EP1164207A2 - Method for preparing metal oxide film - Google Patents
Method for preparing metal oxide film Download PDFInfo
- Publication number
- EP1164207A2 EP1164207A2 EP00308173A EP00308173A EP1164207A2 EP 1164207 A2 EP1164207 A2 EP 1164207A2 EP 00308173 A EP00308173 A EP 00308173A EP 00308173 A EP00308173 A EP 00308173A EP 1164207 A2 EP1164207 A2 EP 1164207A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal oxide
- solution
- substrate
- organic solvent
- metal
- 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.)
- Withdrawn
Links
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 153
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 153
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000000758 substrate Substances 0.000 claims abstract description 99
- 239000002904 solvent Substances 0.000 claims abstract description 54
- 239000003960 organic solvent Substances 0.000 claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- 238000007669 thermal treatment Methods 0.000 claims abstract description 10
- 238000000151 deposition Methods 0.000 claims abstract description 8
- 238000009792 diffusion process Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 74
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 48
- 150000003839 salts Chemical class 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- -1 Pb Bi Inorganic materials 0.000 claims description 21
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000006460 hydrolysis reaction Methods 0.000 claims description 15
- 150000002894 organic compounds Chemical class 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 229920006395 saturated elastomer Polymers 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 10
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000004703 alkoxides Chemical class 0.000 claims description 6
- MKUWVMRNQOOSAT-UHFFFAOYSA-N but-3-en-2-ol Chemical compound CC(O)C=C MKUWVMRNQOOSAT-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 150000001491 aromatic compounds Chemical class 0.000 claims description 5
- 239000003849 aromatic solvent Substances 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 229910052762 osmium Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910052706 scandium Inorganic materials 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- RCJMVGJKROQDCB-UHFFFAOYSA-N 2-methylpenta-1,3-diene Chemical compound CC=CC(C)=C RCJMVGJKROQDCB-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 3
- 230000009918 complex formation Effects 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- HJQMNGOBTOPZLE-UHFFFAOYSA-N 1,3-oxazole;thiophene Chemical compound C=1C=CSC=1.C1=COC=N1 HJQMNGOBTOPZLE-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 229940095102 methyl benzoate Drugs 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 4
- 230000008021 deposition Effects 0.000 claims 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims 1
- 238000003980 solgel method Methods 0.000 abstract description 9
- 239000010936 titanium Substances 0.000 description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- KTUQUZJOVNIKNZ-UHFFFAOYSA-N butan-1-ol;hydrate Chemical compound O.CCCCO KTUQUZJOVNIKNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- WRMFBHHNOHZECA-UHFFFAOYSA-N butan-2-olate Chemical compound CCC(C)[O-] WRMFBHHNOHZECA-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
- C23C18/143—Radiation by light, e.g. photolysis or pyrolysis
Definitions
- the present invention relates to a method for preparing a metal oxide film on a substrate by using a sol-gel method, which is appropriate for use as an optical material, a photoelectric converter material, an electronic material, a surface protection film, a capacitor, a piezoelectric element, an SAW filter, a ferroelectric material and a ferroelectric memory.
- a metal oxide film is generally formed by employing a chemical vapor deposition (CVD) method, a physical vapor deposition (PVD) method or a sol-gel method.
- CVD chemical vapor deposition
- PVD physical vapor deposition
- a metal oxide film having a larger surface area is hardly prepared by using the CVD or the PVD, and the need for a vacuum system in these methods provides an increase in costs, thereby arising an economical problem.
- the sol-gel method free from the economical problem offers excellent feasibility, and is regarded as a low-cost preparation method for metal oxide films.
- the conventional sol-gel method may be used for preparing a metal oxide film made by fine particles.
- the method is conducted by dissolving a metal salt in an alcoholic solvent, adding an acidic or an alkaline catalyst in the alcoholic solvent, and depositing the solvent on a substrate by brushing or dipping followed by drying and heating.
