JPH1167285A - Photoelectric conversion element and photo electrochemical cell - Google Patents
Photoelectric conversion element and photo electrochemical cellInfo
- Publication number
- JPH1167285A JPH1167285A JP9246050A JP24605097A JPH1167285A JP H1167285 A JPH1167285 A JP H1167285A JP 9246050 A JP9246050 A JP 9246050A JP 24605097 A JP24605097 A JP 24605097A JP H1167285 A JPH1167285 A JP H1167285A
- Authority
- JP
- Japan
- Prior art keywords
- group
- integer
- photoelectric conversion
- ring
- sulfur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 50
- 239000004065 semiconductor Substances 0.000 claims abstract description 37
- 239000010419 fine particle Substances 0.000 claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 23
- 239000011593 sulfur Substances 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000001841 imino group Chemical group [H]N=* 0.000 claims abstract description 21
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 16
- 239000011669 selenium Substances 0.000 claims abstract description 16
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 16
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 6
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 239000000975 dye Substances 0.000 claims description 54
- 125000001424 substituent group Chemical group 0.000 claims description 28
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- 238000012546 transfer Methods 0.000 claims description 8
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- 125000002843 carboxylic acid group Chemical group 0.000 claims description 4
- VXPLXMJHHKHSOA-UHFFFAOYSA-N propham Chemical compound CC(C)OC(=O)NC1=CC=CC=C1 VXPLXMJHHKHSOA-UHFFFAOYSA-N 0.000 claims description 4
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
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- 239000000203 mixture Substances 0.000 description 4
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
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- 238000002360 preparation method Methods 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
- 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
- 229940126062 Compound A Drugs 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000002252 acyl 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
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 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 2
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- 125000005842 heteroatom Chemical group 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 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
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- 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
- YJUUZFWMKJBVFJ-UHFFFAOYSA-N 1,3-dimethylimidazolidin-4-one Chemical compound CN1CN(C)C(=O)C1 YJUUZFWMKJBVFJ-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
- SJJCQDRGABAVBB-UHFFFAOYSA-N 1-hydroxy-2-naphthoic acid Chemical compound C1=CC=CC2=C(O)C(C(=O)O)=CC=C21 SJJCQDRGABAVBB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-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
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Substances CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- JGXDUSIXAAJIQK-UHFFFAOYSA-N methyl n-[2-amino-5-(diethylamino)phenyl]carbamate Chemical compound CCN(CC)C1=CC=C(N)C(NC(=O)OC)=C1 JGXDUSIXAAJIQK-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
- 238000002156 mixing Methods 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
- 230000003472 neutralizing effect Effects 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 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
- 229910000484 niobium oxide Inorganic materials 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
- 229920002113 octoxynol Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000002971 oxazolyl group Chemical group 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
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 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
- 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
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000001376 precipitating effect Effects 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
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-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
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000010898 silica gel chromatography Methods 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
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000012247 sodium ferrocyanide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 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
- 150000004763 sulfides Chemical class 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
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 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
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-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
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 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
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/652—Cyanine dyes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- 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
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Photoreceptors In Electrophotography (AREA)
- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は光電変換素子および
これを用いた光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光電
気化学電池に関する。The present invention relates to a photoelectric conversion element and a photoelectrochemical cell using the same, and more particularly, to a photoelectric conversion element and a photoelectrochemical cell using semiconductor fine particles sensitized with a dye.
【0002】[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。2. Description of the Related Art Photoelectric conversion elements are used in various optical sensors, copying machines, and photovoltaic devices. Various types of photoelectric conversion elements have been put into practical use, such as those using metals, those using semiconductors, those using organic pigments and dyes, and those combining these.
【0003】米国特許4927721号、同46845
37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
活発に検討されている。[0003] US Patent Nos. 4,927,721 and 46,845
No. 37, No. 5,084,365, No. 5,350,644, No. 5,463,057, No. 5,525,440 and JP-A-7-249790 describe a photoelectric conversion element using semiconductor fine particles sensitized with a dye (hereinafter, referred to as a photoelectric conversion element). Dye-sensitized photoelectric conversion elements), or materials and manufacturing techniques for producing the same. The first advantage of this method is that an inexpensive oxide semiconductor such as titanium dioxide can be used without purification to a high degree of purity, so that a relatively inexpensive photoelectric conversion element can be provided. The second advantage is that since the absorption of the dye used is broad, light in almost all visible wavelength regions can be converted into electricity. Since these features are advantageous when applied to a photoelectric conversion element (so-called solar cell) for converting solar energy into electricity, application to this area is being actively studied.
【0004】しかしながらこのタイプの色素増感光電変
換素子に用いられるルテニウム錯体色素はきわめて高価
であり、その使用量が比較的少ないとはいえコスト上昇
の要因となっている。このような理由から、安価な有機
色素を用いた色素増感光電変換素子の開発が求められて
いた。However, the ruthenium complex dye used in this type of dye-sensitized photoelectric conversion element is extremely expensive, and causes a rise in cost, although its use is relatively small. For these reasons, development of a dye-sensitized photoelectric conversion element using an inexpensive organic dye has been demanded.
【0005】[0005]
【発明が解決しようとする課題】本発明の第一の目的は
有機色素を用い変換効率にすぐれた安価な色素増感光電
変換素子を提供することであり、第二の目的はこのよう
な光電変換素子を用いた光電気化学電池を提供すること
である。A first object of the present invention is to provide an inexpensive dye-sensitized photoelectric conversion element having an excellent conversion efficiency using an organic dye, and a second object of the present invention is to provide such a photoelectric conversion element. An object of the present invention is to provide a photoelectrochemical cell using a conversion element.
【0006】[0006]
【課題を解決するための手段】研究の結果、下記の
(1)〜(5)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
(I)および(II)で表される色素から選ばれた少なく
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。As a result of research, it has been found that the following (1) to (5) are suitable for the purpose of the present invention. (1) A photoelectric conversion device having at least a conductive support and a photosensitive layer, wherein the photosensitive layer is sensitized by at least one selected from dyes represented by the following general formulas (I) and (II). A photoelectric conversion element, characterized in that the photoelectric conversion element contains semiconductor fine particles.
