dye, a method of increasing the ref lexibi 1 ity of a platinum counter electrode to accelerate the absorption of solar light, a method of mixing oxide semiconductor particles having a size of several micrometers with light scattering materials, and the like have been developed.
  • these conventional methods limitedly improve the photoelectric conversion efficiency of a solar cell. Therefore, it is keenly required to develop novel technologies for improving the photoelectric conversion efficiency.
  • the present inventors have repeatedly researched methods of improving the photoelectric conversion efficiency of a dye-sensitized solar cell. As a result, they found that, when a dye-sensitized solar cell comprises a working electrode including a nano oxide layer adsorbed with both a dye and a ligand from which charge can be transferred to metal, the adsorbed dye and ligand simultaneously generate electric current, and thus the efficiency thereof is improved compared to that of a conventional dye-sensit ized ' solar cell adsorbed with only dye. Based on these findings, the present invention was com leted.
  • the present invention relates to a hybrid solar cell which can improve photoelectric conversion efficiency by combining a dye-sensitized solar cell with a 1 igand-to-metal charge-transfer solar cell which is actively being researched now.
  • a hybrid solar cell is referred to as a "dye-sensiti zed/ 1 igand-to-metal charge-transfer hybrid solar cell”.
  • the present invention has been made to solve the above- mentioned problems, and an object of the present invention is to provide a dye-sensi ti zed/ 1 igand-to-metal charge-transfer hybrid solar cell having improved photoelectric conversion efficiency, which can solve, namely the problem of the low photoelectric conversion efficiency of the conventional dye-sensitized solar cell, and a method of manufacturing the same.
  • an aspect of the present invention provides a method of manufacturing a dye-sensit i zed/1 igand-to-metal charge-transfer hybrid solar cell, comprising the steps of: forming a nano- oxide layer on a transparent substrate including a transparent conductive oxide layer formed thereon (step 1); immersing the transparent substrate including the nano-oxide layer formed thereon into a dye solution prepared by mixing a dye, an organic solvent and a compound selected from the group consisting of salicylic acid, a salicylic acid derivative, catechol, sal icylaldehyde, saccharine, sal icylamide, 1,4,5,8-naphthalenetetracarboxyl ic acid, anhydrous 1,4,5,8-naphthalenetetracarboxyl ic acid, anhydrous 1,8- naphthalic acid, 1-naphthoic acid, naphthol blue black and naphthol green B and thus adsorbing the dye
  • Another aspect of the present invention provides a dye- sensit i zed/1 igand-to-metal charge-transfer hybrid solar cell, comprising a working electrode including a nano-oxide layer composed of nano-oxide particles adsorbed with dyes and ligands.
  • the present invention provides a dye-sens itized/ligand-to-metal charge- transfer hybrid solar cell comprising a working electrode including a nano oxide layer adsorbed with both dye and ligand, and a method of manufacturing the same.
  • the dye-sensitized/ligand-to-metal charge-transfer hybrid solar cell according to the present invention is characterized in that current density and open voltage is improved, thus increasing photoelectric conversion efficiency.
  • FIG. 1 is a sectional side view showing a dye-sensitized/ligand-to- metal charge-transfer hybrid solar cell comprising a working electrode including a nano oxide layer adsorbed with both dye and salicylic acid as a ligand according to an embodiment of the present invention
  • FIG. 2 is a sectional side view showing a conventional dye-sensitized solar eel 1 ;
  • FIG. 3 shows the photographs and ultraviolet-visible light absorption spectra of the working electrodes manufactured in Example 1 and Comparative Examples 1 and 2;
  • FIG. 4 is a graph showing the current-voltage curves of the dye- sensitized solar cells manufactured in Example 1 and Comparative Examples 1 and 2.
  • the method of manufacturing a dye-sensitized/ligand-to-metal charge- transfer hybrid solar cell comprises the steps of: forming a nano-oxide layer on a transparent substrate including a transparent conductive oxide layer formed thereon (step 1); immersing the transparent substrate including the nano-oxide layer formed thereon into a dye solution prepared by mixing a dye, an organic solvent and a compound selected from the group consisting of salicylic acid, a salicylic acid derivative, catechol, sal icylaldehyde, saccharine, sal icylamide, 1,4,5,8-naphthalenetetracarboxyl ic acid, anhydrous 1,4,5,8-naphthalenetetracarboxyl ic acid, anhydrous 1,8-naphthal ic acid, 1- naphthoic acid, naphthol blue black and naphthol green B and thus adsorbing the dye and ligands on nano-oxide particles to fabricate a working electrode (step 2); forming a dye solution prepared
  • FIG. 1 is a sectional side view showing a dye-sensitized/ligand-to- metal charge-transfer hybrid solar cell comprising a working electrode including a nano oxide layer adsorbed with both dye and salicylic acid as a ligand according to an embodiment of the present invention
  • a nano-oxide layer is formed on a transparent substrate 1 including a transparent conductive oxide layer formed thereon.