- the bonding strength among the particles of the metal oxide film prepared in this manner is weak at the time the metal oxide film is formed because the particles are fine. Accordingly, when a thick metal oxide film is formed in a single process, a crack is likely generated.
- a dry inert gas is introduced to remove moisture in air during the sol preparation or the metal oxide film formation, and the dispersion stability of metal oxide particles in the sol continues only for about 1 to 3 months.
- a solution containing polymerized titanium dioxide or a complex containing a metal oxide oligomer and an aromatic compound solvent is applied onto a titanium substrate by dipping and thermal treatment to form the mixed diffused layer.
- the dipping and the thermal treatment allow the titanium component in the titanium substrate and the metal component in the surface layer to diffuse toward each other to form an intermediate layer for strongly bonding the substrate and the surface metal oxide layer.
- this process is appropriate for making a stacked structure consisting of two or more layers in which at least part of adjacent layers are mixed with each other, the process is inappropriate for making a crack-free homogeneous layer or film used as an optical material, a photoelectric converter material, an electronic material, a surface protection film, a piezoelectric element, an, a ferroelectric material and a ferroelectric memory.
- an object of the present invention is to provide a method for preparing a metal oxide film on a substrate by using the metal oxide oligomer and the organic solvent.
- the present invention provides, in a first aspect thereof, a method for preparing a metal oxide film including the steps of: forming a solution containing a complex including a metal oxide oligomer and an organic solvent; depositing the solution on a substrate; removing at least part of the organic solvent from the solution on the substrate; and thermally treating the substrate for converting the metal oxide oligomer into the corresponding metal oxide film.
- the present invention provides, in a second aspect thereof, a method for preparing a metal oxide film including the steps of: dissolving a metal salt into an organic solvent; adding a water-alcohol solution to the organic solvent to form a solution containing a complex including a metal oxide oligomer and the organic solvent; depositing the solution on a substrate; removing at least part of the organic solvent from the solution on the substrate; and thermally treating the substrate for converting the metal oxide oligomer into the corresponding metal oxide film.
- oligomer-solvent complex at least part of the solvent in the complex containing the metal oxide oligomer and the organic solvent (hereinafter referred to as "oligomer-solvent complex") is removed before converting the metal oxide oligomer into the metal oxide film by means of the thermal treatment.
- the present inventors Based on the fact that the immediate heating of the substrate on which the oligomer-solvent complex is formed induces the diffusion of component between the metals in the substrate and in the metal oxide oligomer, the present inventors have investigated a technique for holding the metal oxide oligomer on the surface of the substrate while maintaining the structure of the metal oligomer as much as possible, which is once prepared in the oligomer-solvent complex and is homogeneous and substantially crack-free, to reach to the present invention.
- an organic solvent is used as a solvent for forming, together with the metal oxide oligomer, the oligomer-solvent complex.
- the organic solvent includes an unsaturated organic solvent and a saturated organic solvent.
- the unsaturated organic compound in the solvent includes an aromatic compound having one or more 6-membered rings consisting of carbons, a heterocyclic aromatic compound, an aliphatic or an alicyclic hydrocarbon compound having a carbon-carbon double bond or a carbon-carbon triple bond, a heterocyclic compound having a carbon-carbon double bond or a carbon-hetero atom double bond and an alcohol compound having not less than three carbon atoms and a carbon-carbon double bond.
- the unsaturated organic compound includes benzene, ethylbenzene, ethoxybenzene, nitrobenzene, toluene, xylene, aniline, dimethylaniline, acetophenone, methylbenzoate, ethylbenzoate, pyridine, picoline, furan, thiophene oxazole, thiazale, 2-methylpyridine, hexene, 1-butene, 2-methyl-1,3-pentadiene, cyclopentene, pyran, 1-buten-3-ol and ethyl acetate.
