CN103189452A - Novel ruthenium-based dye and method for producing same - Google Patents
Novel ruthenium-based dye and method for producing same Download PDFInfo
- Publication number
- CN103189452A CN103189452A CN2011800526100A CN201180052610A CN103189452A CN 103189452 A CN103189452 A CN 103189452A CN 2011800526100 A CN2011800526100 A CN 2011800526100A CN 201180052610 A CN201180052610 A CN 201180052610A CN 103189452 A CN103189452 A CN 103189452A
- Authority
- CN
- China
- Prior art keywords
- chemical formula
- replacement
- dye
- compound
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000000975 dye Substances 0.000 claims abstract description 103
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004408 titanium dioxide Substances 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 180
- 150000001875 compounds Chemical class 0.000 claims description 49
- 239000004065 semiconductor Substances 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 19
- 206010070834 Sensitisation Diseases 0.000 claims description 18
- 230000008313 sensitization Effects 0.000 claims description 18
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- LAXRNWSASWOFOT-UHFFFAOYSA-J (cymene)ruthenium dichloride dimer Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ru+2].[Ru+2].CC(C)C1=CC=C(C)C=C1.CC(C)C1=CC=C(C)C=C1 LAXRNWSASWOFOT-UHFFFAOYSA-J 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 23
- 239000000758 substrate Substances 0.000 description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- -1 polyethylene terephthalate Polymers 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 229940126214 compound 3 Drugs 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 150000003839 salts Chemical group 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- BCCGKQFZUUQSEX-WBPXWQEISA-N (2r,3r)-2,3-dihydroxybutanedioic acid;3,4-dimethyl-2-phenylmorpholine Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O.OC(=O)[C@H](O)[C@@H](O)C(O)=O.O1CCN(C)C(C)C1C1=CC=CC=C1 BCCGKQFZUUQSEX-WBPXWQEISA-N 0.000 description 3
- YNIKFTIVYVQEAU-UHFFFAOYSA-N 5-heptadecan-9-ylthieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=C(C(CCCCCCCC)CCCCCCCC)S2 YNIKFTIVYVQEAU-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- NMFKEMBATXKZSP-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2.S1C=CC2=C1C=CS2 NMFKEMBATXKZSP-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000003809 water extraction Methods 0.000 description 3
- BHQCQFFYRZLCQQ-UHFFFAOYSA-N (3alpha,5alpha,7alpha,12alpha)-3,7,12-trihydroxy-cholan-24-oic acid Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 BHQCQFFYRZLCQQ-UHFFFAOYSA-N 0.000 description 2
- OOWFYDWAMOKVSF-UHFFFAOYSA-N 3-methoxypropanenitrile Chemical compound COCCC#N OOWFYDWAMOKVSF-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004380 Cholic acid Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229930188620 butyrolactone Natural products 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- BHQCQFFYRZLCQQ-OELDTZBJSA-N cholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 BHQCQFFYRZLCQQ-OELDTZBJSA-N 0.000 description 2
- 229960002471 cholic acid Drugs 0.000 description 2
- 235000019416 cholic acid Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229940125773 compound 10 Drugs 0.000 description 2
- KXGVEGMKQFWNSR-UHFFFAOYSA-N deoxycholic acid Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 KXGVEGMKQFWNSR-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- JUGDWSNYRIPJGE-UHFFFAOYSA-N 1-[acetyl(dibutyl)stannyl]ethanone Chemical compound CCCC[Sn](C(C)=O)(C(C)=O)CCCC JUGDWSNYRIPJGE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QKPVEISEHYYHRH-UHFFFAOYSA-N 2-methoxyacetonitrile Chemical compound COCC#N QKPVEISEHYYHRH-UHFFFAOYSA-N 0.000 description 1
- LQYXNJNEDCJEGG-UHFFFAOYSA-N 2-methylpropan-2-ol;titanium Chemical compound [Ti].CC(C)(C)O LQYXNJNEDCJEGG-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- XNTYYYINMGRBQW-ZEZONBOOSA-N 3,12-Diketocholanic acid Chemical compound C([C@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)C(=O)C1 XNTYYYINMGRBQW-ZEZONBOOSA-N 0.000 description 1
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Cc1ccccc1 Chemical compound Cc1ccccc1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- DLYVTEULDNMQAR-SRNOMOOLSA-N Cholic Acid Methyl Ester Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@H](C)CCC(=O)OC)[C@@]2(C)[C@@H](O)C1 DLYVTEULDNMQAR-SRNOMOOLSA-N 0.000 description 1
- RDFLLVCQYHQOBU-GPGGJFNDSA-O Cyanin Natural products O([C@H]1[C@H](O)[C@H](O)[C@H](O)[C@H](CO)O1)c1c(-c2cc(O)c(O)cc2)[o+]c2c(c(O[C@H]3[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O3)cc(O)c2)c1 RDFLLVCQYHQOBU-GPGGJFNDSA-O 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229920003944 DuPont™ Surlyn® 1702 Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- RUDATBOHQWOJDD-BSWAIDMHSA-N chenodeoxycholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)CC1 RUDATBOHQWOJDD-BSWAIDMHSA-N 0.000 description 1
- 229960001091 chenodeoxycholic acid Drugs 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- RDFLLVCQYHQOBU-ZOTFFYTFSA-O cyanin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC(C(=[O+]C1=CC(O)=C2)C=3C=C(O)C(O)=CC=3)=CC1=C2O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 RDFLLVCQYHQOBU-ZOTFFYTFSA-O 0.000 description 1
- KXGVEGMKQFWNSR-LLQZFEROSA-N deoxycholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 KXGVEGMKQFWNSR-LLQZFEROSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- WLPSNBGDESCKIL-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO WLPSNBGDESCKIL-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- ZFTKWAVDJBKFCS-UHFFFAOYSA-N iodine;pyridine Chemical compound [I].C1=CC=NC=C1 ZFTKWAVDJBKFCS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- NRHMKIHPTBHXPF-TUJRSCDTSA-M sodium cholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 NRHMKIHPTBHXPF-TUJRSCDTSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
-
- 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
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/0075—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of an heterocyclic ring
-
- 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
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
-
- 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
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/14—Styryl dyes
- C09B23/145—Styryl dyes the ethylene chain carrying an heterocyclic residue, e.g. heterocycle-CH=CH-C6H5
-
- 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
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/24—Disazo or polyazo compounds
- C09B45/32—Disazo or polyazo compounds containing other metals
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
Abstract
The present invention relates to a novel ruthenium -based Dye and a method for manufacturing the same, and more particularly, to a Dye which is used as a Dye in a Dye-Sensitized Solar Cell (Dye-Sensitized Solar Cell), exhibits significantly improved photoelectric conversion efficiency compared to conventional dyes, has enhanced binding force with titanium dioxide, and has excellent short circuit photocurrent density (Jsc) and molar absorption coefficient, thereby greatly improving the efficiency of the Solar Cell, and a method for manufacturing the same.
