IE85728B1 - Ruthenium complex and photoelectric component using the same - Google Patents
Ruthenium complex and photoelectric component using the same Download PDFInfo
- Publication number
- IE85728B1 IE85728B1 IE2009/0754A IE20090754A IE85728B1 IE 85728 B1 IE85728 B1 IE 85728B1 IE 2009/0754 A IE2009/0754 A IE 2009/0754A IE 20090754 A IE20090754 A IE 20090754A IE 85728 B1 IE85728 B1 IE 85728B1
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- IE
- Ireland
- Prior art keywords
- ruthenium complex
- dye
- bipyridyl
- solar cell
- sensitized solar
- Prior art date
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- 239000012327 Ruthenium complex Substances 0.000 title claims abstract description 43
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
- FXPLCAKVOYHAJA-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 FXPLCAKVOYHAJA-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- MQBIGZBUVUVDKE-UHFFFAOYSA-N [2-(4-phosphonopyridin-2-yl)pyridin-4-yl]phosphonic acid Chemical compound OP(O)(=O)C1=CC=NC(C=2N=CC=C(C=2)P(O)(O)=O)=C1 MQBIGZBUVUVDKE-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical group [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 5
- GZWLNFKBSYRWRA-UHFFFAOYSA-N 2-(4-sulfopyridin-2-yl)pyridine-4-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=NC(C=2N=CC=C(C=2)S(O)(=O)=O)=C1 GZWLNFKBSYRWRA-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims 1
- 239000000758 substrate Substances 0.000 description 41
- 239000010410 layer Substances 0.000 description 30
- 239000000975 dye Substances 0.000 description 29
- 239000000463 material Substances 0.000 description 26
- 239000000243 solution Substances 0.000 description 24
- 239000011521 glass Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 19
- 239000002245 particle Substances 0.000 description 13
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 11
- -1 poly(ethylene terephthalate) Polymers 0.000 description 9
- 229910001887 tin oxide Inorganic materials 0.000 description 9
- LTNAYKNIZNSHQA-UHFFFAOYSA-L 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid;ruthenium(2+);dithiocyanate Chemical compound N#CS[Ru]SC#N.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 LTNAYKNIZNSHQA-UHFFFAOYSA-L 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- JJWJFWRFHDYQCN-UHFFFAOYSA-J 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylate;ruthenium(2+);tetrabutylazanium;dithiocyanate Chemical compound [Ru+2].[S-]C#N.[S-]C#N.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1 JJWJFWRFHDYQCN-UHFFFAOYSA-J 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 4
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000011112 polyethylene naphthalate Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 description 4
- 239000012780 transparent material Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 150000003303 ruthenium Chemical class 0.000 description 3
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- SLPKYEWAKMNCPT-UHFFFAOYSA-N 2,6-dimethyl-1-(3-[3-methyl-5-isoxazolyl]-propanyl)-4-[2-methyl-4-isoxazolyl]-phenol Chemical compound O1N=C(C)C=C1CCCOC1=C(C)C=C(C=2N=C(C)OC=2)C=C1C SLPKYEWAKMNCPT-UHFFFAOYSA-N 0.000 description 2
- UUIMDJFBHNDZOW-UHFFFAOYSA-N 2-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC=N1 UUIMDJFBHNDZOW-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 229910008559 TiSrO3 Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- OOWFYDWAMOKVSF-UHFFFAOYSA-N 3-methoxypropanenitrile Chemical compound COCCC#N OOWFYDWAMOKVSF-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910007674 ZnO—Ga2O3 Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002907 osmium Chemical class 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- 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
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
- C09B69/04—Dyestuff salts, e.g. salts of acid dyes with basic dyes of anionic dyes with nitrogen containing compounds
-
- 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
-
- H01L51/0086—
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
ABSTRACT The present invention relates to a ruthenium complex and a photoelectric component using the same and, more particularly, to a ruthenium complex, which is used for the dye-sensitized solar cell (DSSC), and a photoelectric component using the same.
