JP2004290794A - Photocatalytic material - Google Patents
Photocatalytic material Download PDFInfo
- Publication number
- JP2004290794A JP2004290794A JP2003085565A JP2003085565A JP2004290794A JP 2004290794 A JP2004290794 A JP 2004290794A JP 2003085565 A JP2003085565 A JP 2003085565A JP 2003085565 A JP2003085565 A JP 2003085565A JP 2004290794 A JP2004290794 A JP 2004290794A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalytic
- zno
- type
- nitrogen
- optical semiconductor
- 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
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- 239000000463 material Substances 0.000 title claims abstract description 33
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 29
- 239000004065 semiconductor Substances 0.000 claims abstract description 22
- 239000011941 photocatalyst Substances 0.000 claims abstract description 21
- 230000003287 optical effect Effects 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 47
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 238000004544 sputter deposition Methods 0.000 claims description 21
- 239000003973 paint Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 239000000969 carrier Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 11
- 230000007547 defect Effects 0.000 abstract description 4
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 4
- 230000006866 deterioration Effects 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 230000000452 restraining effect Effects 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 27
- -1 Ta 3 O 5 Inorganic materials 0.000 description 17
- 239000011787 zinc oxide Substances 0.000 description 13
- 239000010408 film Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
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- 238000000034 method Methods 0.000 description 5
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- 229960000907 methylthioninium chloride Drugs 0.000 description 3
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- 230000005355 Hall effect Effects 0.000 description 2
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- 230000001443 photoexcitation Effects 0.000 description 2
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- 229920000642 polymer Polymers 0.000 description 2
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- BVNZLSHMOBSFKP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxysilane Chemical compound CC(C)(C)O[SiH3] BVNZLSHMOBSFKP-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
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- JRGQKLFZSNYTDX-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)propyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCOCC1CO1 JRGQKLFZSNYTDX-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- MBNRBJNIYVXSQV-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propane-1-thiol Chemical compound CCO[Si](C)(OCC)CCCS MBNRBJNIYVXSQV-UHFFFAOYSA-N 0.000 description 1
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- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
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- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
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- VGWJKDPTLUDSJT-UHFFFAOYSA-N diethyl dimethyl silicate Chemical compound CCO[Si](OC)(OC)OCC VGWJKDPTLUDSJT-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000009189 diving Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001810 electrochemical catalytic reforming Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- MABAWBWRUSBLKQ-UHFFFAOYSA-N ethenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C=C MABAWBWRUSBLKQ-UHFFFAOYSA-N 0.000 description 1
- BQRPSOKLSZSNAR-UHFFFAOYSA-N ethenyl-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)C=C BQRPSOKLSZSNAR-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- MYEJNNDSIXAGNK-UHFFFAOYSA-N ethyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](CC)(OC(C)C)OC(C)C MYEJNNDSIXAGNK-UHFFFAOYSA-N 0.000 description 1
- ZVQNVYMTWXEMSF-UHFFFAOYSA-N ethyl-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](CC)(OC(C)(C)C)OC(C)(C)C ZVQNVYMTWXEMSF-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000013611 frozen food Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- DPTKSEHTOJHGOV-UHFFFAOYSA-N hexyl-tri(propan-2-yloxy)silane Chemical compound CCCCCC[Si](OC(C)C)(OC(C)C)OC(C)C DPTKSEHTOJHGOV-UHFFFAOYSA-N 0.000 description 1
- QECCXOBPOBIUMS-UHFFFAOYSA-N hexyl-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CCCCCC[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C QECCXOBPOBIUMS-UHFFFAOYSA-N 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- HLXDKGBELJJMHR-UHFFFAOYSA-N methyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(OC(C)C)OC(C)C HLXDKGBELJJMHR-UHFFFAOYSA-N 0.000 description 1