Description
Technical field
The present invention relates to a kind of novel ruthenium based dye and manufacture method of in dye sensitization solar battery (Dye-Sensitized Solar Cell), using as dyestuff thereof.
Background technology
1991 Switzerland state-run Lausanne Instituto Superior Technico (EPFL) Michael's lattice Lay after just your (Michaelgratzel) research group has developed dye sensitization nano rice corpuscles titanium oxide solar cell, carried out much the researchs about this field.Dye sensitization solar battery is solar cell than existing silicon, manufacturing cost is significantly low, therefore, has the possibility that can replace existing uncrystalline silicon solar cell, different with silicon solar cell, dye sensitization solar battery is generating the right dye molecule in electronics-hole (hole) and transmit the transition metal oxide of the electronics that is generated as the photoelectrochemistry solar cell of main composition material by absorbing visible light.
As the representative dyestuff that is used for dye sensitization solar battery, can enumerate following compound in the past.
* TBA: TBuA positively charged ion
But, still require than bonding force, photoelectric transformation efficiency, short-circuit photocurrent density (the short circuit photocurrent density of above-mentioned dyestuff raising with the oxide semiconductor particulate, Jsc) and molar absorptivity, further improve efficient and the weather resistance of solar cell, thereby need study practical situation that Here it is to reactive monoazo dyestuffs.
Summary of the invention
Technical problem
In order to solve the problem of aforesaid conventional art, the object of the present invention is to provide a kind of dyestuff and manufacture method thereof, described dyestuff shows the photoelectric transformation efficiency that significantly improves than dyestuff in the past, make with the oxide semiconductor particulate bonding force strengthen, and short-circuit photocurrent density (short circuit photocurrent density, Jsc) and the molar absorptivity excellence, thus can improve the efficient of solar cell greatly.
In addition, the solar cell that the object of the present invention is to provide a kind of dye-sensitized photoelectric conversion device and efficient to significantly improve, described dye-sensitized photoelectric conversion device shows the photoelectric transformation efficiency that significantly improves by comprising above-mentioned dyestuff, with the oxide semiconductor particulate bonding force strengthen, and (short circuit photocurrent density is Jsc) with the molar absorptivity excellence for short-circuit photocurrent density.
The means of dealing with problems
To achieve these goals, the invention provides the dyestuff shown in the following Chemical formula 1.
[Chemical formula 1]
In the above-mentioned Chemical formula 1, Me is Ru or Os, and a1 ring can not have substituting group independently of one another or have substituting group more than 1, as substituting group, can be halogen atom, amide group, cyano group, hydroxyl, nitro, acyl group, C
1-30Alkyl or C
1-30Alkoxyl group, Y are hydrogen, Na or TBA (trimethyl carbinol),
In addition, X
1, X
2Be the compound shown in methyl or the following Chemical formula 2 independently of one another, at least one among X1 and the X2 is the compound shown in the Chemical formula 2,
[Chemical formula 2]
In the above-mentioned Chemical formula 2, A be selected from by
With
In the group of forming more than a kind, at this moment, X is selected from independently of one another by O, S, Se, Si and NR
5In the group of forming, R
1To R
4Be selected from the C by hydrogen, replacement or non-replacement independently of one another
1-12The C of alkyl, replacement or non-replacement
6-30The C of aryl and replacement or non-replacement
6-20In the group that heteroaryl is formed, perhaps can be connected to each other and form ring, R
5C for hydrogen or replacement or non-replacement
1-30Alkyl, n are 1 to 10 integer,
B is the compound shown in the compound shown in the following chemical formula 3 or the following chemical formula 4,
[chemical formula 3]
[chemical formula 4]
In the above-mentioned chemical formula 3, Ar
1, Ar
2And Ar
3Be selected from the C by replacement or non-replacement independently of one another
6-50The C of aryl, replacement or non-replacement
6-20In the group that heteroaryl is formed, perhaps can be connected to each other and form ring, * is bound fraction, in the above-mentioned chemical formula 4, and R
6And R
7Be the C of replacement or non-replacement independently of one another
1-30Alkyl, * are bound fraction.
In addition, the invention provides the manufacture method of the dyestuff shown in a kind of Chemical formula 1, it is characterized in that, the compound of following chemical formula 5 is reacted with the compound of stating chemical formula 6, chemical formula 7 and chemical formula 8 successively.
[chemical formula 5]
[chemical formula 6]
[RuCl
2(p-cymene)]
2
[chemical formula 7]
[chemical formula 8]
NH
4NCS
In the above-mentioned chemical formula 5,6,7 and 8, X
1, X
2Identical with definition above with the definition of a1.
In addition, the invention provides a kind of dye-sensitized photoelectric conversion device, it is characterized in that, comprise the oxide semiconductor particulate that load has compound shown in the above-mentioned Chemical formula 1.
In addition, the invention provides a kind of dye sensitization solar battery, it is characterized in that, comprise above-mentioned dye-sensitized photoelectric conversion device.
