JP4148375B2 - Photoelectric conversion element and photoelectrochemical cell - Google Patents
Photoelectric conversion element and photoelectrochemical cell Download PDFInfo
- Publication number
- JP4148375B2 JP4148375B2 JP21977598A JP21977598A JP4148375B2 JP 4148375 B2 JP4148375 B2 JP 4148375B2 JP 21977598 A JP21977598 A JP 21977598A JP 21977598 A JP21977598 A JP 21977598A JP 4148375 B2 JP4148375 B2 JP 4148375B2
- Authority
- JP
- Japan
- Prior art keywords
- photoelectric conversion
- general formula
- dye
- conversion element
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000006243 chemical reaction Methods 0.000 title claims description 52
- 239000000975 dye Substances 0.000 claims description 64
- 239000004065 semiconductor Substances 0.000 claims description 36
- 239000010419 fine particle Substances 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 125000001424 substituent group Chemical group 0.000 claims description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 9
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine group Chemical group N1=CCC2=CC=CC=C12 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- WOHLSTOWRAOMSG-UHFFFAOYSA-N 2,3-dihydro-1,3-benzothiazole Chemical compound C1=CC=C2SCNC2=C1 WOHLSTOWRAOMSG-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims description 2
- ROBKVGDBQLURAF-UHFFFAOYSA-N 1,4-dihydroquinoline Chemical compound C1=CC=C2CC=CNC2=C1 ROBKVGDBQLURAF-UHFFFAOYSA-N 0.000 claims 1
- MXMZCLLIUQEKSN-UHFFFAOYSA-N benzimidazoline Chemical compound C1=CC=C2NCNC2=C1 MXMZCLLIUQEKSN-UHFFFAOYSA-N 0.000 claims 1
- -1 n-dodecyl Chemical group 0.000 description 36
- 239000010410 layer Substances 0.000 description 35
- 239000011521 glass Substances 0.000 description 20
- 125000000623 heterocyclic group Chemical group 0.000 description 16
- 150000001721 carbon Chemical group 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 125000002950 monocyclic group Chemical group 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- KXNQKOAQSGJCQU-UHFFFAOYSA-N benzo[e][1,3]benzothiazole Chemical compound C1=CC=C2C(N=CS3)=C3C=CC2=C1 KXNQKOAQSGJCQU-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000011245 gel electrolyte Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052714 tellurium Inorganic materials 0.000 description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IRFSXVIRXMYULF-UHFFFAOYSA-N 1,2-dihydroquinoline Chemical compound C1=CC=C2C=CCNC2=C1 IRFSXVIRXMYULF-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 2
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- BHQCQFFYRZLCQQ-UHFFFAOYSA-N (3alpha,5alpha,7alpha,12alpha)-3,7,12-trihydroxy-cholan-24-oic acid Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 BHQCQFFYRZLCQQ-UHFFFAOYSA-N 0.000 description 1
- JCWLOGAMQQPDKR-UHFFFAOYSA-N 1,2,3,4,4a,5-hexahydroquinoline Chemical compound C1=CCC2CCCNC2=C1 JCWLOGAMQQPDKR-UHFFFAOYSA-N 0.000 description 1
- YJUUZFWMKJBVFJ-UHFFFAOYSA-N 1,3-dimethylimidazolidin-4-one Chemical compound CN1CN(C)C(=O)C1 YJUUZFWMKJBVFJ-UHFFFAOYSA-N 0.000 description 1
- OGYGFUAIIOPWQD-UHFFFAOYSA-N 1,3-thiazolidine Chemical compound C1CSCN1 OGYGFUAIIOPWQD-UHFFFAOYSA-N 0.000 description 1
- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical compound C1C=CNC=C1 YNGDWRXWKFWCJY-UHFFFAOYSA-N 0.000 description 1
- IOWQHNLDXBGENT-UHFFFAOYSA-N 1-hexyl-4-(1-hexylpyridin-1-ium-4-yl)pyridin-1-ium Chemical compound C1=C[N+](CCCCCC)=CC=C1C1=CC=[N+](CCCCCC)C=C1 IOWQHNLDXBGENT-UHFFFAOYSA-N 0.000 description 1
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 1
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 1
- VZRIFNLQJXPRJI-UHFFFAOYSA-M 2,3-dimethyl-1,3-benzothiazol-3-ium;iodide Chemical compound [I-].C1=CC=C2[N+](C)=C(C)SC2=C1 VZRIFNLQJXPRJI-UHFFFAOYSA-M 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- POXIZPBFFUKMEQ-UHFFFAOYSA-N 2-cyanoethenylideneazanide Chemical group [N-]=C=[C+]C#N POXIZPBFFUKMEQ-UHFFFAOYSA-N 0.000 description 1
- VSWICNJIUPRZIK-UHFFFAOYSA-N 2-piperideine Chemical compound C1CNC=CC1 VSWICNJIUPRZIK-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LUAZZOXZPVVGSO-UHFFFAOYSA-N Benzyl viologen Chemical compound C=1C=C(C=2C=C[N+](CC=3C=CC=CC=3)=CC=2)C=C[N+]=1CC1=CC=CC=C1 LUAZZOXZPVVGSO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004380 Cholic acid Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 description 1
- PQBAWAQIRZIWIV-UHFFFAOYSA-N N-methylpyridinium Chemical compound C[N+]1=CC=CC=C1 PQBAWAQIRZIWIV-UHFFFAOYSA-N 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- LJOOWESTVASNOG-UFJKPHDISA-N [(1s,3r,4ar,7s,8s,8as)-3-hydroxy-8-[2-[(4r)-4-hydroxy-6-oxooxan-2-yl]ethyl]-7-methyl-1,2,3,4,4a,7,8,8a-octahydronaphthalen-1-yl] (2s)-2-methylbutanoate Chemical compound C([C@H]1[C@@H](C)C=C[C@H]2C[C@@H](O)C[C@@H]([C@H]12)OC(=O)[C@@H](C)CC)CC1C[C@@H](O)CC(=O)O1 LJOOWESTVASNOG-UFJKPHDISA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical compound C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- SKOLWUPSYHWYAM-UHFFFAOYSA-N carbonodithioic O,S-acid Chemical compound SC(S)=O SKOLWUPSYHWYAM-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- BHQCQFFYRZLCQQ-OELDTZBJSA-N cholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 BHQCQFFYRZLCQQ-OELDTZBJSA-N 0.000 description 1