- AHQDZKRRVNGIQL-UHFFFAOYSA-N methyl-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](C)(OC(C)(C)C)OC(C)(C)C AHQDZKRRVNGIQL-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229940110728 nitrogen / oxygen Drugs 0.000 description 1
- IHVVJLCVJNNCDK-UHFFFAOYSA-N octadecyl-tri(propan-2-yloxy)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC(C)C)(OC(C)C)OC(C)C IHVVJLCVJNNCDK-UHFFFAOYSA-N 0.000 description 1
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- VPLNCHFJAOKWBT-UHFFFAOYSA-N phenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C1=CC=CC=C1 VPLNCHFJAOKWBT-UHFFFAOYSA-N 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- PCADGSDEFOMDNL-UHFFFAOYSA-N tri(propan-2-yloxy)-(3,3,3-trifluoropropyl)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCC(F)(F)F PCADGSDEFOMDNL-UHFFFAOYSA-N 0.000 description 1
- MQVCTPXBBSKLFS-UHFFFAOYSA-N tri(propan-2-yloxy)-propylsilane Chemical compound CCC[Si](OC(C)C)(OC(C)C)OC(C)C MQVCTPXBBSKLFS-UHFFFAOYSA-N 0.000 description 1
- MLZOPJVPCGTFGS-UHFFFAOYSA-N tribromo(3,3,3-trifluoropropyl)silane Chemical compound FC(F)(F)CC[Si](Br)(Br)Br MLZOPJVPCGTFGS-UHFFFAOYSA-N 0.000 description 1
- LYZDWEPTQWHDLZ-UHFFFAOYSA-N tribromo(decyl)silane Chemical compound CCCCCCCCCC[Si](Br)(Br)Br LYZDWEPTQWHDLZ-UHFFFAOYSA-N 0.000 description 1
- KVENDAGPVNAYLY-UHFFFAOYSA-N tribromo(ethyl)silane Chemical compound CC[Si](Br)(Br)Br KVENDAGPVNAYLY-UHFFFAOYSA-N 0.000 description 1
- VRUFDMFAHKOFOT-UHFFFAOYSA-N tribromo(hexyl)silane Chemical compound CCCCCC[Si](Br)(Br)Br VRUFDMFAHKOFOT-UHFFFAOYSA-N 0.000 description 1
- KBSUPJLTDMARAI-UHFFFAOYSA-N tribromo(methyl)silane Chemical compound C[Si](Br)(Br)Br KBSUPJLTDMARAI-UHFFFAOYSA-N 0.000 description 1
- RCEOWKUMFSNHFM-UHFFFAOYSA-N tribromo(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Br)(Br)Br RCEOWKUMFSNHFM-UHFFFAOYSA-N 0.000 description 1
- HPTIEXHGTPSFDC-UHFFFAOYSA-N tribromo(phenyl)silane Chemical compound Br[Si](Br)(Br)C1=CC=CC=C1 HPTIEXHGTPSFDC-UHFFFAOYSA-N 0.000 description 1
- RWRKNKVDHIEKHS-UHFFFAOYSA-N tribromo(propyl)silane Chemical compound CCC[Si](Br)(Br)Br RWRKNKVDHIEKHS-UHFFFAOYSA-N 0.000 description 1
- WEUBQNJHVBMUMD-UHFFFAOYSA-N trichloro(3,3,3-trifluoropropyl)silane Chemical compound FC(F)(F)CC[Si](Cl)(Cl)Cl WEUBQNJHVBMUMD-UHFFFAOYSA-N 0.000 description 1
- HLWCOIUDOLYBGD-UHFFFAOYSA-N trichloro(decyl)silane Chemical compound CCCCCCCCCC[Si](Cl)(Cl)Cl HLWCOIUDOLYBGD-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- LFXJGGDONSCPOF-UHFFFAOYSA-N trichloro(hexyl)silane Chemical compound CCCCCC[Si](Cl)(Cl)Cl LFXJGGDONSCPOF-UHFFFAOYSA-N 0.000 description 1
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- DOEHJNBEOVLHGL-UHFFFAOYSA-N trichloro(propyl)silane Chemical compound CCC[Si](Cl)(Cl)Cl DOEHJNBEOVLHGL-UHFFFAOYSA-N 0.000 description 1
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- JIOBRIJHDZBWDE-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-(3,3,3-trifluoropropyl)silane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)CCC(F)(F)F JIOBRIJHDZBWDE-UHFFFAOYSA-N 0.000 description 1
- WUSDGIZCXCUHAI-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)CCCOCC1CO1 WUSDGIZCXCUHAI-UHFFFAOYSA-N 0.000 description 1
- DIZPPYBTFPZSGK-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-propylsilane Chemical compound CCC[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C DIZPPYBTFPZSGK-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
【0001】
【発明の属する技術分野】
本発明は、高活性な光触媒活性を有する光触媒材料に関する。
【0002】
【従来の技術】
光触媒材料にバンドギャップ以上のエネルギーの光を照射すると電子、正孔が励起し、それらが表面に拡散することで酸化還元反応や親水化反応が発現する。その機能を生かして、光触媒材料は、環境浄化や防汚、セルフクリーニング、防曇などの様々な分野に使用されている。それらの特性を向上させるためには光触媒材料の高活性化が不可欠であり、その手段として、紫外線に対する高感度化や可視光に対する高感度化が検討された。そのうち、紫外線に対する高感度化では、光触媒材料への金属担持(例えば、非特許文献1参照)、遷移金属のドーピング(例えば、非特許文献2参照)が行われた。しかし、金属担持では白金、パラジウムなどの高価な金属を使用するため製品コストが高くなること、遷移金属のドーピングでは、遷移金属のエネルギー準位が電子、正孔の再結合中心になるため光触媒活性が低下することが問題であった。
【0003】
近年、窒素ドープした酸化チタンによる光触媒の可視光化が報告されている(特許文献3)。酸化チタンに窒素ドープをおこなうと、価電子帯を形成する酸素の2p軌道よりも卑なポテンシャル位置に窒素の2p起動が形成し、結果としてバンドギャップが狭くなるため、可視光を吸収できる。前記の酸化チタンへの窒素ドープの具体的な手法として、アンモニア雰囲気での熱処理や、金属酸化物ターゲットを使用し、Ar/N2 気流中で行うスパッタによる光触媒薄膜の作製が報告されている(特許文献3)。しかしながら、これらの方法ではいずれも還元雰囲気で窒素ドープがおこなわれるため、窒素ドープと同時に酸素欠陥が発生する。酸素欠陥によって生じた電子は、Tiイオンに局在化するため、Ti3+ イオンとして結晶中に存在するようになる。この、Ti3+ 準位(酸素欠陥準位)は伝導帯の下端から0.78〜1.1eVの深い位置に存在し、電子正孔対の再結合センターとして働いてしまう。また、n型キャリアである電子が多数存在する場合、光励起で生成した正孔がこの多数キャリアである電子に相殺される。酸化分解反応と親水化反応とも本質的には正孔が関与しているため(例えば、非特許文献3参照)、酸素欠陥が存在し電子が多数キャリアである酸化チタンにおいては、光触媒反応に使用できる正孔数が減少し、酸化分解反応や親水化反応を著しく阻害してしまう。
【0004】
一方、光触媒材料の一つとして知られる酸化亜鉛(ZnO)のp型化が報告されている(例えば、非特許文献4参照)。非特許文献4では、ターゲットとしてZnOを用い、アルゴン/酸素雰囲気下でスパッタすることによって、p型化したZnO薄膜を作製している。非特許文献4では、p型キャリアの起源はスパッタチャンバー内に存在する窒素が原因であると考察されている。この様な方法であると、スパッタチャンバー内の窒素量を制御できないため、窒素ドープ量も制御できない。また、非特許文献4で報告されているp型ZnOのキャリア密度はいずれも1014 (cm−3 )以上と高い。光触媒として使用する場合、光励起した電子正孔対が光触媒反応に利用されるが、p型キャリアである正孔が1014(cm−3)以上と多くなりすぎると、キャリア同士の散乱が顕著になり、光触媒活性を抑制してしまう。
【0005】
【特許文献1】特開2001−205104
【非特許文献1】Science, 1980, 207 ,139.
【非特許文献2】New J. Chem. 1989, 13, 61.
【非特許文献3】J. Phys. Chem. B, 2001, 105, 3023.
【非特許文献4】Appl. Phys. Lett., 2002, 80, 1195.