The invention effect
Novel ruthenium based dye of the present invention shows the photoelectric transformation efficiency that significantly improves than dyestuff in the past, make with the bonding force of oxide semiconductor particulate and strengthen, and short-circuit photocurrent density (short circuit photocurrent density, Jsc) and the molar absorptivity excellence, thus can improve the efficient of solar cell greatly.
Description of drawings
Fig. 1 is the dye composition of the present invention of manufacturing among the embodiment 1 and the absorption spectrum of N719.
Short-circuit photocurrent density (short circuit photocurrent density, Jsc) curve that Fig. 2 measures for the dye sensitization solar battery made from the dye composition of the present invention that uses manufacturing among the embodiment 1.
Short-circuit photocurrent density (short circuit photocurrent density, Jsc) curve of Fig. 3 for measuring with the dye sensitization solar battery that uses the N719 dye composition to make.
Embodiment
Below, describe the present invention in detail.
The inventor confirms, by making compound loaded when the oxide semiconductor particulate is made dye sensitization solar battery shown in the Chemical formula 1, the excellent in te pins of durability with oxide semiconductor particulate mortise, photoelectric transformation efficiency, short-circuit photocurrent density (short circuit photocurrent density, Jsc) and the molar absorptivity height, thereby show the efficient more excellent than existing dye sensitization solar battery, finished the present invention thus.
Dyestuff of the present invention is characterised in that it is represented by following Chemical formula 1.
[Chemical formula 1]
In the above-mentioned Chemical formula 1, Me is Ru or Os, and a1 ring can not have substituting group independently of one another or have substituting group more than 1, as substituting group, can be halogen atom, amide group, cyano group, hydroxyl, nitro, acyl group, C
1-30Alkyl or C
1-30Alkoxyl group, Y are hydrogen, Na or TBA (trimethyl carbinol),
In addition, X
1, X
2Be the compound shown in methyl or the following Chemical formula 2 independently of one another, X
1And X
2In at least one be the compound shown in the Chemical formula 2,
[Chemical formula 2]
In the above-mentioned Chemical formula 2, A be selected from by
With
In the group of forming more than a kind, at this moment, X is selected from independently of one another by O, S, Se, Si and NR
5In the group of forming, R
1To R
4Be selected from the C by hydrogen, replacement or non-replacement independently of one another
1-12The C of alkyl, replacement or non-replacement
6-30The C of aryl and replacement or non-replacement
6-20In the group that heteroaryl is formed, perhaps can be connected to each other and form ring, R
5C for hydrogen or replacement or non-replacement
1-30Alkyl, n are 1 to 10 integer,
B is the compound shown in the compound shown in the following chemical formula 3 or the following chemical formula 4,
[chemical formula 3]
[chemical formula 4]
In the above-mentioned chemical formula 3, Ar
1, Ar
2And Ar
3Be selected from the C by replacement or non-replacement independently of one another
6-50The C of aryl, replacement or non-replacement
6-20In the group that heteroaryl is formed, perhaps can be connected to each other and form ring, * is bound fraction, in the above-mentioned chemical formula 4, and R
6And R
7Be the C of replacement or non-replacement independently of one another
1-30Alkyl, * are bound fraction, preferred R
6And R
7Be C
5-10Alkyl or comprise the C of sulphur
5-10Alkyl.
What in addition, the dyestuff shown in the preferred above-mentioned Chemical formula 1 was following Chemical formula 1-1 to the compound shown in the 1-48 is a kind of.
[Chemical formula 1-1]
[Chemical formula 1-2]
[Chemical formula 1-3]
[Chemical formula 1-4]
[Chemical formula 1-5]
[Chemical formula 1-6]
[Chemical formula 1-7]
[Chemical formula 1-8]
[Chemical formula 1-9]
[Chemical formula 1-10]
[Chemical formula 1-11]
[Chemical formula 1-12]
[Chemical formula 1-13]
[Chemical formula 1-14]
[Chemical formula 1-15]
[Chemical formula 1-16]
[Chemical formula 1-17]
[Chemical formula 1-18]
[Chemical formula 1-19]
[Chemical formula 1-20]
[Chemical formula 1-21]
[Chemical formula 1-22]
[Chemical formula 1-23]
[Chemical formula 1-24]
[Chemical formula 1-25]
[Chemical formula 1-26]
[Chemical formula 1-27]
[Chemical formula 1-28]
[Chemical formula 1-29]
[Chemical formula 1-30]
[Chemical formula 1-31]
[Chemical formula 1-32]
[Chemical formula 1-33]
[Chemical formula 1-34]
[Chemical formula 1-35]
[Chemical formula 1-36]
[Chemical formula 1-37]
[Chemical formula 1-38]
[Chemical formula 1-39]
[Chemical formula 1-40]
[Chemical formula 1-41]
[Chemical formula 1-42]
[Chemical formula 1-43]
[Chemical formula 1-44]
[Chemical formula 1-45]
[Chemical formula 1-46]
[Chemical formula 1-47]
[Chemical formula 1-48]
In addition, the invention provides the manufacture method of the dyestuff shown in a kind of Chemical formula 1, it is characterized in that, the compound that makes following chemical formula 5 reacts with the compound of following chemical formula 6, chemical formula 7 and chemical formula 8 successively.
[chemical formula 5]
[chemical formula 6]
[RuCl
2(p-cymene)]
2
[chemical formula 7]
[chemical formula 8]
NH
4NCS
In the above-mentioned chemical formula 5,6,7 and 8, X
1, X
2Identical with definition above with the definition of a1.
Among the present invention, the compound that is used as initial substance in the manufacturing of the dyestuff of Chemical formula 1 can utilize usual method to make or buy and use.
In addition, the invention provides a kind of dye-sensitized photoelectric conversion device, described dye-sensitized photoelectric conversion device is characterised in that, the dyestuff shown in the above-mentioned Chemical formula 1 of load on the oxide semiconductor particulate.Among the present invention, dye-sensitized photoelectric conversion device is except using the dyestuff shown in the above-mentioned Chemical formula 1, certainly can be suitable for the method for utilizing dyestuff in the past to make the used for solar batteries dye-sensitized photoelectric conversion device, but preferred dye-sensitized photoelectric conversion device of the present invention utilizes the oxide semiconductor particulate at the film of substrate manufacturing oxide semiconductor, and then load organic dye according to the present invention is made on above-mentioned film.