- the saturated organic compound includes an aliphatic hydrocarbon compound, an alicyclic hydrocarbon compound, a heterocyclic compound, and an alcohol compound having not less than three carbon atoms, a carbon-carbon double bond and a halogenated aliphatic hydrocarbon compound.
- the saturated organic compound includes hexane, cyclohexane, petroleum ether, n-butanol, diethyl ether, dioxane, tetrahydrofuran, diethylmercaptane, carbon tetrachloride, chloroform and carbon tetrafluoride.
- the solvent employable in the present invention is not restricted thereto, the solvent is desirably liquid at room temperature and easily removable in a solvent removing step described later.
- the form of a metal salt includes an alkoxide, an organic salt and an inorganic salt.
- the alkoxide includes ethoxide, n-propoxide, iso-propoxide, n-butoxide, iso-butoxide, sec-butoxide, and tert-butoxide.
- the organic salt includes a phenolate, a carboxylate, and a 1, 3-diketone-type salt.
- the inorganic salt includes a chloride, a sulfate and a nitrate.
- the chloride When the chloride is used as the metal salt, hydrogen chloride may be produced in one or more of the subsequent steps.
- the hydrogen chloride may deteriorate the metal oxide film.
- a basic aromatic solvent such as aniline, pyridine and nitrobenzene excludes the hydrogen chloride or chloride ion by means of the coordination with its nitrogen atom. Accordingly, the basic aromatic solvent is preferably used when the metal chloride is used as the metal salt.
- the metal in the metal salt includes Mg, Al, Si, Ca, Sc, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Cr, Sr, Y, Zr, Nb, Mo, In, Sn, Sb, Cs, Ba, Ta, W, Ru, Os, Ir, Pb Bi, La, Ce and Gd.
- the oligomer-solvent complex is prepared by using the unsaturated or the saturated organic solvent.
- the metal salt is dissolved into or suspended in the organic solvent such that the metal ion concentration in the solvent is adjusted to be between 0.01 and 3 mol/liter. If the metal ion concentration is below 0.01 mol/liter, the distance between the adjacent metals is so large that the metal oxide oligomer cannot be smoothly formed in a step mentioned below. On the other hand, if the metal ion concentration exceeds 3 moL/liter, the distance between the adjacent metals is so small that the three-dimensional growth of the metal oxide oligomer cannot be suppressed in the step mentioned below, thereby hardly providing the planar metal oxide oligomer.
- a water-alcohol mixed solution (aqueous alcohol) is desirably added to the solution including the organic solvent and the metal salt dissolved or suspended therein, thereby subjecting the metal salt to hydrolysis and dehydration condensation to prepare the metal oxide oligomer formed by a plurality of units "Me-O (metal-oxygen)".
- the addition is preferably conducted at a temperature between 0 and 100 °C followed by heating at a temperature between 0 and 200 °C for effecting the hydrolysis and the dehydration condensation.
- the reactions proceed insufficiently at a temperature below 0 °C, and the control of the formation of the oligomer-solvent complex is hardly achieved at a temperature exceeding 200 °C because the reactions proceed too rapidly.
- the reactions may be conducted under pressure.
- the oligomer-solvent complex is prepared.
- the oligomer-solvent complex may be prepared by an alternative process.
- the alcohol used in the water-alcohol mixed solution is not especially restricted, and includes ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol and glycerin.
- the exemplified alcohols have a role of controlling the activity of the water for decreasing the hydrolysis reaction rate, thereby gradually growing the metal oxide oligomer. Accordingly, the ratio of the water in the water-alcohol mixed solution significantly affects the hydrolysis reaction rate. When the reaction rate is too rapid, the metal oxide oligomer produced by the hydrolysis has a disturbed arrangement. Conversely, when the reaction rate is too slow, a longer period of time is required to complete the reaction thereby reducing the efficiency though the arrangement is not disturbed.
- the ratio of the water in the water-alcohol mixed solution is preferably between 0.1 and 20 % in weight.