【0007】[0007]
【化2】 Embedded image
【0008】[一般式(I)中、R11およびR12は各々
1価の置換基を表し、n11は0〜4の整数であり、n12
は0〜3の整数である。X1は酸素、硫黄、セレン、テ
ルル、イミノ基、アルキレン基またはアルケニレン基を
表し、Y1は酸素、硫黄、セレン、テルル、イミノ基、
インモニウム基またはメチレン基を表す。n11が2以上
の整数である時R11同士が結合して環を形成してもよ
く、n12が2以上の整数である時R12同士が結合して環
を形成してもよく、Y1とR12とが結合して環を形成し
てもよい。一般式(II)中、R21,R22およびR24は各
々1価の置換基を表し、n21およびn24は各々0〜4の
整数であり、n22は0〜3の整数である。R23は水素、
アルキル基、アリール基または複素環残基を表す。X2
は酸素、硫黄、セレン、テルル、イミノ基、アルキレン
基またはアルケニレン基を表し、Y2は酸素、硫黄、セ
レン、テルル、イミノ基、インモニウム基またはメチレ
ン基を表す。B2は窒素またはメチン基を表す。n21が
2以上の整数である時R21同士が結合して環を形成して
もよく、n22が2以上の整数である時R22同士が結合し
て環を形成してもよく、n24が2以上の整数である時R
24同士が結合して環を形成してもよく、R22,B2,R
24およびY2から選ばれた2つ以上が結合して環を形成
してもよい。] (2) 一般式(I)中のX1が酸素または硫黄であ
り、一般式(II)中のX2が酸素または硫黄である上記
(1)の光電変換素子。 (3) 一般式(I)で表される色素が置換基として少
なくとも1つの酸性基を有し、一般式(II)で表される
色素が置換基として少なくとも1つの酸性基を有する上
記(1)または(2)の光電変換素子。 (4) 酸性基のうちの少なくとも1つがカルボン酸
基、スルホン酸基、リン酸モノエステル基およびリン酸
ジエステル基から選ばれた上記(3)の光電変換素子。 (5) 上記(1)〜(4)のいずれかの光電交換素子
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。[In the general formula (I), R 11 and R 12 each represent a monovalent substituent, n 11 is an integer of 0 to 4, and n 12
Is an integer of 0 to 3. X 1 represents oxygen, sulfur, selenium, tellurium, imino group, alkylene group or alkenylene group, Y 1 represents oxygen, sulfur, selenium, tellurium, imino group,
Represents an immonium group or a methylene group. When n 11 is an integer of 2 or more, R 11 may be bonded to each other to form a ring, and when n 12 is an integer of 2 or more, R 12 may be bonded to each other to form a ring, Y 1 and R 12 may combine to form a ring. In the general formula (II), R 21 , R 22 and R 24 each represent a monovalent substituent, n 21 and n 24 are each an integer of 0 to 4, and n 22 is an integer of 0 to 3. . R 23 is hydrogen,
Represents an alkyl group, an aryl group or a heterocyclic residue. X 2
Represents oxygen, sulfur, selenium, tellurium, imino group, alkylene group or alkenylene group, and Y 2 represents oxygen, sulfur, selenium, tellurium, imino group, immonium group or methylene group. B 2 represents a nitrogen or methine group. When n 21 is an integer of 2 or more, R 21 may be bonded to each other to form a ring, and when n 22 is an integer of 2 or more, R 22 may be bonded to each other to form a ring, When n 24 is an integer of 2 or more, R
24 may combine with each other to form a ring, and R 22 , B 2 , R
Two or more selected from 24 and Y 2 may combine to form a ring. (2) The photoelectric conversion device according to the above (1), wherein X 1 in the general formula (I) is oxygen or sulfur, and X 2 in the general formula (II) is oxygen or sulfur. (3) The above-mentioned (1), wherein the dye represented by the general formula (I) has at least one acidic group as a substituent, and the dye represented by the general formula (II) has at least one acidic group as a substituent. ) Or (2). (4) The photoelectric conversion element according to (3), wherein at least one of the acidic groups is selected from a carboxylic acid group, a sulfonic acid group, a phosphoric acid monoester group, and a phosphoric acid diester group. (5) A photoelectrochemical cell having the photoelectric exchange element according to any one of (1) to (4), and further having at least a charge transfer layer and a counter electrode.
【0009】[0009]
【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(I)、(II)で表
される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。このような色素を用いることによって、変換効
率にすぐれた色素増感光電変換素子を低コストで得るこ
とができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below 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 dyes represented by formulas (I) and (II). ing. By using such a dye, a dye-sensitized photoelectric conversion element having excellent conversion efficiency can be obtained at low cost.
【0010】一般式(I)、(II)について説明する
と、一般式(I)中、R11およびR12は各々1価の置換
基を表し、n11は0〜4の整数であり、n12は0〜3の
整数である。X1は酸素、硫黄、セレン、テルル、イミ
ノ基、アルキレン基またはアルケニレン基を表し、Y1
は酸素、硫黄、セレン、テルル、イミノ基、インモニウ
ム基またはメチレン基を表す。n11が2以上の整数であ
る時R11同士が結合して環を形成してもよく、n12が2
以上の整数である時R12同士が結合して環を形成しても
よく、Y1とR12とが結合して環を形成してもよい。The general formulas (I) and (II) will be described. In the general formula (I), R 11 and R 12 each represent a monovalent substituent, n 11 is an integer of 0 to 4, 12 is an integer of 0 to 3. X 1 represents oxygen, sulfur, selenium, tellurium, an imino group, an alkylene group or alkenylene group, Y 1
Represents oxygen, sulfur, selenium, tellurium, imino, immonium or methylene. n 11 is 2 or more integer which when R 11 may combine with each other to form a ring, n 12 is 2
When it is the above integer, R 12 may be bonded to each other to form a ring, or Y 1 and R 12 may be bonded to each other to form a ring.
