WO2010049042A2 - A dye comprising a chromophore to which an acyloin group is attached - Google Patents
A dye comprising a chromophore to which an acyloin group is attached Download PDFInfo
- Publication number
- WO2010049042A2 WO2010049042A2 PCT/EP2009/006888 EP2009006888W WO2010049042A2 WO 2010049042 A2 WO2010049042 A2 WO 2010049042A2 EP 2009006888 W EP2009006888 W EP 2009006888W WO 2010049042 A2 WO2010049042 A2 WO 2010049042A2
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- WO
- WIPO (PCT)
- Prior art keywords
- formula
- dye
- represented
- chromophore
- group
- Prior art date
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- MWKAGZWJHCTVJY-UHFFFAOYSA-N 3-hydroxyoctadecan-2-one Chemical group CCCCCCCCCCCCCCCC(O)C(C)=O MWKAGZWJHCTVJY-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 46
- 239000004065 semiconductor Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 25
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 22
- 239000003446 ligand Substances 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 230000001699 photocatalysis Effects 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 235000010290 biphenyl Nutrition 0.000 claims description 11
- 239000004305 biphenyl Substances 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 229910052740 iodine Inorganic materials 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium dioxide Chemical compound O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 claims description 4
- 150000004696 coordination complex Chemical class 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 3
- 230000005670 electromagnetic radiation Effects 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 150000002902 organometallic compounds Chemical class 0.000 claims description 3
- 239000002957 persistent organic pollutant Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910018572 CuAlO2 Inorganic materials 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910002370 SrTiO3 Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 125000002950 monocyclic group Chemical group 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 2
- 125000003367 polycyclic group Chemical group 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 16
- 238000003786 synthesis reaction Methods 0.000 abstract description 16
- 238000004873 anchoring Methods 0.000 abstract description 12
- 239000000975 dye Substances 0.000 description 182
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- 239000003480 eluent Substances 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 0 CC(C)(*)C(*1)=CC=C1C(C)(C)C(C(C1=O)=*)=C1O Chemical compound CC(C)(*)C(*1)=CC=C1C(C)(C)C(C(C1=O)=*)=C1O 0.000 description 5
- 239000001044 red dye Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229940093499 ethyl acetate Drugs 0.000 description 4
- 235000019439 ethyl acetate Nutrition 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000003306 harvesting Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001443 photoexcitation Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241001125929 Trisopterus luscus Species 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006378 damage Effects 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
- 229960003964 deoxycholic acid Drugs 0.000 description 1
- 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 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- OKKJLVBELUTLKV-VMNATFBRSA-N methanol-d1 Chemical compound [2H]OC OKKJLVBELUTLKV-VMNATFBRSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000004424 polypyridyl Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- -1 propoxy, iso-propoxy Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004984 smart glass Substances 0.000 description 1
- OGJKMZVUJJYWKO-CYBMUJFWSA-N stepharine Chemical compound C([C@H]1NCCC=2C=C(C(=C3C=21)OC)OC)C13C=CC(=O)C=C1 OGJKMZVUJJYWKO-CYBMUJFWSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- ARYHTUPFQTUBBG-UHFFFAOYSA-N thiophen-2-ylboronic acid Chemical compound OB(O)C1=CC=CS1 ARYHTUPFQTUBBG-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
-
- 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
-
- 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
- C09B57/007—Squaraine dyes
-
- 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
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/78—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with other reactive groups
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/652—Cyanine dyes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- a dye comprising a chromophore to which an acyloin group is attached
- the present invention relates to a dye comprising a chromophore to which an acyloin group is attached, to a method of synthesis of such dye, to an electronic device comprising such dye and to the use of such dye.
- the dye-sensitised solar cell (B. O'Regan and M. Gratzel, Nature 353 (1991) 737; WO 91/16719 [A]) is a photovoltaic device that offers high energy-conversion efficiencies at low cost.
- DSSC dye-sensitised solar cell
- these functions are separated.
- Light is absorbed by a sensitizer dye which is anchored to the surface of a semiconductor such as nanocrystalline TiO 2 .
- the charge separation takes place at the interface via photo-induced electron injection from the dye into the conduction band of the semiconductor.
- the dye molecule is regenerated from a counter electrode via a redox couple in the electrolyte.
- the redox couple is regenerated in turn at the counter-electrode the circuit being completed by electron transport through the external load.
- the efficiency of a DSSC is determined by the number of collected and injected photons, and thus by the light absorbed by the dye sensitizer.
- One of the main criteria of a dye to act as efficient sensitizer in DSSC is its adsorbtion (by chemisorption) onto the semiconductor surface. Further, for high efficiencies, the ideal sensitizer should absorb efficiently over a broad range of solar spectrum.
- the dye Upon photo-excitation the dye should inject electrons into the conduction band of the semiconductor with a quantum yield of unity. To minimize energy losses during electron transfer, the energy level of its excited state should be well matched with the lower bound of the conduction band of the semiconductor. Its redox potential should be well matched with that of the redox couple so that the dye regeneration via electron donation is possible.
- the photoexcited electrons located in the bipyridyl ligands can be very efficiently injected in the conduction band of the semiconductor via the carboxyl-anchor groups. This process has been shown to be very fast. [Y. Tachibana, J. E. Moser, M. Gratzel, D.R. Klug, J.R. Durrant, J. Phys. Chem. 1996, 100, 20056]
- the recombination process between the injected electrons in TiO 2 and the dye-cations is a slow process.
- the slow recombination is considered to be a result of the large separation between semiconductor and the Ru 3+ by the bipyridyl ligands.
- the molecular design of these Ru-complexes is successful in an efficient charge separation and thus, high energy conversion efficiency.
- the energy conversion efficiency of the DSSC is limited by the light-harvesting capacity of these Ru-dyes to absorb the sunlight.
- the photo-active region of the photovoltaic device is reduced to the visible part of the solar spectrum, and within that, to the shorter wavelength region. The photons of the longer wavelength region are not harvested and cannot be converted to electrical energy.
- Adsorption and charge injection could be further demonstrated with other anchoring groups like sulfonic acid, hydroxyl, triethoxysilane, catechol group and boronic acid, but no solar cells with significant efficiency of DSSC could be achieved with dyes having such anchoring groups (a) Gratzel et al, New. J. Chem., 2000, 24, 651-652; b) Ford et al., J. Phys. Chem. B, 1994, 98, 3822; c) Lavicmiri et al., J. Photochem. Photobiol., A, 2004, 166, 91.).
- Nanoporous semiconductors such as TiO 2
- TiO 2 are key components in the process of hetere- genous photocatalysis applied in the field of photocatalytic hydrogen production or photolytic water purification (Arakawa et al., J.Photochem.Photobiol. A, 2000, 63-69; b) Chanon, Eds. Elsevier, Photoinduced Electron Transfer, 1988).
- Most photocatalysts, such as nanoiporous TiO 2 are active under UV irradiation, and their inactivity in the visible light region (solar light) limits their practical application.
- One of the strategies to overcome this is the anchoring of charge transfer dyes to the surface of the wide band gap semiconductor rendering them sensitive to visible sun light.
- the dyes are generally linked to the semiconductor through a carboxylate linkages via a ester linkage.
- This linkage is quite unstable in water which is the environment in such processes.
- anchoring groups for attaching dyes on the semiconductor surfaces.
- an object of the present invention to provide for improved dyes with intense absorption in the visible and long wavelength region of the solar spectrum. It was another object of the present invention to provide for dyes which can be easily covalently attached to nanocrystalline wide band gap semiconductors, such as TiO 2 , SnO 2 etc. It was furthermore an object of the present invention to provide for dyes that allow an efficient charge transfer from the dye to the semiconductor. It was furthermore an object of the present invention to provide for dyes that are easily accessible due simple methods of preparation.
- a dye comprising a chromophore to which an acyloin group is attached, said dye being represented by formula Ia or Ib:
- said chromophore is an organic or metal-organic compound absorbing electromagnetic radiation in the range from 300-1200 nm, or a subrange thereof, preferably 350-500 nm or 500-750 nm or 350-700 nm, wherein A is selected from H, or any cyclic or acyclic alkyl, or any straight or branched chain moiety of general formula -(CH 2 )M-R, -[(C ⁇ C) nl -(CH 2 ) n2 ] p -R, - [(CH 2 ) nl -X O 2 Jp-R, or halogen, such as F, Cl, Br, I, or moieties containing heteroatoms, such as NO 2 , CN, NR 2 , -OH or any substituted or non-substituted phenyl or biphenyl or heteroaryl, or moieties forming a ring structure with said acyloin group, wherein, at each occurrence and
- the dye according to the present invention comprises a chromophore to which an acyloin group is attached, said dye being represented by formula 2a, 2b, 2c, 2d, 2e, 2f, 2g, 2h, 2i, or 2j
- A, X, nl, n2, n, p are as defined above, and wherein Y, at each occurrence, is independently selected from -CR 2 , O, S, NR, -CR, R being as defined above.