【0006】
【発明が解決しようとする課題】
光触媒活性低下の原因となる酸素欠陥の生成を抑制し、多数キャリアが正孔となるようなp型半導体を含む高活性な光触媒材料を提供する。
【0007】
【課題を解決するための手段】
バンドギャップが2.8eV以上で、キャリア密度が1013(cm−3)以下のp型光半導体を含むことを特徴とする光触媒材料を提供する。
前記、光触媒材料を提供するためには、酸素欠陥を生成させずに、アクセプタレベルを形成する不純物をドーピングする必要がある。本発明の好ましい態様においては、前記p型光半導体は窒素をドープしたZnOであって、前記窒素をドープしたZnOの製造方法として、ターゲットをZnとし、O2/N2雰囲気下でのスパッタリングによって得られることを特徴とする光触媒材料を提供することができる。
【0008】
【発明の実施の形態】
p型半導体とは、光励起をしない状態での多数キャリアが正孔である半導体を意味する。すなわち、半導体に不純物をドープし、価電子帯よりも卑なポテンシャル位置にアクセプタレベルが形成されたものがp型半導体である。
光触媒として強力な電子の還元力、正孔の酸化力を発揮させるためには、バンドギャップが2.8eV以上の半導体であることが望ましい。本発明に使用する半導体はバンドギャップ2.8eV以上であって、例えば、TiO2 、SnO2 、ZnO 、SrTiO3 、WO3 、ZrO2 、Nb2O5 、Bi2O3 、Ta3O5 、CeO2 、BaTiO3 、CaTiO3 、MgTiO3 、MgTi2O6 、KTaO3 、NbO3 、KNbO3 、LaNbO4 、WNb2O3 、SrNb2O6 、BaNb2O6 、NiNb2O6 、ZnNb2O6 、TiNb2O7 、BaSnO3 からなる群より選択される少なくとも一つが好適に使用できる。
【0009】
本発明の光触媒材料において、p型特性を発現させるためのドーパントとして、窒素、硫黄、リン、炭素からなる群より選択される少なくとも一つが好適に使用できる。更に、本発明の好ましい態様においては、ZnOに窒素がドープされている。窒素をドープする位置は、格子酸素の一部を置換、光触媒材料の格子間、結晶粒界のいずれか、ないし、これらの組み合わせが可能である。このように窒素をドープすることによって、窒素の2p軌道が酸素の2p軌道で形成される価電子帯よりも負の位置にアクセプタレベルを形成しp型特性を呈する。
【0010】
前記p型半導体のキャリア密度は1013 (cm−3 )以下であることが好ましい。キャリア密度を低くすることで、光励起した場合のキャリア同士の散乱を防ぐことができ、光触媒反応の起源である電子、正孔の移動度が向上し、結果として高い光触媒活性を発現することができる。
【0011】
本発明の好ましい態様においては、光触媒材料の成膜装置としてスパッタ装置を使用する。スパッタ装置のチャンバー内部では、導入した窒素ガスが解離し、高エネルギーの窒素プラズマが生成するため、光触媒材料への窒素ドープを容易に行うことができる。スパッタ装置には、直流スパッタ、高周波スパッタ、マグネトロンスパッタ、イオンビームスパッタ、ECRスパッタなどの形式があるが、そのいずれの形式でも成膜可能である。
前記スパッタ法による製造方法において、ターゲット材料は金属ターゲットの使用が好ましい。酸化物ターゲットを使用した場合、スパッタリング現象によってはじき出された粒子は酸化物分子の集団(クラスター)で形成されているため、結晶中への均一な窒素ドープが困難になる。
また、前記スパッタ法による製造方法において、ガスとして酸素・窒素の混合ガスを使用する。酸素を使用することで酸素欠陥の生成を抑制することができる。好適なガス混合比はO2 /N2 =10/90から30/70が好ましい。窒素量が70未満では窒素量が足りないためにドーピングが不十分となり、窒素量が90を超えると非晶質、もしくは窒化物を形成するため不適である。
前記スパッタ法による製造方法において、プラズマ出力は600W以下が好ましい。600Wをこえると、プラズマの平均自由行程が増大し、成膜時にダメージが増加する可能性がある。
前記スパッタ法による製造方法において、反応ガスの全圧は5.0×10−3 torr以上が好ましい。5.0×10−3 torr未満では、プラズマの平均自由行程が増大し、成膜時にダメージが増加する可能性がある。
【0012】
スパッタ法とは異なる製造方法として、CVD、蒸着、MBE(モレキュラービームエピタキシー)、レーザーアブレーション、イオンプレーティングも使用可能であるが、その場合は窒素分子をプラズマ状に解離させるため、ラジカルソースが必要である。
【0013】
本発明の光触媒材料を製造する更に異なる方法として、半導体粉末や薄膜をアンモニア、炭化水素、りん酸、硫化水素からなる群より選択される各種反応性ガスのうち少なくとも一つを含む気流中で熱処理することで作製することができる。また、半導体の前駆体の粉末や薄膜をアンモニア、炭化水素、りん酸、硫化水素からなる群より選択される各種反応性ガスのうち少なくとも一つを含む気流中で熱処理することで作製しても良い。
【0014】
本発明の光触媒材料を塗料として使用することができる。この場合、本発明の光触媒材料とバインダー、溶媒、フィラー、増粘剤、着色顔料、界面活性剤等と混合して使用することができる。
前記塗料として使用する場合のバインダーとして、例えば、シロキサン結合を有する物質を好適に使用することができる。シロキサン結合を有する化合物の表面には水との親和性の高いシラノール基が存在しており、暗所における親水性の維持性の機能を持たせたり、強めたりする効果があり、降雨によるセルフクリーン効果が向上する。前記シロキサン結合を有する物質としては水ガラス等のアルカリシリケート、コロイダルシリカ、アルミノシリケート化合物を使用することもできる。アルミノシリケート化合物はシリケート化合物のSiの一部をAlで置換した化合物であって、更に電荷を補償するためにH+やLi+、Na+、K+、Rb+、Cs+、Fr+などのアルカリ金属イオンやBe2+、Mg2+、Ca2+、Sr2+、Ba2+、Ra2+などのアルカリ土類金属イオンが含有されていてもよい。前記シリケート結合を有する化合物のSiの一部をAlで置換した物や、ゼオライトなどを使用することができる。
【0015】
前記シロキサン結合を有する物質として、シリコーンエマルジョンを用いることができる。シリコーンエマルジョンとしては、メチルトリクロルシラン、メチルトリブロムシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリイソプロポキシシラン、メチルトリt−ブトキシシラン;エチルトリクロルシラン、エチルトリブロムシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリイソプロポキシシラン、エチルトリt−ブトキシシラン;n−プロピルトリクロルシラン、n−プロピルトリブロムシラン、n−プロピルトリメトキシシラン、n−プロピルトリエトキシシラン、n−プロピルトリイソプロポキシシラン、n−プロピルトリt−ブトキシシラン;n−ヘキシルトリクロルシラン、n−ヘキシルトリブロムシラン、n−ヘキシルトリメトキシシラン、n−ヘキシルトリエトキシシラン、n−ヘキシルトリイソプロポキシシラン、n−ヘキシルトリt−ブトキシシラン;n−デシルトリクロルシラン、n−デシルトリブロムシラン、n−デシルトリメトキシシラン、n−デシルトリエトキシシラン、n−デシルトリイソプロポキシシラン、n−デシルトリt−ブトキシシラン;n−オクタデシルトリクロルシラン、n−オクタデシルトリブロムシラン、n−オクタデシルトリメトキシシラン、n−オクタデシルトリエトキシシラン、n−オクタデシルトリイソプロポキシシラン、n−オクタデシルトリt−ブトキシシラン;フェニルトリクロルシラン、フェニルトリブロムシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、フェニルトリイソプロポキシシラン、フェニルトリt−ブトキシシラン;テトラクロルシラン、テトラブロムシラン、テトラメトキシシラン、テトラエトキシシラン、テトラブトキシシラン、ジメトキシジエトキシシラン;ジメチルジクロルシラン、ジメチルジブロムシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン;ジフェニルジクロルシラン、ジフェニルジブロムシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン;フェニルメチルジクロルシラン、フェニルメチルジブロムシラン、フェニルメチルジメトキシシラン、フェニルメチルジエトキシシラン;トリクロルヒドロシラン、トリブロムヒドロシラン、トリメトキシヒドロシラン、トリエトキシヒドロシラン、トリイソプロポキシヒドロシラン、トリt−ブトキシヒドロシラン;ビニルトリクロルシラン、ビニルトリブロムシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリイソプロポキシシラン、ビニルトリt−ブトキシシラン;トリフルオロプロピルトリクロルシラン、トリフルオロプロピルトリブロムシラン、トリフルオロプロピルトリメトキシシラン、トリフルオロプロピルトリエトキシシラン、トリフルオロプロピルトリイソプロポキシシラン、トリフルオロプロピルトリt−ブトキシシラン;γ−グリシドキシプロピルメチルジメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルトリイソプロポキシシラン、γ−グリシドキシプロピルトリt−ブトキシシラン;γ−メタアクリロキシプロピルメチルジメトキシシラン、γ−メタアクリロキシプロピルメチルジエトキシシラン、γ−メタアクリロキシプロピルトリメトキシシラン、γ−メタアクリロキシプロピルトリエトキシシラン、γ−メタアクリロキシプロピルトリイソプロポキシシラン、γ−メタアクリロキシプロピルトリt−ブトキシシラン;γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルメチルジエトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリイソプロポキシシラン、γ−アミノプロピルトリt−ブトキシシラン;γ−メルカプトプロピルメチルジメトキシシラン、γ−メルカプトプロピルメチルジエトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、γ−メルカプトプロピルトリイソプロポキシシラン、γ−メルカプトプロピルトリt−ブトキシシラン;β−(3、4−エポキシシクロヘキシル)エチルトリメトキシシラン、β−(3、4−エポキシシクロヘキシル)エチルトリエトキシシランの部分加水分解物、脱水宿重合物を好適に使用することができる。
【0016】
更に、前記塗料として使用する場合のバインダーとして、フッ素樹脂エマルジョンを使用することができる。フッ素樹脂エマルジョンを含む塗膜は化学的安定性が高く、また、耐候性も高い。
前記フッ素樹脂エマルジョンとしては、例えばポリテトラフルオロエチレン、ポリフッ化ビニリデン、ポリフッ化ビニル、ポリクロロトリフルオロエチレン、テトラフルオロエチレン−ヘキサフルオロプロピレンコポリマー、エチレン−テトラフルオロエチレンコポリマー、エチレン−クロロトリフルオロエチレンコポリマー、テトラフルオロエチレン−パーフルオロアルキルビニルエーテルコポリマー、パーフルオロシクロポリマー、ビニルエーテル−フルオロオレフィンコポリマー、ビニルエステル−フルオロオレフィンコポリマー、テトラフルオロエチレン−ビニルエーテルコポリマー、クロロトリフルオロエチレン−ビニルエーテルコポリマー、テトラフルオロエチレンウレタン架橋体、テトラフルオロエチレンエポキシ架橋体、テトラフルオロエチレンアクリル架橋体、テトラフルオロエチレンメラミン架橋体等フルオロ基を含有するポリマーのエマルジョン等から選択される少なくとも一つが好適に利用できる。
【0017】
前記塗料として使用する場合、溶媒は、光触媒材料とバインダーが分散するものであれば特に制限されない。例えば、水、アルコール類、エーテル類、アセトン、2−ブタノン、メチルプロピルケトン、メチルブチルケトン、ジプロピルケトン等のケトン類、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸アミル、酪酸エチル等のエステル類、ベンゼン、トルエン、キシレン、クロロホルム、ペンタン、ヘキサン、シクロヘキサン等の脂肪族、芳香族、脂環式の炭化水素、石油類等の一般的な溶媒が挙げられ、これらを単独、もしくは混合して用いることができる。また、沸点が100℃以上と比較的高い溶媒を加えるとレベリング性向上が期待できる。
【0018】
フィラーとしては一般的に使われるウィスカー、マイカ、タルクなどを用いることが出来る。
着色顔料としては有機系のものは光触媒により徐々に分解される恐れがあるため、無機系のものを用いることが好ましい。 無機顔料としては、酸化チタン、亜鉛華、ベンガラ、酸化クロム、コバルトブルー、鉄黒などの金属酸化物系、アルミナホワイト、黄色酸化鉄などの金属水酸化物系、紺青などのフェロシアン化合物系、黄鉛、ジンクロメート、モリブデンレッドなどのクロム酸鉛系、硫化亜鉛、朱、カドミウムイエロー、カドミウムレッドなどの硫化物、セレン化合物、バライト、沈降性硫酸バリウムなどの硫酸塩系、重質炭酸カルシウム、沈降性炭酸カルシウムなどの炭酸塩系、含水珪酸塩、クレイ、群青などの珪酸塩系、カーボンブラックなどの炭素系、アルミニウム粉、ブロンズ粉、亜鉛粉などの金属粉系、雲母・酸化チタン系などのパール顔料系などが挙げられる。
【0019】
本発明において、光触媒材料の電気抵抗率、ホール起電力、キャリア密度、移動度、キャリアの属性は、ホール効果測定装置、ゼーベック係数測定装置によって測定可能である。
【0020】
本発明の光触媒材料は、好ましくは基板に対して垂直方向に成長した柱状構造を有している。柱状構造においては表面積が増大するため、光触媒活性が高くなる。また、柱状構造においては表面粗さが大きくなるため、表面の水との接触角が低くなり、親水化現象を利用した防曇やセルフクリーニング等の用途に対して有利に働く。
【0021】
本発明において、光触媒材料を適用しうる基材として、自己洗浄が期待できる用途としては、例えば、外壁や屋根のような建物外装、窓枠、自動車、鉄道車両、航空機、船舶、自転車、オートバイのような乗物の外装及び塗装、窓ガラス、看板、交通標識、防音壁、ビニールハウス、碍子、乗物用カバー、テント材、反射板、雨戸、網戸、太陽電池用カバー、太陽熱温水器等の集熱器用カバー、街灯、舗道、屋外照明、人工滝、人工噴水用石材、タイル、橋、温室、外壁材、壁間や碍子間のシーラー、ガードレール、ベランダ、自動販売機、エアコン室外機、野外ベンチ、各種表示装置、シャッター、料金所、料金ボックス、屋根樋、車両用ランプ保護カバー、防塵カバー及び塗装、機械装置や物品の塗装、広告塔の外装及び塗装、構造部材、及びそれら物品に貼着可能なフィルム、ワッペンなどである。
【0022】
本発明において、光触媒材料を適用しうる基材として、防曇用途においては、例えば、浴室用又は洗面所用鏡、車両用バックミラー、歯科用歯鏡、道路鏡のような鏡;眼鏡レンズ、光学レンズ、写真機レンズ、内視鏡レンズ、照明用レンズ、半導体製造用レンズのようなレンズ;プリズム;建物や監視塔の窓ガラス;自動車、鉄道車両、航空機、船舶、潜水艇、雪上車、ロープウエイのゴンドラ、遊園地のゴンドラ、宇宙船のような乗り物の窓ガラス;自動車、鉄道車両、航空機、船舶、潜水艇、雪上車、スノーモービル、オートバイ、ロープウエイのゴンドラ、遊園地のゴンドラのような乗り物の風防ガラス;防護用又はスポーツ用ゴーグル又はマスク(潜水用マスクを含む)のシールド;ヘルメットのシールド;冷凍食品陳列ケースのガラス;計測機器のカバーガラス、及びそれら物品に貼着可能なフィルム、ワッペンなどである