- the hydrolysis proceeds so slowly that the economical operations cannot be attained.
- the ratio exceeds 20 % in weight, the hydrolysis proceeds so abruptly that the hydrous metal oxide particles may be agglomerated.
- the water-alcohol mixed solution is desirably added to the metal salt such that 0.1 to 3 mol/liter of the water is present per 1 mol/liter of the metal salt.
- the hydrolysis proceeds so slowly that the economical operations cannot be attained.
- the volume of the water exceeds 3 mol/liter, the hydrolysis proceeds so rapidly that the three-dimensional growth of the metal oxide oligomer cannot be suppressed in the step mentioned below, thereby hardly providing the planar metal oxide oligomer.
- optimum liquid mixed with the water in the mixed solution is an alcohol.
- another solvent may be used with or in place of the alcohol.
- the double bond of the solvent coordinates to the metal ion of the metal salt and metal oxide oligomer during the hydrolysis and the dehydration condensation.
- the solvent is the aromatic compound or the heterocyclic aromatic compound
- the dehydration condensation of the metal hydroxide proceeds along the aromatic ring to form the complex having a planar structure formed by the metal oxide oligomer and the aromatic compound solvent.
- the unsaturated organic solvent makes a bond to the metal oxide oligomer by coordinating the ⁇ -electron to the metal oxide oligomer, thereby forming the three-layered sandwich structure essentially consisting of (the unsaturated organic solvent) - (the metal oxide oligomer) - (the unsaturated organic solvent).
- the saturated organic solvent having no ⁇ -electron may be used with or in place of the unsaturated organic solvent. Since the saturated organic solvent is also highly hydrophobic and the water is hardly dissolved in the saturated organic solvent, the attack of the water to the metal salt is suppressed to decrease the hydrolysis reaction rate, thereby forming a metal oxide oligomer having a homogeneous network.
- the solution containing the oligomer-solvent complex was stable even after the solution was stored for one year in a cold dark place.
- the solution containing the oligomer-solvent complex is concentrated depending on necessity, the solution is applied on a substrate, on which the metal oxide film is to be formed, by means of brush painting, spray coating, spin coating, and dip coating. Since the existence of the excess water is not preferable in the subsequent steps, the solvent containing the complex in which the water may remain can be replaced with a non-aqueous solvent.
- the substrate employable in the present invention is not especially restricted, and may be appropriately selected depending on a purpose and a usage.
- the material of the substrate includes a single crystal such as silicon wafer, polycrystal glass, a metal, a polymer and ceramic, and the shape may be a thick plate, a small fragment, a bead, a ring, a cylinder, a fiber or a chain.
- the concentration of the oligomer-solvent complex applied to the substrate is desirably between 0.01 and 5 mol/liter. When the concentration is out of the range, the solution is concentrated or diluted before the complex is applied on the substrate.
- the applying procedure can be conducted preferably in a solvent atmosphere including hydrophobic solvent vapor.
- the solvent may be the same as or different from that used for forming the complex.
- any organic compound other than the solvent in the oligomer-solvent complex can be used, including an unsaturated organic compound and a saturated organic compound, for example, aliphatic hydrocarbon, heterocyclic hydrocarbon, alicyclic hydrocarbon containing a hetero atom and an alcohol having a relatively longer carbon chain the number of which is three or more.
- the thickness of the metal oxide film prepared in this manner on the substrate in a single film forming process is generally between 0.01 and 5 ⁇ m.
- the film thickness is mainly controlled by the concentration and volume of the metal oxide oligomer in the solution containing the oligomer-solvent complex prepared in the previous step.
- the above procedure may be repeated for obtaining a thicker metal oxide film.
- the oligomer-solvent complex thus prepared is thermally treated to form the metal oxide film on the substrate.
- the heating is performed after at least part of the solvent containing the oligomer-solvent complex on the substrate is removed.