- the dye according to the present invention is represented by formula 2d, 2e, 2f, or 2h
- said chromophore is selected from the moieties shown in formula 3
- any combination of the moieties represented by formula 3, wherein said chromophore is linked to said acycloin group by any of the C-atoms or X or Y or R within said chromophore, wherein Z is one or more moieties which, at each occurrence, is independently selected from H, or any cyclic or acyclic alkyl, or any straight or branched chain moiety of general formula ⁇ (CH 2 ) nl -R, -[(CR CR) nl -(CH 2 ) n2 ] p -R, -[(C ⁇ C) nl -(CH ⁇ J p -R, -[(CH 2 ) nl -X n2 ] p -R, or halogen, such as F, Cl, Br, I, or moieties containing heteroatoms, such as NO 2 , CN, NR 2 , -OH or any substituted or non-substituted phenyl
- the dye according to the present invention is represented by formula 5
- the dye according to the present invention is represented by formula 6
- the dye according to the present invention is represented by formula 7
- said chromophore is a metal complex selected from the structures represented by formula 14
- M being Ruthenium Ru, Osmium Os, or Iridium Ir, preferably Ruthenium,
- Hal being independently selected from Cl, Br, I, CN, -NCS, preferably -NCS with n3, n4, n5 being integers which, at each occurrence, are independently 0-4, preferably 2 or 3,
- L and L' being organic heterocyclic ligands containing nitrogen atoms which are linked by N-atoms to the respective metal M, and wherein either one of L and L', or both L and L' are linked to the acyloin group by any of the C-atoms within said ligands.
- said ligands L and I/ are independently, at each occurrence, mono- or polycyclic, condensed rings or such rings covalently bonded to each other.
- said ligands L and L' are independently, at each occurrence, selected from the group comprising
- said chromophore is a metal complex represented by formula 16 (L"UM' (formula 16)
- M' Palladium Pd, Platinum Pt or Nickel Ni, preferably Pd, and n6 being an integer 0-4, preferably 1 -2, and L" being an organic heterocyclic ligand containing nitrogen atoms, said ligand being linked by one or several of said N-atoms to the respective metal M', and said ligand being linked to said acycloin group by any of the C-atoms within said ligand.
- said ligand L" is selected from the group comprising
- the device according to the present invention is a solar cell, preferably a dye-sensitized solar cell (DSSC), said solar cell further comprising a photoactive semiconductor porous material.
- DSSC dye-sensitized solar cell
- the device according to the present invention contains a charge- transporting agent which is a liquid, polymer gel based or solid state electrolyte.
- the device according to the present invention is a solar cell wherein said dye is chemisorbed to said photoactive semiconductor porous material.
- the device according to the present invention further comprises at least one other dye.
- said at least one other dye is a dye according to the present invention.
- said at least one other dye is a dye selected from structures 15, 27-32:
- said photoactive semiconductor porous material is selected from TiO 2 , SnO 2 , ZnO, Nb 2 O 5 , ZrO 2 , CeO 2 , WO 3 , Cr 2 O 3 , CrO 2 , CrO 3 , SiO 2 , Fe 2 O 3 , CuO, Al 2 O 3 , CuAlO 2 , SrTiO 3, SrCu 2 O 2 , ZrTiO 4 , preferably TiO 2 , and combinations of the foregoing.
- said photoactive semiconductor porous material has one or several of the following features:
- - contains particles having an average diameter or length in the range of from 1 run to 40 run, preferably 15-30 nm
- first kind of particles having an average diameter or length in the range of from 1 nm to 30 nm
- second kind of particles having an average diameter in the range of from 30 nm to 100 nm and/or a length in the range of from 100 nm to 5 ⁇ m.
- the objects of the present invention are also solved by the use of a dye according to the present invention as a sensitizer in a dye-sensitized solar cell.
- said use is together with at least one other dye.
- said at least one other dye is a dye as defined above, or a dye selected from structures 15, 27-32:
- said use together with at least one other dye is in a dye-sensitized solar cell having a tandem geometry (as, e.g., described in Example 9 below), or the mixture of a dye in accordance with the present invention and at least one other dye is used for coating an electrode of said dye-sensitized solar cell.
- a dye according to the present invention as a photosensitzer in a photocatalytic process, such as photocatalysed hydrogen production or photocatalytic degradation of organic pollutants. It should be noted that any photocatalytic process may be useful in the context of the present invention.
- the dye molecules are adsorbed to the nanoporous particles via self-assembling out of a dye solution or a dyes-mixture solution.
- electronic devices comprising a dye in accordance with the present invention include energy supply devices for portable electronic devices and displays, such as solar cell panels for or incorporated in mobile phones, notebooks, laptops, portable audio-tape players, MP3-players, remote controls, e-cards, e-books, e-readers, portable CD-players, portable DVD-players, cameras, digicams, GPS devices, portable sensors, displays integrated in electronic devices.
- Examples of electronic devices in accordance with the present invention also include portable solar chargers for batteries of any of the afore-mentioned devices.
- electronic devices in accordance with the present invention include smart windows, on-roof- applications, especially in areas where a grid connection is not possible, e.g. camping cars, boats.
- the electronic device in accordance with the present invention is an energy supply device, and said energy supply device is a solar cell panel, such panel is preferably a dye- sensitized solar cell panel (DSSC panel) (see also figure 21).
- DSSC panel dye- sensitized solar cell panel
- the objects of the present invention are also solved by the use of a dye according to the present invention, for the sensitization of the photocatalyst, such as TiO 2 , in photocatalytic processes, e.g in photocatalysed hydrogen production , photocatalytic splitting of water or photo- catalytic decomposition of pollutants..
- a dye according to the present invention for the sensitization of the photocatalyst, such as TiO 2 , in photocatalytic processes, e.g in photocatalysed hydrogen production , photocatalytic splitting of water or photo- catalytic decomposition of pollutants.
- chromophore As used herein, the term “dye” is meant to refer to a chromophore to which an acyloin group is attached.
- chromophore as used herein, is meant to refer to an organic or metal- organic compound which is able to absorb electromagnetic radiation in the range of from 350 nra to 1100 nm, or a subrange thereof, e.g 350-500 nm or 500-850 run, or 350-850 nm.
- An acyloin group is the moiety which is included in the structure of the dyes according to present invention and is represented by formula 18
- anchoring group is meant to refer to any functional group that allows a covalent coupling (chemisorption) of the entity to which such anchoring group belongs, to a surface, for example the surface of a nanoporous semiconductor layer within a solar cell.
- a dye is referred to as being "chemisorbed” to a layer or surface, if the dye is covalently coupled thereto.
- formula 3 which exemplifies a "chromophore” in accordance with the present invention, the term “a combination of the moieties represented by formula 3" is used. This is meant to encompass any molecule wherein one or several of the structures given in formula 3 are covalently linked to each other to also produce a "chromophore”.
- substituted phenyl/biphenyl is meant to refer to any phenyl/biphenyl wherein a hydrogen has been replaced by a substituent, such as a halogen, NO 2 , NH 2 , OH or other suitable functional groups.
- substituents have for example been defined above as Z, which substituents may also be substitutents at a phenyl or biphenyl.
- the inventors have surprisingly found that using acyloin groups as anchoring groups for a dye allows an efficient covalent attachment of such dye to nanoporous surfaces of photoactive layers, such as TiO 2 -layers.
- the dyes having the acyloin group attached as anchoring group can be used as sensitizers in solar cells but also for sensitizing the photocatalyst which are mosly wide band gap oxide semiconductors such as TiO 2 , to extend the photocatalytic activity of the photocatalysts into the visible light region. This is particular important for example in the field of heterogeneous photocatalysis such as photolytic hydrogen production or photo- catylytic water production or photocatalytic destruction of organic pollutants.
- the number of dyes that can be potentially used in such applications is strongly increased.
- the synthesis of such dyes is surprisingly simple.
- the dyes according to the present invention show high quantum efficiency similar to that of the standard red-dye. If one therefore combines the dyes of the present invention with other dyes, such as other organic dyes or standard red dye or standard black dye, a broad range of the solar spectrum may be harvested. That makes the dyes of the present invention very promising to be used together with other dyes, such as organic dyes, standard red dye or standard black dye or further dyes according to the present invention with absorption maxima at different wavelengths.
- a dye sensitized solar cell comprising a dye according to the present invention, and, in addition thereto, one or more further dyes, is herein also referred to as a multiple- dyes sensitized solar cell (M-DSSC).
- said one or more further dyes is also a dye according to the present invention.