Description
Field of the Invention The present invention relates to a ruthenium complex and a photoelectric component using the same and, more particularly, to a ruthenium complex, which is used for the dye-sensitized solar cell (DSSC), and a photoelectric component using the same. 2.Description of RelatedArt With the development of industrial technology, the serious problems that the whole world is facing today are the energy crisis and the enviromnental pollution. In order to solve the global energy crisis and to reduce the environmental pollution, one of the effective means is the solar cell, which can convert the solar energy into the electricity. Since the dye-sensitized solar cell has the advantages -' of low manufacturing cost, large-scale production, great flexibility, light transmittance, and being capable of use in the buildings, the application of the dye-sensitized solar cell becomes more and more attractive.
Currently, Gréitzel er al. have disclosed a series of literatures, for example, 0’Regan, B.; Grtitzel, M. Nature 1991, 353, 737, which shows the practicability of the dye-sensitized solar cell. The general structure of the dye-sensitized solar cell comprises an anode, a cathode, a nalno-porous titanium dioxide layer, a dye, and electrolyte, wherein the _dye plays a critical role in the conversion eficiency of the dye-sensitized solar cell. The dye suitable for the dye-sensitized solar cell must have characteristics in broad absorption spectrum, high molar absorption coefficient, thermal stability, and light stability.
Gratzel’s lab has published a serious of ruthenium complexes as the dyes for the dye-sensitized solar cell. Gratzel’s lab published a » dye-sensitized solar cell prepared with a N3 dye in 1993, and the conversion efficiency of the dye-sensitized solar cell is 10.0% under the illumination of AM 1.5 stimulated light. The incident photon-to-current conversion efficiency (IPCE) value of the N3 dye is 80% in the range of 400 to 600 nm.
Although hundreds of dye complexes have developed, the conversion efficiency of those dye complexes is not as good as that of the N3 dye. The structure of the N3 dye is represented by the following formula (a).
COOH (a) In 2003, Gratzel’s lab published a dye-sensitized solar cell prepared with a N719 dye, and the conversion efficiency of the dye-sensitized solar cell is improved to 10.85% under the illumination of AM 1.5 stimulated light, wherein the structure of the N719 dye is represented by the tollowing formula (b).
COOTBA (b) Gréitzel’s lab also published a dye-sensitized solar cell prepared with a black dye in 2004, and the conversion efficiency of the . dye-sensitized solar cell is 11.04% under the illumination of AM 1.5 stimulated light. The black dye can enhance the spectral response in red and near-IR region, so the conversion efficiency of the dye-sensitized solar cell can be improved. The structure of the black dye is represented by the following formula (c).
In addition to the ruthenium complexes such as the N3 dye, the N719 dye, and the black dye, other types of dye compounds, which can be used in the dye-sensitized ‘solar cell, are platinum complexes, osmium complexes, iron complexes, and copper complexes. However, the results of various researches show that the conversion efficiency of the ruthenium complexes is still better than other types of dye compounds.
The dyes for the dye-sensitized solar cell influence the conversion efliciency greatly. Hence, it is desirable to provide a dye compound, which can improve the conversion efficiency of the dye-sensitized solar cell.
SUMMARY OF THE INVENTION The present invention is to provide a novel ruthenium complex, ‘Which is used for a dye-sensitized solar cell to improve the photoelectric efficiency of the dye-sensitized solar cell.
The present invention is also to provide a dye-sensitized solar cell, which has excellent photoelectric property.
Hence, the present invention provides a ruthenium complex, which is represented by the following formula (I): RUL2(NC S)2Am (I) wherein L is 2,2’-bipyridyl-4,4’-dicarboxylic acid, 2,2’—bipyridyl—4,4’—disulfonic _ acid, or 2,2’-bipyridyl-4,4’-diphosphonic acid; - A is a quaternary phosphonium cation; and m is l, 2, 3, or4.
In the above formula (I), L can be 2,2’-bipyridyl-4,4’-dicarboxylic acid, 2,2’-bipyridyl—4,4’-disulfonic acid, or ,2’-bipyridyl-4,4’-diphosphonic acid. Preferably, L is 2,2’-bipyridyl-4,4’-dicarboxylic acid.
