TWI383988B - 新型釕金屬錯合物及用此錯合物製作之光電元件 - Google Patents
新型釕金屬錯合物及用此錯合物製作之光電元件 Download PDFInfo
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- TWI383988B TWI383988B TW098134108A TW98134108A TWI383988B TW I383988 B TWI383988 B TW I383988B TW 098134108 A TW098134108 A TW 098134108A TW 98134108 A TW98134108 A TW 98134108A TW I383988 B TWI383988 B TW I383988B
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- Prior art keywords
- dye
- metal complex
- sensitized solar
- bipyridine
- benzyl
- Prior art date
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- 239000012327 Ruthenium complex Substances 0.000 title description 2
- 150000004696 coordination complex Chemical class 0.000 claims description 26
- 239000010953 base metal Substances 0.000 claims description 25
- 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 22
- 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 18
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 17
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000975 dye Substances 0.000 description 30
- 239000000758 substrate Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 22
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 239000004065 semiconductor Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910001887 tin oxide Inorganic materials 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- -1 polyethylene terephthalate Polymers 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000000075 oxide glass Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- LULNJFDMQSRXHK-UHFFFAOYSA-L 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid 4-nonyl-2-(4-nonylpyridin-2-yl)pyridine ruthenium(2+) dithiocyanate Chemical compound [Ru+2].[S-]C#N.[S-]C#N.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1.CCCCCCCCCC1=CC=NC(C=2N=CC=C(CCCCCCCCC)C=2)=C1 LULNJFDMQSRXHK-UHFFFAOYSA-L 0.000 description 3
- 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 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000434 metal complex dye Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 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 2