Among the present invention, as the substrate of the film that forms oxide semiconductor, preferably its surface has the substrate of electroconductibility, also can use the substrate of selling on the market.As concrete example, can utilize on the surface of glass or surface that polyethylene terephthalate or polyethersulfone etc. have a macromolecular material of the transparency forms the substrate of metallic films such as the film of the conductive metal oxides such as stannic oxide that are coated with indium, fluorine, antimony or steel, silver, gold.At this moment, electroconductibility is preferably below 1000 Ω usually, is preferably especially below 100 Ω.
In addition, as the oxide semiconductor particulate, be preferably metal oxide.As concrete example, can use the oxide compound of titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum, vanadium etc.Wherein be preferably the oxide compound of titanium, tin, zinc, niobium, indium etc., wherein more preferably titanium oxide, zinc oxide, stannic oxide most preferably are titanium oxide.Above-mentioned oxide semiconductor can use separately, also can mix or coat semi-conductive surface and use.
In addition, the particle diameter of above-mentioned oxide semiconductor particulate is preferably 1-500nm, 1-100nm more preferably in median size.In addition, the particulate of this oxide semiconductor can mix the particulate of the particulate of big particle diameter and small particle size or utilize in the mode of multilayer.
Above-mentioned oxide semiconductor thin-film can be made by the following method: make directly film forming method on substrate of oxide semiconductor particulate by atomizer spray etc.; With substrate as electrode and the method that electricity consumption is separated out the semiconductive particles film; With the slurries of semiconductive particles or contain by the precursor with semiconductive particles such as semi-conductor alkoxide and be hydrolyzed after the paste of the particulate made coats on the substrate, the method of carrying out drying, solidify or burning till etc., wherein, preferably paste is coated method on the substrate.Adopt under the situation of this method, above-mentioned slurries can utilize usual method to be dispersed in the dispersion medium by the oxide semiconductor particulate with secondary aggregation, and making its average primary particle diameter is that 1-20nm obtains.
As the dispersion medium that disperses slurries, so long as the dispersion medium that semiconductive particles is disperseed, just can be not particularly limited to use, can utilize alcohol such as water, ethanol, ketone such as acetone, methyl ethyl diketone, or hydrocarbon such as hexane, they can be mixed and use, wherein, consider from reducing slurry viscosity variation aspect, preferably make water.In addition, be purpose with the dispersion state of steady oxide semiconductive particles, can use dispersion stabilizer.As the object lesson of operable dispersion stabilizer, can enumerate acid such as acetic acid, hydrochloric acid, nitric acid, methyl ethyl diketone, vinylformic acid, polyoxyethylene glycol, polyvinyl alcohol etc.
Can the substrate that be coated with slurries be burnt till, this firing temperature is more than 100 ℃, is preferably more than 200 ℃, and the upper limit is roughly below the fusing point (softening temperature) of base material in addition, is limited to 900 ℃ on usually, is preferably below 600 ℃.In the present invention, firing time is not particularly limited, but preferably is roughly in 4 hours.
In the present application, the film thickness on substrate is advisable with 1-200 μ m, is preferably 1-50 μ m.When implementing to burn till, the welding of the part of the film of oxide semiconductor particulate possibility, such welding does not cause special influence to the present invention.
Can also implement secondary treatment to above-mentioned oxide semiconductor thin-film.As an example, in the solution of the alkoxide of the metal identical with semi-conductor, muriate, nitride, sulfide etc., directly according to the different substrate deposit film, carry out drying or burn till again, thereby improve the performance of semiconductor film.As metal alkoxide, can enumerate ethanol titanium salt, Virahol titanium salt, trimethyl carbinol titanium salt, positive dibutyl diacetyl tin etc., can utilize their alcoholic solution.As muriate, for example can enumerate titanium tetrachloride, tin tetrachloride, zinc chloride etc., can utilize their aqueous solution.The oxide semiconductor thin-film of Huo Deing is made of the particulate of oxide semiconductor like this.
In addition, in the present invention, there is no particular limitation for the method for carried dye on the oxide semiconductor particulate that forms with film like, as object lesson, can enumerate the method for in the dyestuff shown in the above-mentioned Chemical formula 1 being used the solution that the solvent of its dissolving can be dissolved and make or the dispersion liquid that the dyestuff dispersion is made, flooding the substrate that is provided with above-mentioned oxide semiconductor thin-film.Concentration in solution or the dispersion liquid can suitably determine according to dyestuff.Depositing temperature is roughly normal temperature to the boiling point of solvent, and in addition, depositing time is about 1 minute to 48 hours.As the object lesson that can be used for the solvent of dissolving dye, can enumerate methyl alcohol, ethanol, acetonitrile, dimethyl sulfoxide (DMSO), dimethyl formamide, acetone, the trimethyl carbinol etc.The dye strength of solution is generally 1 * 10
-6M-1M, be preferably 1 * 10
-5M-1 * 10
-1M.Can obtain the photo-electric conversion element of the present invention with film like oxide semiconductor particulate by dye sensitization thus.
In the present invention, the dyestuff shown in the Chemical formula 1 of load can be a kind, also can mix multiple.And, under the situation of mixing, can only use dyestuff of the present invention, and can mix other dyestuff or metallized dye.There is no particular limitation for the example of the metallized dye that can mix, but preferred document M.K.Nazeeruddin, A.Kay, I.Rodicio, R.Humphry-Baker, E.Muller, P.Liska, N.Vlachopoulos, M.Gratzel, J.Am.Chem.Soc., the 115th volume, ruthenium complex or its quaternary salt shown in 6382 pages (1993), phthalocyanine, porphyrin etc., as mixing the organic dye that utilizes, can enumerate the phthalocyanine of no metal, porphyrin, perhaps cyanin, merocyanine, oxonols (oxonol), tritane system, WO2002/011213 number methyne based dye such as disclosed acrylic acid series dyestuff, perhaps xanthene system, azo system, anthraquinone is the dyestuff of perylene system etc.Under the situation of utilizing dyestuff more than 2 kinds, dyestuff can be adsorbed in semiconductor film successively, also can mixed dissolution and adsorb.