- the partial removal of the solvent prevents the diffusion and mixing between the substrate and the metal oxide oligomer, thereby forming the homogeneous and substantially crack-free metal oxide film on the substrate.
- a preferable removal rate is between 20 and 80 %.
- the solvent removal can be conducted by any process in which the diffusion and the mixing between the substrate and the metal oxide oligomer do not occur, for example, by heating the substrate to a temperature at which the diffusion does not take place in an inert gas atmosphere, in the air, or by placing the substrate under a reduced pressure without heating, or by indirectly irradiating, on the surface of the substrate, infrared ray from an infrared lamp or ultraviolet ray from an ultraviolet lamp after the substrate is placed in a vessel saturated with organic solvent vapor.
- the infrared ray provides the thermal effect on the solvent at least part of which is removed from the substrate by means of vaporization.
- the ultraviolet ray having no or little thermal effect is applied to the solvent on the substrate, the ultraviolet ray decomposes at least part of the solvent.
- the solvent fragments having a smaller molecular size formed by the solvent decomposition easily leave the substrate without heating.
- the solvent used for the irradiation may be the same as or different from that used for the complex formation or the application to the substrate.
- the substrate having the metal oxide oligomer and the organic solvent at least part of which is removed is thermally treated to form the metal oxide film on the surface of the substrate.
- the thermal treatment is preferably conducted at a temperature between 100 and 1300 °C to form the metal oxide film.
- the heating out of the temperature range may invite unfavorable results.
- the heating below 100 °C sometimes makes it difficult to crystallize the metal oxide film, and the heating exceeding 1300 °C sometimes precipitates unwanted crystals in addition to the desired ones.
- the metal oxide film prepared in this manner is homogenous and substantially crack-free because the metal oxide oligomer is thermally treated after at least part of the solvent is removed.
- the substrate having the homogeneous and crack-free metal oxide film thereon is useful as an optical material, a photoelectric converter material, an electronic material and a surface protection film, and more concretely, these include a capacitor, a piezoelectric element, an SAW filter, a ferroelectric material and a ferroelectric memory.
- the present invention includes, other than the metal oxide film formation on the substrate, formation of an oligomer-solvent complex solution containing a metal oxide oligomer and an organic solvent, and formation of metal oxide powders.
- the oligomer-solvent complex solution employable for the application to the substrate is also used in other usage.
- the metal oxide powders having the desired homogeneous structure may be prepared by removing at least part of the organic solvent from the metal oxide oligomer-solvent complex solution followed by the thermal treatment.
- titanium-n-butoxide acting as a metal salt was dissolved in benzene acting as an unsaturated organic solvent at a concentration of 1 mol/liter and stirred in an ice bath
- aqueous butanol (water-butanol mixed solution) having 4.0 molar concentration was added dropwise to the titanium-n-butoxide solution such that 1.6 moles of the butanol per 1 mole of the titanium ion existed in the solution.
- the bath temperature was elevated to 80 to 90 °C.
- the solution was concentrated by using an evaporator and then diluted such that the titanium ion concentration was adjusted to be 1 mol/liter.
- infrared ray from an infrared lamp was indirectly irradiated through the wall of the glass vessel to the substrate in the benzene atmosphere separated from the lamp by about 20 cm for 15 minutes for drying followed by the further drying at 120 °C for 30 minutes.
- the substrate was thermally treated at 580 °C for 1 hour, the substrate was allowed to stand for cooling until the temperature thereof reached to room temperature, thereby forming a metal oxide film on the substrate.
- the thickness of the metal oxide film thus obtained was measured by using EPMA (electron probe microanalysis) to be about 0.6 ⁇ m.
- FIG.1 A microphotograph taken with a scanning electron microscope (SEM) showing the surface of the metal oxide film thus obtained is shown in Fig.1.
- the microphotograph shows the formation of a substantially crack-free metal oxide film.