- organic dyes have high absorption coefficients. This means it needs less amount of dye to absorb the same amount of light. Less amount of one dye on a surface enables the use of more dyes with different absorption properties, ideally being a mixture of dyes absorbing the whole range of the sun spectrum.
- Figure 1 shows a synthesis scheme of one example dye in accordance with the present invention being represented by general formula 2e, E being Cl or an alkoxy group, preferably eth- oxy, propoxy, iso-propoxy or butoxy, X being as defined above, chromophore being as defined above,
- Figure 2 shows a synthesis scheme of one example dye in accordance with the present invention being represented by general formula 2h, E, Y, X, n ls n 2 , p, chromophore being as defined above, Hal “ being I “ , Cl ' , Br “ , NCS “ or SCN “ ,
- Figure 3 shows a synthesis scheme of one example dye in accordance with the present invention being represented by general formula 5, E, Z, R 11 -Ri 3 , X being as defined above,
- Figure 4 shows a synthesis scheme of one example dye in accordance with the present invention being represented by general formula 9, X, Y, Z, R 1 being as defined above,
- Figure 5 shows the molecular structure of some dyes according to present invention
- Figure 6 shows the synthesis of one example dye in accordance with the present invention being represented by formula 1 ,
- Figure 7 shows the synthesis of one example dye in accordance with the present invention being represented by formula 2,
- Figure 8 shows the synthesis of one example dye in accordance with the present invention being represented by formula 5
- Figure 9 shows a photograph of the adsorption of dye in accordance with the present invention being represented by formula 1 on a TiO 2 layer
- Figure 10 shows a table indicating the performance of a dye sensitized solar cell prepared with a dye in accordance with the present invention being represented by formula 1 by measuring the efficiency of solar cells by means of sulphur lamp,
- FIG 11 shows the incident photon to current efficiency (IPCE) plotted against wavelength for a dye in accordance with the present invention being represented by formula 1 ,
- Figure 12 shows a table displaying the performance of various dye sensitized solar cells prepared with a dye in accordance with the present invention being represented by formula 1 in mixture with other dyes and in comparison to other sensitizers,
- Figure 13 shows the incident photon to current efficiency of a dye in accordance with the present invention being represented by formula 1, of a dye being represented by formula 14 (figure 15) and a mixture of these two dyes, plotted against wavelength,
- Figure 14 shows a table indicating the performance of a dye sensitized solar cell prepared with a dye in accordance with the present invention being represented by formula 1 in comparison with organic dye being represented by formula 16 (figure 15), by measuring the efficiency of solar cells by means of sun simulator,
- FIG 15 shows the structure of other sensitizers that were used for comparison and in mixture with dyes according to present invention (sensitizers 14, 15 and 16).
- Figure 16 shows structures 17-26 which are exemplary dyes in accordance with the present invention.
- Figure 17 shows exemplary structures 15, 27-32 of other dyes which can be used together with the dyes in accordance with the present invention.
- Figures 18-20 show various tables and IPCE curves showing the efficiencies of solar cells, as prepared and described in Examples 11) to 13).
- Figure 21 shows various embodiments of electronic devices in accordance with the present invention wherein energy supply devices, such as solar cell panels, preferably dye sensitized solar cell panels (DSSCs) have been incorporated.
- energy supply devices such as solar cell panels, preferably dye sensitized solar cell panels (DSSCs) have been incorporated.
- DSSCs dye sensitized solar cell panels
- dye 1 1) Synthesis of one embodiment of a dye in accordance with the present invention, in this case dye 1:
- Figure 6 shows the synthesis scheme of dye 1 in accordance with the present invention.
- Figure 7 shows the synthesis scheme of dye 2 in accordance with the present invention.
- Figure 8 shows the synthesis scheme of dye 5 in accordance with the present invention.
- UV/VIS (acetonitrile): ⁇ max 404 run.
- Figure 9 shows a photograph of the adsorption of dye 1 in accordance with the present invention on a TiO 2 layer
- the substrate with screen printed nanoporous TiO2 particles is poured and kept in a dye or dyes mixture solution for at least Ih.
- the dye molecules having the acy- loin group as anchor group are able to adsorb onto the nanoporous layer via self-assembling.
- the effective adsorption and chemisorption (covalent coupling) of the dyes with acyloin group onto semiconductor surface is proved by the stable color of the substrate even after the substrate was washed with an organic solvent.
- the DSSCs are assembled as follows: A 30-nm-thick bulk TiO 2 blocking layer is formed on FTO (approx. 100 nm on glass or flexible substrate). A 5-30 ⁇ m-thick porous layer of TiO 2 semiconductor particles of 0.1882 cm 2 active area multi-printed by screen printing on the blocking layer and sintered at 450 0 C for half an hour. Dye molecules are adsorbed to the nanoporos particles via self-assembling out of a dye-solution.
- the dye-solution consists of a single dye or single dye and an additive, such as deoxycholic acid or a mixture of dye in different ratio or a mixture of dye in different ratio and an additive.
- the porous layer is filled with liquid electrolyte containing IVI 3 " as redox couple (15 mM) by drop casting. A reflective platinum back electrode is attached with a distance of 6 ⁇ m from the porous layer.
- the quality of the cells is evaluated by means of current density (J) and voltage (V) characteristics under illumination with light from a) a sulphur lamp (IKL Celsius, Light Drive 1000) with an intensity of 100 mW cm "2 . If not otherwise stated, the results are averages over three cells. b) a sun simulator (AMI .5G YSS-150) with an intensity of 100 mW cm '2 . If not otherwise stated, the results are averages over three cells.
- Vmax - voltage at maximum power point Jm ax current at maximum power point
- IPCE incident photon to current efficiency
- Figure 11 shows the IPCE plotted verses wavelength for sensitizer 1.
- the efficiency of the DSSC prepared with sensitizer dye 1 shows high efficiency (>7%). There are only few other organic dyes, such as dye 16, showing such high performance. However, the superiority of the dyes according to present invention lies not only in the high efficiencies of the DSSCs achieved when using these dyes, but also in their simple preparation ( Figures 1-4).
- Sensitizer dye 1 shows an IPCE value of 0.9 in its maximum at ca. 490 nm. That means that the photons absorbed in this region from the sun can be converted to almost 90% to current by injection into conduction band of TiO 2 . Such a high value is rarely achieved and only with few dyes, such as the Ruthenium based standard red dye.
- the solar cells were prepared by method described in Example 6 and measured according to Example 7a.
- DSSCs prepared with the respective single sensitizer dye were prepared and measured. The performance and the efficiency of DSSCs are shown in Figure 12.
- a mixture of the dye in accordance with the present invention, in this case dye 1, with either an organic dye 14 or with a Ruthenium based dye (black dye) 15 yields an increase in short current density and thus, a drastic increase in DSSC efficiency.
- Figure 13 shows the IPCE curve of the individual dyes 1 and 14, and the IPCE curve of a 1 :1 mixture of these dyes.
- the individual dyes are photo-active in different region of the solar spectrum.
- the DSSCs were prepared by method described in Example 6 and measured according to Example 7b.
- the DSSCs were prepared by the method described in Example 6 and by using 25 ⁇ m TiO 2 layer and measured according to Example 7b. The efficiency and IPCE curve are shown in figure 18a and 18b, respectively.
- IPCE incident photon to current efficiency
- the solar cells were prepared by method described in Example 6 and measured according to Example 7b. For comparison also DSSC prepared with the respective single sensitizer dye 15 was prepared and measured. The efficiency is shown in figure 19. As can be seen, the efficiencies by using a mixture of dyes for sensitization are much higher than that using only a single dye as sensitizer. 13) Performance of solar cells prepared with a mixture of the respective dye and organic dye 14.
- the solar cells were prepared by method described in Example 6 and measured according to Example 7b. For comparison also DSSC prepared with the respective single sensitizer dye 14 was prepared and measured.
- the present invention provides for new sensitizer dyes which are useful for being employed in solar cells as well as in photocatalytic applications. They readily adsorb to nanoporous semiconductor layers and are easily manufactured.
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Abstract
The present invention relates to a dye comprising a chromophore to which an acyloin group as anchoring group is attached, to a method of synthesis of such dye, to an electronic device comprising such dye and to the use of such dye.
Description
Sony Corporation
A dye comprising a chromophore to which an acyloin group is attached
The present invention relates to a dye comprising a chromophore to which an acyloin group is attached, to a method of synthesis of such dye, to an electronic device comprising such dye and to the use of such dye.