- 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 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JODIJOMWCAXJJX-UHFFFAOYSA-N [O-2].[Al+3].[O-2].[Zn+2] Chemical compound [O-2].[Al+3].[O-2].[Zn+2] JODIJOMWCAXJJX-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- BCVXHSPFUWZLGQ-UHFFFAOYSA-N mecn acetonitrile Chemical compound CC#N.CC#N BCVXHSPFUWZLGQ-UHFFFAOYSA-N 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 150000003303 ruthenium Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 1
- IKTPBRAHAAMNHV-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid Chemical compound N1=C(C=C(C=C1)C(=O)O)C1=NC=CC(=C1)C(=O)O.N1=C(C=C(C=C1)C(=O)O)C1=NC=CC(=C1)C(=O)O IKTPBRAHAAMNHV-UHFFFAOYSA-N 0.000 description 1
- OOWFYDWAMOKVSF-UHFFFAOYSA-N 3-methoxypropanenitrile Chemical compound COCCC#N OOWFYDWAMOKVSF-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- BOVHNGMHUHXNOF-UHFFFAOYSA-N [O-2].[Al+3].[Al+3].[O-2].[Zn+2] Chemical compound [O-2].[Al+3].[Al+3].[O-2].[Zn+2] BOVHNGMHUHXNOF-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical compound CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 description 1
- FKPSBYZGRQJIMO-UHFFFAOYSA-M benzyl(triethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC1=CC=CC=C1 FKPSBYZGRQJIMO-UHFFFAOYSA-M 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 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
- 239000001177 diphosphate Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
- C07D213/71—Sulfur atoms to which a second hetero atom is attached
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
-
- 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
-
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Description
本發明係關於一種釕金屬錯合物及用此錯合物製作之光電元件,特別是一種適用於染料敏化太陽能電池(Dye-Sensitized Solar Cell,DSC)之釕金屬錯合物及染料敏化太陽能電池。
隨著人類文明發展,全球面臨嚴重的能源危機及環境污染等問題,以光電太陽能電池將太陽能直接轉變成能源,是解決全世界能源危機及降低環境污染的重要方法之一;其中染料敏化太陽能電池因其製造成本低、可製成大尺度面積、具有可撓性及透光性與可用於建築物上等優異特性,而成為一種有前景的新型太陽能電池。