- 229960002471 cholic acid Drugs 0.000 description 1
- 235000019416 cholic acid Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940127204 compound 29 Drugs 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 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
- 238000000151 deposition Methods 0.000 description 1
- 150000005690 diesters Chemical group 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229940118019 malondialdehyde Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- OIRDBPQYVWXNSJ-UHFFFAOYSA-N methyl trifluoromethansulfonate Chemical compound COS(=O)(=O)C(F)(F)F OIRDBPQYVWXNSJ-UHFFFAOYSA-N 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- PCILLCXFKWDRMK-UHFFFAOYSA-N naphthalene-1,4-diol Chemical compound C1=CC=C2C(O)=CC=C(O)C2=C1 PCILLCXFKWDRMK-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000012247 sodium ferrocyanide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 125000000626 sulfinic acid group Chemical group 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は光電変換素子およびこれを用いた電気化学電池に関し、詳しくは色素で増感された半導体微粒子を用いた光電変換素子および電気化学電池に関する。
【０００２】
【従来の技術】
光電変換素子は各種の光センサー、複写機、光発電装置に用いられている。光電変換素子には金属を用いたもの、半導体を用いたもの、有機顔料や色素を用いたもの、あるいはこれらを組み合わせたものなどの様々な方式が実用化されている。
【０００３】
米国特許４９２７７２１号、同４６８４５３７号、同５０８４３６５号、同５３５０６４４号、同５４６３０５７号、同５５２５４４０号の各明細書および特開平７−２４９７９０号公報には、色素によって増感された半導体微粒子を用いた光電変換素子（以後、色素増感光電変換素子と略す）、もしくはこれを作成するための材料および製造技術が開示されている。この方式の第一の利点は二酸化チタン等の安価な酸化物半導体を高純度に精製することなく用いることができるため、比較的安価な光電変換素子を提供できる点にある。第二の利点は用いられる色素の吸収がブロードなため、可視光線のほぼ全ての波長領域の光を電気に変換できることである。これらの特徴は太陽エネルギーを電気に変換することを目的とした光電変換素子（いわゆる太陽電池）に応用する際に有利であることから、この方面への応用が検討されている。
【０００４】
しかしながら、この方式の色素増感光電変換素子で高い変換効率を実現するには増感色素として高価なルテニウム錯体色素を用いなければならず、実用化の障害となることが懸念される。このような理由から、有機色素のような安価な色素によって増感され、高い効率で光電変換することのできる光電変換素子の開発が望まれていた。
【０００５】
【発明が解決しようとする課題】
本発明の目的は有機色素を用いた色素増感光電変換素子を提供することである。第二の目的はこのような光電変換素子を用いて変換効率の向上した光電気化学電池を提供することである。
【０００６】
【課題を解決するための手段】
研究の結果、下記の（１）〜（６）が本発明の目的に適うことを突き止めた。（１） 少なくとも導電性支持体および感光層を有する光電変換素子であって、
前記感光層が、下記一般式（１）および（２）で表されるポリメチン色素から選択された少なくとも１種によって増感された半導体微粒子を含有することを特徴とする光電変換素子。
【０００７】
【化３】
［一般式（１）中、Ｒ11、Ｒ12、Ｒ13およびＲ14は各々水素原子または１価の置換基を表す。Ｒ11〜Ｒ14は互いに結合して環を形成してもよい。Ｒ15はアルキル基を表す。Ａ11は炭素原子および窒素原子とともに３ないし９員環を形成するための原子団を表し、Ａ12は炭素原子とともに３ないし９員環を形成するための原子団を表す。Ｘは酸素原子または硫黄原子を表し、ｎ1は１〜４の整数を表す。一般式（１）で表される化合物は分子全体の電荷に応じて対イオンを有してもよい。
一般式（２）中、Ｒ21、Ｒ22、Ｒ23およびＲ24は各々水素原子または１価の置換基を表す。Ｒ21〜Ｒ24は互いに結合して環を形成してもよい。Ｒ25はアルキル基を表す。Ａ21は炭素原子および窒素原子とともに５ないし９員環を形成するための原子団を表し、Ａ22は炭素原子とともに５ないし９員環を形成するための原子団を表す。Ｘは酸素原子または硫黄原子を表し、ｎ2は０〜３の整数を表す。一般式（２）で表される化合物は分子全体の電荷に応じて対イオンを有してもよい。］
（２） 一般式（１）で表されるポリメチン色素において炭素原子、窒素原子、およびＡ11によって構成される複素環が、ベンゾチアゾリン、インドレニン、ナフトチアゾリン、またはベンゾインドレニンである上記（１）に記載の光電変換素子。
（３） 一般式（２）で表されるポリメチン色素において炭素原子、窒素原子、およびＡ21によって構成される複素環がジヒドロキノリンである上記（１）に記載の光電変換素子。
（４） 一般式（１）で表されるポリメチン色素において炭素原子、およびＡ12によって構成される環が、ロダニンまたは下記一般式（３）で表される上記（１）または（２）に記載の光電変換素子。
【０００９】
【化４】
［一般式（３）中、Ｒ31はアルキル基を表し、Ｒ32およびＲ33は各々独立にシアノ基またはカルボキシル基を表す。］
（５） ポリメチン色素が少なくとも１つのカルボキシル基を有する上記（１）〜（４）のいずれかに記載の光電変換素子。
（６） 上記（１）〜（５）のいずれかに記載の光電変換素子を有し、さらに少なくとも電荷移動層および対向電極を有する光電気化学電池。
【００１１】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明の光電変換素子は、導電性支持体上に感光層を有するものであり、感光層には一般式（１）、（２）で表されるポリメチン色素によって増感された半導体微粒子が含有されている。このように、一般式（１）、（２）で表されるポリメチン色素を用いることによって、変換効率に優れた色素増感光電変換素子を得ることができる。また、コスト面で有利である。
【００１２】
一般式（１）で表されるポリメチン色素について詳しく説明する。一般式（１）においてＲ11、Ｒ12、Ｒ13およびＲ14は各々水素原子または１価の置換基を表す。１価の置換基としてはアルキル基ないしアルケニル基（例えばメチル、エチル、ブチル、イソブチル、ｎ−ドデシル、シクロヘキシル、ビニル、アリル、ベンジル、フェネチル等）、アリール基（例えばフェニル、トリル、ナフチル等）、複素環残基（例えばピリジル基、イミダゾリル基、フリル基、チエニル基、オキサゾリル基、チアゾリル基、ベンズイミダゾリル基、キノリル基等）、ハロゲン原子（例えば、フッ素、塩素、臭素）、アルコキシ基（例えばメトキシ、エトキシ、ベンジルオキシ等）、アリールオキシ基（例えばフェノキシ等）、アルキルチオ基（例えばメチルチオ、エチルチオ等）、アリールチオ基（例えばフェニルチオ等）、ヒドロキシ基および酸素陰イオン、ニトロ基、シアノ基、アミド基（例えばアセチルアミノ、ベンゾイルアミノ等）、スルホンアミド基（例えばメタンスルホニルアミノ、ベンゼンスルホニルアミノ等）、ウレイド基（例えば、３ーフェニルウレイド等）、ウレタン基（例えばイソブトキシカルボニルアミノ、カルバモイルオキシ等）、エステル基（例えばアセトキシ、ベンゾイルオキシ、メトキシカルボニル、フェノキシカルボニル等）、カルバモイル基（例えばＮ−メチルカルバモイル、Ｎ，Ｎ−ジフェニルカルバモイル等）、スルファモイル基（例えばＮ−フェニルスルファモイル等）、アシル基（例えばアセチル、ベンゾイル等）、アミノ基（アミノ、メチルアミノ、アニリノ、ジフェニルアミノ等）、スルホニル基（例えばメチルスルホニル等）、ホスホニル基およびそのエステル、ホスホニルオキシ基およびそのエステル、カルボキシル基、スルホ基等が挙げられる。置換基の炭素原子上にはさらに上記の置換基があっても良い。
【００１３】
Ｒ11〜Ｒ14で代表されるメチン鎖置換基は互いに結合して３〜９員の単環もしくは多環性の芳香環、複素環、もしくは脂環式の環を形成してもよい。好ましい環としてはシクロブテン、シクロペンテン、シクロヘキセン、ベンゼン、デヒドロデカリン、ピリジン、ジヒドロピリジン、テトラヒドロピリジン、フラン、ジヒドロフラン、チオフェン、ジヒドロチオフェン、ヘキサヒドロキノリン等が挙げられる。これらすべての環はさらに３〜８員の芳香環、複素環、もしくは脂環式の環が縮合していてもよい。一般式（１）においてＲ15は総炭素数１〜１２の置換もしくは無置換のアルキル基を表す。アルキル基の例、置換基の例はＲ11〜Ｒ14の説明で述べたことが当てはまる。
【００１４】
一般式（１）においてＡ11は炭素原子、窒素原子とともに３〜９員の単環もしくは縮合環を形成するための原子団を表す。原子団の中で環を構成する原子としては炭素、窒素、酸素、硫黄、セレン、テルルである。Ａ11で完成される複素環としてはピロリジン、チアゾリジン、オキサゾリジン、チアゾリン、オキサゾリン、ベンゾチアゾリン、ベンゾオキサゾリン、インドレニン、ナフトチアゾリン、ナフトオキサゾリン、ベンゾインドレニン等が挙げられ、なかでもベンゾチアゾリン、インドレニン、ナフトチアゾリン、ベンゾインドレニンが好ましい。これらは前述の置換基を有していてもよい。
【００１５】
Ａ12は炭素原子とともに３〜９員の単環もしくは縮合環を形成するための原子団を表す。原子団の中で環を構成する原子としては炭素、窒素、酸素、硫黄、セレン、テルルである。Ａ12で完成される環としては、複素環が好ましく、さらには５員の複素環の環状ケトン（チオケトンも含む）が好ましい。これらは置換基を有していてもよい。置換基は前述のもの以外に置換エキソメチレン基、置換ポリメチン基が挙げられる。
【００１６】
置換エキソメチレン基における置換基の例としてはシアノ基、カルボキシル基、スルホニル基、アシル基、および複素環残基などが挙げられる。複素環残基は四級窒素原子に基づく電荷を有していてもよい。置換エキソメチレン基の具体例としてはジシアノメチレン、１−シアノ−１−カルボキシメチレン、１−メタンスルホニル−１−カルボキシメチレン、１−シアノ−１−アセチルメチレン、１−（３−メチルベンゾオキサゾリウム−２−イル）メチレンなどが挙げられる。置換ポリメチン基の例としては下記一般式（４）で表される基が挙げられる。
【００１７】
【化５】