  • a glass substrate or a transparent plastic substrate may be used as the transparent substrate 1 used in the present invention.
  • the transparent plastic substrate may be made of polyethyleneterephthalate (PET), polyethylenenaphthalate (PEN), polyethylene (PE) , polyethersulfone (PES), polycarbonate (PC), polyarylate (PAR), polyimide (PI) or the like, but the present invention is not limited thereto.
  • the transparent conductive oxide layer is formed on the transparent substrate 1.
  • the transparent conductive oxide layer may be made of fluorine- doped tin oxide (FTO), indium tin oxide (ITO), indium zinc oxide (IZO), indium zinc tin oxide (IZTO), aluminum zinc oxide (AZO), indium tin oxide- silver-indium tin oxide (ITO-Ag-ITO) , indium zinc oxide-silver-indium zinc oxide (IZO-Ag-IZO) , indium zinc tin oxide-silver-indium zinc tin oxide (IZTO- Ag-IZTO), aluminum zinc oxide-silver-aluminum zinc oxide (AZO-Ag-AZO) or the like, preferably, fluorine-doped tin oxide (FTO).
  • This transparent conductive oxide layer may be formed using any one method selected from among sputtering, chemical vapor deposition (CVD), evaporation, thermal oxidation, and electrochemical anodization (deposition
  • the nano-oxide layer may be composed of a transition metal oxide, particularly, titanium dioxide, and may be formed by applying a composition containing titanium dioxide onto the transparent conductive oxide layer using a doctor blade method, a screen printing method or the like.
  • step 2 the transparent substrate 1 including the nano-oxide layer formed thereon is immersed into a dye solution prepared by mixing a dye, an organic solvent and a compound selected from the group consisting of salicylic acid (2-hydroxybenzoic acid; C 7 H 6 0 3 ), a salicylic acid derivative, catechol (1,2-benzendiol ; 063 ⁇ 40 2 ), sal icy1 aldehyde (2-hydroxybenzaldehyde;
  • This step is an essential step of the method of manufacturing a dye-sensiti zed/1 igand-to-metal charge-transfer hybrid solar cell according to the present invention.
  • the dye solution may be prepared by dissolving 5 ⁇ 95 wt% of the dye and 5 - 95 wt% of the compound in an organic solvent.
  • the organic solvent may be selected from the group consisting of ethanol, methanol, propanol, isopropanol, and acetonitri le.
  • the dye visible 1 ight-absorbable materials including ruthenium composites may be used.
  • a dye which can improve efficiency by accelerating the absorption of long wavelengths in visible light and a new-type dye which can easily emit electrons may also be used as the dye.
  • the dye solution in which the dye and the compound selected from the group consisting of salicylic acid, a salicylic acid derivative, catechol, sal icylaldehyde, saccharine, sal icylamide, 1 ,4,5,8-naphthalenetetracarboxyl ic acid, anhydrous 1,4,5,8-naphthalenetetracarboxyl ic acid, anhydrous 1,8-naphthal ic acid, 1- naphthoic acid, naphthol blue black and naphthol green B are simultaneously dissolved in the organic solvent may be used.
  • the compound selected from the group consisting of salicylic acid, a salicylic acid derivative, catechol, sal icylaldehyde, saccharine, sal icylamide, 1,4,5,8-naphthalenetetracarboxyl ic acid, anhydrous 1,4,5,8- naphthalenetetracarboxyl ic acid, anhydrous 1,8-naphthal ic acid, 1-naphthoic acid, naphthol blue black and naphthol green B has a structure including a carboxy group or a hydroxy group or a structure including a carboxy group and a hydroxy group
  • the ligands 60 can be adsorbed on the surfaces of the nano- oxide particles 40.
  • the salicylic acid derivative used in the present invention may be represented by Chemical Formula 1 below:
  • Xi to X4 may be each independently selected from the group consisting of a hydrogen atom, a heavy hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, an alkenyl group of 2 - 30 carbon atoms, a substituted or unsubstituted condensed aromatic ring of 10 ⁇ 60 carbon atoms, a substituted or unsubstituted styryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted carboxyl group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted cycloalkyl group of 3 ⁇ 40 carbon atoms, a substituted or unsubstituted cycloalkenyl group of 3 ⁇ 40 carbon atoms, a substituted or unsubstituted
  • the Xi to X4 may be each independently substituted by one or more substituent groups selected from the group consisting of a hydrogen atom, a heavy hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkylsilyl group of 1 ⁇ 10 carbon atoms, an alkyl group of 1 - 40 carbon atoms, an alkoxy group of 1 ⁇ 40 carbon atoms, an alkylamino group of 1 ⁇ 40 carbon atoms, an aryl group of 6 ⁇ 30 carbon atoms, an aryloxy group of 6 ⁇ 30 carbon atoms, an aryl amino group of 6 ⁇ 30 carbon atoms, an arylsilyl group of 6 ⁇ 30 carbon atoms, and a heteroaryl group of 3 ⁇ 40 carbon atoms.