近年,等人發表一系列染料敏化太陽能電池相關文獻(例如O’Regan,B.;,M.Nature 1991
,353
,737)顯示染料敏化太陽能電池具有實用性。一般而言,染料敏化太陽能電池的結構包括有陰/陽電極、奈米二氧化鈦、染料及電解質;其中染料對電池效率有關鍵性的影響,理想的染料要具有可以吸收較大範圍的太陽光譜、高莫耳吸收係數(absorption coefficient)、高溫安定性及光安定性等。
實驗室發表了一系列釕錯合物作為染料敏化太陽能電池中的染料。1993年實驗室發表使用N3染料所製備之染料敏化太陽能電池,其效率達10.0%(AM 1.5)。N3染料的單波光之光電流轉換效率(IPCE)值在400nm~600nm範圍可達80%,而其後所開發的數百種釕錯合物染料,其效能測試皆無法超越N3染料。N3染料之結構如下式(a)所示。
直至2003年實驗室再發表使用N719染料所製備之染料敏化太陽能電池,其效率提升到10.85%(AM 1.5)。N719染料之結構如下式(b)所示。
而後2004年同實驗室發表使用黑染料(Black dye)所製備之染料敏化太陽能電池,其效率則達到11.04%(AM 1.5)。黑染料可強化紅光區和紅外光區的光譜應答,從而提昇染料敏化太陽能電池的效能。黑染料之結構如下式(c)所示。
除了實驗室發表之N3染料、N719染料與黑染料等相關系列之釕錯合物之外,其他類似的有鉑錯合物、鋨錯合物、鐵錯合物、銅錯合物...等等。但是許多研究都顯示釕錯合物的效率仍為較佳。
由於染料敏化太陽能電池中的染料對電池效率有關鍵性的影響。因此,尋找可以提高染料敏化太陽能電池效率的染料分子,是改善染料敏化太陽能電池效率的重要方法之一。
本發明提供一種新型釕金屬錯合物,其適用於染料敏化太陽能電池,可以增加染料敏化太陽能電池之光電效率。
本發明另提供一種染料敏化太陽能電池,其有較高的光電效率。
本發明之釕金屬錯合物,其結構如下式(I):RuL1
L2
(NCS)2
Am
(I)其中L1
為2,2’-雙吡啶-4,4’-二甲酸(2,2’-bipyridyl-4,4’-dicarboxylic acid)、2,2’-雙吡啶-4,4’-二磺酸(2,2’-bipyridyl-4,4’-disulfonic acid)或2,2’-雙吡啶-4,4’-二磷酸(2,2’-bipyridyl-4,4’-diphosphonic acid);L2
為2,2’-雙吡啶-4,4’-二壬烷(2,2’-bipyridyl-4,4’-dinonyl)或2,2’-雙吡啶-4,4’-雙十三烷(2,2’-bipyridine-4,4’-ditridecyl);A為X+
R1
R2
R3
R4
、 ,其中,X為N或P,R1
、R2
、R3
、及R4
各自獨立分別為C1-20
烷基(alkyl)、苯基(phenyl)或苯甲基(benzyl),R5
為C1-20
烷基;m為1或2。
於上述式(I)中L1
可為2,2’-雙吡啶-4,4’-二甲酸、2,2’-雙吡啶-4,4’-二磺酸或2,2’-雙吡啶-4,4’-二磷酸。較佳的,L1
為2,2’-雙吡啶-4,4’-二甲酸。
於上述式(I)中L2
可為2,2’-雙吡啶-4,4’-二壬烷、2,2’-雙吡啶-4,4’-雙十三烷;較佳的,L1
為2,2’-雙吡啶-4,4’-二壬烷。
於上述式(I)中,A可為X+
R1
R2
R3
R4
、 ,其中,X為N或P,R1
、R2
、R3
、及R4
各自獨立分別為C1-20
烷基、苯基或苯甲基,R5
為C1-20
烷基;較佳的,A為P+
R1
R2
R3
R4
,其中R1
、R2
、R3
、及R4
各自獨立分別為C1-20
烷基、苯基或苯甲基;更佳的,A為N+
R1
R2
R3
R4
,其中R1
、R2
、R3
、及R4
各自獨立分別為C1-20
烷基、苯基或苯甲基;最佳的,A為N+
R1
R2
R3
R4
,其中R1
、R2
、R3
、及R4
各自獨立分別為C1-20
烷基、苯基或苯甲基。
於上述式(I)中,m可為1至2的整數;較佳的,m為1的整數。
上述式(I)之釕金屬錯合物具體實例有:
另一方面,本發明亦提供一種染料敏化太陽能電池,其含有上述之釕金屬錯合物。
本發明之染料敏化太陽能電池,包括:(a)含有上述釕金屬錯合物之光電陽極(photoanode);(b)陰極(cathode);以及(c)位於光電陽極及陰極之間的電解質層(electrolyte layer)。
於本發明之染料敏化太陽能電池中,光電陽極包括有:透明基板、透明導電膜、多孔性半導體膜、以及釕金屬錯合物染料。