一般式（４）中、Ｒ41、Ｒ42、およびＲ43は一般式（１）中のＲ11と同義である。Ｒ44は一般式（１）中のＲ15と同義である。ｎ3は０〜３の整数を表す。Ａ3は一般式（１）中のＡ11と同義である。星印は一般式（１）のＡ12との結合部位を示す。
【００１９】
特に、Ａ12で完成される複素環としては、アルキル基（例えばメチル、エチル、カルボキシメチル、カルボキシエチル）等で置換されていてもよいロダニン、および一般式（３）で表される複素環が好ましい。
【００２０】
一般式（３）中、Ｒ31はアルキル基（例えばメチル、エチル、カルボキシメチル、カルボキシエチル、フェネチル、アリル）を表す。Ｒ32、Ｒ33は各々シアノ基またはカルボキシル基を表し、これらは同一でも異なるものであってもよい。
【００２１】
一般式（１）においてｎ1は１〜４の整数を表す。メチン鎖の長さは色素の吸収波長に関係し、ｎ1の値が大きいほど長波な光を吸収するので目的に応じて適宜調節される。
【００２２】
一般式（１）で表される化合物は分子全体の電荷に応じて対イオンを有してもよい。対イオンとしては特に制限はなく有機、無機のいずれでもよい。代表的な例としてはハロゲンイオン（フッ素イオン、塩素イオン、臭素イオン、沃素イオン）、水酸イオン、過塩素酸イオン、テトラフルオロホウ酸イオン、ヘキサフルオロりん酸イオン、酢酸イオン、トリフルオロ酢酸イオン、メタンスルホン酸イオン、パラトルエンスルホン酸イオン、トリフルオロメタンスルホン酸イオン等のアニオン、アルカリ金属（リチウム、ナトリウム、カリウム等）、アルカり土類金属（マグネシウム、カルシウム等）、アンモニウム、アルキルアンモニウム（例えばジエチルアンモニウム、テトラブチルアンモニウム等）、ピリジニウム、アルキルピリジニウム（例えばメチルピリジニウム）、グアニジニウム、テトラアルキルホスホニウム等のカチオンが挙げられる。
【００２３】
一般式（１）で表される化合物は酸性基を有する場合、半導体微粒子への吸着性に優れるため特に好ましい。酸性基としては水−テトラヒドロフラン混合溶媒（体積比５０対５０）中のｐＫａが１０以下のものが好ましい。特に好ましくはカルボキシル基、スルホン酸基、スルフィン酸基、ホスホン酸基、水酸基、リン酸モノエステルおよびジエステル基等である。このうちカルボキシル基が最も好ましい。これらの基はアルカリ金属等と塩を形成したものであってもよい。また分子内塩を形成していてもよい。
【００２４】
次に一般式（２）ついて説明する。一般式（２）おいてＲ21〜Ｒ24は一般式（１）におけるＲ11と同義である。Ｒ25は一般式（１）のＲ15と同義である。Ａ21は炭素原子、窒素原子とともに５ないし９員の単環もしくは縮合環を形成するための原子団を表す。Ａ21で完成される複素環はジヒドロキノリン等が特に好ましい。これらはＡ11と同様の置換基を有していてもよい。
【００２５】
Ａ22は炭素原子とともに３〜９員の単環もしくは縮合環を形成するための原子団を表す。原子団の中で環を構成する原子としては炭素、窒素、酸素、硫黄、セレン、テルルである。Ａ22で完成される環としてはＡ12で完成される環と同様のものが挙げられ、これらは置換基を有していてもよい。置換基は前述のＡ12に対する置換基と同様のものである。Ａ22で完成される環の好ましいものはＡ12で完成される環と同様である。ｎ2は０〜３の整数を表す。一般式（２）で表される化合物は分子全体の電荷に応じて前述の対イオンを有してもよい。一般式（２）で表される化合物も前述の酸性基を有するのが好ましく、酸性基としてはカルボキシル基が最も好ましい。
【００２６】
以下に一般式（１）または（２）で表されるポリメチン色素の好ましい具体例を示す。
【００２７】
【化６】
【化７】
【化８】
【化９】
【化１０】
【化１１】
一般式（１）または（２）で表される本発明のポリメチン色素は、エフ・エム・ハーマー（F.M.Harmer）著「ヘテロサイクリック・コンパウンズ−シアニン・ダイズ・アンド・リレイテッド・コンパウンズ（Heterocyclic Compounds-Cyanine Dyes and Related Compounds ）」、ジョン・ウィリー・アンド・サンズ (John Willey & Sons) 社、ニューヨーク、ロンドン、１９９４年刊、ディー・エム・スターマー(D.M.Sturmer) 著「ヘテロサイクリック・コンパウンズ−スペシャル・トピックス・イン・ヘテロサイクリック・ケミストリー(Heterocyclic Compounds - Special Topics In Heterocyclic Chemistry）」、第１８章、第１４節４８２項から５１５項、ジョン・ウィリー・アンド・サンズ(John Willey & Sons)社、ニューヨーク、ロンドン、１９７７年刊、「ロッズ・ケミストリー・オブ・カーボン・コンパウンズ(Rodd's Chemistry of Carbon Compounds)」2nd Edition Vol.4, PartB、第１５章３６９項から４２２項、エルセビア・サイエンス・パブリック・カンパニー・インク(Eisevier Science Publishing Company Inc.)社、ニューヨーク、１９７７年刊、英国特許第１０７７６１１号などに記載の方法で合成することができる。
【００３４】
次に、本発明に用いられるポリメチン色素の合成法を具体例を挙げて説明するが、本発明はこれらに限定されない。
【００３５】
合成例１ 例示化合物（１）の合成
下記の合成ルートにて本発明の例示化合物（１）を合成した。
【００３６】
【化１２】
２，３−ジメチルベンゾチアゾリウムヨージド４０ｇとマロンジアルデヒドビスフェニルイミン５１ｇを１５０ｍｌの無水酢酸中、１４０℃にて二時間加熱撹拌した。反応液を１リットルの酢酸エチル中に注ぎ、析出した結晶を濾取することにより、化合物（１ａ）４５ｇを得た。
【００３８】
化合物（１ａ）２０ｇ、Ｎ−（２−フェニルエチル）ロダニン９．１ｇをメタノール１００ｍｌに溶解し、トリエチルアミン５．３１ｇを加えた。これを５０℃にて１０分間撹拌し、析出した結晶を濾過して化合物（１ｂ）１１．９ｇを得た。
【００３９】
化合物（１ｂ）１．５４ｇを塩化メチレンに溶解し１０℃にてトリフルオロメタンスルホン酸メチル０．４ｍｌを徐々に滴下し化合物（１ｃ）とした。別の容器に０．３ｇのシアノ酢酸を５ｍｌのテトラヒドロフランに溶解し、１０℃にてリチウムジイソプロピルアミドの２モル／ｌ溶液（アルドリッチ製）３．６ｍｌを加えた。得られた淡黄色のサスペンジョンを、化合物（１ｃ）の溶液中に０℃にて徐々に滴下した。反応液を直ちに５％酢酸水溶液２００ｍｌ中に注ぐと目的である本発明の例示化合物（１）の結晶０．３４ｇが得られた。
【００４０】
次に本発明のポリメチン色素を応用した色素増感光電変換素子、および光電気化学電池について詳しく説明する。
【００４１】
本発明において色素増感光電変換素子は導電性支持体、および導電性支持体上に塗設されるポリメチン色素の吸着した半導体微粒子の層（感光層）よりなる電極である。感光層は目的に応じて設計され単層構成でも多層構成でもよい。一層の感光層中の色素は一種類でも多種の混合でもよい。感光層に入射した光は色素を励起する。励起色素はエネルギーの高い電子を有しており、この電子が色素から半導体微粒子の伝導帯に渡され、さらに拡散によって導電性支持体に到達する。この時色素分子は酸化体となっているが、電極上の電子が外部回路で仕事をしながら色素酸化体に戻るのが光電気化学電池であり、色素増感光電変換素子はこの電池の負極として働く。
【００４２】
以下、導電性支持体、および感光層について詳しく説明する。
【００４３】
導電性支持体は金属のように支持体そのものに導電性があるものか、または表面に導電剤層を有するガラスもしくはプラスチックの支持体である。後者の場合好ましい導電剤としては金属（例えば白金、金、銀、銅、アルミニウム、ロジウム、インジウム等）、炭素、もしくは導電性の金属酸化物（インジウム−スズ複合酸化物、酸化スズにフッ素をドープしたもの等）が挙げられる。この場合の導電剤層の厚さは０．０５〜１０μm であることが好ましい。
【００４４】
導電性支持体は表面抵抗が低いほどよい。好ましい表面抵抗の範囲としては５０Ω/cm2以下であり、さらに好ましくは１０Ω/cm2以下である。この下限に特に制限はないが、通常０．１Ω/cm2程度である。
【００４５】
導電性支持体は実質的に透明であることが好ましい。実質的に透明であるとは光の透過率が１０％以上であることを意味し、５０％以上であることが好ましく、８０％以上が特に好ましい。透明導電性支持体としてはガラスもしくはプラスチックに導電性の金属酸化物を塗設したものが好ましい。このときの導電性の金属酸化物の塗布量はガラスもしくはプラスチックの支持体１m2当たり０．１〜１００g が好ましい。透明導電性支持体を用いる場合、光は支持体側から入射させることが好ましい。
【００４６】
感光層に用いられる半導体微粒子は金属のカルコゲニド（例えば酸化物、硫化物、セレン化物等）またはペロブスカイトの微粒子である。金属のカルコゲニドとしては好ましくはチタン、スズ、亜鉛、タングステン、ジルコニウム、ハフニウム、ストロンチウム、インジウム、セリウム、イットリウム、ランタン、バナジウム、ニオブ、もしくはタンタルの酸化物、硫化カドミウム、セレン化カドミウム等が挙げられる。ペロブスカイトとしては好ましくはチタン酸ストロンチウム、チタン酸カルシウム等が挙げられる。これらのうち酸化チタン、酸化亜鉛、酸化スズ、酸化タングステンが特に好ましい。
【００４７】
これらの半導体微粒子の粒径は、投影面積を円に換算したときの直径を用いた平均粒径で１次粒子として０．００１〜１μm 、分散物の平均粒径として０．０１〜１００μm であることが好ましい。
【００４８】
半導体微粒子を導電性支持体上に塗設する方法としては、半導体微粒子の分散液またはコロイド溶液を導電性支持体上に塗布する方法、半導体微粒子の前駆体を導電性支持体上に塗布し空気中の水分によって加水分解して半導体微粒子膜を得る方法などが挙げられる。半導体微粒子の分散液を作成する方法としては乳鉢ですり潰す方法、ミルを使って粉砕しながら分散する方法、あるいは半導体を合成する際に溶媒中で微粒子として析出させそのまま使用する方法等が挙げられる。分散媒としては水または各種の有機溶媒（例えばメタノール、エタノール、ジクロロメタン、アセトン、アセトニトリル、酢酸エチル等）が挙げられる。分散の際、必要に応じてポリマー、界面活性剤、酸、もしくはキレート剤などを分散助剤として用いてもよい。
【００４９】
半導体微粒子は多くの色素を吸着することができるように表面積の大きいものが好ましい。例えば半導体微粒子を支持体上に塗設した状態で、その表面積が投影面積に対して１０倍以上であることが好ましく、１００倍以上であることがより好ましい。この上限には特に制限はないが、通常５０００倍程度である。
【００５０】
一般に、半導体微粒子の層の厚みが大きいほど単位面積当たりに担持できる色素の量が増えるため光の吸収効率が高くなるが、発生した電子の拡散距離が増すため電荷再結合によるロスも大きくなる。半導体微粒子層（すなわち感光層）の好ましい厚みは素子の用途によって異なるが、典型的には０．１〜１００μm である。光電気化学電池として用いる場合は１〜５０μm であることが好ましく、３〜３０μm であることがより好ましい。半導体微粒子は支持体に塗布した後に粒子同士を密着させるために１００〜８００℃の温度で１０分〜１０時間焼成してもよい。
【００５１】
なお、半導体微粒子の支持体１m2当たりの塗布量は０．５〜５００g 、さらには５〜１００g が好ましい。
【００５２】