【0011】また、一般式(II)中、R21,R22および
R24は各々1価の置換基を表し、n21およびn24は各々
0〜4の整数であり、n22は0〜3の整数である。R23
は水素、アルキル基、アリール基または複素環残基を表
す。X2は酸素、硫黄、セレン、テルル、イミノ基、ア
ルキレン基またはアルケニレン基を表し、Y2は酸素、
硫黄、セレン、テルル、イミノ基、インモニウム基また
はメチレン基を表す。B2は窒素またはメチン基を表
す。n21が2以上の整数である時R21同士が結合して環
を形成してもよく、n22が2以上の整数である時R22同
士が結合して環を形成してもよく、n24が2以上の整数
である時R24同士が結合して環を形成してもよく、
R22,B2,R24およびY2から選ばれた2つ以上が結合
して環を形成してもよい。In the general formula (II), R 21 , R 22 and R 24 each represent a monovalent substituent, n 21 and n 24 each represent an integer of 0 to 4, and n 22 represents 0 to 4 It is an integer of 3. R 23
Represents hydrogen, an alkyl group, an aryl group or a heterocyclic residue. X 2 represents oxygen, sulfur, selenium, tellurium, imino group, alkylene group or alkenylene group, Y 2 represents oxygen,
Represents sulfur, selenium, tellurium, imino group, immonium group or methylene group. B 2 represents a nitrogen or methine group. When n 21 is an integer of 2 or more, R 21 may be bonded to each other to form a ring, and when n 22 is an integer of 2 or more, R 22 may be bonded to each other to form a ring, When n 24 is an integer of 2 or more, R 24 may combine with each other to form a ring,
Two or more selected from R 22 , B 2 , R 24 and Y 2 may combine to form a ring.
【0012】さらに詳しく説明すると、一般式(I)、
(II)中、R11、R12、R21、R22およびR24で表され
る1価の置換基の例としては、アルキル基(例えばメチ
ル、エチル、イソブチル、n−ドデシル、シクロヘキシ
ル、ビニル、アリル、ベンジル等)、アリール基(例え
ばフェニル、ナフチル等)、複素環残基(例えばピロリ
ジニル基、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)、メルカプト基、硫黄陰イオ
ン、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(Na+、K+等と塩を形成
していてもよい)、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(例えばアミノ、メチルアミ
ノ、ジメチルアミノ、メチルエチルアミノ、ジエチルア
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(カルボキシラト基や塩を形成したもの
も含む)、スルホ基(スルホナト基や塩を形成したもの
も含む)等が挙げられる。これらはさらに置換基を有し
ていてもよい。More specifically, the general formula (I):
In (II), examples of the monovalent substituent represented by R 11 , R 12 , R 21 , R 22 and R 24 include an alkyl group (eg, methyl, ethyl, isobutyl, n-dodecyl, cyclohexyl, vinyl , Allyl, benzyl, etc.), aryl groups (eg, phenyl, naphthyl, etc.), heterocyclic residues (eg, pyrrolidinyl, pyridyl, imidazolyl, furyl, thienyl, oxazolyl, thiazolyl, benzimidazolyl, quinolyl) Etc.), halogen atoms (for example,
Fluorine, chlorine, bromine), alkoxy groups (eg, methoxy, ethoxy, benzyloxy, etc.), aryloxy groups (eg, phenoxy, etc.), mercapto groups, sulfur anions, alkylthio groups (eg, methylthio, ethylthio, etc.), arylthio groups (eg, Phenylthio, etc.), hydroxy group and oxygen anion (which may form a salt with Na + , K +, etc.), nitro group, cyano group, amide group (eg, acetylamino, benzoylamino etc.), sulfonamide group ( For example, methanesulfonylamino, benzenesulfonylamino, etc.), a ureido group (eg, 3-phenylureido), a urethane group (eg, isobutoxycarbonylamino, carbamoyloxy, etc.), and an ester group (eg, acetoxy, benzoyloxy, methoxycarbonyl, phenoxy) Cal Sulfonyl, etc.), a carbamoyl group (such as N- methylcarbamoyl, N, N- diphenylcarbamoyl, etc.), a sulfamoyl group (e.g., N- phenylsulfamoyl), an acyl group (e.g. acetyl,
Benzoyl, etc.), amino group (eg, amino, methylamino, dimethylamino, methylethylamino, diethylamino, anilino, diphenylamino, etc.), sulfonyl group (eg, methylsulfonyl, etc.), phosphonyl group and its ester, phosphonyloxy group and its ester,
Examples thereof include a carboxyl group (including a carboxylate group and a salt) and a sulfo group (including a sulfonato group and a salt). These may further have a substituent.
【0013】R11で表される1価の置換基のうち少なく
とも1つはアミノ基、ヒドロキシ基、酸素陰イオン、ア
ルコキシ基、メルカプト基、硫黄陰イオン、アルキルチ
オ基、およびアリールチオ基よりなる群から選ばれた1
価の置換基であることが好ましい。At least one of the monovalent substituents represented by R 11 is selected from the group consisting of amino groups, hydroxy groups, oxygen anions, alkoxy groups, mercapto groups, sulfur anions, alkylthio groups, and arylthio groups. The chosen one
It is preferably a valent substituent.
【0014】一般式(II)中のR23は水素原子、アルキ
ル基、アリール基または複素環残基を表す。これらは置
換基を有してもよい。R23としては水素原子、アルキル
基、アリール基が好ましい。R 23 in the formula (II) represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic residue. These may have a substituent. R 23 is preferably a hydrogen atom, an alkyl group, or an aryl group.
【0015】R23で表されるアルキル基、アリール基、
複素環残基の具体例としては、R11、R12、R21、
R22、R24のところのものと同様のものを挙げることが
できる。Alkyl groups, aryl groups denoted by R 23,
Specific examples of the heterocyclic residue include R 11 , R 12 , R 21 ,
It can be exemplified the same ones at the R 22, R 24.
【0016】n11、n21およびn24は0〜4の整数を、
n12およびn22は0〜3の整数を表す。n11、n24は1
〜4が好ましい。n12、n21およびn22については特に
制限はない。N 11 , n 21 and n 24 are each an integer of 0 to 4,
n 12 and n 22 represents an integer of 0 to 3. n 11 and n 24 are 1
To 4 are preferable. There are no particular restrictions on n 12 , n 21 and n 22 .