  • the substituents group may be identical to or different from each other, may be bonded with each other to form a saturated or unsaturated ring, and may be adhered or
  • the saturated or unsaturated ring may have a cyclic structure of 5 membered rings to 8 membered rings, and the substituent groups may be adhered or fused to each other by a pendant method.
  • the substituent group is identical with a substituted cycloalkyl group of 3 ⁇ 40 carbon atoms.
  • saturated or unsaturated ring may include saturated cyclic hydrocarbons of 4 ⁇ 12 carbon atoms, such as cyclobutane, cyclobutane, eye 1opentane , cyclohexane, cycloheptane, adamantine, noborane and the like; cycloalkenes of 4 ⁇ 12 carbon atoms, such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene and the like; cycloalkadienes of 6 ⁇ 12 carbon atoms, such as cyclohexadiene, cycloheptadiene, cyclooctadiene and the like; and aromatic rings of 5 ⁇ 50 carbon atoms, such as benzene, naphthalene, phenanthrene, anthracene, pyrene, acenaphthylene and the like.
  • the aryl group which is a substituent group used in the above salicylic derivative, means a carbocyclic aromatic system including one or more rings, and the rings may be adhered or fused to each other by a pendant method.
  • Specific examples of the aryl group may include aromatic groups, such as a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracene group, a pyrene group, a fluoranthene group, a perylene group, a coronene group, a chrysene group, a picene group, a fluorene group, a triphenylene group, a rubicene group and the like.
  • the heteroaryl group which is a substituent group used in the above salicylic derivative, means a carbocyclic aromatic system carbon including one or more rings composed of one, two or three heteroatoms selected from among N, 0, P and S and 5 ⁇ 30 residual carbon atoms, and the rings may be adhered or fused to each other by a pendant method.
  • heteroaryl group may include a pyrrole group, a pyrazine group, a pyridine group, a triazine group, a thiophene group, a carbazole group, an indole group, a quinoline group, a phenanthrol ine group, a phenazine group, a phenoxyazine group, a benzothiazine group and the like.
  • One or more hydrogen atoms of the heteroaryl group may be substituted with the substituent group, as in the alkyl group.
  • the transparent substrate 1 including the nano-oxide layer formed thereon, fabricated in step 1 is immersed in the dye solution (in which the dye and ligand are dissolved in an organic solvent), and is then maintained for a predetermined time such that the dye 50 and ligand 60 sufficiently adsorb on the surfaces of nano-oxide particles 40, and thus the surface void of the nano-oxide particles 40 is minimized, thereby fabricating the working electrode 10.
  • the dye solution in which the dye and ligand are dissolved in an organic solvent
  • a metal layer 30 is formed on a transparent substrate 1 including a transparent conductive oxide layer formed thereon to fabricate a counter electrode 20.
  • the counter electrode 20 may be fabricated by forming the transparent conductive oxide layer on the transparent substrate 1 and then forming the metal layer 30 on the transparent conductive oxide layer.
  • the metal layer 30 may be made of an electroconduct ive material, preferably, a precious metal such as platinum (Pt) or the like. Since platinum (Pt) has high ref lexibi 1 ity, transmitted visible light is reflected from an interior surface of a solar cell, thus improving light absorption efficiency. In addition to platinum (Pt), other precious metals having low resistance may also be used to make the metal layer 30.
  • a precious metal such as platinum (Pt) or the like. Since platinum (Pt) has high ref lexibi 1 ity, transmitted visible light is reflected from an interior surface of a solar cell, thus improving light absorption efficiency.
  • platinum (Pt) has high ref lexibi 1 ity, transmitted visible light is reflected from an interior surface of a solar cell, thus improving light absorption efficiency.
  • other precious metals having low resistance may also be used to make the metal layer 30.
  • step 4 the working electrode 10 fabricated in step 2 and the counter electrode 20 fabricated in step 3 are joined such that they face each other, and then an electrolyte is charged therebetween.
  • microholes are formed in the counter electrode 20, and the electrolyte is charged therebetween through the microholes, and then the microholes are sealed using a polymer resin to manufacture a dye-sensitized/1 igand-to-metal charge-transfer hybrid solar cell.
  • the present invention provides a working electrode of a dye- sensitized/1 igand-to-metal charge-transfer hybrid solar cell, the working electrode comprising a nano-oxide layer composed of nano-oxide particles adsorbed with dyes and ligands.