The dye-sensitised solar cell (DSSC) (B. O'Regan and M. Gratzel, Nature 353 (1991) 737; WO 91/16719 [A]) is a photovoltaic device that offers high energy-conversion efficiencies at low cost. In contrast to the silicon-based systems, where the semiconductor assumes both the task of light absorption and charge carrier transport, in DSSCs these functions are separated. Light is absorbed by a sensitizer dye which is anchored to the surface of a semiconductor such as nanocrystalline TiO2. The charge separation takes place at the interface via photo-induced electron injection from the dye into the conduction band of the semiconductor. The dye molecule is regenerated from a counter electrode via a redox couple in the electrolyte. The redox couple is regenerated in turn at the counter-electrode the circuit being completed by electron transport through the external load.
The efficiency of a DSSC is determined by the number of collected and injected photons, and thus by the light absorbed by the dye sensitizer. One of the main criteria of a dye to act as efficient sensitizer in DSSC is its adsorbtion (by chemisorption) onto the semiconductor surface. Further, for high efficiencies, the ideal sensitizer should absorb efficiently over a broad range of solar spectrum. Upon photo-excitation the dye should inject electrons into the conduction band of the semiconductor with a quantum yield of unity. To minimize energy losses during electron transfer, the energy level of its excited state should be well matched with the lower bound of the conduction band of the semiconductor. Its redox potential should be well matched with that of the redox couple so that the dye regeneration via electron donation is possible.
The best photovoltaic performance has so far been achieved with carboxyl groups containing polypyridyl complexes of ruthenium (known as red-dye and black-dye). [ M.K. Nazeeruddin, A. Kay, I. Rodicio, R. Humphry-Baker, E. Mϋller, P. Liska, N. Vlachoppoulos, M. Gratzel, J Am. Chem. Soc, 1993, 115, 6382]. The photoexcitation of a Ru-complex results in an in-
tramolecular metal-to-ligand charge-transfer (MLCT) transition. The photoexcited electrons located in the bipyridyl ligands can be very efficiently injected in the conduction band of the semiconductor via the carboxyl-anchor groups. This process has been shown to be very fast. [Y. Tachibana, J. E. Moser, M. Gratzel, D.R. Klug, J.R. Durrant, J. Phys. Chem. 1996, 100, 20056] In contrast, for these complexes the recombination process between the injected electrons in TiO2 and the dye-cations is a slow process. The slow recombination is considered to be a result of the large separation between semiconductor and the Ru3+ by the bipyridyl ligands. Thus, the molecular design of these Ru-complexes is successful in an efficient charge separation and thus, high energy conversion efficiency.
However, the energy conversion efficiency of the DSSC is limited by the light-harvesting capacity of these Ru-dyes to absorb the sunlight. The photo-active region of the photovoltaic device is reduced to the visible part of the solar spectrum, and within that, to the shorter wavelength region. The photons of the longer wavelength region are not harvested and cannot be converted to electrical energy.
So far most of the dyes employed as photosensitizers in the field of DSSC have as anchoring group carboxylic acid groups to anchor on to nanoporous semiconductor. This limits the pool of all dyes, organic, inorganic and hybrid that can be used as sensitizer. Other anchoring group which show good properties and have been more intensively studied are phosphonic acid groups (a) Gratzel et al, J. Phys. Chem. B, 2004, 108, 17553; b) W. Choi et al, J. Physl. Chem. B, 2006, 110, 14792-14799). Adsorption and charge injection could be further demonstrated with other anchoring groups like sulfonic acid, hydroxyl, triethoxysilane, catechol group and boronic acid, but no solar cells with significant efficiency of DSSC could be achieved with dyes having such anchoring groups (a) Gratzel et al, New. J. Chem., 2000, 24, 651-652; b) Ford et al., J. Phys. Chem. B, 1994, 98, 3822; c) Lakhimiri et al., J. Photochem. Photobiol., A, 2004, 166, 91.).
Nanoporous semiconductors, such as TiO2, are key components in the process of hetere- genous photocatalysis applied in the field of photocatalytic hydrogen production or photolytic water purification (Arakawa et al., J.Photochem.Photobiol. A, 2000, 63-69; b) Chanon, Eds. Elsevier, Photoinduced Electron Transfer, 1988). Most photocatalysts, such as nanoiporous TiO2, are active under UV irradiation, and their inactivity in the visible light region (solar light) limits their practical application. One of the strategies to overcome this is the anchoring of charge transfer dyes to the surface of the wide band gap semiconductor rendering them
sensitive to visible sun light. As above, the dyes are generally linked to the semiconductor through a carboxylate linkages via a ester linkage. This linkage is quite unstable in water which is the environment in such processes. There is a need on alternative effective and stable anchoring groups for attaching dyes on the semiconductor surfaces.
Accordingly, it was an object of the present invention to provide for improved dyes with intense absorption in the visible and long wavelength region of the solar spectrum. It was another object of the present invention to provide for dyes which can be easily covalently attached to nanocrystalline wide band gap semiconductors, such as TiO2, SnO2 etc. It was furthermore an object of the present invention to provide for dyes that allow an efficient charge transfer from the dye to the semiconductor. It was furthermore an object of the present invention to provide for dyes that are easily accessible due simple methods of preparation.
All these objects are solved by a dye comprising a chromophore to which an acyloin group is attached, said dye being represented by formula Ia or Ib:
( Chromophore)
formula Ia
or
wherein said chromophore is an organic or metal-organic compound absorbing electromagnetic radiation in the range from 300-1200 nm, or a subrange thereof, preferably 350-500 nm or 500-750 nm or 350-700 nm, wherein A is selected from H, or any cyclic or acyclic alkyl, or any straight or branched chain moiety of general formula -(CH2)M-R,
-[(C≡C)nl-(CH2)n2]p-R, - [(CH2)nl -X O2Jp-R, or halogen, such as F, Cl, Br, I, or moieties containing heteroatoms, such as NO2, CN, NR2, -OH or any substituted or non-substituted phenyl or biphenyl or heteroaryl, or moieties forming a ring structure with said acyloin group,
wherein, at each occurrence and independently, nl and n2 = 0 - 12, preferably 0-4, p = 0-6, preferably 0-2, wherein X is selected from -CR2, O, S, NR, -CR, wherein R is selected from H or any straight or branched alkyl chain of general formula - CnH2n+1, or -COOR1, -OR1, -SR1, -NRJ 2, or F, Cl, Br, I, O, N, NO2, CN, CF3, wherein R1 is H or any straight or branched alkyl chain of general formula -CnH2n+], or any substituted or non- substituted phenyl or biphenyl, heteroaryl, n = 0-12, preferably 0-6.
In one embodiment, the dye according to the present invention comprises a chromophore to which an acyloin group is attached, said dye being represented by formula 2a, 2b, 2c, 2d, 2e, 2f, 2g, 2h, 2i, or 2j
formula 2a
[ Chromophore]
formula 2b
[ Chromophore)
formula 2c
[Chromophore]
formula 2d
( Chromophore]
formula 2e
[Chromophore
formula 2g
[Chromophore)
formula 2h
( Chromophore
formula 2i
formula 2j
wherein A, X, nl, n2, n, p are as defined above, and wherein Y, at each occurrence, is independently selected from -CR2, O, S, NR, -CR, R being as defined above.
In one embodiment, the dye according to the present invention is represented by formula 2d, 2e, 2f, or 2h
In one embodiment, said chromophore is selected from the moieties shown in formula 3
(formula 3)
or any combination of the moieties represented by formula 3, wherein said chromophore is linked to said acycloin group by any of the C-atoms or X or Y or R within said chromophore, wherein Z is one or more moieties which, at each occurrence, is independently selected from H, or any cyclic or acyclic alkyl, or any straight or branched chain moiety of general formula ■ (CH2)nl-R, -[(CR=CR)nl-(CH2)n2]p-R, -[(C≡C)nl -(CH^Jp-R, -[(CH2)nl-Xn2]p-R, or halogen, such as F, Cl, Br, I, or moieties containing heteroatoms, such as NO2, CN, NR2, -OH or any substituted or non-substituted phenyl or biphenyl or heteroaryl, preferably represented by formula 4
(formula 4)
and wherein R, X, Y, n, nl5 n2 and p are as defined in claim 1.
In one embodiment, the dye according to the present invention is represented by formula 5
(formula 5)
wherein R]1, Rj2, R13, at each occurrence, are independently selected from H or any straight or branched alkyl chain of general formula -CnH2n+1, or -COOR1, -OR1, -SR1, -NR^, or F, Cl, Br, I, O, N, NO2, CN, CF3, wherein R1 is H or any straight or branched alkyl chain of general formula -CnH2n+1 or any substituted or non-substituted phenyl or biphenyl, heteroaryl, n = O- 12 preferably 0-6, and wherein X and Z are as defined in claim 4.