In addition, among the present invention, on the film of oxide semiconductor particulate during carried dye, in order to prevent the combination between the dyestuff, preferred carried dye in the presence of inclusion compound.As above-mentioned inclusion compound, can use cholic acid classes such as Septochol, dehydrodeoxycholic acid, gallodesoxycholic acid, Methyl cholate, Sodium cholic acid, steroid based compounds such as polyethylene oxide, cholic acid, crown ether, cyclodextrin, calixarene, polyethylene oxide etc.
In addition, behind carried dye, the compound that can have acidic-group with amine compound or acetic acid, the propionic acid etc. of 4-tert .-butylpyridine etc. etc. is handled the semi-conducting electrode surface.Treatment process for example can be used in the ethanolic soln of amine the dipping method etc. of substrate of semiconductive particles film of dyestuff that has been provided with load.
In addition, the invention provides to comprise that above-mentioned dye sensitization photo-electric conversion element is the dye sensitization solar battery of feature, except having utilized load, use has the dye-sensitized photoelectric conversion device of oxide semiconductor particulate of the dyestuff shown in the above-mentioned Chemical formula 1, can certainly use usual method that in the past used photo-electric conversion element to make solar cell etc., as concrete example, the photo-electric conversion element electrode (negative electrode) of the dyestuff shown in the Chemical formula 1 can be arranged by load on the oxide semiconductor particulate, counter electrode (anode), redox electrolytes matter, formations such as hole transporting material or p-type semi-conductor.
As the example of the concrete manufacture method of dye sensitization solar battery of the present invention, preferably make as follows: in the step of conductive clear substrate coating titanium oxide paste; Burn till the substrate that is coated with paste and the step that forms thin film of titanium oxide; The substrate that will be formed with thin film of titanium oxide is immersed in the mixing solutions that is dissolved with the dyestuff shown in the Chemical formula 1, forms the step of the oxidation titanium film electrode that is adsorbed with dyestuff; The step of second glass substrate that is formed with counter electrode is set at an upper portion thereof; Form the step in the hole (hole) that connects second glass substrate and counter electrode; Between above-mentioned counter electrode and the above-mentioned oxidation titanium film electrode that is adsorbed with dyestuff, the thermal plastic high polymer film is set, and implements hot pressing process, thereby make the step of above-mentioned counter electrode and oxidation titanium film electrode engagement; Inject electrolytical step by above-mentioned hole to the thermal plastic high polymer film between above-mentioned counter electrode and the oxidation titanium film electrode; And the step that seals with above-mentioned thermal plastic high polymer.
The form of above-mentioned redox electrolytes matter, hole transporting material, p-type semi-conductor etc. can be enumerated liquid, congealed solid (gel and gel phase), solid etc.As liquid state, can enumerate respectively with redox electrolytes matter, melting salt, hole transporting material, p-type semi-conductor etc. be dissolved in respectively in the solvent or normal temperature melting salt etc., under the situation of congealed solid (gel and gel phase), can enumerate respectively make they be included in polymeric matrix or the low molecule jelling agent etc. etc.As solid, can use redox electrolytes matter, melting salt, hole transporting material, p-type semi-conductor etc.
As hole transporting material, can use and utilize electroconductive polymers such as sulfonamide derivatives or polyacetylene, polyaniline, Polythiophene, the material of the discotic mesogenic phase of triphenylene based compound etc.In addition, can use CuI, CuSCN etc. as the p-type semi-conductor.As counter electrode, preferably have electroconductibility and the reduction reaction of redox electrolytes matter is played katalysis.For example, can use on glass or polymeric membrane evaporation platinum, carbon, rhodium, ruthenium etc. perhaps are coated with the counter electrode of electrically conductive microparticle.
As the redox electrolytes matter that is used in solar cell of the present invention, can use the halogen reducto oxydative system ionogen that halide-ions is formed as halogen compounds and the halogenic molecule of counter ion, the burning reduction of metal complex such as Ferrocyanide salt-Ferrocyanide salt or ferrocene-ferricinium ion, cobalt complex etc. is that organic oxidation reduction such as ionogen, alkyl sulfhydryl-alkyl disulfide, viologen dyestuff, quinhydrones-quinone are ionogen etc., preferred halogen reducto oxydative system ionogen.As the preferred iodine molecule of halogenic molecule in the halogen reducto oxydative system ionogen of being formed by halogen compounds-halogenic molecule.In addition, as halide-ions can be used LiI, NaI, KI, CaI as the halogen compounds of counter ion
2, MgI
2, metal halide salt such as CuI, the perhaps organic ammonium salt of halogens such as tetraalkyl ammonium iodide, imidazoles iodine, pyridine iodine, perhaps I
2
In addition, when redox electrolytes matter was existed by the form of the solution that comprises it, this solvent can use the solvent that has inertia on the electrochemistry.As object lesson, can enumerate acetonitrile, Texacar PC, ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile, ethylene glycol, propylene glycol, Diethylene Glycol, triethylene glycol, butyrolactone, glycol dimethyl ether, methylcarbonate, 1,3-dioxolane, methyl-formiate, 2-methyltetrahydrofuran, 3-methoxyl group-oxazolidines-2-ketone, tetramethylene sulfone, tetrahydrofuran (THF), water etc., preferred especially acetonitrile, Texacar PC, ethylene carbonate, 3-methoxypropionitrile, ethylene glycol, 3-methoxyl group-oxazolidines-2-ketone, butyrolactone etc.Above-mentioned solvent can use a kind or mixing use.Under the situation of gel phase positive electrolyte, can use the material that in the matrix of oligopolymer, polymkeric substance etc., contains ionogen or electrolyte solution, perhaps in low molecule jelling agent etc., contain the material of ionogen or electrolyte solution equally.The concentration of redox electrolytes matter is preferably 0.01-99 weight %, more preferably 0.1-30 weight %.