於本發明之染料敏化太陽能電池中,光電陽極之透明基板之材質並無特別限制,只要是透明的基材均可使用。較佳地,透明基板之材質為對於由染料敏化太陽能電池外部侵入之水分或氣體具有良好的遮斷性、耐溶劑性、耐候性等之透明基材。透明基板之具體列舉,包括有:石英、玻璃等透明無機基板;聚乙烯對苯二甲酸酯(PET)、聚(萘二甲酸乙二酯)(PEN)、聚碳酸酯(PC)、聚乙烯(PE)、聚丙烯(PP)、聚醯亞胺(PI)等透明塑膠基板,但是,並非限定於這些。此外,透明基板之厚度並無特別限制,可依照透光率、
染料敏化太陽能電池特性要求而自由選擇。較佳的,透明基板之材質為玻璃。
此外,於本發明之染料敏化太陽能電池中,透明導電膜的材料可為氧化銦錫(ITO)、氟摻雜的氧化錫(FTO)、氧化鋅-三氧化二鎵(ZnO-Ga2
O3
)、氧化鋅-三氧化二鋁(ZnO-Al2
O3
)、或以鍚(Sn)為基礎的氧化物材料。
再者,於本發明之染料敏化太陽能電池中,多孔性半導體膜可用半導體微粒所製成。適當的半導體微粒可包括:矽、二氧化鈦、二氧化錫、氧化鋅、三氧化鎢、五氧化二鈮、三氧化鈦鍶、及其組合;較佳的,半導體微粒是二氧化鈦。半導體微粒的平均粒徑為5至500奈米,較佳的為10至50奈米。多孔性半導體膜的厚度為5~25微米。
於本發明之染料敏化太陽能電池中,釕金屬錯合物染料如上所述之釕金屬錯合物。
此外,作為染料敏化太陽能電池之陰極材料並無特別限制,可包括任何具有傳導性之材料。或者,陰極材料也可以是一絕緣材料,只要有傳導層形成於朝向光電陽極的表面上。電化學穏定的物質就可作為陰極,且適用於陰極材料的非限制實例包括:鉑、金、碳、及其相似物。
再者,作為染料敏化太陽能電池之電解質層並無特別限制,可包括任何具有電子及/或電洞傳導性之基材。
另一方面,本發明更提供一種染料溶液,其含有上述之釕金屬錯合物。
本發明之染料溶液中,係包含:(A)含量為0.01~1重量百分比之上述釕金屬錯合物;以及(B)含量為99~99.99重量百分比之有機溶劑,其中,有機溶劑係選自由乙腈、甲醇、乙醇、丙醇、丁醇、二甲基甲醯胺、及N-甲基吡咯烷酮所組成之群組。
本發明之釕金屬錯合物可以下列方式合成。
順
-二硫氰基(2,2’-雙吡啶-4,4’-二甲酸基)(2,2’-雙吡啶-4,4’-二壬烷)釕(II)(cis
-di(thiocyanato)(2,2’-bipyridyl-4,4’-dicarboxylic acid)(2,2’-bipyridyl-4,4’-dinonyl)ruthen-ium(II),Z907 dye)依照Nature Material, 2003
,2
,402-407的方法合成。
將順
-二硫氰基2,2’-雙吡啶-4,4’-二甲酸基)(2,2’-雙吡啶-4,4’-二壬烷)釕(II)分散於去離子水中,滴入10%氫氧化四丁基胺(tetrabutylammonium hydroxide)水溶液至反應液中,使pH值大約落在11左右,持續攪拌直到釕金屬錯合物完全溶於水中,再用0.1 M的硝酸(nitric acid)水溶液調整pH值到4.6,即可得到式(I-1)之釕金屬錯合物。
本發明之染料敏化太陽能電池的製造方法並無特別限制,可用一般已知的方法製造。
透明基板之材質並無特別限制,只要是透明的基材均可使用。較佳地,透明基板之材質為對於由染料敏化太陽能電池外部侵入之水分或氣體具有良好的遮斷性、耐溶劑
性、耐候性等之透明基材,具體列舉,有石英、玻璃等透明無機基板,聚乙烯對苯二甲酸酯(PET)、聚(萘二甲酸乙二酯)(PEN)、聚碳酸酯(PC)、聚乙烯(PE)、聚丙烯(PP)、聚醯亞胺(PI)等透明塑膠基板,但是,並非限定於這些。透明基板之厚度並無特別限制,可以藉由透光率、染料敏化太陽能電池特性要求而自由選擇。在一具體實施例中,透明基板是使用玻璃基板。
透明導電膜的材料可以選自氧化銦錫(ITO)、氟摻雜的氧化錫(FTO)、氧化鋅-三氧化二鎵(ZnO-Ga2
O3
)、氧化鋅-三氧化二鋁(ZnO-Al2
O3
)、以及鍚為基礎的氧化物材料。在一具體實施例中,透明導電膜是使用氟摻雜的氧化錫。
多孔性半導體膜是用半導體微粒所製成。適當的半導體微粒包括有矽、二氧化鈦、二氧化錫、氧化鋅、三氧化鎢、五氧化二鈮、三氧化鈦鍶及其組合。首先,先將半導體微粒配製成糊狀物,再將其塗佈到透明導電基板上,塗佈方法可用刮墨刀、網印、旋轉塗佈、噴灑等或一般濕式塗佈。此外,為了得到適當的膜厚,可以塗佈一次或多次。半導體膜層可以為單層或多層,多層是指各層使用不同粒徑的半導體微粒。例如,可先塗佈粒徑為5至50奈米的半導體微粒,其塗佈厚度為5至20微米,然後再塗佈粒徑為200至400奈米的半導體微粒,其塗佈厚度為3至5微米。然後在50至100℃乾燥後,再於400至500℃燒結30分鐘可製得一多層半導體膜層。
釕金屬錯合物染料可以溶於適當的溶劑配製成染料溶液。適當的溶劑包括有乙腈、甲醇、乙醇、丙醇、丁醇、二甲基甲醯胺、N-甲基吡咯烷酮或其混合物,但是,並非限定於這些。在此,將塗佈有半導體膜的透明基板浸泡到染料溶液中,讓其充分吸收染料溶液中的染料,並於染料吸收完成後取出乾燥,可製得一染料敏化太陽能電池之光電陽極。