本発明において、半導体微粒子はポリメチン色素の吸着により増感されているが、半導体微粒子に色素を吸着させるには色素溶液の中によく乾燥した半導体微粒子を長時間浸漬する方法が一般的である。色素溶液は必要に応じて５０℃ないし１００℃に加熱してもよい。色素の吸着は半導体微粒子の塗布前に行っても塗布後に行ってもよい。また、半導体微粒子と色素を同時に塗布して吸着させても良い。未吸着の色素は洗浄によって除去する。塗布膜の焼成を行う場合は色素の吸着は焼成後に行うことが好ましい。焼成後、塗布膜表面に水が吸着する前にすばやく色素を吸着させるのが特に好ましい。吸着する色素は１種類でもよいし、数種混合して用いてもよい。混合する場合、本発明のポリメチン色素同士を混合してもよいし、米国特許４９２７７２１号、同４６８４５３７号、同５０８４３６５号、同５３５０６４４号、同５４６３０５７号、同５５２５４４０号の各明細書、および特開平７−２４９７９０号公報に記載の錯体色素と本発明の色素を混合してもよい。用途が光電気化学電池である場合、光電変換の波長域をできるだけ広くするように混合する色素が選ばれる。
【００５３】
色素の使用量は、全体で、支持体１m2当たり０．０１〜１００mモルが好ましく、より好ましくは０．１〜５０mモル、特に好ましくは０．５〜１０mモルである。この場合、本発明のポリメチン色素の使用量は５モル％以上とすることが好ましい。
【００５４】
また、色素の半導体微粒子に対する吸着量は半導体微粒子１g に対して０．００１〜１mモルが好ましく、より好ましくは０．１〜０．５mモルである。
【００５５】
このような色素量とすることによって、半導体における増感効果が十分に得られる。これに対し、色素量が少ないと増感効果が不十分となり、色素量が多すぎると、半導体に付着していない色素が浮遊し増感効果を低減させる原因となる。
【００５６】
また、会合など色素同士の相互作用を低減する目的で無色の化合物を共吸着させてもよい。共吸着させる疎水性化合物としてはカルボキシル基を有するステロイド化合物（例えばコール酸）等が挙げられる。
【００５７】
色素を吸着した後にアミン類を用いて半導体微粒子の表面を処理してもよい。好ましいアミン類としてはピリジン、４−ｔｅｒｔ−ブチルピリジン、ポリビニルピリジン等が挙げられる。これらは液体の場合はそのまま用いてもよいし有機溶媒に溶解して用いてもよい。
【００５８】
なお、本発明では、導電性支持体と感光層との界面近傍において、導電剤と半導体微粒子とが相互に拡散して混合していてもよい。
【００５９】
このようにして作成された色素増感光電変換素子は各種のセンサーや光再生型の光電気化学電池に応用することができる。光電気化学電池に応用する場合、図１に示すように電荷移動層と対向電極が必要である。
【００６０】
図１に示される光電気化学電池１は導電性支持体２上に感光層３を有し、さらに感光層３上に電荷移動層４と対向電極５が設けられたものである。
【００６１】
以下、電荷移動層と対向電極について詳しく説明する。
【００６２】
電荷移動層は色素の酸化体に電子を補充する機能を有する層である。代表的な例としては酸化還元対を有機溶媒に溶解した液体、酸化還元対を有機溶媒に溶解した液体をポリマーマトリクスに含浸したいわゆるゲル電解質、酸化還元対を含有する溶融塩などが挙げられる。
【００６３】
酸化還元対としては、例えば沃素と沃化物（例えば沃化リチウム、沃化テトラブチルアンモニウム、沃化テトラプロピルアンモニウム等）の組み合わせ、アルキルビオローゲン（例えばメチルビオローゲンクロリド、ヘキシルビオローゲンブロミド、ベンジルビオローゲンテトラフルオロボレート）とその還元体の組み合わせ、ポリヒドロキシベンゼン類（例えばハイドロキノン、ナフトハイドロキノン等）とその酸化体の組み合わせ、２価と３価の鉄錯体（例えば赤血塩と黄血塩）の組み合わせ等が挙げられる。これらのうち沃素と沃化物の組み合わせが好ましい。これらを溶かす有機溶媒としては非プロトン性の極性溶媒（例えばアセトニトリル、炭酸プロピレン、炭酸エチレン、ジメチルホルムアミド、ジメチルスルホキシド、スルホラン、１，３−ジメチルイミダゾリノン、３−メチルオキサゾリジノン等）が好ましい。ゲル電解質のマトリクスに使用されるポリマーとしては例えばポリアクリロニトリル、ポリビニリデンフルオリド等が挙げられる。溶融塩としては例えば沃化リチウムと他の少なくとも１種類のリチウム塩（例えば酢酸リチウム、過塩素酸リチウム等）が挙げられ、これらにポリエチレンオキシド等のポリマーを混合することにより、室温での流動性を高めてもよい。この場合のポリマーの添加量は１〜５０wt% である。
【００６４】
酸化還元対は電子のキャリアになるのである程度の濃度が必要である。液体あるいはゲル電解質として用いる場合の溶液中の好ましい濃度としては合計で０．０１モル／ｌ以上であり、より好ましくは０．１モル／ｌ以上であり、特に好ましくは０．３モル／ｌ以上である。この場合の上限には特に制限はないが、通常５モル／ｌ程度である。
【００６５】
対向電極は光電気化学電池の正極として働くものである。対向電極は通常前述の導電性支持体と同義であるが、強度が十分に保たれるような構成では支持体は必ずしも必要でない。ただし、支持体を有する方が密閉性の点で有利である。
【００６６】
感光層に光が到達するためには、前述の導電性支持体と対向電極の少なくとも一方は実質的に透明でなければならない。本発明の光電気化学電池においては、導電性支持体が透明であって太陽光を支持体側から入射させるのが好ましい。この場合対向電極は光を反射する性質を有することがさらに好ましい。光電気化学電池の対向電極としては金属もしくは導電性の酸化物を蒸着したガラス、またはプラスチックが好ましく、白金を蒸着したガラスが特に好ましい。
【００６７】
光電気化学電池では構成物の蒸散を防止するために電池の側面をポリマーや接着剤等で密封することが好ましい。
【００６８】
このようにして得られる光電気化学電池の特性は、ＡＭ１．５Ｇで１００mW/cm2のとき、開放電圧０．０１〜３Ｖ、短絡電流密度０．００１〜２０mA/cm2、形状因子０．１〜０．９９、変換効率０．００１〜２５％である。
【００６９】
【実施例】
以下に本発明の色素増感光電変換素子および光電気化学電池の作成方法について実施例によって具体的に説明するが、本発明はこれらに限定されない。
【００７０】
実施例１
二酸化チタン分散液の調製
内側をテフロンコーティングした内容積２００ｍｌのステンレス製ベッセルに二酸化チタン（日本アエロジル社 ＤｅｇｕｓｓａＰ−２５）１５ｇ、水４５ｇ、分散剤（アルドリッチ社製、ＴｒｉｔｏｎＸ−１００）１ｇ、直径０．５ｍｍのジルコニアビーズ（ニッカトー社製）３０ｇを入れ、サンドグラインダーミル（アイメックス社製）を用いて１５００ｒｐｍにて２時間分散した。分散物からジルコニアビーズを濾過して除いた。この場合の二酸化チタンの平均粒径は２．５μm であった。このときの粒径はＭＡＬＶＥＲＮ社製マスターサイザーにて測定したものである。
【００７１】
光電変換素子の作成
フッ素をドープした酸化スズをコーティングした導電性ガラス（旭硝子製 ＴＣＯガラスを２０ｍｍ×２０ｍｍの大きさに切断加工したもの）の導電面側にガラス棒を用いて上記の分散液を塗布した。なお、導電性ガラスの表面抵抗は約３０Ω/cm2であった。
【００７２】
この際導電面側の一部（端から３ｍｍ）に粘着テープを張ってスペーサーとし、粘着テープが両端に来るようにガラスを並べて一度に８枚ずつ塗布した。塗布後、室温にて１日間風乾し、粘着テープを剥した（粘着テープのついていた部分は光電変換測定の際、計測器と電気的な接触をとるために利用される）。次に、このガラスを電気炉（ヤマト科学製マッフル炉ＦＰ−３２型）に入れ、４５０℃にて３０分間焼成した。ガラスを取り出し冷却した後、表１に示す例示化合物の色素のエタノール溶液（３×１０-4モル／ｌ）に３時間浸漬した。色素の染着したガラスを４−ｔｅｒｔ−ブチルピリジンの１０wt% エタノール溶液に３０分間浸漬した後、エタノールで洗浄し自然乾燥させた。このようにして得られる感光層の厚さは１０μm であり、半導体微粒子の塗布量は２０g/m2とした。色素の塗布量は、色素の種類に応じ、適宜０．１〜１０mモル/m2の範囲から選択した。
【００７３】
反射スペクトルの測定
上記の光電変換素子を積分球を装着した分光光度計（日立製作所Ｕ−３５００型）を用いて反射スペクトルを測定した。表１には最も長波長側の吸収ピークにおける波長と吸光度の値を示した。
【００７４】
光電気化学電池の作成
図１の光電気化学電池の一態様として図２に示すような光電気化学電池を作成した。図２の光電気化学電池１０は、ガラス支持体１１上に導電剤層１２を有する導電性支持体上に感光層１３を設けた構成の上記の光電変換素子を用いたものであり、感光層１３上に電荷移動層である電解液層１４を有し、さらに対向電極として白金蒸着ガラス１５を配置したものである。この作成において、上記の光電変換素子をこれと同じ大きさの白金蒸着ガラスと重ねあわせた（図２、光電変換素子の未塗布部分を白金蒸着ガラスに接触させないようにずらしてある）。次に、両ガラスの隙間に毛細管現象を利用して電解液（アセトニトリルとＮ−メチル−２−オキサゾリジノンの体積比９０対１０の混合物を溶媒とした沃素０．０５モル／ｌ、沃化リチウム０．５モル／ｌの溶液）を滲み込ませた。
【００７５】
光電変換効率の測定
５００Ｗのキセノンランプ（ウシオ製）の光をＡＭ１．５Ｇフィルター（Ｏｒｉｅｌ社製）およびシャープカットフィルター（ＫｅｎｋｏＬ−４２）を通すことにより紫外線を含まない模擬太陽光を発生させた。この光の強度は５０mW/cm2であった。
【００７６】
上記の光電変換素子にこの光を照射し、発生した電気を電流電圧測定装置（ケースレー２３８型）にて測定した。これにより求められた光化学電池の開放電圧、短絡電流、形状因子、および変換効率を表１にまとめた。
【００７７】
【表１】
表１より明らかなように、いずれの色素でも光電変換特性が認められる。さらに詳細に見ると、カルボキシル基を有しない色素（例示化合物２９）に比べてカルボキシル基を有する色素（例示化合物１、２１、２２、２３）は色素の染着性にすぐれ、その結果として光電変換効率が高いことがわかる。
【００７９】
【発明の効果】
本発明により有機色素を用いた色素増感光電変換素子が提供されることが明らかとなった。従って、このような光電変換素子を用いて光電気化学電池を構成することができた。
【図面の簡単な説明】
【図１】本発明の光電気化学電池の一構成例を示す断面図である。
【図２】実施例で用いた光電気化学電池の一構成例を示す断面図である。
【符号の説明】
１、１０ 光電気化学電池
２ 導電性支持体
３、１３ 感光層
４ 電荷移動層
５ 対向電極
１１ ガラス支持体
１２ 導電剤層
１４ 電解液層
１５ 白金蒸着ガラス[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photoelectric conversion element and an electrochemical cell using the photoelectric conversion element, and more particularly to a photoelectric conversion element and an electrochemical cell using semiconductor fine particles sensitized with a dye.
[0002]
[Prior art]
Photoelectric conversion elements are used in various optical sensors, copying machines, and photovoltaic power generation devices. Various systems such as those using metals, semiconductors, organic pigments and dyes, or combinations thereof have been put to practical use as photoelectric conversion elements.