- a metal oxide film was prepared using the same procedures as those of Example 1 except that titanium-n-butoxide was dissolved in benzene at a concentration of 0.5 mol/liter and stirred at 5 °C, and a water-butanol mixed solution containing 1.5 mol/liter of water was added dropwise to the titanium-n-butoxide solution such that 0.2 mole of the water per 1 mole of the titanium-n-butoxide existed in the solution followed by the stirring for 1 hour at 5 °C, thereby adjusting the final concentration of the titanium ion to be 0.5 mol/liter.
- the thickness of the metal oxide film thus obtained was about 0.1 ⁇ m. The observation of the surface state of the substrate revealed that the substrate was homogeneous and crack-free.
- a metal oxide film was prepared using the same procedures as those of Example 1 except that, in place of the indirect irradiation of the infrared ray, the substrate was heated at a temperature range between 40 and 60 °C under a reduced pressure (133 h Pa). The thickness of the metal oxide film thus obtained was about 0.6 ⁇ m. The observation of the surface state of the substrate revealed that the substrate was homogeneous and crack-free.
- a metal oxide film was prepared using the same procedures as those of Example 1 except that acetophenone was employed as the unsaturated organic solvent in place of the benzene.
- the thickness of the metal oxide film thus obtained was about 0.4 ⁇ m.
- the observation of the surface state of the substrate revealed that the substrate was homogeneous and crack-free.
- a metal oxide film was prepared using the same procedures as those of Example 1 except that pyridine was employed in place of the benzene.
- the thickness of the metal oxide film was about 0.5 ⁇ m. The observation of the surface state of the substrate revealed that the substrate was homogeneous and crack-free.
- a metal oxide film was prepared using the same procedures as those of Example 1 except that ⁇ -picoline was employed in place of the benzene.
- the thickness of the metal oxide film was about 0.5 ⁇ m. The observation of the surface state of the substrate revealed that the substrate was homogeneous and crack-free.
- a metal oxide film was prepared using the same procedures as those of Example 1 except that cyclohexene was employed in place of the benzene.
- the thickness of the metal oxide film was about 0.4 ⁇ m. The observation of the surface state of the substrate revealed that the substrate was homogeneous and crack-free.
- a metal oxide film was prepared using the same procedures as those of Example 1 except that 1-buten-3-ol was employed in place of the benzene.
- the thickness of the metal oxide film was about 0.6 ⁇ m. The observation of the surface state of the substrate revealed that the substrate was homogeneous and crack-free.
- a metal oxide film was prepared using the same procedures as those of Example 1 except that n-hexane was employed in place of the benzene.
- the thickness of the metal oxide film was about 0.6 ⁇ m. The observation of the surface state of the substrate revealed that the substrate was homogeneous and crack-free.
- a metal oxide film was prepared using the same procedures as those of Example 1 except that tetrahydrofuran was employed in place of the benzene.
- the thickness of the metal oxide film was about 0.5 ⁇ m. The observation of the surface state of the substrate revealed that the substrate was homogeneous and crack-free.
- a metal oxide film was prepared using the same procedures as those of Example 1 except that n-butanol was employed in place of the benzene.
- the thickness of the metal oxide film was about 0.4 ⁇ m. The observation of the surface state of the substrate revealed that the substrate was homogeneous and crack-free.
- a metal oxide film was prepared using the same procedures as those of Example 1 except that zirconium-n-butoxide was employed as a metal salt in place of the titanium-n-butoxide.
- the thickness of the metal oxide film thus obtained was about 0.3 ⁇ m.
- the observation of the surface state of the substrate revealed that the substrate was homogeneous and crack-free.
- Barium acetate was added to the solution containing the titanium ion of 1 mol/liter prepared in Example 1 such that the equimolar barium ion to the titanium ion was present. After the bath temperature was raised to 80 to 90 °C and the reaction was allowed to proceed for 8 hours, the solution was concentrated by using an evaporator and diluted such that the barium titanate concentration was adjusted to be 1 mol/liter.