In the above formula (1), A may be a quaternary phosphonium cation. Preferably, A is PlR1R2R3R4, wherein R1, R2, R3, and R4 are each independently C140 alkyl, phenyl, or benzyl. More preferably, A is tetraallcylphosphonium, benzyl trialkylphosphonium, or phenyl trialkylphosphonium, and the alkyl is cm alkyl. T In the above formula (I), m may be 1, 2, 3, or 4. Preferably, m is 2, or 3. More preferably, In is 2.
The specific examples of ruthenium complex represented by the above formula (I) are: 'P+(CH;CH;CH;CH3)4 / 7 \ I N‘C& \ Ru ’/ / / \N\\C *5 H0 \ o 0‘ P+(CI-IzCH;CH;CI-I;.)4 (I-1) o o'P*(cH,cH3)3(1>h) ‘ P+(CH;CH3)3(Ph) (1-2) '1’+(CH2CH3)3((CH2)11CH3) ' 1’+(CH2CH3)3((CH2)nCH2.) (1-3) (‘in o: P— 0' P+(CH2CHzCI-I;CH3)4 .—.1|’—o' 1>*(cH2cH,CH2cH3)4 on (1-4) The present invention provides a dye-sensitized solar cell, which comprises the aforementioned ruthenium complex.
In addition, the dye-sensitized solar cell of the present invention comprises: a photoanode comprising the aforementioned ruthenium complex; a cathode; and an electrolyte layer disposed between the phoroanode and the cathode.
In the dye—sensitized solar cell of the present invention, the photoanode comprises: a transparent substrate, a transparent conductive layer, a porous semiconductive layer, and a dye of the ruthenium complex.
In the dye-sensitized solar cell of the present invention, the material of the transparent substrate is not particularly limited, as long as the material of the substrate is a transparent material. Preferably, the material of the transparent substrate is a transparent material with good moisture resistance, solvent resistance and weather resistance. Thus, the dye-sensitized solar cell can resist moisture or gas from outsides bysthe transparent substrate. The specific examples of the transparent substrate include, but are not limited to, transparent inorganic substrates, such as quartz and glass; transparent plastic substrates, such as poly(ethylene terephthalate) (PET), poly(ethylene 2,6-naphthalate) (PEN), polycarbonate (PC), polyethylene (PE), polypropylene (PP), and polyimide (PI).
Additionally, the thickness of the transparent substrate is not particularly limited, and can be changed according to the transmittance and the demands for the properties of the dye-sensitized solar cell. Preferably, the material of the transparent substrate is glass.
Furthermore, in the dye-sensitized solar cell of the present invention, the material of the transparent conductive layer can be indium tin oxide (ITO), fluorine-doped tin oxide (FTO), Zn0-Ga;_O3, ZnO-A1203, or tin-based oxides.
In addition, in the dye-sensitized solar cell of the present invention, the porous semiconductive layer is made of semiconductor particles.
Suitable semiconductor particles may include Si, TiO2, SnO2, ZnO, W03, Nb2O5, TiSrO3, and the combination thereof. Preferably, the semiconductor _ particles are made from TiO2. The average diameter of the semiconductor particles may be 5 to 500 nm. Preferably, the average diameter of the semiconductor particles is 10 to 50 mn. Furthermore, thethickness of the porous» semiconductive layer is 5-25 urn.
In the dye-sensitized solar cell of the present invention, the ruthenium complex may be the aforementioned ruthenium complex.
Besides, the material of the cathode for the dye-sensitized solar cell is not particularly limited, and may include any material with conductivity.
. Otherwise, the material of the cathode can be an insulating material, as long as there is a conductive layer formed on the surface of the cathode, wherein the surface of the cathode is faced to the photoanode. The material of the cathode can be a material with electrochemical stability. The unlimited examples suitable for the material of the cathode include Pt, Au, C, or the like.