【0023】
【実施例】
基板として低アルカリガラス(コーニング製7059)を用意し、それを高周波マグネトロンスパッタ装置のチャンバー内部に設置し、表1に記載した条件(#1〜6)で試料を作製した。高周波マグネトロンスパッタ装置として島津製作所製HSM−752、Znターゲットとして高純度化学研究所製Zn(純度:99.999%)、ZnOターゲットとして高純度化学研究所製ZnO(純度:99.99%)を使用した。
次に、#1〜6の結晶構造、膜厚、電気抵抗率、ホール起電力、キャリア密度、移動度、キャリアの属性を測定した。結晶構造の測定にはXRD(マック・サイエンス製MXP−18)、膜厚の測定にはSEM(日立製作所製S−4100)を用いた。また、ホール効果測定装置(東陽テクニカ製RESITEST8200)によって、電気抵抗率、ホール起電力、キャリア密度、移動度、キャリアの属性を測定した。
この結果、#1〜6の結晶構造(ウルツ鉱型のものを「ZnO」と記載)、膜厚、電気抵抗率、ホール起電力、キャリア密度、移動度、キャリアの属性を表2に示し、#1、#5のホール起電力の磁場依存性をそれぞれ図2、3に示す。図2、3の直線の傾きが正の場合にp型、負の場合にn型となる。なお、表2の#3、4については、試料の電気抵抗率が測定限界を超えたため、電気抵抗率、ホール起電力、キャリア密度、移動度、キャリアの属性を求めることができず「−」と記載した。
この結果、#1、#2試料がp型伝導性、つまり、本発明の実施例であり、#3〜#6はn型伝導性のため、比較例となる。
【0024】
【表1】
【0025】
【表2】
【0026】
続いて、#1〜6の光触媒活性を分解活性指数で評価した。分解活性指数は、光触媒製品フォーラムが規定した「光触媒製品における湿式分解性能試験方法」に記載している酸化分解力の指標である。具体的には、下記の方法で測定した。
(1)試料を1cm角に切断し、内径35mm、高さ9mmのガラス製シャーレに入れる。
(2)濃度1.0×10−5 M 、2.0×10−5 Mのメチレンブルー水溶液を用意する。1.0×10−5 Mの液を試験液、2.0×10−5 Mの液を吸着液として使用する。
(3)図4に示す構成のブースを用意し、空のガラス製シャーレに試験液を6ml入れ、ガラス製シャーレの底面で紫外線強度(λ=360nm)が1mW・cm−2となるように、ブラックライト蛍光ランプの高さを調整する。ここで、紫外線強度の調整には、携帯型の紫外線強度計を使用した。
(4)(1)のガラス製シャーレに、吸着液を6ml入れる。
(5)10cm角のガラス板をシャーレに乗せ、暗所で12時間静置する。
(6)吸着液を完全に取り出し、試験液をガラス製シャーレに6ml入れる。
(7)試験液の吸光度スペクトルを分光光度計で測定する。波長範囲は600〜700nm、波長間隔は1nm、測定速度は400nm・min−1である。吸光度スペクトルの最大値をAbs(0)とする。
(8)試験液を戻し、試料と試験液を入れたガラス製シャーレを図4のように設置し、紫外線を24時間照射する。
(9)(7)の条件で、試験液の吸光度スペクトルを測定する。吸光度スペクトルの最大値をAbs(24)とする。
(10)分解活性指数を算出する。
【0027】
【数1】
【0028】
なお、本測定では、メチレンブルー試薬として和光純薬工業製メチレンブルー4水和物(137−06982)、分光光度計として日本分光製Ubest−55、紫外線強度計としてトプコン製UD−36、ブラックライト蛍光ランプとして東芝ライテック製FL20S BLBを使用した。その結果を図1に示す。#1、2の分解活性指数は、#3〜6の分解活性指数より大きく、#1、2で高い光触媒活性を示した。すなわち、窒素/酸素混合気流中で、Znターゲットを使用してスパッタ法で成膜した窒素ドープのZnOにおいて、高度な光触媒活性が発現した。
【0029】
【発明の効果】
本発明では、ターゲットをZnとし、O2/N2雰囲気下でスパッタにより得られる窒素ドープしたZnOを提供した。その光触媒材料のキャリアの属性はp型を示し、高い光触媒活性(酸化分解力)を示した。
【図面の簡単な説明】
【図1】#1〜#6試料の分解活性を示すグラフ
【図2】#1試料のホール起電力の磁場依存性を示すグラフ
【図3】#5試料のホール起電力の磁場依存性を示すグラフ
【図4】分解活性指数を測定するためのブースの構成図[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a photocatalytic material having high photocatalytic activity.
[0002]
[Prior art]
When the photocatalytic material is irradiated with light having an energy equal to or greater than the band gap, electrons and holes are excited, and diffused to the surface, whereby an oxidation-reduction reaction or a hydrophilic reaction is developed. Taking advantage of this function, photocatalytic materials are used in various fields such as environmental purification, antifouling, self-cleaning, and antifogging. In order to improve these properties, high activation of the photocatalyst material is indispensable, and as a means thereof, higher sensitivity to ultraviolet light and higher sensitivity to visible light have been studied. Among them, in increasing the sensitivity to ultraviolet light, metal loading on a photocatalytic material (for example, see Non-Patent Document 1) and doping of a transition metal (for example, see Non-Patent Document 2) have been performed. However, in the case of metal loading, expensive products such as platinum and palladium are used, which increases the product cost. In the case of transition metal doping, the energy level of the transition metal becomes the recombination center of electrons and holes, so photocatalytic activity Was a problem.