作為陰極的材料並無特別限制,可包括任何具有傳導性之材料。或者,陰極材料也可以是一絕緣材料,只要有傳導層形成於朝向光電陽極的表面上。此外,電化學穏定的物質就可作為陰極,且適用於陰極材料的非限制實例包括:鉑、金、碳、及其相似物。
電解質層並無特別限制,可以包括任何具有電子及/或電洞傳導性之基材。另外,液態電解質可以是含碘的乙腈溶液、含碘的N-甲基吡咯烷酮溶液、或含碘的3-甲氧基丙腈溶液。在一具體實例中,液態電解質為一含有碘的乙腈溶液。
本發明之染料敏化太陽能電池一具體製造方式如下。
首先,將包括具有粒徑為20~30奈米(nm)之氧化鈦微粒的糊狀物,藉由一次或數次的網印塗佈在覆蓋有氟摻雜的氧化錫(FTO)玻璃板上,而後在450℃燒結30分鐘。
將釕金屬錯合物溶於乙腈(acetonitrile)及三級
-丁醇(t
-butanol)的混合液1/1(v/v)中,配成釕金屬錯合物染料溶液。接著,將上述含有多孔氧化鈦膜的玻璃板浸泡在染料
溶中,讓其吸收染料溶液中的染料後,取出乾燥即可得到一光電陽極(photoanode)。
將覆蓋有氟摻雜的氧化錫玻璃板鑽一直徑為0.75毫米之注入口,以備注入電解質用。再將氯化鉑酸(H2
PtCl6
)溶液塗佈在覆蓋有氟摻雜的氧化錫玻璃板上,然後加熱到400℃處理15分鐘即可得到一陰極(cathode)。
然後,將厚度60微米的熱塑性聚合物膜配置在光電陽極和陰極之間,在120至140℃下施加壓力於此二電極,以黏合此兩電極。
將電解液(0.03 M I2
/0.3 M LiI/0.5 M三級丁基吡啶的乙腈溶液)注入,再用熱塑性聚合物膜將注入口密封,即可得到本發明之染料敏化電池。
以下實例僅用以說明本發明,本發明之申請專利範圍並不會因此而受限制。若無特別註明,則溫度為攝氏溫度,份數及百分比係以重量計。重量份數和體積份數之關係就如同公斤和公升之關係。
合成順
-二硫氰基(2,2’-雙吡啶-4,4’-二甲酸基)(2,2’-雙吡啶-4,4’-二壬烷)釕(II)(四丁基銨)(cis
-di(thiocyanato(2,2’-bipyridyl-4,4’-dicarboxylic acid)(2,2’-bipyridyl-4,4’-dinonyl)ruthenium(II)(tetrabutylammonium))(I-1)
將1份順
-二硫氰基2,2’-雙吡啶-4,4’-二甲酸基)(2,2’-雙吡啶-4,4’-二壬烷)釕(II)(cis
-di(thiocyanato)(2,2’-bipyridyl-4,4’-dicarboxylic acid)(2,2’-bipyridyl-4,4’-
dinonyl)ruthenium(II),Z907 dye)(依照Nature Material, 2003
,2
,402-407的方法合成)以及10份離子水加入反應瓶中攪拌分散,再滴入10%氫氧化四丁基胺(tetrabutylammonium hydroxide)水溶液至反應液中,使pH值大約落在11左右,持續攪拌直到釕金屬錯合物完全溶於水中,再用0.1 M的硝酸(nitric acid)水溶液調整pH值到4.6,攪拌18小時後以燒結玻璃過濾器(sintered glass filter)過濾收集產物,並用5份pH 4.1的蒸餾水沖洗產物,得到式(I-1)之黑色固體產物0.43份,產率85%。
合成順
-二硫氰基(2,2’-雙吡啶-4,4’-二甲酸基)(2,2’-雙吡啶-4,4’-二壬烷)釕(II)雙(四丁基銨)(cis
-di(thiocyanato)(2,2’-bipyridyl-4,4’-dicarboxylic acid)(2,2’-bipyridyl-4,4’-dinonyl)ruthenium(II)bis(tetrabutylammonium))(I-2)
將1份順
-二硫氰基2,2’-雙吡啶-4,4’-二甲酸基)(2,2’-雙吡啶-4,4’-二壬烷)釕(II)(cis
-di(thiocyanato)(2,2’-bipyridyl-4,4’-dicarboxylic acid)(2,2’-bipyridyl-4,4’-dinonyl)ruthenium(II),Z907 dye)(依照Nature Material, 2003
,2
,402-407的方法合成)以及10份離子水加入反應瓶中攪拌分散,再滴入10%氫氧化四丁基胺(tetrabutylammonium hydroxide)水溶液至反應液中,使pH值大約落在11左右,持續攪拌直到釕金屬錯合物完全溶於水中,再用0.1 M的硝酸(nitric acid)水溶液調整pH值到