Furthermore, the material used in the electrolyte layer of the dye-sensitized solar cell is not particularly limited, and can be any material, which can transfer electrons and/ or holes.
Other objects, advantages, and novel features of the invention will become more apparent from the following detailed description DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The ruthenium complex of the present invention can be synthesized by the following methods. cis~di(thiocyanato)—N,N’-bis(2,2’-bipyridyl-4,4’-dicarboxylic acid)ruthenium(II) (N3 dye) is synthesized according to the method described in Inorganic Chemistry, Vol. 38 , No. 26, 1999, 6298-6305. cis-di(thiocyanato)—N,N’-bis(2,2’-bipyridyl-4,4’-dicarboxylic acid)ruthenium(II) is dissolved in distilled water, and 10% aqueous solution of tetrabutylphosphonium hydroxide reagent (TCI Co. Ltd.) is added thereto to adjust the pH value of the reaction solution to 11. Then, the reaction solution is concentrated to obtain a viscous liquid. The viscous liquid is dissolved in methanol, and the diethyl ether is added thereto to precipitate a product. After the wet solid product is taken out and dried under vacuum for 1 day, the dried solid product is dissolved in distilled water, andthen the pH value of the resulted solution is adjusted below 5 with 0.1 M nitric acid(,q). Finally, the ruthenium complex of formula (1-1) is obtained. P The method for manufacturing the dye-sensitized solar cell of the present invention is not particularly limited, and the dye-sensitized solar cell of the present invention can be manufacture by the known methods in the art. .
The material of the transparent substrate is not particularly limited, as long as the material of the substrate is a transparent material. Preferably, the material of the transparent substrate is a transparent material with good moisture resistance, solvent resistance and weather resistance. Thus, the dye-sensitized solar cell can resist moisture or gas from outsides by the transparent substrate. The specific examples of the transparent substrate include, but are not limited to, transparent inorganic substrates, such as quartz and glass; transparent plastic substrates, such as poly(ethylene terephthalate) (PET), poly(ethylene 2,6—naphthalate) (PEN), polycarbonate (PC), polyethylene (PE), polypropylene (PP), and polyimide (PI).
Additionally, the thickness of the transparent substrate is not particularly limited, and can be changed according to the transmittance and the demands for the properties of the dye—sensitized solar cell. In a specific embodiment, the material of the transparent substrate is a glass substrate.
Furthermore, the material of the transparent conductive layer can be indium tin oxide (ITO), fluorine-doped tin oxide (FTO), ZnO—Ga2O3, ZnO-A1203, or tin-based oxides. In a specific embodiment, fluorine-doped - tin oxide is used for the transparent conductive layer.
In addition, the porous semiconductive layer is made of semiconductor particles. Suitable semiconductor particles may include Si, TiO2, SnO2, ZnO, W03, Nb2O5, TiSrO3, and the combination thereof. First, the semiconductor particles are prepared in a form of paste, and then the paste is coated on the transparent conductive substrate. The coating method used herein can be blade coating, spin coating, spry coating, or wetting coating. Additionally, the coating can be held for one time or many times, in order to obtain a porous semiconductive layer with suitable thickness. The semiconductive layer can be a single layer or multiple layers, wherein each layer of the multiple layers is formed by semiconductor particles with difierent diameters. For example, the semiconductor particles with diameters of 5 to 50 nm is coated in a thickness of 5 to 20 um, and then the semiconductor particles with diameters of 200 to 400 nm is coated in a thickness of 3 to 5 um thereon. After drying the coated substrate under 50-100°C, the coated substrate is sintered under 400-500°C for 30 min to obtain a multilayer semicondictive layer.
The ruthenium complex can be dissolved in a suitable solvent to prepare a dye solution. Suitable solvents include, but are not limited to, acetonitrile, methanol, ethanol, propanol, butanol, dimethyl formamide, N-methylpyrrolidinone, and the combination thereof. Herein, the transparent substrate coated with the semiconductive layer is dipped into a dye solution to make the semiconductive layer absorb the dye in the dye solution completely. After the dye absorption is completed, the transparent substrate coated with the semiconductive layer is taken out and dried.