- the diluted solution was coated on a quartz glass plate which had been degreased and cleaned by using a spin-coater. After the quartz glass plate subjected to drying was sintered for 1 hour at 700 °C by using an electric furnace in the atmosphere, the glass plate was spontaneously cooled to room temperature to form a metal oxide film.
- the metal oxide film thus obtained was analyzed by using an X-ray diffraction apparatus, and an X-ray diffraction pattern obtained by the analysis is shown in Fig.2. The formation of barium titanate is confirmed by the X-ray diffraction pattern.
- Example 1 The solution prepared in Example 1 containing 0.96 mole of the titanium ion, and the solution prepared in Example 12 containing 1.04 moles of the zirconium ion were mixed. After the bath temperature was raised to 80 to 90 °C and the reaction was allowed to proceed for 4 hours, equimolar lead acetate to the total of the titanium ion and the zirconium ion was added to the mixed solution. After the reaction was allowed to proceed for 8 hours at the bath temperature of 80 to 90 °C, the solution was concentrated by using an evaporator and diluted such that the composite metal oxide concentration was adjusted to be 1 mol/liter.
- the diluted solution was coated on a quartz glass plate which had been degreased and cleaned by using a spin-coater. After the quartz glass plate subjected to drying was sintered for 1 hour at 700 °C by using an electric furnace in the atmosphere, the glass plate was spontaneously cooled to room temperature to form a metal oxide film.
- the metal oxide film thus obtained was analyzed by using an X-ray diffraction apparatus, and an X-ray diffraction pattern obtained by the analysis is shown in Fig.3. The formation of PZT is confirmed by the X-ray diffraction pattern.
- the resulting solution containing the complex was concentrated by using an evaporator until the titanium ion concentration became to 1.5 mol/liter to obtain a titanium oxide-containing solution.
- the substrate After a glass substrate which had been degreased and cleansed was dipped in the titanium oxide-containing solution, the substrate was pulled up from the solution at a rate of 0.15 mm/sec. by using a stepping motor and spontaneously dried in air at about 25 °C for 1 hour. After a thermal treatment at 500 °C for 1 hour in an electric furnace including air, the substrate was spontaneously cooled down to room temperature.
- the thickness of the metal oxide film measured with a film thickness measuring apparatus (tradename: F20, available from Filmetrics Corporation) was about 1.2 ⁇ m.
- a metal oxide film was prepared by using a conventional sol-gel method based on the method described in Yogyo Kyokaishi 95, 150 (1987).
- the substrate was pulled up from the solution at a rate of 0.15 mm/sec. by using a stepping motor and air-dried. After a thermal treatment at 580 °C for 1 hour for forming a metal oxide film, the substrate was spontaneously cooled down to room temperature. The thickness of the metal oxide film obtained was about 0.07 ⁇ m.
- FIG.2 A microphotograph taken with a scanning electron microscope (SEM) showing the surface of the metal oxide film thus obtained is shown in Fig.2.
- the microphotograph shows the formation of distinctive fine cracks scattered in the metal oxide film formed by the sol in which the metal oxide particles were dispersed.
- Example 12 After a titanium substrate pretreated by the same procedures as those of Example 12 was dipped for 5 minutes in the solution of which a concentration was adjusted similarly to Example 12, the substrate was pulled up from the solution at a rate of 0.15 mm/sec. by using a stepping motor and was immediately heat-treated at 580 °C for 1 hour. After the heat treatment, the substrate was spontaneously cooled down to room temperature. The observation of the surface state of the substrate thus obtained revealed that the titanium metal in the substrate and the zirconium oxide in the metal oxide film were mutually diffused to each other to form a mixed layer at an interface thereof.