In one embodiment, the dye according to the present invention is represented by formula 6
(formula 6)
or is represented by any of structures 17-26:
In one embodiment, the dye according to the present invention is represented by formula 7
(formula 7)
wherein R11, Z, and X are as defined in claim 5, or is represented by formula 8
(formula 8) wherein Rn, R12, Ri3, Z, X and Y are as defined above, or is represented by formula 9
wherein Rn, Z, X and Y are as defined above, or is represented by formula 10
(formula 10) wherein R, Z, X and n are as defined above, or is represented by formula 1 1
(formula 11) wherein R, Z, X, Y and n are as defined above, or is represented by formula 12
(formula 12) wherein R, Z, Y, X and n are as defined above, or is represented by formula 13
(formula 13) wherein R, Z, X, Y, n are as defined above.
In one embodiment, said chromophore is a metal complex selected from the structures represented by formula 14
(L)n3(L')n4M(Hal)n5
(formula 14)
M being Ruthenium Ru, Osmium Os, or Iridium Ir, preferably Ruthenium,
Hal being independently selected from Cl, Br, I, CN, -NCS, preferably -NCS with n3, n4, n5 being integers which, at each occurrence, are independently 0-4, preferably 2 or 3,
and L and L' being organic heterocyclic ligands containing nitrogen atoms which are linked by N-atoms to the respective metal M, and wherein either one of L and L', or both L and L' are linked to the acyloin group by any of the C-atoms within said ligands.
In one embodiment, said ligands L and I/ are independently, at each occurrence, mono- or polycyclic, condensed rings or such rings covalently bonded to each other.
In one embodiment, said ligands L and L' are independently, at each occurrence, selected from the group comprising
(formula 15)
wherein Z is as defined above.
In one embodiment, said chromophore is a metal complex represented by formula 16
(L"UM' (formula 16)
M' being Palladium Pd, Platinum Pt or Nickel Ni, preferably Pd, and n6 being an integer 0-4, preferably 1 -2, and L" being an organic heterocyclic ligand containing nitrogen atoms, said ligand being linked by one or several of said N-atoms to the respective metal M', and said ligand being linked to said acycloin group by any of the C-atoms within said ligand.
In one embodiment, said ligand L" is selected from the group comprising
(formula 17)
wherein Z is as defined above.
The objects of the present invention are also solved by an electronic device comprising a dye as defined above.
In one embodiment, the device according to the present invention is a solar cell, preferably a dye-sensitized solar cell (DSSC), said solar cell further comprising a photoactive semiconductor porous material.
In one embodiment, the device according to the present invention contains a charge- transporting agent which is a liquid, polymer gel based or solid state electrolyte.
In one embodiment, the device according to the present invention is a solar cell wherein said dye is chemisorbed to said photoactive semiconductor porous material.
In one embodiment, the device according to the present invention further comprises at least one other dye.
In one embodiment, said at least one other dye is a dye according to the present invention.
In one embodiment, said at least one other dye is a dye selected from structures 15, 27-32:
In one embodiment, said photoactive semiconductor porous material has one or several of the following features:
- a thickness of 1-100 μm, preferably 5-30 μm,
- consists of one or more layers
- contains particles having an average diameter or length in the range of from 1 run to 40 run, preferably 15-30 nm
-is a mixture of at least a first and second kind of particles, said first kind of particles having an average diameter or length in the range of from 1 nm to 30 nm, and said second kind of particles having an average diameter in the range of from 30 nm to 100 nm and/or a length in the range of from 100 nm to 5 μm.
The objects of the present invention are also solved by the use of a dye according to the present invention as a sensitizer in a dye-sensitized solar cell.
In one embodiment, said use is together with at least one other dye.
In one embodiment, said at least one other dye is a dye as defined above, or a dye selected from structures 15, 27-32:
In one embodiment, said use together with at least one other dye is in a dye-sensitized solar cell having a tandem geometry (as, e.g., described in Example 9 below), or the mixture of a dye in accordance with the present invention and at least one other dye is used for coating an electrode of said dye-sensitized solar cell.
The objects of the present invention are also solved by the use of a dye according to the present invention, as a photosensitzer in a photocatalytic process, such as photocatalysed hydrogen production or photocatalytic degradation of organic pollutants. It should be noted that any photocatalytic process may be useful in the context of the present invention.
In one embodiment, during preparation of the device, the dye molecules are adsorbed to the nanoporous particles via self-assembling out of a dye solution or a dyes-mixture solution.
Examples of electronic devices comprising a dye in accordance with the present invention include energy supply devices for portable electronic devices and displays, such as solar cell panels for or incorporated in mobile phones, notebooks, laptops, portable audio-tape players, MP3-players, remote controls, e-cards, e-books, e-readers, portable CD-players, portable DVD-players, cameras, digicams, GPS devices, portable sensors, displays integrated in electronic devices. Examples of electronic devices in accordance with the present invention also include portable solar chargers for batteries of any of the afore-mentioned devices. Moreover, electronic devices in accordance with the present invention include smart windows, on-roof- applications, especially in areas where a grid connection is not possible, e.g. camping cars, boats. If the electronic device in accordance with the present invention is an energy supply device, and said energy supply device is a solar cell panel, such panel is preferably a dye- sensitized solar cell panel (DSSC panel) (see also figure 21).
The objects of the present invention are also solved by the use of a dye according to the present invention, for the sensitization of the photocatalyst, such as TiO2, in photocatalytic processes, e.g in photocatalysed hydrogen production , photocatalytic splitting of water or photo- catalytic decomposition of pollutants..
As used herein, the term "dye" is meant to refer to a chromophore to which an acyloin group is attached. The term "chromophore", as used herein, is meant to refer to an organic or metal- organic compound which is able to absorb electromagnetic radiation in the range of from 350 nra to 1100 nm, or a subrange thereof, e.g 350-500 nm or 500-850 run, or 350-850 nm. An acyloin group is the moiety which is included in the structure of the dyes according to present invention and is represented by formula 18
HO O
(formula 18)
The term "anchoring group", as used herein, is meant to refer to any functional group that allows a covalent coupling (chemisorption) of the entity to which such anchoring group belongs, to a surface, for example the surface of a nanoporous semiconductor layer within a solar cell.
A dye is referred to as being "chemisorbed" to a layer or surface, if the dye is covalently coupled thereto.
With reference to formula 3 which exemplifies a "chromophore" in accordance with the present invention, the term "a combination of the moieties represented by formula 3" is used. This is meant to encompass any molecule wherein one or several of the structures given in formula 3 are covalently linked to each other to also produce a "chromophore".
The term "substituted phenyl/biphenyl" is meant to refer to any phenyl/biphenyl wherein a hydrogen has been replaced by a substituent, such as a halogen, NO2, NH2, OH or other suitable functional groups. Such substituents have for example been defined above as Z, which substituents may also be substitutents at a phenyl or biphenyl.
The inventors have surprisingly found that using acyloin groups as anchoring groups for a dye allows an efficient covalent attachment of such dye to nanoporous surfaces of photoactive layers, such as TiO2-layers. The dyes having the acyloin group attached as anchoring group can be used as sensitizers in solar cells but also for sensitizing the photocatalyst which are mosly wide band gap oxide semiconductors such as TiO2, to extend the photocatalytic activity of the photocatalysts into the visible light region. This is particular important for example in the field of heterogeneous photocatalysis such as photolytic hydrogen production or photo- catylytic water production or photocatalytic destruction of organic pollutants. In using the approach in accordance with the present invention, the number of dyes that can be potentially used in such applications is strongly increased. Moreover, the synthesis of such dyes is surprisingly simple.
The dyes according to the present invention show high quantum efficiency similar to that of the standard red-dye. If one therefore combines the dyes of the present invention with other dyes, such as other organic dyes or standard red dye or standard black dye, a broad range of the solar spectrum may be harvested. That makes the dyes of the present invention very promising to be used together with other dyes, such as organic dyes, standard red dye or standard black dye or further dyes according to the present invention with absorption maxima at different wavelengths. A dye sensitized solar cell comprising a dye according to the present invention, and, in addition thereto, one or more further dyes, is herein also referred to as a multiple-
dyes sensitized solar cell (M-DSSC). Preferably, said one or more further dyes is also a dye according to the present invention.
Further, organic dyes have high absorption coefficients. This means it needs less amount of dye to absorb the same amount of light. Less amount of one dye on a surface enables the use of more dyes with different absorption properties, ideally being a mixture of dyes absorbing the whole range of the sun spectrum.