[0003]
U.S. Pat. Nos. 4,927,721, 4,684,537, 5,084,365, 5,350,644, 5,463,057, and 5,525,440 and JP-A-7-249790 used semiconductor fine particles sensitized with a dye. A photoelectric conversion element (hereinafter abbreviated as a dye-sensitized photoelectric conversion element), or a material and a manufacturing technique for producing the photoelectric conversion element are disclosed. The first advantage of this method is that an inexpensive oxide semiconductor such as titanium dioxide can be used without being purified with high purity, so that a relatively inexpensive photoelectric conversion element can be provided. The second advantage is that the absorption of the dye used is broad, so that light in almost all wavelength regions of visible light can be converted into electricity. Since these characteristics are advantageous when applied to a photoelectric conversion element (so-called solar cell) for the purpose of converting solar energy into electricity, application in this direction is being studied.
[0004]
However, in order to achieve high conversion efficiency with this type of dye-sensitized photoelectric conversion element, an expensive ruthenium complex dye must be used as the sensitizing dye, which may be a hindrance to practical use. For these reasons, it has been desired to develop a photoelectric conversion element that can be sensitized by an inexpensive dye such as an organic dye and can perform photoelectric conversion with high efficiency.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a dye-sensitized photoelectric conversion element using an organic dye. A second object is to provide a photoelectrochemical cell having improved conversion efficiency using such a photoelectric conversion element.
[0006]
[Means for Solving the Problems]
As a result of the research, it was found that the following (1) to (6) are suitable for the purpose of the present invention. (1) A photoelectric conversion element having at least a conductive support and a photosensitive layer,
The photoelectric conversion element, wherein the photosensitive layer contains semiconductor fine particles sensitized by at least one selected from polymethine dyes represented by the following general formulas (1) and (2).
[0007]
[Chemical 3]
[In general formula (1), R 11 , R 12 , R 13 And R 14 Each represents a hydrogen atom or a monovalent substituent. R 11 ~ R 14 May combine with each other to form a ring. R 15 Represents an alkyl group. A 11 Represents an atomic group for forming a 3- to 9-membered ring with a carbon atom and a nitrogen atom, and A 12 Represents an atomic group for forming a 3- to 9-membered ring with a carbon atom. X represents an oxygen atom or a sulfur atom, and n 1 Represents an integer of 1 to 4. The compound represented by the general formula (1) may have a counter ion according to the charge of the whole molecule.
In general formula (2), R twenty one , R twenty two , R twenty three And R twenty four Each represents a hydrogen atom or a monovalent substituent. R twenty one ~ R twenty four May combine with each other to form a ring. R twenty five Represents an alkyl group. A twenty one Represents an atomic group for forming a 5- to 9-membered ring with a carbon atom and a nitrogen atom, and A twenty two Represents an atomic group for forming a 5- to 9-membered ring with a carbon atom. X represents an oxygen atom or a sulfur atom, and n 2 Represents an integer of 0 to 3. The compound represented by the general formula (2) may have a counter ion according to the charge of the whole molecule. ]
(2) In the polymethine dye represented by the general formula (1), a carbon atom, a nitrogen atom, and A 11 The photoelectric conversion element according to (1), wherein the heterocyclic ring is benzothiazoline, indolenine, naphthothiazoline, or benzoindolenine.
(3) A carbon atom, a nitrogen atom, and A in the polymethine dye represented by the general formula (2) twenty one The photoelectric conversion element according to the above (1), wherein the heterocycle constituted by dihydroquinoline.
(4) a carbon atom in the polymethine dye represented by the general formula (1), and A 12 The photoelectric conversion element as described in said (1) or (2) by which the ring comprised by a rhodanine or following General formula (3) is represented.
[0009]
[Formula 4]
[In general formula (3), R 31 Represents an alkyl group, R 32 And R 33 Each independently represents a cyano group or a carboxyl group. ]
(5) The photoelectric conversion element according to any one of (1) to (4), wherein the polymethine dye has at least one carboxyl group.
(6) A photoelectrochemical cell comprising the photoelectric conversion device according to any one of (1) to (5) above, and further comprising at least a charge transfer layer and a counter electrode.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The photoelectric conversion element of the present invention has a photosensitive layer on a conductive support, and the photosensitive layer contains semiconductor fine particles sensitized by the polymethine dyes represented by the general formulas (1) and (2). Has been. Thus, the dye-sensitized photoelectric conversion element excellent in conversion efficiency can be obtained by using the polymethine dyes represented by the general formulas (1) and (2). Moreover, it is advantageous in terms of cost.
[0012]
The polymethine dye represented by the general formula (1) will be described in detail. In the general formula (1), R 11 , R 12 , R 13 And R 14 Each represents a hydrogen atom or a monovalent substituent. As monovalent substituents, alkyl groups or alkenyl groups (for example, methyl, ethyl, butyl, isobutyl, n-dodecyl, cyclohexyl, vinyl, allyl, benzyl, phenethyl, etc.), aryl groups (for example, phenyl, tolyl, naphthyl, etc.), Heterocyclic residues (eg, pyridyl, imidazolyl, furyl, thienyl, oxazolyl, thiazolyl, benzimidazolyl, quinolyl, etc.), halogen atoms (eg, fluorine, chlorine, bromine), alkoxy groups (eg, methoxy) , Ethoxy, benzyloxy etc.), aryloxy groups (eg phenoxy etc.), alkylthio groups (eg methylthio, ethylthio etc.), arylthio groups (eg phenylthio etc.), hydroxy groups and oxygen anions, nitro groups, cyano groups, amide groups (Eg acetylamino Benzoylamino etc.), sulfonamide groups (eg methanesulfonylamino, benzenesulfonylamino etc.), ureido groups (eg 3-phenylureido etc.), urethane groups (eg isobutoxycarbonylamino, carbamoyloxy etc.), ester groups (eg Acetoxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, etc.), carbamoyl groups (eg N-methylcarbamoyl, N, N-diphenylcarbamoyl etc.), sulfamoyl groups (eg N-phenylsulfamoyl etc.), acyl groups (eg acetyl, Benzoyl etc.), amino group (amino, methylamino, anilino, diphenylamino etc.), sulfonyl group (eg methylsulfonyl etc.), phosphonyl group and its ester, phosphonyloxy group and its ester , Carboxyl group, etc. sulfo group. The above substituents may be further present on the carbon atom of the substituent.
[0013]
R 11 ~ R 14 May be bonded to each other to form a 3- to 9-membered monocyclic or polycyclic aromatic ring, heterocyclic ring, or alicyclic ring. Preferred rings include cyclobutene, cyclopentene, cyclohexene, benzene, dehydrodecalin, pyridine, dihydropyridine, tetrahydropyridine, furan, dihydrofuran, thiophene, dihydrothiophene, hexahydroquinoline and the like. All these rings may be further condensed with a 3- to 8-membered aromatic ring, heterocyclic ring or alicyclic ring. In the general formula (1), R 15 Represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms in total. Examples of alkyl groups, examples of substituents are R 11 ~ R 14 This is the case in the explanation of.
[0014]
In the general formula (1), A 11 Represents an atomic group for forming a 3- to 9-membered monocyclic or condensed ring together with a carbon atom and a nitrogen atom. The atoms constituting the ring in the atomic group are carbon, nitrogen, oxygen, sulfur, selenium and tellurium. A 11 Examples of the heterocyclic ring completed in pyrrolidine, thiazolidine, oxazolidine, thiazoline, oxazoline, benzothiazoline, benzoxazoline, indolenine, naphthothiazoline, naphthoxazoline, benzoindolenine, among others, benzothiazoline, indolenine, naphtho Thiazoline and benzoindolenin are preferred. These may have the aforementioned substituents.
[0015]
A 12 Represents an atomic group for forming a 3- to 9-membered monocyclic or condensed ring with a carbon atom. The atoms constituting the ring in the atomic group are carbon, nitrogen, oxygen, sulfur, selenium and tellurium. A 12 The ring completed by is preferably a heterocyclic ring, more preferably a 5-membered heterocyclic cyclic ketone (including a thioketone). These may have a substituent. Examples of the substituent include a substituted exomethylene group and a substituted polymethine group other than those described above.
[0016]
Examples of the substituent in the substituted exomethylene group include a cyano group, a carboxyl group, a sulfonyl group, an acyl group, and a heterocyclic residue. The heterocyclic residue may have a charge based on a quaternary nitrogen atom. Specific examples of the substituted exomethylene group include dicyanomethylene, 1-cyano-1-carboxymethylene, 1-methanesulfonyl-1-carboxymethylene, 1-cyano-1-acetylmethylene, 1- (3-methylbenzoxazolium -2-yl) methylene and the like. Examples of the substituted polymethine group include a group represented by the following general formula (4).
[0017]
[Chemical formula 5]
In general formula (4), R 41 , R 42 And R 43 Is R in the general formula (1) 11 It is synonymous with. R 44 Is R in the general formula (1) 15 It is synonymous with. n Three Represents an integer of 0 to 3. A Three Is A in the general formula (1) 11 It is synonymous with. The star is A in the general formula (1) 12 The binding site is shown.
[0019]
In particular, A 12 As the heterocyclic ring completed by the above, a rhodanine optionally substituted with an alkyl group (for example, methyl, ethyl, carboxymethyl, carboxyethyl) and the heterocyclic ring represented by the general formula (3) are preferable.
[0020]
In general formula (3), R 31 Represents an alkyl group (for example, methyl, ethyl, carboxymethyl, carboxyethyl, phenethyl, allyl). R 32 , R 33 Each represents a cyano group or a carboxyl group, which may be the same or different.
[0021]
N in general formula (1) 1 Represents an integer of 1 to 4. The length of the methine chain is related to the absorption wavelength of the dye, and n 1 The larger the value of, the longer the light that is absorbed.
[0022]
The compound represented by the general formula (1) may have a counter ion according to the charge of the whole molecule. The counter ion is not particularly limited and may be either organic or inorganic. Typical examples are halogen ion (fluorine ion, chlorine ion, bromine ion, iodine ion), hydroxide ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, acetate ion, trifluoroacetate ion. , Anions such as methanesulfonate ion, paratoluenesulfonate ion, trifluoromethanesulfonate ion, alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (magnesium, calcium, etc.), ammonium, alkylammonium (e.g. Cations such as diethylammonium, tetrabutylammonium, etc.), pyridinium, alkylpyridinium (for example, methylpyridinium), guanidinium, tetraalkylphosphonium and the like.