[0003]
In recent years, visualization of a photocatalyst with nitrogen-doped titanium oxide has been reported (Patent Document 3). When titanium oxide is doped with nitrogen, 2p activation of nitrogen is formed at a potential position lower than the 2p orbital of oxygen forming the valence band, and as a result, the band gap is narrowed, so that visible light can be absorbed. As a specific method of doping nitrogen into titanium oxide, a heat treatment in an ammonia atmosphere or the production of a photocatalytic thin film by sputtering using a metal oxide target in an Ar / N 2 gas stream has been reported ( Patent Document 3). However, in any of these methods, nitrogen doping is performed in a reducing atmosphere, so that oxygen defects occur simultaneously with nitrogen doping. The electrons generated by the oxygen deficiency are localized in Ti ions, so that they are present in the crystal as Ti 3+ ions. The Ti 3+ level (oxygen defect level) exists at a depth of 0.78 to 1.1 eV from the lower end of the conduction band, and acts as a recombination center for electron-hole pairs. When a large number of electrons as n-type carriers are present, holes generated by photoexcitation are offset by the electrons as majority carriers. Since holes are essentially involved in both the oxidative decomposition reaction and the hydrophilization reaction (for example, see Non-Patent Document 3), titanium oxide having oxygen vacancies and electrons as majority carriers is used for photocatalytic reactions. The number of holes that can be formed is reduced, and the oxidative decomposition reaction and the hydrophilization reaction are significantly inhibited.
[0004]
On the other hand, it has been reported that zinc oxide (ZnO), which is known as one of photocatalyst materials, has become p-type (for example, see Non-Patent Document 4). In Non-Patent
[0005]
[Patent Document 1] JP-A-2001-205104
[Non-Patent Document 1] Science, 1980, 207, 139.
[Non-patent document 2] New J. et al. Chem. 1989, 13, 61.
[Non-Patent Document 3] Phys. Chem. B, 2001, 105, 3023.
[Non-Patent Document 4] Appl. Phys. Lett. , 2002, 80, 1195.
[0006]
[Problems to be solved by the invention]
Provided is a highly active photocatalytic material containing a p-type semiconductor in which generation of oxygen vacancies causing a decrease in photocatalytic activity is suppressed and a majority carrier becomes a hole.
[0007]
[Means for Solving the Problems]
Provided is a photocatalyst material including a p-type optical semiconductor having a band gap of 2.8 eV or more and a carrier density of 10 13 (cm −3 ) or less.
In order to provide the photocatalytic material, it is necessary to dope an impurity that forms an acceptor level without generating oxygen defects. In a preferred aspect of the present invention, the p-type optical semiconductor is nitrogen-doped ZnO. As a method for producing the nitrogen-doped ZnO, Zn is used as a target, and sputtering is performed in an O 2 / N 2 atmosphere. A photocatalyst material characterized by being obtained can be provided.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
A p-type semiconductor refers to a semiconductor in which majority carriers are holes in a state without photoexcitation. That is, a semiconductor in which an impurity is doped into a semiconductor and an acceptor level is formed at a potential position lower than the valence band is a p-type semiconductor.
In order to exert strong electron-reducing power and hole-oxidizing power as a photocatalyst, a semiconductor having a band gap of 2.8 eV or more is desirable. The semiconductor used in the present invention has a band gap of 2.8 eV or more. For example, TiO 2 , SnO 2 , ZnO, SrTiO 3 , WO 3 , ZrO 2 , Nb 2 O 5 , Bi 2 O 3 , Ta 3 O 5 , CeO 2, BaTiO 3, CaTiO 3, MgTiO 3, MgTi 2
[0009]
In the photocatalyst material of the present invention, at least one selected from the group consisting of nitrogen, sulfur, phosphorus, and carbon can be suitably used as a dopant for expressing p-type characteristics. Furthermore, in a preferred embodiment of the present invention, nitrogen is doped into ZnO. The position of doping with nitrogen can be a part of lattice oxygen, any of lattices of photocatalytic material, a crystal grain boundary, or a combination thereof. By doping with nitrogen as described above, the acceptor level is formed at a position where the 2p orbital of nitrogen is more negative than the valence band formed by the 2p orbital of oxygen, and exhibits p-type characteristics.
[0010]
The carrier density of the p-type semiconductor is preferably 10 13 (cm −3 ) or less. By lowering the carrier density, scattering of carriers when photoexcited can be prevented, the mobility of electrons and holes, which are the origin of the photocatalytic reaction, is improved, and as a result, high photocatalytic activity can be exhibited. .
[0011]
In a preferred embodiment of the present invention, a sputtering device is used as a photocatalytic material film forming device. Inside the chamber of the sputtering apparatus, the introduced nitrogen gas is dissociated, and a high-energy nitrogen plasma is generated, so that the photocatalytic material can be easily doped with nitrogen. The sputtering apparatus includes types such as direct current sputtering, high frequency sputtering, magnetron sputtering, ion beam sputtering, and ECR sputtering, and any of these types can be used for film formation.
In the manufacturing method by the sputtering method, it is preferable to use a metal target as the target material. In the case where an oxide target is used, particles ejected by the sputtering phenomenon are formed of a group (cluster) of oxide molecules, so that uniform nitrogen doping into the crystal becomes difficult.
Further, in the manufacturing method by the sputtering method, a mixed gas of oxygen and nitrogen is used as a gas. By using oxygen, generation of oxygen vacancies can be suppressed. The preferred gas mixture ratio is O 2 / N 2 = 10/90 to 30/70. If the amount of nitrogen is less than 70, doping becomes insufficient because the amount of nitrogen is insufficient, and if the amount of nitrogen exceeds 90, amorphous or nitride is formed, which is not suitable.
In the manufacturing method by the sputtering method, the plasma output is preferably 600 W or less. If it exceeds 600 W, the mean free path of the plasma increases, and there is a possibility that damage during film formation may increase.
In the manufacturing method by the sputtering method, the total pressure of the reaction gas is preferably 5.0 × 10 −3 torr or more. If it is less than 5.0 × 10 −3 torr, the mean free path of plasma increases, and there is a possibility that damage during film formation may increase.