Furthermore, reference is made to the figures, wherein
Figure 1 shows a synthesis scheme of one example dye in accordance with the present invention being represented by general formula 2e, E being Cl or an alkoxy group, preferably eth- oxy, propoxy, iso-propoxy or butoxy, X being as defined above, chromophore being as defined above,
Figure 2 shows a synthesis scheme of one example dye in accordance with the present invention being represented by general formula 2h, E, Y, X, nls n2, p, chromophore being as defined above, Hal" being I", Cl', Br", NCS" or SCN",
Figure 3 shows a synthesis scheme of one example dye in accordance with the present invention being represented by general formula 5, E, Z, R11-Ri3, X being as defined above,
Figure 4 shows a synthesis scheme of one example dye in accordance with the present invention being represented by general formula 9, X, Y, Z, R1 being as defined above,
Figure 5 shows the molecular structure of some dyes according to present invention,
Figure 6 shows the synthesis of one example dye in accordance with the present invention being represented by formula 1 ,
Figure 7 shows the synthesis of one example dye in accordance with the present invention being represented by formula 2,
Figure 8 shows the synthesis of one example dye in accordance with the present invention being represented by formula 5,
Figure 9 shows a photograph of the adsorption of dye in accordance with the present invention being represented by formula 1 on a TiO2 layer,
Figure 10 shows a table indicating the performance of a dye sensitized solar cell prepared with a dye in accordance with the present invention being represented by formula 1 by measuring the efficiency of solar cells by means of sulphur lamp,
Figure 11 shows the incident photon to current efficiency (IPCE) plotted against wavelength for a dye in accordance with the present invention being represented by formula 1 ,
Figure 12 shows a table displaying the performance of various dye sensitized solar cells prepared with a dye in accordance with the present invention being represented by formula 1 in mixture with other dyes and in comparison to other sensitizers,
Figure 13 shows the incident photon to current efficiency of a dye in accordance with the present invention being represented by formula 1, of a dye being represented by formula 14 (figure 15) and a mixture of these two dyes, plotted against wavelength,
Figure 14 shows a table indicating the performance of a dye sensitized solar cell prepared with a dye in accordance with the present invention being represented by formula 1 in comparison with organic dye being represented by formula 16 (figure 15), by measuring the efficiency of solar cells by means of sun simulator,
Figure 15 shows the structure of other sensitizers that were used for comparison and in mixture with dyes according to present invention (sensitizers 14, 15 and 16).
Figure 16 shows structures 17-26 which are exemplary dyes in accordance with the present invention.
Figure 17 shows exemplary structures 15, 27-32 of other dyes which can be used together with the dyes in accordance with the present invention.
Figures 18-20 show various tables and IPCE curves showing the efficiencies of solar cells, as prepared and described in Examples 11) to 13).
Figure 21 shows various embodiments of electronic devices in accordance with the present invention wherein energy supply devices, such as solar cell panels, preferably dye sensitized solar cell panels (DSSCs) have been incorporated.
Moreover reference is made to the following examples which are given to illustrate, not to limit the present invention.
Examples
1) Synthesis of one embodiment of a dye in accordance with the present invention, in this case dye 1:
Figure 6 shows the synthesis scheme of dye 1 in accordance with the present invention.
An equimolar amount of Ia and diethylester derivative of squaric acid Ib in ethanol is heated in presence of small amount triethylamine to 70°C for 4 h. The solvent is removed and the crude product is purified by column chromatography on silica gel with n-hexane/ethylacetate as eluent to yield the pure product Ic.
In next step, to derivative Ic in ethanol aqueous NaOH is added and the mixture stirred for 2 h at 50 0C. After cooling, aq. HCl is added and the solvent is removed. The crude product is purified by column chromatography on silica gel with dichloromethane/methanol as eluent. The dye 1 in accordance with the present invention is isolated as yellow solid.
2) Synthesis of one embodiment of a dye in accordance with the present invention, in this case dye 2:
Figure 7 shows the synthesis scheme of dye 2 in accordance with the present invention.
An equimolar amount of 2a and diethylester derivative of squaric acid Ib in ethanol and in presence of small amount triethylamine is heated to 80°C for 6 h. The solvent is removed and the crude product is purified by column chromatography on silica gel with n- hexane/ethylacetate as eluent to yield the pure intermediate 2b.
In next step, to 2b in ethanol aqueous NaOH is added and the mixture stirred for 2 h at 50 °C. After cooling, aq. HCl is added and the solvent is removed. The crude product is purified by
column chromatography on silica gel with dichloromethane/methanol as eluent. The dye 2 in accordance with the present invention is isolated as yellow-orange solid.
3) Synthesis of one embodiment of a dye in accordance with the present invention, in this case dye 5:
Figure 8 shows the synthesis scheme of dye 5 in accordance with the present invention.
An equimolar amount of brominated derivative 5a and diethylester derivative of squaric acid Ib in ethanol and in presence of small amount triethylamine is heated to 80°C for 6 h. The solvent is removed and the crude product is purified by column chromatography on silica gel with n-hexane/ethylacetate as eluent to yield the pure intermediate 5b.
In a next step, to a mixture of 5b in of toluene/methanol, 1.2 equivalents of thienyl boronic acid, 1 mol% Pd-catalyst, 10 equivalents K2CO3 are added. The mixture is allowed to stir at 120°C for 12h. After cooling the solvent is evaporated. The crude product is purified by column chromatography on silica gel with n-hexane/ethylacetate as eluent to yield pure 5c. In a subsequent reaction to 5c in ethanol, aqueous NaOH is added and the mixture stirred for 2 h at 50 °C. After cooling, aq. HCl is added and the solvent is removed. The crude product is purified by column chromatography on silica gel with dichloromethane/methanol as eluent. The pure dye 5 in accordance with the present invention is isolated as orange solid.
4) Analytical data of dye 1 C18H19NO3 (297.36)
IH NMR (400MHz, MeOD): δ= 14.8 (s, IH, -OH), 7.27-7.20(m, 2H, arH), 6.98-6.92 (m, 2H, arH), 5.70 (s, IH, =CH-), 3.95 (t, 2H, N-CH2), 1.84-1.75 (m, 2H, CH2-Pr), 1.65 (s, 6H, arCH3), 1.06 (t, 6H, CH3-Pr)
ESI MS m/z = 297.8 [M+].
UV/VIS (acetonitrile): λmax = 404 run.
5) Effective adsorption of the dye on TiO2
Figure 9 shows a photograph of the adsorption of dye 1 in accordance with the present invention on a TiO2 layer
For device preparation, the substrate with screen printed nanoporous TiO2 particles is poured and kept in a dye or dyes mixture solution for at least Ih. The dye molecules having the acy-
loin group as anchor group are able to adsorb onto the nanoporous layer via self-assembling. The effective adsorption and chemisorption (covalent coupling) of the dyes with acyloin group onto semiconductor surface is proved by the stable color of the substrate even after the substrate was washed with an organic solvent.
6) General protocol for preparing solar cells
The DSSCs are assembled as follows: A 30-nm-thick bulk TiO2 blocking layer is formed on FTO (approx. 100 nm on glass or flexible substrate). A 5-30 μm-thick porous layer of TiO2 semiconductor particles of 0.1882 cm2 active area multi-printed by screen printing on the blocking layer and sintered at 450 0C for half an hour. Dye molecules are adsorbed to the nanoporos particles via self-assembling out of a dye-solution. The dye-solution consists of a single dye or single dye and an additive, such as deoxycholic acid or a mixture of dye in different ratio or a mixture of dye in different ratio and an additive. The porous layer is filled with liquid electrolyte containing IVI3 " as redox couple (15 mM) by drop casting. A reflective platinum back electrode is attached with a distance of 6 μm from the porous layer.
7) Measuring the efficiency of DSSCs containing at least one of the sensitizer dye produced by the method of the present invention.
The quality of the cells is evaluated by means of current density (J) and voltage (V) characteristics under illumination with light from a) a sulphur lamp (IKL Celsius, Light Drive 1000) with an intensity of 100 mW cm"2. If not otherwise stated, the results are averages over three cells. b) a sun simulator (AMI .5G YSS-150) with an intensity of 100 mW cm'2. If not otherwise stated, the results are averages over three cells.
The efficiency of a photovoltaic device is calculated as follows: η = Pout / Pin = FF x (Jsc x Voc) / (L x A) with FF = Vmax x Imax / V0C x Isc
FF = fill factor
Voc = open circuit voltage
Jsc = short current density
L = intensity of illumination = 100 mW/cm2
A = active area = 0.24 cm2
Vmax - voltage at maximum power point
Jmax = current at maximum power point
An important parameter for judging the performance of a dye as sensitizer in DSSC is the IPCE curve. The IPCE curve reflects the photo-activity of the sensitizer dyes at different wavelengths (IPCE = incident photon to current efficiency).
The respective structure of the dyes is given in Figure 5 and 15.
8) Efficiency of the DSSC by using dye 1 as sensitizer
The performance and the efficiency of DSSCs prepared by method described in 6 and measured by method described in 7a with dye I are shown in figure 10. Figure 11 shows the IPCE plotted verses wavelength for sensitizer 1.
The efficiency of the DSSC prepared with sensitizer dye 1 shows high efficiency (>7%). There are only few other organic dyes, such as dye 16, showing such high performance. However, the superiority of the dyes according to present invention lies not only in the high efficiencies of the DSSCs achieved when using these dyes, but also in their simple preparation (Figures 1-4).