[0023]
When the compound represented by the general formula (1) has an acidic group, it is particularly preferable because of its excellent adsorptivity to semiconductor fine particles. As the acidic group, those having a pKa of 10 or less in a water-tetrahydrofuran mixed solvent (volume ratio 50:50) are preferable. Particularly preferred are carboxyl group, sulfonic acid group, sulfinic acid group, phosphonic acid group, hydroxyl group, phosphoric acid monoester and diester group. Of these, carboxyl groups are most preferred. These groups may form a salt with an alkali metal or the like. In addition, an inner salt may be formed.
[0024]
Next, the general formula (2) will be described. R in general formula (2) twenty one ~ R twenty four Is R in the general formula (1) 11 It is synonymous with. R twenty five Is R in the general formula (1) 15 It is synonymous with. A twenty one Represents an atomic group for forming a 5- or 9-membered monocyclic or condensed ring together with a carbon atom and a nitrogen atom. A twenty one The heterocyclic ring completed by is particularly preferably dihydroquinoline. These are A 11 And may have the same substituent.
[0025]
A twenty two Represents an atomic group for forming a 3- to 9-membered monocyclic or condensed ring with a carbon atom. The atoms constituting the ring in the atomic group are carbon, nitrogen, oxygen, sulfur, selenium and tellurium. A twenty two As a ring completed in A 12 Examples of the ring completed in the above can be mentioned, and these may have a substituent. Substituent is the aforementioned A 12 It is the same as the substituent for A twenty two A preferred ring completed with 12 This is similar to the ring completed in n 2 Represents an integer of 0 to 3. The compound represented by the general formula (2) may have the aforementioned counter ion according to the charge of the whole molecule. The compound represented by the general formula (2) also preferably has the aforementioned acidic group, and the carboxyl group is most preferable as the acidic group.
[0026]
Preferred specific examples of the polymethine dye represented by the general formula (1) or (2) are shown below.
[0027]
[Chemical 6]
[Chemical 7]
[Chemical 8]
[Chemical 9]
[Chemical Formula 10]
Embedded image
The polymethine dye of the present invention represented by the general formula (1) or (2) is “Heterocyclic Compounds-Cyanine” by FM Harmer (FMHarmer). Dyes and Related Compounds ”, John Willey & Sons, New York, London, 1994, DMSturmer“ Heterocyclic Compounds-Special Topics in “Heterocyclic Compounds-Special Topics In Heterocyclic Chemistry”, Chapter 18, Sections 482-515, John Willey & Sons, New York, London, Published in 1977, “Rods Chemistry of Carbon Co.” "Rodd's Chemistry of Carbon Compounds" 2nd Edition Vol.4, Part B, Chapter 15, 369-422, Eisevier Science Public Company Inc., New York, 1977, It can be synthesized by the method described in British Patent No. 1077611.
[0034]
Next, the method for synthesizing the polymethine dye used in the present invention will be described with specific examples, but the present invention is not limited to these.
[0035]
Synthesis Example 1 Synthesis of Exemplary Compound (1)
Exemplified compound (1) of the present invention was synthesized by the following synthesis route.
[0036]
Embedded image
40 g of 2,3-dimethylbenzothiazolium iodide and 51 g of malondialdehyde bisphenylimine were heated and stirred at 140 ° C. for 2 hours in 150 ml of acetic anhydride. The reaction solution was poured into 1 liter of ethyl acetate, and the precipitated crystals were collected by filtration to obtain 45 g of Compound (1a).
[0038]
20 g of compound (1a) and 9.1 g of N- (2-phenylethyl) rhodanine were dissolved in 100 ml of methanol, and 5.31 g of triethylamine was added. This was stirred at 50 ° C. for 10 minutes, and the precipitated crystals were filtered to obtain 11.9 g of Compound (1b).
[0039]
Compound (1b) (1.54 g) was dissolved in methylene chloride, and 0.4 ml of methyl trifluoromethanesulfonate was gradually added dropwise at 10 ° C. to obtain Compound (1c). In a separate container, 0.3 g of cyanoacetic acid was dissolved in 5 ml of tetrahydrofuran, and 3.6 ml of a 2 mol / l lithium diisopropylamide solution (manufactured by Aldrich) was added at 10 ° C. The obtained pale yellow suspension was gradually added dropwise at 0 ° C. to the solution of the compound (1c). When the reaction solution was immediately poured into 200 ml of 5% aqueous acetic acid, 0.34 g of the target compound of the exemplified compound (1) of the present invention was obtained.
[0040]
Next, the dye-sensitized photoelectric conversion element and the photoelectrochemical cell to which the polymethine dye of the present invention is applied will be described in detail.
[0041]
In the present invention, the dye-sensitized photoelectric conversion element is an electrode comprising a conductive support and a layer (photosensitive layer) of semiconductor fine particles adsorbed with a polymethine dye coated on the conductive support. The photosensitive layer is designed according to the purpose and may have a single layer structure or a multilayer structure. The dyes in one photosensitive layer may be one kind or a mixture of various kinds. Light incident on the photosensitive layer excites the dye. The excitation dye has electrons with high energy, and these electrons are transferred from the dye to the conduction band of the semiconductor fine particles, and further reach the conductive support by diffusion. At this time, the dye molecule is an oxidant, but the electrons on the electrode return to the dye oxidant while working in the external circuit, and the dye-sensitized photoelectric conversion element is the negative electrode of this battery. Work as.
[0042]
Hereinafter, the conductive support and the photosensitive layer will be described in detail.
[0043]
The conductive support is a support made of glass or plastic having a conductive agent layer on the surface, such as a metal, which is conductive in itself. In the latter case, preferred conductive agents are metals (eg, platinum, gold, silver, copper, aluminum, rhodium, indium, etc.), carbon, or conductive metal oxides (indium-tin composite oxide, tin oxide doped with fluorine. Etc.). In this case, the thickness of the conductive agent layer is preferably 0.05 to 10 μm.
[0044]
The lower the surface resistance of the conductive support, the better. The preferred surface resistance range is 50 Ω / cm 2 Or less, more preferably 10 Ω / cm 2 It is as follows. This lower limit is not particularly limited, but is usually 0.1Ω / cm 2 Degree.
[0045]
It is preferable that the conductive support is substantially transparent. Substantially transparent means that the light transmittance is 10% or more, preferably 50% or more, particularly preferably 80% or more. As the transparent conductive support, a glass or plastic coated with a conductive metal oxide is preferable. At this time, the amount of conductive metal oxide applied is 1 m of glass or plastic support. 2 0.1 to 100 g per unit is preferred. When a transparent conductive support is used, light is preferably incident from the support side.
[0046]
Semiconductor fine particles used in the photosensitive layer are metal chalcogenides (for example, oxide, sulfide, selenide, etc.) or perovskite fine particles. Preferred examples of the metal chalcogenide include titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, tantalum oxide, cadmium sulfide, and cadmium selenide. Preferred perovskites include strontium titanate and calcium titanate. Of these, titanium oxide, zinc oxide, tin oxide, and tungsten oxide are particularly preferable.
[0047]
The particle diameters of these semiconductor fine particles are 0.001 to 1 μm as primary particles and 0.01 to 100 μm as the average particle diameter of the dispersion in terms of the average particle diameter when the projected area is converted into a circle. It is preferable.
[0048]
The method of coating the semiconductor fine particles on the conductive support includes a method in which a dispersion or colloidal solution of semiconductor fine particles is applied on the conductive support, and a precursor of semiconductor fine particles is applied on the conductive support and air is applied. Examples thereof include a method of obtaining a semiconductor fine particle film by hydrolysis with moisture therein. Examples of a method for preparing a dispersion of semiconductor fine particles include a method of pulverizing with a mortar, a method of dispersing while pulverizing using a mill, or a method of depositing fine particles in a solvent and using them as they are when a semiconductor is synthesized. . Examples of the dispersion medium include water or various organic solvents (for example, methanol, ethanol, dichloromethane, acetone, acetonitrile, ethyl acetate, etc.). During dispersion, a polymer, surfactant, acid, chelating agent, or the like may be used as a dispersion aid as necessary.
[0049]
The semiconductor fine particles preferably have a large surface area so that many dyes can be adsorbed. For example, in a state where the semiconductor fine particles are coated on the support, the surface area is preferably 10 times or more, more preferably 100 times or more the projected area. Although there is no restriction | limiting in particular in this upper limit, Usually, it is about 5000 times.
[0050]
In general, as the thickness of the semiconductor fine particle layer increases, the amount of dye that can be carried per unit area increases, so that the light absorption efficiency increases. The preferred thickness of the semiconductor fine particle layer (that is, the photosensitive layer) varies depending on the use of the device, but is typically 0.1 to 100 μm. When used as a photoelectrochemical cell, the thickness is preferably 1 to 50 μm, more preferably 3 to 30 μm. The semiconductor fine particles may be fired at a temperature of 100 to 800 ° C. for 10 minutes to 10 hours in order to adhere the particles to each other after being applied to the support.
[0051]
Semiconductor fine particle support 1m 2 The coating amount per unit is preferably 0.5 to 500 g, more preferably 5 to 100 g.
[0052]
In the present invention, the semiconductor fine particles are sensitized by the adsorption of polymethine dye. In order to adsorb the dye to the semiconductor fine particles, a method of immersing well-dried semiconductor fine particles in a dye solution for a long time is general. The dye solution may be heated to 50 ° C. to 100 ° C. as necessary. The adsorption of the dye may be performed before or after application of the semiconductor fine particles. Further, the semiconductor fine particles and the pigment may be applied and adsorbed simultaneously. Unadsorbed dye is removed by washing. When baking a coating film, it is preferable to adsorb | suck a pigment | dye after baking. It is particularly preferable that the dye is quickly adsorbed after the baking and before water adsorbs on the surface of the coating film. One type of dye may be adsorbed or a mixture of several types may be used. In the case of mixing, the polymethine dyes of the present invention may be mixed together, US Pat. Nos. 4,927,721, 4,684,537, 5,084,365, 5,350,644, 5,463,057, 5,525,440, and You may mix the complex pigment | dye described in 7-249790, and the pigment | dye of this invention. When the application is a photoelectrochemical cell, a dye to be mixed is selected so as to make the wavelength range of photoelectric conversion as wide as possible.