Finally, a photoanode for a dye—sensitized solar cell is obtained.
Besides, the material of the cathode for the dye-sensitized solar cell is not particularly limited, and may include any material with conductivity.
Otherwise, the material of the cathode can be an insulating material, as long as there is a conductive layer formed on the surface of the cathode, wherein the surface of the cathode is faced to the photoanode. The material of the cathode can be a material with electrochemical stability. The unlimited examples suitable for the material of the cathode include Pt, Au, C, or the like.
Furthermore, the material used in the electrolyte layer of the dye—sensitiZed solar cell is not particularly limited, and can be any material, which can transfer electrons and/or holes. In addition, the liquid electrolyte can be a solution of acetonitrile containing iodine, a solution of N-methyl-2—pyrro1idinone containing iodine, or a solution of 3-methoxy propionitrile containing iodine. In a specific embodiment, the liquid electrolyte can be a solution of acetonitrile containing iodine.
V One specific method for manufacturing the dy e-sensitized solar cell of the present invention is presented as follow.
First, a paste containing TiO2 particles with diameter of 20~30 nm is coated on a glass substrate covered with fluorine-doped tin oxide (FTO) for one time or several times. Then, the coated glass substrate is sintered under °C for 30 min.
The ruthenium complex is dissolved in a mixture of acetonitrile and t-butanol (1 :1 v/V) to formulate a dye solution of ruthenium complex. Then, the aforementioned glass substrate with porous TiO_7_ layer is dipped into the dye solution. After the porous Ti02 layer absorbs the dye in the dye solution, the resulted glass substrate is taken out and dried. Finally, a photoanode is obtained.
A glass substrate covered with fluorine~doped tin oxide is drilled to form an inlet with a diameter of 0.75 pm, wherein the inlet is used for injecting the electrolyte. Then, a solution of I-I2PtCl6 is coated on the glass substrate covered with fluorine-doped tin oxide, and the glass substrate is heated to 400°C for 15 min to obtain a cathode.
Sequentially, a thermoplastic polymer layer with a thickness of 60 pm is disposed between the photoanode and the cathode. These two electrodes are pressed under 120 to 140 °C to adhere with each other.
Then, an electrolyte is injected, wherein the electrolyte is a solution of acetonitrile containg 0.03 M12/0.3 M Lil/0.5 M t-butyl-pyridine. After the inlet is sealed with thermoplastic polymer layer, a dye—sensitized solar cell of the present invention is obtained.
The following examples are intended for the purpose of illustration of the present invention. However, the scope of the present invention should be defined as the claims appended hereto, and the following examples should not be construed as in any way limiting the scope of the present invention. Without specific explanations, the unit of the parts and percentages used in the examples is calculated by weight, and the temperature is represented by Celsius degrees ("C). The relation between the parts by weight and the parts by volume is just like the relation between kilogram and liter.
Example 1 Synthesis of cis-di(thiocyanato)-N,N’-bis(2,2’—bipyridy1-4,4’-dicarboxylic acid)ruthenium(II)bis(tetrabutyl phosphonium) (I-1) .50 part of cis-di(thiocyanato)—N,N’~bis(2,2’-bipyridyl- 4,4’-dicarboxylic acid)ruthenium(H) (N3 dye), which was prepared according to the method described in Inorganic Chemistry, Vol. 3 8 , No. 26, 1999, 6298-6305, and 10 parts of distilled water were added into a reaction flask, and the reaction solution was mixed and stirred. Then, 10% aqueous solution of tetrabutylphosphonium hydroxide reagent (TCI Co. Ltd.) was added into the reaction solution drop by drop to adjust the pH value of the reaction solution to 11. The rotary—evaporator was used for removing the solvent from the reaction solution to obtain a Viscous liquid. The viscous liquid was dissolved in methanol, diethyl ether was added thereto to obtain a precipitate, and the wet solid precipitate was taken out and dried under vacuum for 1 day. The dried solid was dissolved in 10 parts of distilled water, and 0.1 M nitric acidm) was used to adjust the pH value of the resulted solution below 5. The sintered glass filter was used for filtering the product out, and 5 parts of distilled water with pH 5 was used for washing the product. Finally, 0.39 part of black solid product (Is-1) was obtained, and the yield of the product (1-1) was 75.9%.