【0017】X1、X2は、酸素、硫黄、セレン、テル
ル、イミノ基、アルキレン基(例えばメチレン基、エチ
レン基、ベンジリデン基など)、またはアルケニレン基
(例えばビニレン基など)を表す。イミノ基、アルキレ
ン基、アルケニレン基は置換基を有していてもよい。こ
のとき、アルキレン基、アルケニレン基の置換基として
は特に制限はなく、アルキル基等が挙げられる。また、
アルキレン基、アルケニレン基において、置換基同士が
結合して環を形成してもよく、このような環としてはベ
ンゼン環等が挙げられる。イミノ基の置換基としては、
アルキル基、アリール基、アシル基、アルコキシカルボ
ニル基、カルボキシル基、カルバモイル基が好ましい。
このうちX1、X2としては酸素、硫黄が好ましい。X 1 and X 2 represent oxygen, sulfur, selenium, tellurium, imino, alkylene (eg, methylene, ethylene, benzylidene) and alkenylene (eg, vinylene). The imino group, alkylene group, and alkenylene group may have a substituent. At this time, the substituent of the alkylene group or alkenylene group is not particularly limited, and examples thereof include an alkyl group. Also,
In the alkylene group and the alkenylene group, the substituents may be bonded to each other to form a ring, and examples of such a ring include a benzene ring. As a substituent of the imino group,
Preferred are an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carboxyl group, and a carbamoyl group.
Of these, X 1 and X 2 are preferably oxygen and sulfur.
【0018】Y1およびY2は酸素、硫黄、セレン、テル
ル、イミノ基、インモニウム基、メチレン基を表す。こ
のうちイミノ基、インモニウム基、メチレン基は置換基
を有してもよい。この時、イミノ基の置換基の好ましい
例は前述の通りである。Y 1 and Y 2 represent oxygen, sulfur, selenium, tellurium, imino, immonium or methylene. Of these, the imino group, immonium group, and methylene group may have a substituent. At this time, preferred examples of the substituent of the imino group are as described above.
【0019】置換インモニウム基の例としてはアルキル
インモニウム基(例えばメチルインモニウム基、ベンジ
ルインモニウム基、シクロヘキシルインモニウム基な
ど)、ジアルキルインモニウム基(例えばジメチルイン
モニウム基、ジエチルインモニウム基など)、アルキル
アリールインモニウム基(例えばメチルフェニルインモ
ニウム基など)、アリールインモニウム基(例えばフェ
ニルインモニウム基など)、ジアリールインモニウム基
(例えばジフェニルインモニウム基など)が挙げられ
る。これらはさらに置換基を有していてもよい。また置
換基同士が結合して環を形成してもよい。Examples of the substituted immonium group include an alkyl immonium group (such as a methyl immonium group, a benzyl immonium group and a cyclohexyl immonium group), and a dialkyl immonium group (such as a dimethyl immonium group and a diethyl immonium group). ), An alkylaryl immonium group (such as a methylphenyl immonium group), an aryl immonium group (such as a phenyl immonium group), and a diaryl immonium group (such as a diphenyl immonium group). These may further have a substituent. Further, the substituents may be bonded to each other to form a ring.
【0020】置換メチレン基の例としてはジシアノメチ
レン基、1−アセチル−1−シアノメチレン基、1,1
−ジアセチルメチレン基、1−シアノ−1カルボキシメ
チレン基、1−メトキシカルボニル−1−シアノメチレ
ン基、1,1−ビス(メトキシカルボニル)メチレン基
などが挙げられる。Examples of the substituted methylene group include dicyanomethylene group, 1-acetyl-1-cyanomethylene group, 1,1
-Diacetylmethylene group, 1-cyano-1carboxymethylene group, 1-methoxycarbonyl-1-cyanomethylene group, 1,1-bis (methoxycarbonyl) methylene group and the like.
【0021】Y1、Y2としては酸素、イミノ基、インモ
ニウム基、メチレン基が好ましい。As Y 1 and Y 2 , oxygen, imino group, immonium group and methylene group are preferable.
【0022】B2は窒素またはメチン基を表す。メチン
基は置換基を有してもよい。このうち窒素がより好まし
い。B 2 represents a nitrogen or methine group. The methine group may have a substituent. Of these, nitrogen is more preferred.
【0023】一般式(I)において、n11≧2の時、R
11同士が結合して、ベンゼン環等の炭素環や窒素等を含
むヘテロ環を形成してもよく、これらの環はさらに置換
基を有していてもよい。またn12≧2の時、R12同士が
結合して、ベンゼン環等の環を形成してもよく、これら
の環はさらに置換基を有していてもよい。また、Y1と
R12(2つ以上のR12であってもよい)とが結合して炭
素環やヘテロ環を形成してもよく、これらの環はさらに
置換基を有していてもよい。In the general formula (I), when n 11 ≧ 2, R
11 may combine with each other to form a carbon ring such as a benzene ring or a hetero ring containing nitrogen or the like, and these rings may further have a substituent. When n 12 ≧ 2, R 12 may combine with each other to form a ring such as a benzene ring, and these rings may further have a substituent. Further, Y 1 and R 12 (which may be two or more R 12 ) may combine to form a carbon ring or a hetero ring, and these rings may further have a substituent. Good.
【0024】また、一般式(II)において、n21、
n22、n24≧2のとき、R21同士、R22同士、R24同士
は各々結合して環を形成してもよい。また、R22、
R24、B2およびY2から選ばれた2つ以上が結合して環
を形成してもよく、このような環としては、例えばR22
とR24とが結合して形成されたヘテロ環や、R24とY2
とが結合して形成された縮合環を有していてもよいヘテ
ロ環等を挙げることができる。これらの環はさらに置換
基を有していてもよい。In the general formula (II), n 21 ,
When n 22 and n 24 ≧ 2, R 21 s , R 22 s , and R 24 s may be bonded to each other to form a ring. R 22 ,
Two or more selected from R 24, B 2 and Y 2 may be combined with each other to form a ring, as such rings, for example, R 22
Heterocyclic or where the R 24 is formed by bonding a, R 24 and Y 2
And a heterocyclic ring which may have a condensed ring formed by bonding to the above. These rings may further have a substituent.
【0025】一般式(I)または(II)で表される化合
物は半導体微粒子への吸着性を向上させるために酸性基
を有することが好ましい。ここで酸性基とは水−テトラ
ヒドロフラン混合溶媒(体積比50対50)中のpKa
が10以下のものをいい、好ましくはカルボン酸基、ス
ルホン酸基、スルフィン酸基、水酸基、ホスホン酸基、
リン酸モノエステルおよびジエステル基等であり、特に
好ましくはカルボン酸基、スルホン酸基、リン酸モノエ
ステルおよびジエステル基である。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。The compound represented by the general formula (I) or (II) preferably has an acidic group in order to improve the adsorptivity to semiconductor fine particles. Here, the acidic group is defined as pKa in a mixed solvent of water and tetrahydrofuran (volume ratio of 50 to 50).