[0053]
The total amount of dye used is 1m on the support. 2 The amount is preferably from 0.01 to 100 mmol, more preferably from 0.1 to 50 mmol, particularly preferably from 0.5 to 10 mmol. In this case, the amount of the polymethine dye of the present invention is preferably 5 mol% or more.
[0054]
The amount of the dye adsorbed on the semiconductor fine particles is preferably 0.001 to 1 mmol, more preferably 0.1 to 0.5 mmol, per 1 g of the semiconductor fine particles.
[0055]
By using such a dye amount, a sensitizing effect in a semiconductor can be sufficiently obtained. On the other hand, when the amount of the dye is small, the sensitizing effect becomes insufficient, and when the amount of the dye is too large, the dye not attached to the semiconductor floats and causes the sensitizing effect to be reduced.
[0056]
Further, a colorless compound may be co-adsorbed for the purpose of reducing the interaction between dyes such as association. Examples of the hydrophobic compound to be co-adsorbed include steroid compounds having a carboxyl group (for example, cholic acid).
[0057]
After adsorbing the dye, the surface of the semiconductor fine particles may be treated with amines. Preferable amines include pyridine, 4-tert-butylpyridine, polyvinylpyridine and the like. These may be used as they are in the case of a liquid, or may be used by dissolving in an organic solvent.
[0058]
In the present invention, the conductive agent and the semiconductor fine particles may be diffused and mixed with each other in the vicinity of the interface between the conductive support and the photosensitive layer.
[0059]
The dye-sensitized photoelectric conversion element thus prepared can be applied to various sensors and photoregenerative photoelectrochemical cells. When applied to a photoelectrochemical cell, a charge transfer layer and a counter electrode are required as shown in FIG.
[0060]
A
[0061]
Hereinafter, the charge transfer layer and the counter electrode will be described in detail.
[0062]
The charge transfer layer is a layer having a function of replenishing electrons to the oxidant of the dye. Typical examples include a liquid in which a redox couple is dissolved in an organic solvent, a so-called gel electrolyte in which a polymer matrix is impregnated with a liquid in which a redox pair is dissolved in an organic solvent, and a molten salt containing the redox couple.
[0063]
Examples of the redox pair include a combination of iodine and iodide (eg, lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, etc.), alkyl viologen (eg, methyl viologen chloride, hexyl viologen bromide, benzyl viologen tetrafluoroborate). ) And a reduced form thereof, a combination of polyhydroxybenzenes (eg, hydroquinone, naphthohydroquinone, etc.) and an oxidized form thereof, a combination of a divalent and trivalent iron complex (eg, red blood salt and yellow blood salt), and the like. It is done. Of these, a combination of iodine and iodide is preferred. As the organic solvent for dissolving them, an aprotic polar solvent (for example, acetonitrile, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl sulfoxide, sulfolane, 1,3-dimethylimidazolinone, 3-methyloxazolidinone, etc.) is preferable. Examples of the polymer used for the matrix of the gel electrolyte include polyacrylonitrile and polyvinylidene fluoride. Examples of the molten salt include lithium iodide and at least one other lithium salt (for example, lithium acetate, lithium perchlorate, etc.). By mixing these with a polymer such as polyethylene oxide, the fluidity at room temperature. May be increased. In this case, the amount of the polymer added is 1 to 50 wt%.
[0064]
Since the redox couple becomes an electron carrier, a certain concentration is required. The preferred concentration in the solution when used as a liquid or gel electrolyte is 0.01 mol / l or more in total, more preferably 0.1 mol / l or more, and particularly preferably 0.3 mol / l or more. It is. The upper limit in this case is not particularly limited, but is usually about 5 mol / l.
[0065]
The counter electrode serves as the positive electrode of the photoelectrochemical cell. The counter electrode is usually synonymous with the conductive support described above, but the support is not necessarily required in a configuration in which the strength is sufficiently maintained. However, having a support is advantageous in terms of hermeticity.
[0066]
In order for light to reach the photosensitive layer, at least one of the conductive support and the counter electrode described above must be substantially transparent. In the photoelectrochemical cell of the present invention, the conductive support is preferably transparent, and sunlight is preferably incident from the support side. In this case, the counter electrode more preferably has a property of reflecting light. The counter electrode of the photoelectrochemical cell is preferably glass or plastic deposited with a metal or conductive oxide, and glass deposited with platinum is particularly preferred.
[0067]
In the photoelectrochemical battery, it is preferable to seal the side surface of the battery with a polymer, an adhesive, or the like in order to prevent evaporation of components.
[0068]
The characteristics of the photoelectrochemical cell thus obtained are 100 mW / cm at AM 1.5G. 2 Open circuit voltage 0.01-3V, short circuit current density 0.001-20mA / cm 2 The shape factor is 0.1 to 0.99, and the conversion efficiency is 0.001 to 25%.
[0069]
【Example】
The method for producing the dye-sensitized photoelectric conversion element and the photoelectrochemical cell of the present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
[0070]
Example 1
Preparation of titanium dioxide dispersion
Teflon-coated stainless steel vessel with inner volume of 200 ml, titanium dioxide (Nippon Aerosil Degussa P-25) 15 g, water 45 g, dispersant (Aldrich Triton X-100) 1 g, 0.5 mm diameter zirconia beads (Nikkato) 30 g), and dispersed for 2 hours at 1500 rpm using a sand grinder mill (manufactured by Imex). The zirconia beads were filtered off from the dispersion. In this case, the average particle diameter of titanium dioxide was 2.5 μm. The particle size at this time is measured with a master sizer manufactured by MALVERN.
[0071]
Creation of photoelectric conversion element
The above dispersion was applied to the conductive surface side of conductive glass coated with tin oxide doped with fluorine (TCO glass manufactured by Asahi Glass cut into a size of 20 mm × 20 mm) using a glass rod. The surface resistance of conductive glass is about 30Ω / cm. 2 Met.
[0072]
At this time, adhesive tape was applied to a part of the conductive surface side (3 mm from the end) to form a spacer, and glass was arranged so that the adhesive tape came to both ends, and 8 sheets were applied at a time. After application, the film was air-dried at room temperature for 1 day, and the adhesive tape was peeled off (the part to which the adhesive tape was attached was used for making electrical contact with the measuring instrument during photoelectric conversion measurement). Next, this glass was put into an electric furnace (a muffle furnace FP-32 manufactured by Yamato Scientific Co., Ltd.) and baked at 450 ° C. for 30 minutes. After the glass is taken out and cooled, it is shown in Table 1. Exemplary compounds Solution of dye in ethanol (3 × 10 -Four Mol / l) for 3 hours. The dyed glass was immersed in a 10 wt% ethanol solution of 4-tert-butylpyridine for 30 minutes, then washed with ethanol and air dried. The thickness of the photosensitive layer thus obtained is 10 μm, and the coating amount of semiconductor fine particles is 20 g / m. 2 It was. The coating amount of the dye is appropriately 0.1 to 10 mmol / m depending on the kind of the dye. 2 Selected from a range of
[0073]
Reflection spectrum measurement
The reflection spectrum was measured using a spectrophotometer (Hitachi, Ltd. U-3500 type) equipped with an integrating sphere. Table 1 shows the wavelength and absorbance values at the absorption peak on the longest wavelength side.
[0074]
Creation of photoelectrochemical cell
As an embodiment of the photoelectrochemical cell of FIG. 1, a photoelectrochemical cell as shown in FIG. 2 was prepared. The
[0075]
Measurement of photoelectric conversion efficiency
Simulated sunlight containing no ultraviolet rays was generated by passing light from a 500 W xenon lamp (made by Ushio) through an AM1.5G filter (made by Oriel) and a sharp cut filter (KenkoL-42). The intensity of this light is 50mW / cm 2 Met.
[0076]
above The photoelectric conversion element was irradiated with this light, and the generated electricity was measured with a current-voltage measuring device (Keutley 238 type). Table 1 summarizes the open circuit voltage, short circuit current, form factor, and conversion efficiency of the photochemical battery thus determined.
[0077]
[Table 1]
As is clear from Table 1, photoelectric conversion characteristics are recognized with any dye. In more detail, the dye having the carboxyl group (
[0079]
【The invention's effect】
It became clear that the present invention provides a dye-sensitized photoelectric conversion element using an organic dye. Therefore, a photoelectrochemical cell could be constructed using such a photoelectric conversion element.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing one structural example of the photoelectrochemical cell of the present invention.
FIG. 2 is a cross-sectional view showing a structural example of a photoelectrochemical cell used in Examples.
[Explanation of symbols]
1, 10 Photoelectrochemical cell
2 Conductive support
3,13 Photosensitive layer
4 Charge transfer layer
5 Counter electrode
11 Glass support
12 Conductive agent layer
14 Electrolyte layer
15 Platinum-deposited glass
Claims (2)
一般式（６）中、Ｒ21、Ｒ22、Ｒ23およびＲ24は各々水素原子または１価の置換基を表す。Ｒ21〜Ｒ24は互いに結合して環を形成してもよい。Ｒ25はアルキル基を表す。Ａ 21 、炭素原子および窒素原子によって形成される環は、 1,4- ジヒドロキノリンを表す。ｎ2は０〜３の整数を表す。Ｒ 31 はアルキル基を表し、Ｒ 32 およびＲ 33 は各々独立にシアノ基またはカルボキシル基を表す。一般式（６）で表される化合物は少なくとも１つのカルボキシル基を有する。一般式（６）で表される化合物は分子全体の電荷に応じて対イオンを有してもよい。］A photoelectric conversion element having at least a conductive support and a photosensitive layer, wherein the photosensitive layer is sensitized by at least one selected from polymethine dyes represented by the following general formulas (5) and (6) A photoelectric conversion element comprising semiconductor fine particles.