Example 2 Preparation of a dye—sensitized solar cell A paste containing TiO2 particles with diameter of 20~30 nm was . coated on a glass substrate covered with fluorine-doped tin oxide (FTO) for one time or several times, wherein the thickness of the glass substrate was 4 mm and the electric resistance of the glass substrate is 1094:]. Then, the coated glass substrate was sintered under 450°C for 30 min, and the thickness of the sintered porous TiO2 layer was 10 to 12 pm.
The ruthenium complex prepared by Example 1 was dissolved in a mixture of acetonitrile and t—butanol (121 V/V), and a dye solution containing 0.5 mM ruthenium complex was prepared. Then, the aforementioned glass substrate covered with porous TiO2 layer was dipped into the dye solution to make the dye adhere on the porous TiO2 layer. After 16 to 24 hours, the resulted glass substrate was taken out and dried, and then a photoanode was . obtained.
A glass substrate covered with fluorine-doped tin oxide was drilled to form an inlet with a diameter of 0.75 tun, wherein the inlet was used for injecting the electrolyte. Then, a solution of H2PtCl5 (2 mg Pt in 1 ml ethanol) was coated on the glass substrate covered with fluorine-doped tin oxide, and the resulted glass substrate was heated to 400°C for 15 min to obtain a cathode.
Sequentially, a thermoplastic polymer layer with a thickness of 60 um was disposed between the photoanode and the cathode. These two electrodes were pressed under 120 to 140 °C to adhere with each other.
Then, an electrolyte was injected, wherein the electrolyte was a solution ofacetonitrile containg 0.03 M12/0.3 M Lil/0.5 M t-butyl—pyridine.
After the inlet was sealed with thermoplastic polymer layer, a dye-sensitized solar cell of the present example was obtained.
Comparative Example The process for preparing the dye-sensitized solar cell of the present comparative example is the same as that described in Example 2, except that the ruthenium complex prepared by Example 1 is substituted with N719.
Testing methods and results Test for the photoelectric characteristics The short circuit current (Jsc), open circuit voltage (Voc), filling factor (FF), photoelectric conversion efficiency (11), and incident photon-to-current conversion efficiency (IPCE) of the dye-sensitized solar cells prepared by Examples 2 and Comparative Example were measured under the illumination of AM 1.5 stimulated light. The testing results-are shown in the following Table 1: Table 1. Testing results of the dye and the dye-sensitized solar cell I V dye SC 2 OC FF 1] (%) (mA/cm ) (V) Example 2 I-1 9.02 0.78 0.63 4.44 Comparative N719 7.36 0.76 0.61 3.38 Example The resting results of Table 1 show that the short circuit current (J Sc), the open circuit voltage (Voc) and the filling factor (FF) of the dye-sensitized solar cell prepared by the ruthenium complex of the present invention are improved, as compared with the dye-sensitized solar cell prepared by the N719 dye. It means that the ruthenium complex of the present invention can improve the photoelectric conversion efficiency of the dye—sensitized solar cell.
In conclusion, the present invention is different from the prior arts in several Ways, such as in purposes, methods and efficiency, or even in technology and research and design. Although the present invention has been explained in relation to its preferred embodiment, it is to be understood that many other possible modifications and variations can be made Without departing from the scope of the invention as hereinafter claimed. Hence, the scope of the present invention should be defined as the claims appended hereto, and the foregoing examples should not be construed as in any way limiting the scope of the present invention.