Means 10 or less, preferably a carboxylic acid group, a sulfonic acid group, a sulfinic acid group, a hydroxyl group, a phosphonic acid group,
Phosphoric acid monoester and diester groups and the like, particularly preferably carboxylic acid group, sulfonic acid group, phosphoric acid monoester and diester groups. These groups may form a salt with an alkali metal or the like. Further, an inner salt may be formed.
【0026】一般式(I)、(II)で表される化合物が
分子全体として電荷を有する場合、電荷を中和するため
の対イオンを有していてもよい。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
ルカリ土類金属(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。When the compound represented by the general formula (I) or (II) has a charge as a whole molecule, it may have a counter ion for neutralizing the charge. The counter ion is not particularly limited and may be either organic or inorganic. Representative examples include halogen ions (fluorine ions, chloride ions, bromine ions, and iodine ions), hydroxide ions, perchlorate ions, tetrafluoroborate ions, hexafluorophosphate ions, acetate ions, and trifluoroacetate ions. , Methanesulfonic acid ion, paratoluenesulfonic acid ion,
Anions such as trifluoromethanesulfonic acid ion, alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (magnesium, calcium, etc.), ammonium, alkylammonium (eg, diethylammonium, tetrabutylammonium, etc.), pyridinium, alkylpyridinium Cations such as (eg, methylpyridinium), guanidinium, and tetraalkylphosphonium.
【0027】次に一般式(I)または(II)で表される
化合物の好ましい具体例を下記に示すが、本発明はこれ
らに限定されない。Next, preferred specific examples of the compound represented by formula (I) or (II) are shown below, but the present invention is not limited thereto.
【0028】[0028]
【化3】 Embedded image
【0029】[0029]
【化4】 Embedded image
【0030】[0030]
【化5】 Embedded image
【0031】[0031]
【化6】 Embedded image
【0032】[0032]
【化7】 Embedded image
【0033】次に、本発明に用いられる色素の合成法を
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。Next, the method of synthesizing the dye used in the present invention will be described with reference to specific examples, but the present invention is not limited thereto.
【0034】合成例 例示化合物(10)および(1
1)の合成 特開平2−275446号11頁〜12頁に記載の合成
法に従い、3−(メトキシカルボニルアミノ)−4−ア
ミノ−N,N−ジエチルアニリンのパラトルエンスルホ
ン酸塩(化合物A)を合成した。Synthesis Examples Exemplified compounds (10) and (1)
Synthesis of 1) According to the synthesis method described in JP-A-2-275446, pp. 11-12, p-toluenesulfonic acid salt of 3- (methoxycarbonylamino) -4-amino-N, N-diethylaniline (compound A) Was synthesized.
【0035】1−ヒドロキシ−2−ナフトエ酸18.8
g、化合物A52.5g、炭酸水素ナトリウム82g、
水500ml、エタノール500ml、酢酸エチル1リット
ルをガラス容器中に混合し激しく撹拌しながら室温にて
過硫酸カリウム20gを徐々に添加した。1時間撹拌し
た後、反応混合物を100mlの濃塩酸を含む水2リット
ル中に注ぎ、有機層を分液し溶媒を留去した。残渣をシ
リカゲルカラムクロマトグラフィー(流出液:ヘキサン
と酢酸エチルの1:1体積混合液)で分離、精製するこ
とにより本発明の化合物(10)3.5gと(11)
2.2gを得た。1-hydroxy-2-naphthoic acid 18.8
g, compound A 52.5 g, sodium hydrogen carbonate 82 g,
500 ml of water, 500 ml of ethanol and 1 liter of ethyl acetate were mixed in a glass container, and 20 g of potassium persulfate was gradually added at room temperature with vigorous stirring. After stirring for 1 hour, the reaction mixture was poured into 2 liters of water containing 100 ml of concentrated hydrochloric acid, the organic layer was separated, and the solvent was distilled off. The residue was separated and purified by silica gel column chromatography (eluent: 1: 1 volume mixture of hexane and ethyl acetate) to give 3.5 g of compound (10) of the present invention and (11)
2.2 g were obtained.
【0036】次に本発明の一般式(I)、(II)で表さ
れる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。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
体上に塗設される色素が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。Next, the dye-sensitized photoelectric conversion device to which the dyes represented by formulas (I) and (II) of the present invention are applied and a photoelectrochemical cell will be described in detail. In the present invention, the dye-sensitized photoelectric conversion element is an electrode composed of a conductive support and a layer (photosensitive layer) of semiconductor fine particles having a dye adsorbed thereon, which is 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 dye in one photosensitive layer may be one kind or a mixture of many kinds. Light incident on the photosensitive layer excites the dye. The excited dye has high-energy electrons, which are transferred from the dye to the conduction band of the semiconductor fine particles and reach the conductive support by diffusion. At this time, the dye molecules are in an oxidized form, but the photoelectrochemical cell returns electrons to the oxidized form while the electrons on the electrodes work in an external circuit, and the dye-sensitized photoelectric conversion element is the negative electrode of this battery. Work as
【0037】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。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0.0
5〜10μm であることが好ましい。Hereinafter, the conductive support and the photosensitive layer will be described in detail. The conductive support is a support such as a metal, which has conductivity, or a glass or plastic support having a conductive agent layer on the surface.
In the latter case, a preferred conductive agent is a metal (eg, platinum,
Gold, silver, copper, aluminum, rhodium, indium, etc., carbon, or a conductive metal oxide (indium-tin composite oxide, tin oxide doped with fluorine, or the like). In this case, the thickness of the conductive agent layer is 0.0
It is preferably from 5 to 10 μm.
【0038】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。The lower the surface resistance of the conductive support, the better.
The preferable range of the surface resistance is 50 Ω / cm 2 or less, and more preferably 10 Ω / cm 2 or less. The lower limit is not particularly limited, but is usually about 0.1 Ω / cm 2 .
【0039】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。この時、金属酸化物の塗
布量は支持体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。Preferably, the conductive support is substantially transparent. Substantially transparent means that light transmittance is 10%
It means that it is at least 50%, preferably at least 50%, particularly preferably at least 80%. As the transparent conductive support, glass or plastic coated with a conductive metal oxide is preferable. At this time, the coating amount of the metal oxide is preferably 0.1 to 100 g per 1 m 2 of the support.