The highest achievable IPCE value is 1.0. Sensitizer dye 1 shows an IPCE value of 0.9 in its maximum at ca. 490 nm. That means that the photons absorbed in this region from the sun can be converted to almost 90% to current by injection into conduction band of TiO2. Such a high value is rarely achieved and only with few dyes, such as the Ruthenium based standard red dye.
9) Efficiency of M-DSSC containing a mixture of dye 1 and the organic dye 14, and a mixture of dye 1 and standard black dye 15.
The solar cells were prepared by method described in Example 6 and measured according to Example 7a. For comparison also DSSCs prepared with the respective single sensitizer dye were prepared and measured. The performance and the efficiency of DSSCs are shown in Figure 12.
A mixture of the dye in accordance with the present invention, in this case dye 1, with either an organic dye 14 or with a Ruthenium based dye (black dye) 15 yields an increase in short current density and thus, a drastic increase in DSSC efficiency.
Figure 13 shows the IPCE curve of the individual dyes 1 and 14, and the IPCE curve of a 1 :1 mixture of these dyes. The individual dyes are photo-active in different region of the solar spectrum. By using a mixture of the dyes, due to additive behaviour of the IPCE curves, a very broad range solar light can be harvested and converted to current.
10) Comparing efficiency of the DSSC prepared with dye according to present invention, namely dye 1, and another organic sensitizer 16 both harvesting light in the same range of the solar spectrum
The DSSCs were prepared by method described in Example 6 and measured according to Example 7b.
The DSSC efficiencies are in the same range of 5%. However, when one compares the structure of the dyes, it becomes clear that the dye according to present invention, namely dye 1, is much more easily synthesized than dye 16.
11) Efficiency of the DSSC by using dye 9 and 2 as sensitizer.
The DSSCs were prepared by the method described in Example 6 and by using 25 μm TiO2 layer and measured according to Example 7b. The efficiency and IPCE curve are shown in figure 18a and 18b, respectively.
The IPCE curve reflects the photo-activity of the sensitizer dyes at different wavelengths (IPCE = incident photon to current efficiency). The highest achievable IPCE value is 1.0. Sensitizer dye 1, 9 and 2 show very high, of almost unity, and wide IPCE values.
12) Performance of solar cells prepared with a mixture of the respective dye and standard Ruthenium Black dye 15
The solar cells were prepared by method described in Example 6 and measured according to Example 7b. For comparison also DSSC prepared with the respective single sensitizer dye 15 was prepared and measured. The efficiency is shown in figure 19. As can be seen, the efficiencies by using a mixture of dyes for sensitization are much higher than that using only a single dye as sensitizer.
13) Performance of solar cells prepared with a mixture of the respective dye and organic dye 14.
The solar cells were prepared by method described in Example 6 and measured according to Example 7b. For comparison also DSSC prepared with the respective single sensitizer dye 14 was prepared and measured.
a) by using 26 μm TiO2 layers as electrode; the efficiency is shown in figure 20a. b) by using 10 μm TiO2 layers as electrode; the efficiency is shown in figure 20b.
The efficiencies on thinner layer are slightly lower than on thick TiO2 layer, but , contrary to Ruthenium based sensitizers, still high enough to show the good performance of the dyes. This is attributed to the strong light absorption property of the dyes according to claim 1-12. In both cases, thin or thick TiO2 layers, the efficiency is increased by using a mixture of dyes for sensitization compared to that using a single dye.
The present invention provides for new sensitizer dyes which are useful for being employed in solar cells as well as in photocatalytic applications. They readily adsorb to nanoporous semiconductor layers and are easily manufactured. The use of an acyloin group as anchoring group for chromophores in such applications, to the best knowledge of the present inventors, has never been reported before.
The features of the present invention disclosed in the specification, the claims and/or in the accompanying drawings, may, both separately, and in any combination thereof, be material for realizing the invention in various forms thereof.
Claims
1. A dye comprising a chromophore to which an acyloin group is attached, said dye being represented by formula Ia or Ib:
( Chromophore) 
formula Ia
or ( Chromophore)
formula Ib
wherein said chromophore is an organic or metal-organic compound absorbing electromagnetic radiation in the range from 300-1200 nm, or a subrange thereof, preferably 350-500 run or 500-750 nm or 350-700 nm, wherein A is selected from H, or any cyclic or acyclic alkyl, or any straight or branched chain moiety of general formula -(CH2)nl-R, -[(CR=CR)nl-(CH2)n2]p-R, -[(C≡C)nl-(CH2)n2]p-R, - [(CH2)H1-Xn2]P-R, or halogen, such as F, Cl, Br, I, or moieties containing heteroatoms, such as NO2, CN, NR2, -OH or any substituted or non-substituted phenyl or biphenyl or heteroaryl, or moieties forming a ring structure with said acyloin group,
wherein, at each occurrence and independently, nl and n2 = 0 - 12, preferably 0-4, p = 0-6, preferably 0-2, wherein X is selected from -CR2, O, S, NR, -CR, wherein R is selected from H or any straight or branched alkyl chain of general formula - CnH2n+1, or -COOR1, -OR1, -SR1, -NR^, or F, Cl, Br, I, O, N, NO2, CN, CF3, wherein R1 is H or any straight or branched alkyl chain of general formula -CnH2n+I, or any substituted or non- substituted phenyl or biphenyl, heteroaryl, n = 0-12, preferably 0-6.
2. The dye according to claim 1 comprising a chromophore to which an acyloin group is attached, said dye being represented by formula 2a, 2b, 2c, 2d, 2e, 2f, 2g, 2h, 2i, or 2j
[ Chromophore] 
formula 2a
( Chromophore) 
formula 2b
( Chromophore) 
formula 2c
( Chromophore) 
formula 2d ( Chromophore) 
formula 2e 
formula 2f 
formula 2g 
formula 2h 
formula 2i
wherein A, X, nl, n2, n, p are as defined in claim 1, and wherein Y, at each occurrence, is independently selected from -CR2, O, S, NR, -CR,
R being as defined in claim 1.
3. The dye according to claim 2, being represented by formula 2d, 2e, 2f, or 2h, as defined in claim 2.
4. The dye according to any of the foregoing claims 1-3, wherein said chromophore is selected from the moieties shown in formula 3
(formula 3)
or any combination of the moieties represented by formula 3, wherein said chromophore is linked to said acycloin group by any of the C-atoms or X or Y or R within said chromophore, wherein Z is one or more moieties which, at each occurrence, is independently selected from H, or any cyclic or acyclic alkyl, or any straight or branched chain moiety of general formula ■ (CH2)ni-R, -[(CR=CR)nl-(CH2)n2]p-R, -[(C≡C)nl-(CH2)n2]p-R, -[(CH2)n i-Xώ]p-R, or halogen, such as F, Cl, Br, I, or moieties containing heteroatoms, such as NO2, CN, NR2, -OH or any substituted or non-substituted phenyl or biphenyl or heteroaryl, preferably represented by formula 4
(formula 4) and wherein R, X, Y, n, ni, n2 and p are as defined in claim 1.
5. The dye according to any of claims 1-4, being represented by formula 5
wherein R11, R12, Rj3, at each occurrence, are independently selected from H or any straight or branched alkyl chain of general formula -CnH2n+1, or -COOR1, -OR1, -SR1, -NR! 2, or F, Cl, Br, I, O, N5 NO2, CN, CF3, wherein R1 is H or any straight or branched alkyl chain of general formula -CnH2n+1 or any substituted or non-substituted phenyl or biphenyl, heteroaryl, n = 0- 12 preferably 0-6, and wherein X and Z are as defined in claim 4.
6. The dye according to claim 5, being represented by formula 6
(formula 6) or being represented by any of structures 17-26:
7. The dye according to any of claims 1-4, being represented by formula 7
(formula 7)
wherein R11, Z, and X are as defined in claim 5, or being represented by formula 8
(formula 8) wherein R11, R12, R13, Z, X and Y are as defined claim 5, or being represented by formula 5 
wherein Rn, Z, X and Y are as defined in claim 5, or being represented by formula 10
(formula 10)
wherein R, Z, X and n are as defined in any of claims 4 and 5, or being represented by formula 11
(formula 11)
wherein R, Z, X, Y and n are as defined in any of claims 4 and 5, or being represented by formula 12
(formula 12)
wherein R, Z, Y, X and n are as defined in any of claims 4 and 5, or being represented by formula 13
wherein R, Z, X, Y, n are as defined in any of claims 4 and 5.