In the general formula (6) , R 21 , R 22 , R 23 and R 24 each represent a hydrogen atom or a monovalent substituent. R 21 to R 24 may combine with each other to form a ring. R 25 represents an alkyl group. The ring formed by A 21 , carbon atom and nitrogen atom represents 1,4 -dihydroquinoline. n 2 represents an integer of 0 to 3. R 31 represents an alkyl group, and R 32 and R 33 each independently represent a cyano group or a carboxyl group. The compound represented by the general formula (6) has at least one carboxyl group. The compound represented by the general formula (6) may have a counter ion according to the charge of the whole molecule. ]
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21977598A JP4148375B2 (en) | 1997-07-18 | 1998-07-17 | Photoelectric conversion element and photoelectrochemical cell |
| DE69823706T DE69823706T2 (en) | 1997-10-23 | 1998-10-22 | Photoelectric conversion assembly and photoelectrochemical cell |
| AT00126792T ATE266246T1 (en) | 1997-10-23 | 1998-10-22 | PHOTOELECTRIC CONVERSION ARRANGEMENT AND PHOTOELECTROCHEMICAL CELL |
| EP00126792A EP1091373B1 (en) | 1997-10-23 | 1998-10-22 | Photoelectric conversion device and photo-electrochemical cell |
| EP98120012A EP0911841B1 (en) | 1997-10-23 | 1998-10-22 | Photoelectric conversion device and photoelectrochemical cell |
| DE69810421T DE69810421T2 (en) | 1997-10-23 | 1998-10-22 | Photoelectric conversion assembly and photoelectrochemical cell |
| AT98120012T ATE230517T1 (en) | 1997-10-23 | 1998-10-22 | PHOTOELECTRIC CONVERSION ARRANGEMENT AND PHOTOELECTROCHEMICAL CELL |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20995897 | 1997-07-18 | ||
| JP33811597 | 1997-11-21 | ||
| JP9-338115 | 1997-11-21 | ||
| JP9-209958 | 1997-11-21 | ||
| JP21977598A JP4148375B2 (en) | 1997-07-18 | 1998-07-17 | Photoelectric conversion element and photoelectrochemical cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11214731A JPH11214731A (en) | 1999-08-06 |
| JP4148375B2 true JP4148375B2 (en) | 2008-09-10 |
Family
ID=27329073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21977598A Expired - Fee Related JP4148375B2 (en) | 1997-07-18 | 1998-07-17 | Photoelectric conversion element and photoelectrochemical cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4148375B2 (en) |
Families Citing this family (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5054269B2 (en) * | 2000-07-27 | 2012-10-24 | 日本化薬株式会社 | Dye-sensitized photoelectric conversion element |
| JP4278080B2 (en) | 2000-09-27 | 2009-06-10 | 富士フイルム株式会社 | High sensitivity light receiving element and image sensor |
| JP5142307B2 (en) * | 2000-11-28 | 2013-02-13 | 独立行政法人産業技術総合研究所 | Semiconductor thin film electrode and photoelectric conversion element using organic dye as photosensitizer |
| TW541330B (en) | 2001-03-07 | 2003-07-11 | Nippon Kayaku Kk | Photo-electric conversion device and oxide semiconductor fine particle |
| CN1524315B (en) | 2001-07-06 | 2013-02-13 | 日本化药株式会社 | Photoelectric conversion element sensitized with coloring matter |
| JP4841248B2 (en) | 2003-03-14 | 2011-12-21 | 日本化薬株式会社 | Dye-sensitized photoelectric conversion element |
| JP4963343B2 (en) * | 2004-09-08 | 2012-06-27 | 日本化薬株式会社 | Dye-sensitized photoelectric conversion element |
| EP1885015A1 (en) | 2005-05-24 | 2008-02-06 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| CA2610759A1 (en) | 2005-06-14 | 2006-12-21 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| AU2007221706B2 (en) | 2006-03-02 | 2011-12-22 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| AU2007270404B2 (en) | 2006-07-05 | 2011-04-28 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized solar cell |
| JP2009135318A (en) | 2007-11-30 | 2009-06-18 | Fujifilm Corp | Photoelectric conversion device, imaging device, and optical sensor |
| KR101137571B1 (en) | 2008-05-12 | 2012-04-19 | 코니카 미놀타 비지니스 테크놀로지즈 가부시키가이샤 | Dye-sensitized solar cell and method for manufacturing the same |
| JP6337561B2 (en) | 2014-03-27 | 2018-06-06 | 株式会社リコー | Perovskite solar cell |
| CN110571334A (en) | 2014-04-16 | 2019-12-13 | 株式会社理光 | Photoelectric conversion element |
| EP3410506B1 (en) | 2016-01-25 | 2022-03-30 | Ricoh Company, Ltd. | Photoelectric conversion element |
| US10651390B2 (en) | 2016-06-08 | 2020-05-12 | Ricoh Company, Ltd. | Tertiary amine compound, photoelectric conversion element, and solar cell |
| EP3552253B1 (en) | 2016-12-07 | 2022-02-16 | Ricoh Company, Ltd. | Photoelectric conversion element |
| US11575095B2 (en) | 2018-03-19 | 2023-02-07 | Ricoh Company, Ltd. | Photoelectric conversion device, process cartridge, and image forming apparatus |
| EP4000098A1 (en) | 2019-07-16 | 2022-05-25 | Ricoh Company, Ltd. | Solar cell module, electronic device, and power supply module |
| CN114341745A (en) | 2019-09-26 | 2022-04-12 | 株式会社理光 | Electronic device and its production method, imaging method and imaging apparatus |
| US20210167287A1 (en) | 2019-11-28 | 2021-06-03 | Tamotsu Horiuchi | Photoelectric conversion element, photoelectric conversion module, electronic device, and power supply module |
| JP7508782B2 (en) | 2020-01-20 | 2024-07-02 | 株式会社リコー | Electronic device and its manufacturing method, image forming method, and image forming apparatus |
| JP7413833B2 (en) | 2020-02-27 | 2024-01-16 | 株式会社リコー | Photoelectric conversion element and photoelectric conversion module |
| EP3872861B1 (en) | 2020-02-27 | 2023-06-28 | Ricoh Company, Ltd. | Photoelectric conversion element and photoelectric conversion module |
| WO2021187373A1 (en) | 2020-03-16 | 2021-09-23 | Ricoh Company, Ltd. | Photoelectric conversion element, photoelectric conversion module, electronic device, and power supply module |
| JP2022144443A (en) | 2021-03-19 | 2022-10-03 | 株式会社リコー | Photoelectric conversion element, electronic device, and power supply module |
| EP4064355A1 (en) | 2021-03-23 | 2022-09-28 | Ricoh Company, Ltd. | Solar cell module |
| EP4092704A1 (en) | 2021-05-20 | 2022-11-23 | Ricoh Company, Ltd. | Photoelectric conversion element and method for producing photoelectric conversion element, photoelectric conversion module, and electronic device |
| US20240357919A1 (en) | 2021-07-29 | 2024-10-24 | Satoshi Yamamoto | Photoelectric conversion element and solar cell module |
| JP2023019661A (en) | 2021-07-29 | 2023-02-09 | 株式会社リコー | Photoelectric conversion element, photoelectric conversion module, and electronic device |
| EP4161234A1 (en) | 2021-09-30 | 2023-04-05 | Ricoh Company, Ltd. | Photoelectric conversion element, photoelectric conversion module, and electronic device |
| CN116096111A (en) | 2021-10-29 | 2023-05-09 | 株式会社理光 | Photoelectric conversion element and photoelectric conversion element module |
| EP4188053A1 (en) | 2021-11-26 | 2023-05-31 | Ricoh Company, Ltd. | Photoelectric conversion element, photoelectric conversion module, electronic device, and partition |
| JP2023137773A (en) | 2022-03-18 | 2023-09-29 | 株式会社リコー | Photoelectric conversion elements, photoelectric conversion modules, electronic equipment, and solar cell modules |
-
1998
- 1998-07-17 JP JP21977598A patent/JP4148375B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11214731A (en) | 1999-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4148375B2 (en) | Photoelectric conversion element and photoelectrochemical cell | |
| JP4148374B2 (en) | Photoelectric conversion element and photoelectrochemical cell | |
| JP4201095B2 (en) | Photoelectric conversion element and photoelectrochemical cell | |
| EP0911841B1 (en) | Photoelectric conversion device and photoelectrochemical cell | |
| JP2000106224A (en) | Photoelectric conversion element and photo electrochemical cell | |
| JP4363553B2 (en) | Electrolyte composition, photoelectric conversion element and photoelectrochemical cell | |
| JPH11185836A (en) | Photoelectric conversion element and photoregeneration type photoelectrochemical cell | |
| JP2004063274A (en) | Photoelectric conversion material, semiconductor electrode, and photoelectric conversion element using the same | |
| WO2010050574A1 (en) | Photoelectrochemical cell | |
| JP2012144688A (en) | Photoelectric conversion element, photoelectrochemical battery, dye for photoelectric conversion element, and dye solution for photoelectric conversion element | |
| JP2000106222A (en) | Semiconductor film for photoelectric conversion element and photo-electrochemical cell | |
| JP5051810B2 (en) | Dye-sensitized photoelectric conversion element | |
| JP2005093307A (en) | Photoelectric conversion element | |
| JP2004235011A (en) | Electrolyte solution using iodine-cyclodextrin clathrate and photoelectric conversion element using the same | |
| JP4460686B2 (en) | Photoelectric conversion element and photoelectrochemical cell | |
| JPH1167285A (en) | Photoelectric conversion element and photoelectrochemical cell | |
| JP4169220B2 (en) | Photoelectric conversion element | |
| JP5405155B2 (en) | Photoelectrochemical cell | |
| JP2001035253A (en) | Electrolyte composition, photoelectric transfer element and photo-electrochemical battery | |
| JP2000150007A (en) | Photoelectric conversion element, its manufacture, and photo electrochemical battery | |
| JPH1197725A (en) | Photoelectric conversion element and photoelectrochemical cell | |
| JP2007112987A (en) | Compound, photoelectric conversion element and photoelectrochemical cell | |
| JP2000036332A (en) | Electrolyte, photoelectric conversion element, and photo-regenerative photo-electrochemical battery | |
| JP2005019252A (en) | Photoelectric conversion material, semiconductor electrode, and photoelectric conversion element using the same | |
| JP2001035552A (en) | Electrolyte composition, photoelectric converting element and photoelectric chemical battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040311 |
|
| RD01 | Notification of change of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7421 Effective date: 20040618 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20061213 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080227 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080331 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20080618 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20080619 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110704 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110704 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120704 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120704 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130704 Year of fee payment: 5 |
|
| LAPS | Cancellation because of no payment of annual fees |