Claims (17)
1. WHAT IS CLABVIED IS: 1A ruthenium complex, which is represented‘ by the following formula (I): RuL2(NCS)2Am (1) wherein L is 2,2’-bipyridyl-4,4’—dicarboxylic acid, 2,2’-bipyridyl-4,4’-disulfonic acid, or 2,2’-bipyridyl-4,4’-diphosphonic acid; A is a quaternary phosphonium cation; and m is 1, 2, 3, or4.
2. The ruthenium complex as claimed in claim 1, wherein L is 2,2’-bipyridyl~4,4’-dicarboxylic acid.
3. The ruthenium complex as claimed in claim 1, wherein L is 2,2’-bipyridyl-4,4’-disulfonic acid.
4. The ruthenium complex as claimed in claim 1, wherein L is 2,2’-bipyridyl-4,4’-diphosphonic acid.
5. The ruthenium complex as claimed in claim 1, wherein A is P+R;R2R3R4, and R1, R2, R3, and R4 are each independently CH0 alkyl, phenyl, or benzyl.
6. The ruthenium complex as claimed in claim 2, wherein A is FR1R2R3R4, and R1, R2, R3, and R4 are each independently C140 alkyl, phenyl, or benzyl.
7. The ruthenium complex as claimed in claim 2, wherein A is trialkylphosphonium, or phenyl tetraalkylphosphonium, benzyl 15 trialkylphosphonium, and the alkyl is CH0 alkyl.
8. The ruthenium complex as claimed in claim 2, wherein m is 2, 3, or 4.
9. The ruthenium complex as claimed in claim 3, wherein A is P+R1R2R3R4, and R1, R2, R3, and R4 are each independently C140 alkyl, phenyl, or benzyl.
10. The ruthenium complex as claimed in claim 3, wherein m is 2, or 3.
11. The ruthenium complex as claimed in claim 4, wherein A is P‘R1R2R3R4, and R1, R2, R3, and R4 are each independently Cl-V20 alkyl, phenyl, or benzyl.
12. The ruthenium complex as claimed in claim 4, wherein m is 2, or 3.
13. The ruthenium complex as claimed in claim 1, wherein the ruthenium complex is a dye compound for a dye—sensitized solar cell.
14. The ruthenium complex as claimed in claim 1, wherein formula (I) is the following formula (1-1), or (I-2): o 0' P+(CH;CH;_CH2CH_~,)4
15. The ruthenium complex as claimed in claim 14, wherein the ruthenium complex is a dye compound for a dye-sensitized solar cell.
16. A dye-sensitized solar cell, comprising: (a) a photoanode, which comprises a ruthenium complex represented by the following formula (I): RuL2(NCS)2Am (I) wherein _ L is 2,2’-bipyridyl-4,4’-dicarboxylic acid, 2,2’-bipyridyl-4,4’-disulfonic acid, or 2,2’-bipyridyl—4,4’-diphosphonic acid; A is a quaternary phosphonium cation; and m is 1, 2, 3, or4; (b) a cathode; and (c) an electrolyte layer disposed between the photoanode and the 15 cathode.
17. A dye solution, comprising: (A) a ruthenium complex represented by the following formula G), wherein the content of the ruthenium complex is 0.01-1 wt%: RUL2(NCS)gAm 0) wherein L is 2,2’-bipyridyl—4,4’-dicarboxylic acid, 2,2’-bipyridy1-4,4’-disulfonic acid, or 2,2’-bipyridyl-4,4’-diphosphonic acid; A is a quaternary phosphonium cation; and mis 1,2,3, or4; and (B) an organic solvent, wherein the content of the organic solvent is 99.99-99 Wt%, and the organic solvent is selected from the group consisting of acetonitrile, methanol, ethanol, propanol, butanol, dimethyl formamide, and N-methylpyrrolidinone. F.F. GORMAN & CO.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNCHINA21/10/2008200810170973.4 | |||
| CN2008101709734A CN101723983B (en) | 2008-10-21 | 2008-10-21 | Ruthenium metal complex and photoelectric element manufactured by using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE20090754A1 IE20090754A1 (en) | 2010-06-23 |
| IE85728B1 true IE85728B1 (en) | 2011-03-16 |
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