When a transparent conductive support is used, light is preferably incident from the support side.
【0040】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。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。The semiconductor fine particles used in the photosensitive layer are metal chalcogenides (eg, oxides, sulfides, selenides, etc.).
Alternatively, it is fine particles of perovskite. The metal chalcogenide preferably includes titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, or tantalum oxide, cadmium sulfide, cadmium selenide, and the like. As the perovskite, strontium titanate, calcium titanate and the like are preferably mentioned. Among these, titanium oxide, zinc oxide, tin oxide and tungsten oxide are particularly preferred. The particle diameter of these semiconductor fine particles is 0.001 to 1 μm as the primary particle as the average particle diameter using the diameter when the projected area is converted into a circle, and 0.01 as the average particle diameter of the dispersion.
It is preferably from 100 to 100 μm.
【0041】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。The method of coating the semiconductor fine particles on the conductive support includes a method of coating a dispersion or a colloid solution of the semiconductor fine particles on the conductive support, and a method of coating the precursor of the semiconductor fine particles on the conductive support. A method of coating and hydrolyzing with water in the air to obtain a semiconductor fine particle film, and the like can be given. Examples of a method for preparing a dispersion of semiconductor fine particles include a method of grinding in a mortar, a method of dispersing while grinding using a mill, and a method of precipitating and using fine particles in a solvent when synthesizing a semiconductor. . Examples of the dispersion medium include water and various organic solvents (eg, methanol, ethanol, dichloromethane, acetone, acetonitrile, ethyl acetate, etc.). At the time of dispersion, a polymer, a surfactant, an acid, a chelating agent, or the like may be used as a dispersing aid, if necessary.
【0042】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。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 the projected area,
More preferably, it is 100 times or more. The upper limit is not particularly limited, but is usually about 5000 times.
【0043】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。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。In general, as the thickness of the layer of semiconductor fine particles increases, the amount of dye that can be supported per unit area increases, so that the light absorption efficiency increases. However, the diffusion distance of generated electrons increases, so that the loss due to charge recombination also increases. growing. 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 are applied at a temperature of 100 to 800 ° C. for 10 minutes to adhere the particles to each other after being applied to the support.
You may bake for 10 hours. The coating amount of the semiconductor fine particles per 1 m 2 of the support is 0.5 to 500 g, and more preferably 5 to 500 g.
100 g is preferred.
【0044】本発明において、半導体微粒子は一般式
(I)、(II)で表される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
着させるか、水を除去した雰囲気中で色素を吸着させる
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、本発明の一
般式(I)、(II)で表される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54
63057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。In the present invention, the semiconductor fine particles are sensitized by the adsorption of the dyes represented by the general formulas (I) and (II). Generally, a method of immersing the semiconductor fine particles thus obtained for a long time is used. The dye solution may be heated to 50 ° C to 100 ° C as needed. The dye may be adsorbed before or after the application of the semiconductor fine particles. Further, the semiconductor fine particles and the dye may be simultaneously applied and adsorbed. Unadsorbed dye is removed by washing. When baking the coating film, it is preferable that the dye is adsorbed after baking. It is particularly preferable that the dye be quickly adsorbed before water is adsorbed on the surface of the coating film after baking, or the dye is adsorbed in an atmosphere from which water has been removed. One type of dye may be adsorbed,
You may mix and use several types. In the case of mixing, the dyes represented by formulas (I) and (II) of the present invention may be mixed with each other, and US Pat. Nos. 4,927,721 and 4,684,537.
Nos. 5084365, 5350644, 54
Complex dyes described in JP-A-63057 and JP-A-5525440 and JP-A-7-249790 may be mixed with the dye of the present invention. When the application is a photoelectrochemical cell, a dye to be mixed is selected so as to widen the wavelength range of photoelectric conversion as much as possible.
【0045】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、本発明の一般式(I)、(II)の色
素の使用量の割合は5モル%以上とすることが好まし
い。The total amount of the dye used is preferably from 0.01 to 100 mmol, more preferably from 0.1 to 50 mmol, particularly preferably from 0.5 to 10 mmol, per 1 m 2 of the support. In this case, the ratio of the amount of the dyes represented by formulas (I) and (II) of the present invention is preferably 5 mol% or more.
【0046】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0.1〜1mモルである。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。The amount of the dye adsorbed on the semiconductor fine particles is preferably 0.001 to 1 mmol, more preferably 0.1 to 1 mmol, per 1 g of the semiconductor fine particles. With such an amount of the dye, a sensitizing effect in the semiconductor can be sufficiently obtained. On the other hand, if the amount of the dye is small, the sensitizing effect becomes insufficient, and if the amount of the dye is too large, the dye not adhering to the semiconductor floats and causes a reduction in the sensitizing effect.
【0047】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。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).
【0048】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。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。After the dye is adsorbed, the surface of the semiconductor fine particles may be treated with an amine. Preferred amines include pyridine, 4-tert-butylpyridine, polyvinylpyridine and the like. When these are liquid, they may be used as they are, or may be used by dissolving them in an organic solvent. In the present invention, the conductive agent and the semiconductor fine particles may be mutually diffused and mixed in the vicinity of the interface between the conductive support and the photosensitive layer.
【0049】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電気化学電池、い
わゆる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。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。The dye-sensitized photoelectric conversion element thus produced can be applied to various sensors and photoregeneration type electrochemical cells, so-called photoelectrochemical cells. When applied to a photoelectrochemical cell, a charge transfer layer and a counter electrode are required as shown in FIG. The photoelectrochemical cell 1 shown in FIG. 1 has a photosensitive layer 3 on a conductive support 2, and further has a charge transfer layer 4 and a counter electrode 5 provided on the photosensitive layer 3.
【0050】以下、電荷移動層と対向電極について詳し
く説明する。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。Hereinafter, the charge transfer layer and the counter electrode will be described in detail. The charge transfer layer is a layer having a function of replenishing the oxidized dye with electrons. Representative examples include a liquid in which a redox couple is dissolved in an organic solvent, a so-called gel electrolyte in which a liquid in which a redox couple is dissolved in an organic solvent is impregnated in a polymer matrix, and a molten salt containing a redox couple.