Solar cell of the present invention can have the photo-electric conversion element (negative electrode) of dyestuff upward to dispose counter electrode (anode) in mode opposed with it by the oxide semiconductor on substrate is particle loaded, and filling contains the solution of redox electrolytes matter and obtains in the middle of their.
Below, in order to help to understand the present invention, disclose preferred embodiment, but following embodiment only being used for illustration the present invention, scope of the present invention is not limited to these following embodiment.
[embodiment]
Be to carry out in argon atmospher with the synthetic relevant reaction of dyestuff, solvent uses the reagent of buying from Sigma's aldrich (Sigma-Adrich) company that is fit to distill.
Synthesizing of embodiment 1 dyestuff
According to the reaction as the reaction formula 1 of following record, make ruthenium based dye compound 4.
[reaction formula 1]
(1) manufacturing of compound 1
With 4,4'-two bromo-2, (20g 63.70mmol) is dissolved among the THF300ml 2'-dipyridyl, and (56.06ml2.5M is in hexane slowly to drip n-Butyl Lithium down at-78 ℃ then, 140mmol), stir after 30 minutes, put into DMF (10.24g, 140.14mmol), under the nitrogen state, in 25 ℃, stirred 6 hours.After stirring end, extract the back with ether 300ml and use the water extraction organic layer, and under chloroform/methanol (1/10), separate by recrystallization.
(2) manufacturing of compound 2
With thieno-[3,2-b] thiophene (10g, 71.31mmol) be dissolved among the THF200ml, (28.52ml2.5M 71.31mmol), stirs after 30 minutes in hexane slowly to drip n-Butyl Lithium down at-78 ℃ then, put into 9-bromine heptadecane (9-bromoheptadecane) (22.77g, 71.31mmol), under the nitrogen state, in 25 ℃, stirred 6 hours.After stir finishing, extract the back with chloroform 200ml and use the water extraction organic layer, carry out column purification and (behind chloroform/hexane=1:1), under chloroform/methanol (1/20), separate by recrystallization.
(3) manufacturing of compound 3
With 2,2'-dipyridyl-4,4'-dicarbaldehyde (15g, 70.69mmol), 2-(heptadecane-9-yl) thieno-[3,2-b] thiophene (26.77g, 70.69mmol) and Trimethylamine 99 (0.42g, 7.07mmol) be dissolved among the acetic anhydride 100ml, under (reflux) condition of backflow, stir then.After stirring end, extract the back with chloroform 300ml and use the water extraction organic layer, and under chloroform/methanol (1/10), separate by recrystallization.
(4) manufacturing of compound 4
Utilize the compound 3 of above-mentioned manufacturing, according to existing document (Chem.Mater.2006,18, synthetic method 5604-5608) is with above-mentioned reaction formula 1 synthetic No. 5 compounds similarly.
Synthesizing of embodiment 2 dyestuffs
According to the reaction as the reaction formula 2 of following record, make ruthenium based dye compound 7.
[reaction formula 2]
(1) manufacturing of compound 5
In the manufacture method of the compound 2 of above-described embodiment 1, replace thieno-[3,2-b] thiophene, utilize thiophene, and synthetic compound 5.
(2) manufacturing of compound 6
In the manufacture method of the compound 3 of above-described embodiment 1, replace 2-(heptadecane-9-yl) thieno-[3,2-b] thiophene, utilize compound 5, and synthetic compound 6.
(3) manufacturing of compound 7
In the manufacture method of the compound 4 of above-described embodiment 1, replace compound 3, utilize compound 6 and synthesize.
Synthesizing of embodiment 3 dyestuffs
According to the reaction as the reaction formula 3 of following record, make ruthenium based dye compound 10.
[reaction formula 3]
(1) manufacturing of compound 8-1
In the manufacture method of the compound 2 of above-described embodiment 1, replace thieno-[3,2-b] thiophene, utilize compound 8, and synthetic compound 8-1.
(2) manufacturing of compound 9
In the manufacture method of the compound 3 of above-described embodiment 1, replace 2-(heptadecane-9-yl) thieno-[3,2-b] thiophene, utilize compound 8-1, and synthetic compound 9.
(3) manufacturing of compound 10
In the manufacture method of the compound 4 of above-described embodiment 1, replace compound 3, utilize compound 9 and synthesize.
Embodiment 4: the physical property measurement of the dyestuff of manufacturing
The absorption spectrum of the dye composition of the present invention of manufacturing in above-described embodiment 1 is shown in following table 1 and Fig. 1.Dyestuff has used to be used as the N719 of the dyestuff of dye sensitization solar battery in the past as a comparison.
Table 1
| ? | λ max(nm) | ε(M -1cm -1) | λ edge(nm) | HOMO(eV) | LUMO(eV) |
| Embodiment 1 | 609 | 11700 | 840 | -5.55 | -3.95 |
| N719 | 515 | 14000 | 731 | -5.50 | -3.80 |
By above-mentioned table 1 and Fig. 1 result as can be known, the dye composition of making among the embodiment 1 of the present invention shows compares obviously high absorbancy with comparative dye, thereby predicts the efficient that can improve solar cell
Though be not recorded in above-mentioned table 1, the dye composition of making among the embodiment 2 and 3 of the present invention also show with above-described embodiment 1 in the absorbancy of the dye composition equity made.