  • the present invention provides a dye-sensitized/1 igand-to- metal charge-transfer hybrid solar cell, comprising a working electrode including a nano-oxide layer composed of nano-oxide particles adsorbed with dyes and ligands.
  • FIG. 2 is a sectional side view showing a conventional dye-sensitized solar cell. Comparing FIG. 1 and FIG. 2, in the working electrode of the dye-sensitized/1 igand-to-metal charge-transfer hybrid solar cell according to the present invention, both ruthenium-based dye and salicylic acid as a ligand are adsorbed on the surfaces of nano-oxide particles (refer to FIG. 1).
  • the photoelectric conversion efficiency thereof can be improved compared to that of a conventional dye-sensitized solar cell adsorbed with only dyes because the adsorbed dyes and ligands simultaneously generate electric current.
  • Such effects will be described in more detail be 1ow .
  • a transparent glass substrate including a fluorine-doped tin oxide transparent conductive oxide layer was provided.
  • a coating composition including titanium dioxide was applied on the transparent conductive oxide layer using a doctor blade method, and was then heat-treated at 550 ° C for 30 minutes to allow nanosized metal oxide particles to come into contact with each other and to be charged with each other, thereby forming a nano-oxide layer having a thickness of about 8 .
  • the coating composition including titanium dioxide was further applied on the nano-oxide layer using the same method, and then heat-treated at 550 ° C for 30 minutes to form a nano-oxide layer having a thickness of about 11 pm.
  • 0.2 mM of ruthenium dithiocyanate-2,2 ' -bipyr idyl-4,4 ' -dicarboxylate and 0.2 mM of salicylic acid were dissolved in ethanol to prepare a dye solution in which both dye and ligand were dissolved.
  • the transparent glass substrate including the nano-oxide layer was immersed in the dye solution for 24 hours, and was then dried to simultaneously adsorb the dye and ligand on the nanosized metal oxide particles, thereby fabricating a working electrode.
  • a transparent glass substrate including a fluorine-doped tin oxide transparent conductive oxide layer was provided.
  • a 2-propanol solution including hexachloroplat inic acid (H 2 PtCl 6 ) was dropped onto the transparent conductive oxide layer, and was then heat-treated at 450 ° C for 30 minutes to form a platinum layer, thereby fabricating a counter electrode.
  • thermoplastic polymer layer having a thickness of 60 /mi was formed using SURLYN (manufactured by Du Pont Corp.), and then the working electrode and counter electrode were put into an oven at 130 ° C and then maintained for 2 minutes to adhere and seal the two electrodes. Subsequently, microholes passing through the working electrode and the counter electrode were formed, and an electrolyte solution was charged in the space between the two electrodes, and then the microholes were sealed with an adhesive.
  • the electrolyte solution was prepared by dissolving 0.1 M Lil, 0.05 M I 2 , 0.5 M 4-tert- butylpyr idine and 0.6 M 1-ethyl-l-methylpyrrol idinium iodide, which is an ionic liquid, in a 3-methoxypropionitri le solvent.
  • Example 2 was conducted using the same method as in Example 1, except that, at the time of preparing a dye solution in which both a dye and a ligand are dissolved, a dye solution in which 0.2 mM of ruthenium dithiocyanate-2,2 ' -bipyr idyl-4,4 ' -dicarboxylate and 0.2 mM of 4- methylsal icyl ic acid were dissolved in ethanol was prepared.
  • Example 3 was conducted using the same method as in Example 1, except that, at the time of preparing a dye solution in which both a dye and a ligand are dissolved, a dye solution in which 0.2 mM of ruthenium dithiocyanate-2,2 ' -bipyr idyl-4,4 ' -dicarboxylate and 0.2 mM of 4- methoxysal icyl ic acid were dissolved in ethanol was prepared. ⁇ 79>
  • a xenon lamp manufactured by Oriel Corp.
  • the solar condition (AM 1.5) of the xenon lamp was compensated using a standard solar cell.
  • FIG. 3 shows the ultraviolet-visible light absorbing spectra of the working electrodes manufactured in Example 1 and Comparative Examples 1 and 2. As shown in FIG. 3, it can be seen that the working electrode manufactured Example 1 has a higher absorbance than the working electrodes manufactured in Comparative Examples 1 and 2.
  • FIG. 4 shows the current-voltage curves of the dye-sensitized solar cells manufactured in Example 1 and Comparative Examples 1 and 2. As shown in FIG. 4, it can be seen that the working electrode manufactured Example 1 has higher efficiency than the working electrodes manufactured in Comparative Examples 1 and 2.

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PCT/KR2009/007376 2009-09-29 2009-12-10 Dye-sensitized/ligand-to-metal charge-transfer hybrid solar cell comprising a working electrode including nano-oxide layer composed of nano-oxide particles adsorbed with dyes and ligands and method of manufacturing the same WO2011040680A2 (en)

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