[0012]
As a manufacturing method different from the sputtering method, CVD, vapor deposition, MBE (molecular beam epitaxy), laser ablation, and ion plating can also be used. In this case, a radical source is required to dissociate nitrogen molecules into plasma. It is.
[0013]
As still another method for producing the photocatalyst material of the present invention, a semiconductor powder or a thin film is heat-treated in an air stream containing at least one of various reactive gases selected from the group consisting of ammonia, hydrocarbons, phosphoric acid, and hydrogen sulfide. Can be produced. In addition, the semiconductor precursor powder or thin film may be prepared by heat treatment in an air stream containing at least one of various reactive gases selected from the group consisting of ammonia, hydrocarbons, phosphoric acid, and hydrogen sulfide. good.
[0014]
The photocatalyst material of the present invention can be used as a paint. In this case, the photocatalyst material of the present invention can be used as a mixture with a binder, a solvent, a filler, a thickener, a coloring pigment, a surfactant and the like.
As the binder when used as the coating material, for example, a substance having a siloxane bond can be suitably used. Silanol groups with high affinity for water are present on the surface of the compound having a siloxane bond, which has the effect of imparting or strengthening the function of maintaining hydrophilicity in a dark place, and is self-cleaning by rainfall. The effect is improved. As the substance having a siloxane bond, an alkali silicate such as water glass, colloidal silica, or an aluminosilicate compound can also be used. The aluminosilicate compound is a compound in which a part of Si of the silicate compound is substituted with Al. In order to further compensate for the charge, H + , Li + , Na + , K + , Rb + , Cs + , Fr + and the like are used. An alkali metal ion or an alkaline earth metal ion such as Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Ra 2+ may be contained. Examples of the compound having a silicate bond in which a part of Si is substituted with Al, zeolite, and the like can be used.
[0015]
As the substance having a siloxane bond, a silicone emulsion can be used. Examples of the silicone emulsion include methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, and methyltri-t-butoxysilane; ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, Ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-t-butoxysilane; n-propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxy Silane, n-propyltri-t-butoxysilane; n-hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriet Sisilane, n-hexyltriisopropoxysilane, n-hexyltri-t-butoxysilane; n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltriiso Propoxysilane, n-decyltri-t-butoxysilane; n-octadecyltrichlorosilane, n-octadecyltribromosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltri t-butoxysilane; phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane Tetrachlorosilane, tetrabromosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane; dimethyldichlorosilane, dimethyldibromosilane, dimethyldimethoxysilane, dimethyldiethoxysilane; diphenyldichlorosilane, diphenyl Dibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane; phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane; trichlorohydrosilane, tribromohydrosilane, trimethoxyhydrosilane, triethoxyhydrosilane , Triisopropoxyhydrosilane, tri-t-butoxyhydrosilane; vinyltrichlorosilane, vinyltribro Silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltri-t-butoxysilane; trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane , Trifluoropropyltriisopropoxysilane, trifluoropropyltri-t-butoxysilane; γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ -Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane; γ-methacryloxy Propylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ-meta Acryloxypropyltri-t-butoxysilane; γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane Γ-aminopropyltri-t-butoxysilane; γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-merca Pt-propyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltri-t-butoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) A partially hydrolyzed product of ethyltriethoxysilane and a dehydrated polymer can be suitably used.
[0016]
Furthermore, a fluororesin emulsion can be used as a binder when used as the paint. A coating film containing a fluororesin emulsion has high chemical stability and high weather resistance.
Examples of the fluororesin emulsion include polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer , Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, perfluorocyclopolymer, vinyl ether-fluoroolefin copolymer, vinyl ester-fluoroolefin copolymer, tetrafluoroethylene-vinyl ether copolymer, chlorotrifluoroethylene-vinyl ether copolymer, crosslinked tetrafluoroethylene urethane , Tetrafluoroethylene epoxy crosslinked product, La fluoroethylene acrylic crosslinked body, at least one selected from the emulsion such as polymers containing tetrafluoroethylene melamine crosslinked body and the like fluoro group can be suitably used.
[0017]
When used as the paint, the solvent is not particularly limited as long as the photocatalytic material and the binder are dispersed. For example, water, alcohols, ethers, acetone, 2-butanone, ketones such as methyl propyl ketone, methyl butyl ketone, dipropyl ketone, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, amyl acetate, ethyl butyrate, etc. Esters, benzene, toluene, xylene, chloroform, pentane, hexane, cyclohexane and other aliphatic, aromatic, alicyclic hydrocarbons, and common solvents such as petroleum. Can be used. When a solvent having a relatively high boiling point of 100 ° C. or higher is added, an improvement in leveling property can be expected.
[0018]
As the filler, commonly used whiskers, mica, talc, and the like can be used.
As a coloring pigment, an organic pigment is preferably used because an organic pigment may be gradually decomposed by a photocatalyst. As inorganic pigments, titanium oxide, zinc oxide, red iron oxide, chromium oxide, cobalt blue, metal oxides such as iron black, alumina white, metal hydroxides such as yellow iron oxide, ferrocyan compounds such as dark blue, Lead chromate such as graphite, zinc chromate, molybdenum red, sulfide such as zinc sulfide, vermilion, cadmium yellow, cadmium red, selenium compound, barite, sulfate such as precipitated barium sulfate, heavy calcium carbonate, Carbonates such as precipitated calcium carbonate, silicates such as hydrated silicates, clay and ultramarine, carbons such as carbon black, metal powders such as aluminum powder, bronze powder and zinc powder, mica / titanium oxide etc. Pearl pigments and the like.
[0019]
In the present invention, the electric resistivity, Hall electromotive force, carrier density, mobility and attributes of the carrier of the photocatalytic material can be measured by a Hall effect measuring device and a Seebeck coefficient measuring device.
[0020]
The photocatalyst material of the present invention preferably has a columnar structure grown in a direction perpendicular to the substrate. Since the surface area is increased in the columnar structure, the photocatalytic activity is increased. Further, in the columnar structure, the surface roughness is large, so that the contact angle of the surface with water is low, which is advantageous for applications such as anti-fogging and self-cleaning utilizing the hydrophilization phenomenon.
[0021]
In the present invention, as a substrate to which the photocatalyst material can be applied, applications in which self-cleaning can be expected include, for example, building exteriors such as outer walls and roofs, window frames, automobiles, railway vehicles, aircraft, ships, bicycles, and motorcycles. Vehicle exterior and paint, window glass, signboards, traffic signs, soundproof walls, greenhouses, insulators, vehicle covers, tent materials, reflectors, rain doors, screen doors, solar cell covers, solar water heaters, etc. Instrument cover, street light, pavement, outdoor lighting, artificial waterfall, artificial fountain stone, tile, bridge, greenhouse, outer wall material, sealer between walls and insulators, guardrail, veranda, vending machine, air conditioner outdoor unit, outdoor bench, Various display devices, shutters, toll booths, toll boxes, roof gutters, lamp protection covers for vehicles, dustproof covers and painting, painting of machinery and articles, exterior and painting of advertising towers, structural members And attaching possible film thereto articles, patch and the like.