8. The dye according to any of claims 1-3, wherein said chromophore is a metal complex selected from the structures represented by formula 14
(L)n3(L')n4M(Hal)n5
(formula 14)
M being Ruthenium Ru, Osmium Os, or Iridium Ir, preferably Ruthenium,
Hal being independently selected from Cl, Br, I, CN, -NCS, preferably -NCS with n3, n4, n5 being integers which, at each occurrence, are independently 0-4, preferably 2 or 3,
and L and L' being organic heterocyclic ligands containing nitrogen atoms which are linked by N-atoms to the respective metal M, and wherein either one of L and L', or both L and L' are linked to the acyloin group by any of the C-atoms within said ligands.
9. The dye according to claim 8, wherein said ligands L and I/ are independently, at each occurrence, mono- or polycyclic, condensed rings or such rings covalently bonded to each other.
10. The dye according to any of claims 8-9, wherein said ligands L and I/ are independently, at each occurrence, selected from the group comprising
z
K rθ / \~\ 
wherein Z is as defined in claim 4.
11. The dye according to any of claims 1 -3 , wherein said chromophore is a metal complex represented by formula 16
(L"UM' (formula 16)
M' being Palladium Pd, Platinum Pt or Nickel Ni, preferably Pd, and n6 being an integer 0-4, preferably 1-2, and L" being an organic heterocyclic ligand containing nitrogen atoms, said ligand being linked by one or several of said N-atoms to the respective metal M', and said ligand being linked to said acycloin group by any of the C-atoms within said ligand.
12. The dye according to claim 11, wherein said ligand L" is selected from the group comprising
(formula 17) wherein Z is as defined in claim 4.
13. An electronic device comprising a dye as defined in any of claims 1-12.
14. The device according to claim 13, which is a solar cell, preferably a dye-sensitized solar cell (DSSC), said solar cell further comprising a photoactive semiconductor porous material.
15. The device according to any of claims 13 and 14, containing a charge-transporting agent which is a liquid, ionic liquid, polymer gel based or solid state electrolyte.
16. The device according to claim 14, which is a solar cell wherein said dye is chemi- sorbed to said photoactive semiconductor porous material.
17. The device according to any of claims 13-16, further comprising at least one other dye.
18. The device according to claim 17, wherein said at least one other dye is a dye according to any of claims 1-12.
19. The device according to claim 17, wherein said at least one other dye selected from structures 15, 27-32:
20. The device according to any of claims 14-19, wherein said photoactive semiconductor porous material is selected from TiO2, SnO2, ZnO, Nb2O5, ZrO2, CeO2, WO3, Cr2O3, CrO2, CrO3, SiO2, Fe2O3, CuO, Al2O3, CuAlO2, SrTiO3, SrCu2O2, ZrTiO4, preferably TiO2, and combinations of the foregoing.
21. The device according claim 20, wherein said photoactive semiconductor porous material has one or several of the following features:
- a thickness of 1-100 μm, preferably 5-30 μm,
- consists of one or more layers - contains particles having an average diameter or length in the range of from 1 nm to 40 nm, preferably 15-30 nm
-is a mixture of at least a first and second kind of particles, said first kind of particles having an average diameter or length in the range of from 1 nm to 30 nm, and said second kind of particles having an average diameter in the range of from 30 nm to 100 nm and/or a length in the range of from 100 nm to 5 μm.
22. Use of a dye according to any of claims 1-12 as a sensitizer in a dye-sensitized solar cell.
23. Use according to claim 22, together with at least one other dye.
24. Use according to claim 23, wherein said at least one other dye is a dye as defined in any of claims 1-12,, or a dye selected from structures 15, 27-32:
25. Use of a dye according to any of claims 1-12, as a photosensitzer in a photocatalytic process, such as photocatalysed hydrogen production or photocatalytic degradation of organic pollutants.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09778687.5A EP2362884B1 (en) | 2008-10-27 | 2009-09-23 | A dye comprising a chromophore to which an acyloin group is attached |
| US13/123,344 US20110265878A1 (en) | 2008-10-27 | 2009-09-23 | Dye comprising a chromophore to which an acyloin group is attached |
| JP2011532511A JP5519681B2 (en) | 2008-10-27 | 2009-09-23 | Dyes containing chromophores with attached acyloin groups |
| CN2009801428911A CN102197097A (en) | 2008-10-27 | 2009-09-23 | A dye comprising a chromophore to which an acyloin group is attached |
| US14/256,458 US9679702B2 (en) | 2008-10-27 | 2014-04-18 | Dye comprising a chromophore to which an acyloin group is attached |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08018743.8 | 2008-10-27 | ||
| EP08018743 | 2008-10-27 | ||
| EP09008155 | 2009-06-22 | ||
| EP09008155.5 | 2009-06-22 |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US13/123,344 A-371-Of-International US20110265878A1 (en) | 2008-10-27 | 2009-09-23 | Dye comprising a chromophore to which an acyloin group is attached |
| US14/256,458 Division US9679702B2 (en) | 2008-10-27 | 2014-04-18 | Dye comprising a chromophore to which an acyloin group is attached |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2010049042A2 true WO2010049042A2 (en) | 2010-05-06 |
| WO2010049042A3 WO2010049042A3 (en) | 2010-10-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2009/006888 WO2010049042A2 (en) | 2008-10-27 | 2009-09-23 | A dye comprising a chromophore to which an acyloin group is attached |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US20110265878A1 (en) |
| EP (1) | EP2362884B1 (en) |
| JP (1) | JP5519681B2 (en) |
| CN (1) | CN102197097A (en) |
| WO (1) | WO2010049042A2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012033444A (en) * | 2010-08-03 | 2012-02-16 | Fujifilm Corp | Photoelectric conversion element, photoelectrochemical battery using the same, and photoelectric conversion element composition |
| JP2012053984A (en) * | 2010-08-03 | 2012-03-15 | Fujifilm Corp | Photoelectric converter, photoelectrochemical cell, and manufacturing methods of photoelectric converter and photoelectrochemical cell |
| JP2012053983A (en) * | 2010-08-03 | 2012-03-15 | Fujifilm Corp | Photoelectric converter and photoelectrochemical cell |
| US20150133678A1 (en) * | 2012-05-07 | 2015-05-14 | Sony Corporation | Organic compounds containing squaric acid or croconic acid moieties for application in electronic devices |
| EP3598465A1 (en) * | 2018-07-16 | 2020-01-22 | Exeger Operations AB | Photovoltaic cell with fiber mesh support and charger for portable electronics |
| US10964486B2 (en) | 2013-05-17 | 2021-03-30 | Exeger Operations Ab | Dye-sensitized solar cell unit and a photovoltaic charger including the solar cell unit |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105181423B (en) * | 2015-09-29 | 2018-04-17 | 上海太阳生物技术有限公司 | Alkaline phosphatase (NAP) dyeing liquor (chemical dyeing method) |
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- 2009-09-23 CN CN2009801428911A patent/CN102197097A/en active Pending
- 2009-09-23 US US13/123,344 patent/US20110265878A1/en not_active Abandoned
- 2009-09-23 WO PCT/EP2009/006888 patent/WO2010049042A2/en active Application Filing
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012033444A (en) * | 2010-08-03 | 2012-02-16 | Fujifilm Corp | Photoelectric conversion element, photoelectrochemical battery using the same, and photoelectric conversion element composition |
| JP2012053984A (en) * | 2010-08-03 | 2012-03-15 | Fujifilm Corp | Photoelectric converter, photoelectrochemical cell, and manufacturing methods of photoelectric converter and photoelectrochemical cell |
| JP2012053983A (en) * | 2010-08-03 | 2012-03-15 | Fujifilm Corp | Photoelectric converter and photoelectrochemical cell |
| US20150133678A1 (en) * | 2012-05-07 | 2015-05-14 | Sony Corporation | Organic compounds containing squaric acid or croconic acid moieties for application in electronic devices |
| US9755155B2 (en) * | 2012-05-07 | 2017-09-05 | Sony Corporation | Organic compounds containing squaric acid or croconic acid moieties for application in electronic devices |
| US10964486B2 (en) | 2013-05-17 | 2021-03-30 | Exeger Operations Ab | Dye-sensitized solar cell unit and a photovoltaic charger including the solar cell unit |
| EP3598465A1 (en) * | 2018-07-16 | 2020-01-22 | Exeger Operations AB | Photovoltaic cell with fiber mesh support and charger for portable electronics |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2362884A2 (en) | 2011-09-07 |
| JP2012506917A (en) | 2012-03-22 |
| US20110265878A1 (en) | 2011-11-03 |
| US9679702B2 (en) | 2017-06-13 |
| US20140224330A1 (en) | 2014-08-14 |
| JP5519681B2 (en) | 2014-06-11 |
| EP2362884B1 (en) | 2017-08-02 |
| CN102197097A (en) | 2011-09-21 |
| WO2010049042A3 (en) | 2010-10-07 |
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