Embodiment 5: the manufacturing of dye sensitization solar battery and physical property measurement
In order to estimate the I-E characteristic of dye composition, utilize TiO
2Transparent layer like that, is made the different solar cell of thickness shown in following table 2 and Fig. 2 to 3.With TiO
2Paste (Solaronix, 13nm paste) carries out silk screen printing and makes TiO
2Transparent layer is with this TiO
2Film 40mM TiCl
4Solution is handled, and drying is 30 minutes under 500 ℃.After treated film is cooled to 60 ℃, the dye composition of making in above-described embodiment 1 of the present invention contained be dipped in the dimethyl formamide solution.(Reference) in contrast used the ethanolic soln of N719.Be adsorbed with the TiO of dyestuff
2Between electrode and the platinum-counter electrode, put into high-temperature fusion film (Surlyn1702, the thickness of 25 μ m) and heating, thus the sandwich cell (sandwich cell) of assembling sealing.As electrolyte solution, used the 3-hexyl-1 of dissolving 0.6M in acetonitrile, the electrolyte solution that the tert .-butylpyridine of the iodine of 2-dimethyl iodate imidazoles, 0.04M, the GSCn of 0.025M and 0.28M forms.Do not carry out the coating of scattering layer (Scattering layer) and AR.
The photoelectrochemical property (photoelectrochemical characteristics) of the solar cell of making using dye composition of the present invention and N719 is measured, and it is shown in Fig. 2 (embodiment 1) to 3 (N719) and following table 2.The photoelectrochemical property of solar cell utilizes Keithley M236 source measuring apparatus to measure, and as light source, has utilized the 300W Xe lamp that possesses AM1.5 spectral filter (Oriel), and to make electrode size be 0.4 * 0.4cm
2, making light intensity is 1sun (100mW/cm
2).Light intensity utilizes the Si solar cell to regulate.
Table 2
In the above-mentioned table 2, Jsc represents short-circuit photocurrent density (short-circuit photocurrent density), the Voc photovoltage (open circuit photovoltage) of representing to open a way, and FF represents packing factor (fill factor).
Shown in above-mentioned table 2 and Fig. 2 to 3, can confirm dye composition of the present invention shows than the very high photoelectric transformation efficiency of N719, though be not recorded in table 2, but the dye composition of making in embodiment 2 and 3 also shows the photoelectric transformation efficiency with embodiment 1 equity, confirm thus, can effectively be used as the dye composition of dye sensitization solar battery.
Applicability on the industry
Novel ruthenium based dye of the present invention shows the photoelectric transformation efficiency that significantly improves than dyestuff in the past, make with the bonding force of oxide semiconductor particulate and strengthen, and short-circuit photocurrent density (short circuit photocurrent density, Jsc) and the molar absorptivity excellence, thus can improve the efficient of solar cell greatly.
Claims (7)
1. the dyestuff shown in the following Chemical formula 1:
Chemical formula 1
In the above-mentioned Chemical formula 1, Me is Ru or Os, and a1 ring can not have substituting group independently of one another or have substituting group more than 1, as substituting group, can be halogen atom, amide group, cyano group, hydroxyl, nitro, acyl group, C
1-30Alkyl or C
1-30Alkoxyl group, Y are hydrogen, Na or trimethyl carbinol TBA, in addition, and X
1, X
2Be the compound shown in methyl or the following Chemical formula 2 independently of one another, X
1And X
2In at least one be the compound shown in the Chemical formula 2,
Chemical formula 2
In the above-mentioned Chemical formula 2, A be selected from by
With
In the group of forming more than a kind, at this moment, X is selected from independently of one another by O, S, Se, Si and NR
5In the group of forming, R
1To R
4Be selected from the C by hydrogen, replacement or non-replacement independently of one another
1-12The C of alkyl, replacement or non-replacement
6-30The C of aryl and replacement or non-replacement
6-20In the group that heteroaryl is formed, perhaps can be connected to each other and form ring, R
5C for hydrogen or replacement or non-replacement
1-30Alkyl, n are 1 to 10 integer, and B is the compound shown in the compound shown in the following chemical formula 3 or the following chemical formula 4,
Chemical formula 3
Chemical formula 4
In the above-mentioned chemical formula 3, Ar
1, Ar
2And Ar
3Be selected from the C by replacement or non-replacement independently of one another
6-50The C of aryl, replacement or non-replacement
6-20In the group that heteroaryl is formed, perhaps can be connected to each other and form ring, * is bound fraction, in the above-mentioned chemical formula 4, and R
6And R
7Be the C of replacement or non-replacement independently of one another
1-30Alkyl, * are bound fraction.
2. ruthenium Ru based dye according to claim 1, wherein, what described dyestuff was following Chemical formula 1-1 to the compound shown in the 1-48 is a kind of:
Chemical formula 1-1
Chemical formula 1-2
Chemical formula 1-3
Chemical formula 1-4
Chemical formula 1-5
Chemical formula 1-6
Chemical formula 1-7
Chemical formula 1-8
Chemical formula 1-9
Chemical formula 1-10
Chemical formula 1-11
Chemical formula 1-12
Chemical formula 1-13
Chemical formula 1-14
Chemical formula 1-15
Chemical formula 1-16
Chemical formula 1-17
Chemical formula 1-18
Chemical formula 1-19
Chemical formula 1-20
Chemical formula 1-21
Chemical formula 1-22
Chemical formula 1-23
Chemical formula 1-24
Chemical formula 1-25
Chemical formula 1-26
Chemical formula 1-27
Chemical formula 1-28
Chemical formula 1-29
Chemical formula 1-30
Chemical formula 1-31
Chemical formula 1-32
Chemical formula 1-33
Chemical formula 1-34
Chemical formula 1-35
Chemical formula 1-36
Chemical formula 1-37
Chemical formula 1-38
Chemical formula 1-39
Chemical formula 1-40
Chemical formula 1-41
Chemical formula 1-42
Chemical formula 1-43
Chemical formula 1-44
Chemical formula 1-45
Chemical formula 1-46
Chemical formula 1-47
Chemical formula 1-48
3. the manufacture method of the dyestuff shown in the Chemical formula 1 is characterized in that, the compound that makes following chemical formula 5 reacts with the compound of following chemical formula 6, chemical formula 7 and chemical formula 8 successively:
Chemical formula 5
Chemical formula 6
[RuCl
2(p-cymene)]
2
Chemical formula 7
Chemical formula 8
NH
4NCS
In the above-mentioned chemical formula 5,6,7 and 8, X
1, X
2Identical with the definition in the claim 1 with the definition of a1.