【0051】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。As the redox couple, for example, a combination of iodine and iodide (eg, lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, etc.), an alkyl viologen (eg, methyl viologen chloride, hexyl viologen bromide, benzyl viologen) Combination of tetrafluoroborate) and its reduced form, combination of polyhydroxybenzenes (eg, hydroquinone, naphthohydroquinone, etc.) and its oxidized form, divalent and trivalent iron complexes (eg, red blood salt and yellow blood salt)
And the like. Of these, a combination of iodine and iodide is preferred. As an organic solvent for dissolving them, aprotic polar solvents (for example, acetonitrile, propylene carbonate, ethylene carbonate, dimethylformamide, dimethylsulfoxide, sulfolane, 1,3-dimethylimidazolinone, 3-methyloxazolidinone, etc.) are 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 (eg, lithium acetate, lithium perchlorate, etc.). May be increased. In this case, the amount of the polymer added is 1 to 50% by weight.
【0052】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。Since the redox couple becomes a carrier of electrons, a certain concentration is required. When used as a liquid or gel electrolyte, the total concentration in the solution is preferably at least 0.01 mol / l, more preferably at least 0.1 mol / l, particularly preferably at least 0.3 mol / l. It is. The upper limit in this case is not particularly limited, but is usually 5
It is about mol / l.
【0053】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。The counter electrode functions as a positive electrode of the photoelectrochemical cell. The counter electrode is usually synonymous with the above-mentioned conductive support, 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.
【0054】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。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。In order for light to reach the photosensitive layer, at least one of the above-described conductive support and the counter electrode must be substantially transparent. In the photoelectrochemical cell of the present invention, it is preferable that the conductive support is transparent and sunlight is incident from the support side. In this case, it is more preferable that the counter electrode has a property of reflecting light. As the counter electrode of the photoelectrochemical cell, glass or plastic on which metal or a conductive oxide is deposited is preferable, and glass on which platinum is deposited is particularly preferable. In a photoelectrochemical cell, it is preferable to seal the side surface of the cell with a polymer, an adhesive, or the like in order to prevent the components from evaporating.
【0055】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/c
m2、形状因子0.1〜0.99、変換効率0.001〜
25%である。The characteristics of the photoelectrochemical cell obtained in this manner are as follows: when the AM 1.5 G is 100 mW / cm 2 , the open-circuit voltage is 0.01 to 3 V, and the short-circuit current density is 0.001 to 20 mA / c.
m 2 , form factor 0.1 ~ 0.99, conversion efficiency 0.001 ~
25%.
【0056】[0056]
【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。EXAMPLES Hereinafter, the method for producing the dye-sensitized photoelectric conversion element and the photoelectrochemical cell of the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.
【0057】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
Degussa P−25)15g、水45g、分散
剤(アルドリッチ社製、Triton X−100)1
g、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をMALVERN社製
マスターサイザーにて測定したところ、25μm であっ
た。Example 1 Preparation of Titanium Dioxide Dispersion 15 g of titanium dioxide (Degussa P-25, Nippon Aerosil Co., Ltd.), 45 g of water, and a dispersant (Triton X, manufactured by Aldrich Co., Ltd.) were placed in a 200-ml stainless steel vessel whose inside was coated with Teflon. -100) 1
g, 30 g of zirconia beads (manufactured by Nikkato) having a diameter of 0.5 mm were dispersed in a sand grinder mill (manufactured by Imex) at 1500 rpm for 2 hours. The zirconia beads were removed from the dispersion by filtration. The average particle size of the titanium dioxide in this case was measured by a master sizer manufactured by MALVERN and found to be 25 μm.
【0058】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表面抵抗は約30Ω/cm2)
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。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枚づつ塗布した。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に示す本発明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10%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
であった。色素の塗布量は、色素の種類に応じ、適宜
0.5〜10mモル/m2の範囲から選択した。Preparation of Photoelectric Conversion Element Conductive glass coated with fluorine-doped tin oxide (TCO glass manufactured by Asahi Glass, 20 mm × 20 mm
Surface resistance of about 30Ω / cm 2 )
The above dispersion was applied to the conductive surface side of using a glass rod. At this time, an adhesive tape was stretched on a part (3 mm from the end) on the conductive surface side to form a spacer, and glass was lined up so that the adhesive tape came to both ends and applied eight sheets at a time. After application,
It was air-dried at room temperature for one day, and the adhesive tape was peeled off (the part with the adhesive tape was used to make electrical contact with a measuring instrument during photoelectric conversion measurement). Next, this glass was put into an electric furnace (muffle furnace FP-32 manufactured by Yamato Scientific Co., Ltd.) and fired at 450 ° C. for 30 minutes. After the glass was taken out and cooled, it was immersed in an ethanol solution (3 × 10 −4 mol / l) of the dye of the present invention shown in Table 1 for 3 hours. The glass on which the dye was dyed was immersed in a 10% ethanol solution of 4-tert-butylpyridine for 30 minutes, then washed with ethanol and dried naturally. The photosensitive layer thus obtained has a thickness of 10 μm, and the coating amount of the semiconductor fine particles is 20 g / m 2.
Met. The coating amount of the dye was appropriately selected from the range of 0.5 to 10 mmol / m 2 according to the type of the dye.
【0059】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には最も長波側の吸収ピークにおける吸
光度の値を示した。Measurement of reflection spectrum The reflection spectrum was measured using a spectrophotometer (U-3500, manufactured by Hitachi, Ltd.) equipped with an integrating sphere for the above photoelectric conversion element. Table 1 shows the values of the absorbance at the absorption peak on the longest wavelength side.
【0060】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。Preparation of Photoelectrochemical Cell As one embodiment of the photoelectrochemical cell of FIG. 1, a photoelectrochemical cell as shown in FIG. 2 was prepared. The photoelectrochemical cell 10 of FIG.
Uses the above-mentioned photoelectric conversion element having a configuration in which a photosensitive layer 13 is provided on a conductive support having a conductive agent layer 12 on a glass support 11, and is a charge transfer layer on the photosensitive layer 13. It has an electrolyte layer 14 and a platinum-deposited glass 15 as a counter electrode. In this creation,
The above-mentioned photoelectric conversion element was overlapped with platinum-deposited glass of the same size (FIG. 2, the uncoated portion of the photoelectric conversion element was shifted so as not to contact the platinum-deposited glass).
Next, an electrolytic solution (a mixture of acetonitrile and N-methyl-2-oxazolidinone at a volume ratio of 90:10, iodine 0.05
Mol / l, 0.5 mol / l of lithium iodide).