[0022]
In the present invention, as a substrate to which the photocatalyst material can be applied, in anti-fog applications, for example, mirrors such as bathroom or toilet mirrors, vehicle rearview mirrors, dental tooth mirrors, road mirrors; spectacle lenses, optics Lenses, camera lenses, endoscope lenses, illumination lenses, lenses such as semiconductor manufacturing lenses; prisms; windows of buildings and towers; automobiles, railway vehicles, aircraft, ships, submersibles, snowmobiles, ropeways Gondolas, amusement park gondola, window glasses for vehicles such as spaceships; vehicles such as cars, railcars, aircraft, ships, submarines, snowmobiles, snowmobiles, motorcycles, ropeway gondola, amusement park gondola Windshield; shield for protective or sports goggles or masks (including diving masks); shield for helmets; cover for frozen food display cases Scan; capable attached to the cover glass, and their article instrumentation film, patch, etc. [0023]
【Example】
A low-alkali glass (7059, manufactured by Corning) was prepared as a substrate, which was placed inside a chamber of a high-frequency magnetron sputtering apparatus, and samples were prepared under the conditions (# 1 to 6) described in Table 1. HSM-752 manufactured by Shimadzu Corporation as a high-frequency magnetron sputtering device, Zn manufactured by Kojundo Chemical Laboratory (purity: 99.999%) as a Zn target, and ZnO manufactured by Kojundo Chemical Laboratory (purity: 99.99%) as a ZnO target. used.
Next, the crystal structure, film thickness, electric resistivity, hole electromotive force, carrier density, mobility, and attributes of carriers of # 1 to # 6 were measured. XRD (MXP-18, manufactured by Mac Science) was used to measure the crystal structure, and SEM (S-4100, manufactured by Hitachi, Ltd.) was used to measure the film thickness. In addition, the electrical resistivity, Hall electromotive force, carrier density, mobility, and attributes of the carrier were measured by a Hall effect measurement device (RESITEST8200 manufactured by Toyo Technica).
As a result, Table 2 shows the crystal structures of # 1 to 6 (the wurtzite type is described as “ZnO”), film thickness, electric resistivity, Hall electromotive force, carrier density, mobility, and carrier attributes. FIGS. 2 and 3 show the magnetic field dependence of the Hall electromotive force of # 1 and # 5, respectively. 2 and 3 are p-type when the inclination of the straight line is positive, and n-type when the inclination is negative. Regarding # 3 and # 4 in Table 2, since the electrical resistivity of the sample exceeded the measurement limit, the electrical resistivity, Hall electromotive force, carrier density, mobility, and carrier attributes could not be obtained, and "-" It was described.
As a result, the # 1 and # 2 samples are p-type conductivity, that is, examples of the present invention, and # 3 to # 6 are comparative examples because of n-type conductivity.
[0024]
[Table 1]
[0025]
[Table 2]
[0026]
Subsequently, the photocatalytic activities of # 1 to # 6 were evaluated by the decomposition activity index. The decomposition activity index is an index of oxidative decomposition power described in “Wet decomposition performance test method for photocatalytic products” specified by the Photocatalyst Product Forum. Specifically, it was measured by the following method.
(1) A sample is cut into a 1 cm square and placed in a glass petri dish having an inner diameter of 35 mm and a height of 9 mm.
(2) An aqueous solution of methylene blue having a concentration of 1.0 × 10 −5 M or 2.0 × 10 −5 M is prepared. A 1.0 × 10 −5 M solution is used as a test solution, and a 2.0 × 10 −5 M solution is used as an adsorbent.
(3) A booth having the configuration shown in FIG. 4 was prepared, 6 ml of the test solution was placed in an empty glass Petri dish, and the ultraviolet intensity (λ = 360 nm) was 1 mW · cm −2 at the bottom of the glass Petri dish. Adjust the height of the black light fluorescent lamp. Here, a portable ultraviolet intensity meter was used for adjusting the ultraviolet intensity.
(4) Put 6 ml of the adsorbed solution into the glass Petri dish of (1).
(5) A glass plate of 10 cm square is placed on a petri dish and allowed to stand in a dark place for 12 hours.
(6) Remove the adsorbed solution completely and put 6 ml of the test solution into a glass petri dish.
(7) Measure the absorbance spectrum of the test solution with a spectrophotometer. The wavelength range is 600 to 700 nm, the wavelength interval is 1 nm, and the measurement speed is 400 nm · min −1 . The maximum value of the absorbance spectrum is defined as Abs (0).
(8) The test solution is returned, and a glass petri dish containing the sample and the test solution is placed as shown in FIG. 4 and irradiated with ultraviolet rays for 24 hours.
(9) Under the conditions of (7), the absorbance spectrum of the test solution is measured. The maximum value of the absorbance spectrum is defined as Abs (24).
(10) Calculate the decomposition activity index.
[0027]
(Equation 1)
[0028]
In this measurement, methylene blue tetrahydrate (137-06982) manufactured by Wako Pure Chemical Industries, Ltd. as a methylene blue reagent, Ubest-55 manufactured by JASCO as a spectrophotometer, UD-36 manufactured by Topcon as an ultraviolet intensity meter, black light fluorescent lamp Was used as FL20S BLB manufactured by Toshiba Lighting & Technology. The result is shown in FIG. The decomposition activity index of # 1 and # 2 was larger than the decomposition activity index of # 3 to # 6, and # 1 and # 2 showed high photocatalytic activity. That is, high photocatalytic activity was exhibited in nitrogen-doped ZnO formed by a sputtering method using a Zn target in a nitrogen / oxygen mixed gas flow.
[0029]
【The invention's effect】
The present invention provides ZnO doped with nitrogen, which is obtained by sputtering in an O 2 / N 2 atmosphere using Zn as a target. The attribute of the carrier of the photocatalyst material was p-type, indicating high photocatalytic activity (oxidative decomposition power).
[Brief description of the drawings]
FIG. 1 is a graph showing the decomposition activity of # 1 to # 6 samples. FIG. 2 is a graph showing the magnetic field dependence of the Hall electromotive force of # 1 sample. FIG. 3 is a graph showing the magnetic field dependence of the Hall electromotive force of # 5 sample. [Figure 4] Diagram of booth configuration for measuring decomposition activity index
Claims (4)
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