4. a dye-sensitized photoelectric conversion device is characterized in that, comprises the have the right oxide semiconductor particulate of requirement 1 described dyestuff of load.
5. dye-sensitized photoelectric conversion device according to claim 4 is characterized in that, described dye-sensitized photoelectric conversion device is to make dye load in the oxide semiconductor particulate in the presence of inclusion compound.
6. dye-sensitized photoelectric conversion device according to claim 4 is characterized in that, it is that the titanium dioxide of 1-500nm is as neccessary composition that described oxide semiconductor particulate comprises median size.
7. a dye sensitization solar battery is characterized in that, comprises the described dye-sensitized photoelectric conversion device of claim 4.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2010-0107418 | 2010-11-01 | ||
| KR20100107418 | 2010-11-01 | ||
| PCT/KR2011/008175 WO2012060587A2 (en) | 2010-11-01 | 2011-10-31 | Novel ruthenium-based dye and preparation method thereof |
| KR10-2011-0111744 | 2011-10-31 | ||
| KR1020110111744A KR101940491B1 (en) | 2010-11-01 | 2011-10-31 | A NOBLE Ru-TYPE SENSITIZERS AND METHOD FOR PREPARING OF IT |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103189452A true CN103189452A (en) | 2013-07-03 |
Family
ID=46265392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800526100A Pending CN103189452A (en) | 2010-11-01 | 2011-10-31 | Novel ruthenium-based dye and method for producing same |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR101940491B1 (en) |
| CN (1) | CN103189452A (en) |
| TW (1) | TW201237115A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016032266A1 (en) * | 2014-08-28 | 2016-03-03 | 주식회사 동진쎄미켐 | Novel ruthenium-based dye and method for preparing same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19815161A1 (en) | 1998-03-27 | 1999-10-07 | Hahn Meitner Inst Berlin Gmbh | Photosensitizer for solar technology applications, process for its production and arrangement for carrying out the process |
| JP2002105346A (en) * | 2000-07-25 | 2002-04-10 | Fuji Photo Film Co Ltd | Metal complex dye, photoelectric conversion element and photocell |
| EP1178084A1 (en) * | 2000-07-31 | 2002-02-06 | Neomat S.A. | Processes for the preparation of carboxylate and phosphonate ruthenium polypyridine dyes and intermediates |
| KR100996236B1 (en) * | 2007-02-12 | 2010-11-23 | 주식회사 동진쎄미켐 | A NOBLE Ru-TYPE SENSITIZERS AND METHOD FOR PREPARING OF IT |
| KR101472308B1 (en) * | 2007-02-21 | 2014-12-15 | 주식회사 동진쎄미켐 | A NOBLE Ru-TYPE SENSITIZERS AND METHOD FOR PREPARING OF IT |
| CN101910322A (en) * | 2007-12-26 | 2010-12-08 | 株式会社东进世美肯 | Novel Ru-type sensitizers and method for the production thereof |
| KR20100128096A (en) * | 2009-05-27 | 2010-12-07 | 주식회사 동진쎄미켐 | Novel ruthenium-based dye and preparation thereof |
| KR20100136931A (en) * | 2009-06-19 | 2010-12-29 | 주식회사 동진쎄미켐 | Novel organic dye and preparation thereof |
-
2011
- 2011-10-31 CN CN2011800526100A patent/CN103189452A/en active Pending
- 2011-10-31 KR KR1020110111744A patent/KR101940491B1/en active IP Right Grant
- 2011-11-01 TW TW100139774A patent/TW201237115A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| KR101940491B1 (en) | 2019-01-21 |
| KR20120046071A (en) | 2012-05-09 |
| TW201237115A (en) | 2012-09-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Seo et al. | Coumarin dyes containing low-band-gap chromophores for dye-sensitised solar cells | |
| Hsieh et al. | Synthesis and characterization of porphyrin sensitizers with various electron-donating substituents for highly efficient dye-sensitized solar cells | |
| Seo et al. | Novel D–A–π–A coumarin dyes containing low band-gap chromophores for dye-sensitised solar cells | |
| KR101352024B1 (en) | Novel thiophene-based dye and preparation thereof | |
| KR100969675B1 (en) | Novel organic dye containing n-arylcarbazole moiety and preparation thereof | |
| CN102803394A (en) | Novel organic dye and method for producing same | |
| CN101679762B (en) | Novel organic dye and preparation method thereof | |
| JP5623396B2 (en) | Novel organic dye compound and method for producing the same | |
| CN102245710B (en) | Novel organic dye containing benzothiadiazole chromophore and preparation method thereof | |
| CN101910322A (en) | Novel Ru-type sensitizers and method for the production thereof | |
| CN101616998B (en) | Noble metal ruthenium type sensitizing agent and preparation method thereof | |
| JP4338981B2 (en) | Dye-sensitized photoelectric conversion element | |
| Mandal et al. | Metal-free bipolar/octupolar organic dyes for DSSC application: A combined experimental and theoretical approach | |
| CN105705586B (en) | Organic dyestuff for dye-sensitized solar cells | |
| Lyons et al. | Silicon-bridged triphenylamine-based organic dyes for efficient dye-sensitised solar cells | |
| JP4274306B2 (en) | Dye-sensitized photoelectric conversion element | |
| JP4230228B2 (en) | Dye-sensitized photoelectric conversion element | |
| Chang et al. | Bistriphenylamine-based organic sensitizers with high molar extinction coefficients for dye-sensitized solar cells | |
| JP4822383B2 (en) | Dye-sensitized photoelectric conversion element | |
| CN102245711A (en) | Novel organic dye containing trialkoxysilyl group and method for producing same | |
| KR100969676B1 (en) | Novel julolidine-based dye and preparation thereof | |
| CN104487522B (en) | Organic dyestuff for DSSC | |
| CN103189452A (en) | Novel ruthenium-based dye and method for producing same | |
| CN101663360A (en) | Noble metal ruthenium type sensitizing agent and preparation method thereof | |
| CN102498176B (en) | Organic dye and method for producing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130703 |