【0061】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(Kenko L−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。Measurement of Photoelectric Conversion Efficiency The light of a 500 W xenon lamp (made by Ushio) was applied to AM1.
Simulated sunlight containing no ultraviolet rays was generated by passing through a 5G filter (manufactured by Oriel) and a sharp cut filter (Kenko L-42). The intensity of this light was 50 mW / cm 2 .
【0062】本発明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。The photoelectric conversion element of the present invention is irradiated with this light,
The generated electricity is measured by a current-voltage measuring device (Keithley 238).
(Type). Table 1 shows the open-circuit voltage, short-circuit current, form factor, and conversion efficiency of the photochemical cell obtained in this way.
Summarized in
【0063】[0063]
【表1】 [Table 1]
【0064】以上より、いずれの色素でも光電変換特性
が認められる。As described above, photoelectric conversion characteristics are recognized for all the dyes.
【0065】[0065]
【発明の効果】本発明により有機色素を用いた安価で変
換効率にすぐれ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。また、これを用いて光電気化学電
池が得られることが確認された。It has been clarified that the present invention provides an inexpensive dye-sensitized photoelectric conversion element using an organic dye and having excellent conversion efficiency. It was also confirmed that a photoelectrochemical cell could be obtained using this.
【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。FIG. 1 is a cross-sectional view showing one configuration example of a photoelectrochemical cell of the present invention.
【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。FIG. 2 is a cross-sectional view illustrating a configuration example of a photoelectrochemical cell used in Examples.
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 DESCRIPTION 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 vapor deposition glass
Claims (5)
有する光電変換素子であって、 前記感光層が、下記一般式(I)および(II)で表され
る色素から選ばれた少なくとも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。 【化1】 [一般式(I)中、R11およびR12は各々1価の置換基
を表し、n11は0〜4の整数であり、n12は0〜3の整
数である。X1は酸素、硫黄、セレン、テルル、イミノ
基、アルキレン基またはアルケニレン基を表し、Y1は
酸素、硫黄、セレン、テルル、イミノ基、インモニウム
基またはメチレン基を表す。n11が2以上の整数である
時R11同士が結合して環を形成してもよく、n12が2以
上の整数である時R12同士が結合して環を形成してもよ
く、Y1とR12とが結合して環を形成してもよい。一般
式(II)中、R21,R22およびR24は各々1価の置換基
を表し、n21およびn24は各々0〜4の整数であり、n
22は0〜3の整数である。R23は水素、アルキル基、ア
リール基または複素環残基を表す。X2は酸素、硫黄、
セレン、テルル、イミノ基、アルキレン基またはアルケ
ニレン基を表し、Y2は酸素、硫黄、セレン、テルル、
イミノ基、インモニウム基またはメチレン基を表す。B
2は窒素またはメチン基を表す。n21が2以上の整数で
ある時R21同士が結合して環を形成してもよく、n22が
2以上の整数である時R22同士が結合して環を形成して
もよく、n24が2以上の整数である時R24同士が結合し
て環を形成してもよく、R22,B2,R24およびY2から
選ばれた2つ以上が結合して環を形成してもよい。]1. A photoelectric conversion element having at least a conductive support and a photosensitive layer, wherein the photosensitive layer is formed of at least one selected from dyes represented by the following general formulas (I) and (II). A photoelectric conversion element comprising sensitized semiconductor fine particles. Embedded image [In the general formula (I), R 11 and R 12 each represent a monovalent substituent, n 11 is an integer of 0 to 4, and n 12 is an integer of 0 to 3. X 1 represents oxygen, sulfur, selenium, tellurium, imino group, alkylene group or alkenylene group, and Y 1 represents oxygen, sulfur, selenium, tellurium, imino group, immonium group or methylene group. When n 11 is an integer of 2 or more, R 11 may be bonded to each other to form a ring, and when n 12 is an integer of 2 or more, R 12 may be bonded to each other to form a ring, Y 1 and R 12 may combine to form a ring. In the general formula (II), R 21 , R 22 and R 24 each represent a monovalent substituent, n 21 and n 24 each represent an integer of 0 to 4,
22 is an integer of 0 to 3. R 23 represents hydrogen, an alkyl group, an aryl group or a heterocyclic residue. X 2 is oxygen, sulfur,
Represents selenium, tellurium, imino group, alkylene group or alkenylene group, and Y 2 represents oxygen, sulfur, selenium, tellurium,
Represents an imino group, an immonium group or a methylene group. B
2 represents a nitrogen or methine group. When n 21 is an integer of 2 or more, R 21 may be bonded to each other to form a ring, and when n 22 is an integer of 2 or more, R 22 may be bonded to each other to form a ring, When n 24 is an integer of 2 or more, R 24 may combine with each other to form a ring, and two or more selected from R 22 , B 2 , R 24 and Y 2 may combine to form a ring May be. ]
であり、一般式(II)中のX2が酸素または硫黄である
請求項1の光電変換素子。2. The photoelectric conversion device according to claim 1, wherein X 1 in the general formula (I) is oxygen or sulfur, and X 2 in the general formula (II) is oxygen or sulfur.
して少なくとも1つの酸性基を有し、一般式(II)で表
される色素が置換基として少なくとも1つの酸性基を有
する請求項1または2の光電変換素子。3. The dye represented by the general formula (I) has at least one acidic group as a substituent, and the dye represented by the general formula (II) has at least one acidic group as a substituent. Item 6. The photoelectric conversion element according to item 1 or 2.
ン酸基、スルホン酸基、リン酸モノエステル基およびリ
ン酸ジエステル基から選ばれた請求項3の光電変換素
子。4. The photoelectric conversion device according to claim 3, wherein at least one of the acidic groups is selected from a carboxylic acid group, a sulfonic acid group, a phosphoric acid monoester group and a phosphoric acid diester group.
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。5. A photoelectrochemical cell comprising the photoelectric exchange element according to claim 1, and further comprising at least a charge transfer layer and a counter electrode.
Priority Applications (1)
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JP9246050A JPH1167285A (en) | 1997-08-27 | 1997-08-27 | Photoelectric conversion element and photo electrochemical cell |
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JP9246050A JPH1167285A (en) | 1997-08-27 | 1997-08-27 | Photoelectric conversion element and photo electrochemical cell |
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JPH1167285A true JPH1167285A (en) | 1999-03-09 |
Family
ID=17142727
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