5.5,攪拌18小時後以燒結玻璃過濾器(sintered glass filter)過濾收集產物,並用5份pH 4.1的蒸餾水沖洗產物,得到式(I-2)之黑色固體產物0.44份,產率70%。
合成順
-二硫氰基(2,2’-雙吡啶-4,4’-二甲酸基)(2,2’-雙吡啶-4,4’-二壬烷)釕(II)(苯甲基三乙基銨)(cis
-di(thiocyanato)(2,2’-bipyridyl-4,4’-dicarboxylic acid)(2,2’-bipyridyl-4,4’-dinonyl)ruthenium(II)(benzyltriethyl ammonium))(I-3)
同實施例1之相同步驟製備本實施例之化合物,除了使用5份去離子水與5份甲醇取代10份離子水進行攪拌分散與使用氫氧化苯甲基三乙基銨(benzyltriethylammonium hydroxide)水溶液(TCI Co.,Ltd.,)取代氫氧化四丁基胺水溶液。得到式(I-3)之黑色固體產物0.35份,產率71%。
合成順
-二硫氰基(2,2’-雙吡啶-4,4’-二甲酸基)(2,2’-雙吡啶-4,4’-二壬烷)釕(II)(四丁基磷)(cis
-di(thiocyanato)(2,2’-bipyridyl-4,4’-dicarboxylic acid)(2,2’-bipyridyl-4,4’-dinonyl)ruthenium(II)(tetrabutylphosphonium))(I-4)
同實施例1之相同步驟製備本實施例之化合物,除了使用5份去離子水與5份甲醇取代10份離子水進行攪拌分散與使用氫氧化四丁基磷(tetrabutylphosphonium hydroxide)水溶液取代氫氧化四丁基胺水溶液。得到式(I-4)之黑色固
體產物0.42份,產率81%。
合成順
-二硫氰基(2,2’-雙吡啶-4,4’-二甲酸基)(2,2’-雙吡啶-4,4’-二壬烷)釕(II)(1-十二烷基吡啶)(cis
-di(thiocyanato)(2,2’-bipyridyl-4,4’-dicarboxylic acid)(2,2’-bipyridyl-4,4’-dinonyl)ruthenium(II)(1-dodecyl pyridinium))(I-5)
同實施例1之相同步驟製備本實施例之化合物,除了使用10份去離子水與5份甲醇取代10份離子水進行攪拌分散與除了使用氫氧1-十二烷基吡啶(1-dodecylpyridin-ium hydroxide)水溶液(用氯化1-十二烷基吡啶試劑(1-dodecylpyridinium chloride reagent,ALDRICH,98%)所配製)取代氫氧化四丁基胺水溶液。得到式(I-5)之黑色固體產物0.32份,產率63%。
將包括具有粒徑為20~30奈米(nm)之氧化鈦微粒的糊狀物,藉由一次或數次的網印塗佈在覆蓋有氟摻雜的氧化錫(FTO)玻璃板上(厚度4 mm,電阻10Ω),使得燒結後的多孔氧化鈦膜的厚度為10至12微米(μm),而後在450℃燒結30分鐘。
將實施例1之釕金屬錯合物溶於乙腈(acetonitrile)及三級
-丁醇(t
-butanol)的混合液1:1(v/v)中,配成釕金屬錯合
物濃度為0.5 M的染料溶液,接著,將上述含有多孔氧化鈦膜的玻璃板浸泡在染料溶中,讓其吸收染料溶液中的染料16至24小時後,取出乾燥即可得到一光電陽極(photoanode)。
將覆蓋有氟摻雜的氧化錫玻璃板鑽一直徑為0.75毫米,以備注入電解質用,再將氯化鉑酸(H2
PtCl6
)溶液(1毫升的乙醇中含有2毫克的鉑)塗佈在氧化錫玻璃板上,然後加熱到400℃處理15分鐘即可得到一陰極(cathode)。
將厚度60微米的熱塑性聚合物膜配置在光電陽極和陰極之間,在120至140℃下施加壓力於此二電極,以黏合該兩電極。
將電解液(0.03 M I2
/0.3 M LiI/0.5 M三級丁基吡啶的乙腈溶液)注入,再用熱塑性聚合物膜將注入口密封,可得本實施例之染料敏化太陽能電池。
同實施例6之相同步驟製備本實施例之染料敏化太陽能電池,除了使用實施例2之釕金屬錯合物取代實施例1之釕金屬錯合物。
同實施例6之相同步驟製備本實施例之染料敏化太陽能電池,除了使用實施例3之釕金屬錯合物取代實施例1
之釕金屬錯合物。
同實施例6之相同步驟製備本實施例之染料敏化太陽能電池,除了使用實施例4之釕金屬錯合物取代實施例1之釕金屬錯合物。
同實施例6之相同步驟製備染料敏化太陽能電池,除了使用Z907取代實施例1之釕金屬錯合物。
將實施例6至10及比較例之染料敏化太陽能電池在AM 1.5的照明下,測試其短路電流(JSC
)、開路電壓(VOC
)、填充因子(FF)、光電轉換效率(η)及單波光光電流轉換效率(Incident Photon to Current Conversion Efficiency,IPCE)。測試結果整理如下表1:
由表1之測試結果顯示,用本發明實施例之釕金屬錯合物所製作的染料敏化太陽能電池,與比較例用Z907所製作的染料敏化太陽能電池相比,本發明之釕金屬錯合物可以提高染料敏化太陽能電池之短路電流、開路電壓及填充因子,因而增加染料敏化太陽能電池的光電轉換效率。
綜上所述,本發明無論就目的、手法及功效,或就其技術層面與研發設計上,再再均顯示其迥異於習知技術之特徵。惟應注意的是,上述諸多實施例僅係為了便於說明故舉例闡述之,然其並非用以限定本發明,任何熟習此技藝者,在不脫離本發明之精神及範圍內,當可作些許之更動與潤飾,因此本發明所主張之權利範圍自應以申請專利範圍所述為準,而非僅限於上述實施例。
上述實施例僅係為了方便說明而舉例而已,本發明所主張之權利範圍自應以申請專利範圍所述為準,而非僅限於上述實施例。
Claims (9)
- 一種釕金屬錯合物,其結構如下式(I):RuL1 L2 (NCS)2 Am (I)其中L1 為2,2’-雙吡啶-4,4’-二甲酸;L2 為2,2’-雙吡啶-4,4’-二壬烷; A為X+ R1 R2 R3 R4 、 ,其中當X為N,R1 為苯甲基,且R2 、R3 、及R4 各自獨立分別為C1-20 烷基、苯基或苯甲基;當X為P,R1 、R2 、R3 、及R4 各自獨立分別為C1-20 烷基、苯基或苯甲基;且R5 為C1-20 烷基;m為1或2。
- 如申請專利範圍第1項所述之釕金屬錯合物,其中A為N+ R1 R2 R3 R4 ,R1 為苯甲基,且R2 、R3 、及R4 各自獨立分別為C1-20 烷基、苯基或苯甲基。
- 如申請專利範圍第1項所述之釕金屬錯合物,其中A為且R5 為C1-20 烷基。
- 如申請專利範圍第1項所述之釕金屬錯合物,其中m為1。
- 如申請專利範圍第1項所述之釕金屬錯合物,其該釕金屬錯合物是一種用於染料敏化太陽能電池之染料化合物。
- 一種釕金屬錯合物,其結構如下下式(I-3)或下式(I-4)。
- 如申請專利範圍第6項所述之釕金屬錯合物,其該釕金屬錯合物是一種用於染料敏化太陽能電池之染料化合物。
- 一種染料敏化太陽能電池,其包括:(a)一光電陽極,其包括一如下式(I)之釕金屬錯合物;RuL1 L2 (NCS)2 Am (I)其中L1 為2,2’-雙吡啶-4,4’-二甲酸;L2 為2,2’-雙吡啶-4,4’-二壬烷;A為X+ R1 R2 R3 R4 、 ,其中當X為N,R1 為苯甲基,且R2 、R3 、及R4 各自獨立分別為C1-20 烷基、苯基或苯甲基;當X為P,R1 、R2 、R3 、及R4 各自獨立分別為C1-20 烷基、苯基或苯甲基;且R5 為C1-20 烷基;m為1或2;(b)一陰極;以及(c)一電解質層,其在光電陽極與陰極間。
- 一種染料溶液,其包括:(A)一如下式(I)之釕金屬錯合物,其含量為0.01~1重量百分比:RuL1 L2 (NCS)2 Am (I)其中L1 為2,2’-雙吡啶-4,4’-二甲酸;L2 為2,2’-雙吡啶-4,4’-二壬烷;A為X+ R1 R2 R3 R4 、 ,其中當X為N,R1 為苯甲基,且R2 、R3 、及R4 各自獨立分別為C1-20 烷基、苯基或苯甲基;當X為P,R1 、R2 、R3 、及R4 各自獨立分別為C1-20 烷基、苯基或苯甲基;且R5 為C1-20 烷基;m為1或2;以及(B)一種有機溶劑,其含量為99.99~99重量百分比,且該有機溶劑係選自由:乙腈、甲醇、乙醇、丙醇、丁醇、二甲基甲醯胺、及N-甲基吡咯烷酮所組成之群組。
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US12/591,768 US8278550B2 (en) | 2009-10-08 | 2009-12-01 | Ruthenium complex and photoelectric component using the same |
GB1016729A GB2474346A (en) | 2009-10-08 | 2010-10-05 | Bis-bipyridyl ruthenium complexes and photoelectric components using the same |
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DE60123714T2 (de) * | 2000-08-15 | 2007-10-04 | FUJI PHOTO FILM CO., LTD., Minamiashigara | Photoelektrische Zelle und Herstellungsmethode |
US7118936B2 (en) * | 2001-10-11 | 2006-10-10 | Bridgestone Corporation | Organic dye-sensitized metal oxide semiconductor electrode and its manufacturing method, and organic dye-sensitized solar cell |
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WO2004102724A1 (ja) * | 2003-05-13 | 2004-11-25 | Asahi Kasei Kabushiki Kaisha | 光電変換素子 |
JP4474596B2 (ja) * | 2003-08-29 | 2010-06-09 | キヤノンアネルバ株式会社 | シリコンナノ結晶構造体の形成方法及び形成装置 |
JP2007066526A (ja) * | 2005-08-29 | 2007-03-15 | Hitachi Ltd | 半導体電極,色素増感太陽電池およびその製造方法 |
US8124777B2 (en) * | 2005-09-22 | 2012-02-28 | Sumitomo Chemical Company, Limited | Compound, photoelectric converter and photoelectrochemical cell |
GB2434158A (en) * | 2005-12-05 | 2007-07-18 | Hydrogen Solar Ltd | Photoelectrochemical system |
KR101146668B1 (ko) * | 2006-11-15 | 2012-05-23 | 삼성에스디아이 주식회사 | 광전 소자용 염료 및 이를 포함하는 광전 소자 |
DE112008000841T5 (de) * | 2007-03-29 | 2010-02-11 | Sumitomo Chemical Company, Limited | Verbindung, photoelektrischer Wandler und photoelektrochemische Zelle |
KR100929812B1 (ko) * | 2007-08-02 | 2009-12-08 | 한국전자통신연구원 | 증가된 에너지 변환 효율을 갖는 태양전지 및 그 제조 방법 |
TWI370120B (en) * | 2008-01-31 | 2012-08-11 | Everlight Chem Ind Corp | Ruthenium complex |
CN101712694B (zh) * | 2008-10-06 | 2012-11-28 | 明德国际仓储贸易(上海)有限公司 | 钌金属络合物及用此络合物制作的光电组件 |
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- 2010-10-07 AU AU2010227029A patent/AU2010227029B2/en not_active Ceased
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US20070209695A1 (en) * | 2004-04-16 | 2007-09-13 | Jsr Corporation | Dye and Dye-Sensitized Solar Cell |
US20090216021A1 (en) * | 2006-02-08 | 2009-08-27 | Shimane Prefectural Government | Photosensitizer Dye |
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AU2010227029B2 (en) | 2012-03-08 |
TW201113291A (en) | 2011-04-16 |
US8278550B2 (en) | 2012-10-02 |
AU2010227029A1 (en) | 2011-04-28 |
GB2474346A (en) | 2011-04-13 |
DE102010042208A1 (de) | 2011-07-14 |
US20110083732A1 (en) | 2011-04-14 |
GB201016729D0 (en) | 2010-11-17 |
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