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Abstract
A method for preparing a metal oxide film using a sol-gel
method including the steps of: forming a solution containing a
complex including a metal oxide oligomer and an organic solvent;
depositing the solution on a substrate; removing at least part of
the organic solvent from the solution on the substrate; and
thermally treating the substrate for converting the metal oxide
oligomer into the corresponding metal oxide film. In this method,
since at least part of the solvent in the oligomer-solvent complex
is removed before converting the metal oxide oligomer into the
metal oxide film by the thermal treatment, the mutual diffusion
between the substrate metal and in the metal oxide oligomer is
prevented to provide a crack-free homogeneous metal oxide film
on the substrate.
Description
The present invention relates to a method for preparing a
metal oxide film on a substrate by using a sol-gel method, which is
appropriate for use as an optical material, a photoelectric
converter material, an electronic material, a surface protection
film, a capacitor, a piezoelectric element, an SAW filter, a
ferroelectric material and a ferroelectric memory.
A metal oxide film is generally formed by employing a
chemical vapor deposition (CVD) method, a physical vapor
deposition (PVD) method or a sol-gel method.
A metal oxide film having a larger surface area is hardly
prepared by using the CVD or the PVD, and the need for a vacuum
system in these methods provides an increase in costs, thereby
arising an economical problem. The sol-gel method free from the
economical problem offers excellent feasibility, and is regarded as
a low-cost preparation method for metal oxide films.
The conventional sol-gel method may be used for preparing
a metal oxide film made by fine particles. The method is conducted
by dissolving a metal salt in an alcoholic solvent, adding an acidic
or an alkaline catalyst in the alcoholic solvent, and depositing the
solvent on a substrate by brushing or dipping followed by drying
and heating. The bonding strength among the particles of the
metal oxide film prepared in this manner is weak at the time the
metal oxide film is formed because the particles are fine.
Accordingly, when a thick metal oxide film is formed in a single
process, a crack is likely generated.
In order to form a crack-free homogeneous and thick metal
oxide film by using the sol-gel method, it is necessary to make the
thickness of the metal oxide film formed in one step as thin as
possible and to repeat the step plural times.
Further, a dry inert gas is introduced to remove moisture in
air during the sol preparation or the metal oxide film formation,
and the dispersion stability of metal oxide particles in the sol
continues only for about 1 to 3 months.
Examples of the sol-gel method using an alcoholic solvent
and a hydrochloric acid or a nitric acid catalyst are described in T.
Yoko, K. Kamiya and S. Sakka, Yogyo Kyokaishi, 95, 150 (1987)
and K. Kato, New Ceramics, 9, No. 8, 28 (1996). The thickness of
the metal oxide film obtained in a single formation process is
reported to be 0.07 to 0.09 µm.
As an improvement of the conventional sol-gel method, a
process of forming a mixed diffused layer on a titanium substrate
employed for an electrode for electrolysis is proposed (JP-A-11(1999)-222690).
In this conventional process, a solution containing
polymerized titanium dioxide or a complex containing a metal
oxide oligomer and an aromatic compound solvent is applied onto
a titanium substrate by dipping and thermal treatment to form
the mixed diffused layer. The dipping and the thermal treatment
allow the titanium component in the titanium substrate and the
metal component in the surface layer to diffuse toward each other
to form an intermediate layer for strongly bonding the substrate
and the surface metal oxide layer.
Although this process is appropriate for making a stacked
structure consisting of two or more layers in which at least part of
adjacent layers are mixed with each other, the process is
inappropriate for making a crack-free homogeneous layer or film
used as an optical material, a photoelectric converter material, an
electronic material, a surface protection film, a piezoelectric
element, an, a ferroelectric material and a ferroelectric memory.
In view of the foregoing, an object of the present invention is
to provide a method for preparing a metal oxide film on a
substrate by using the metal oxide oligomer and the organic
solvent.
The present invention provides, in a first aspect thereof, a
method for preparing a metal oxide film including the steps of:
forming a solution containing a complex including a metal oxide
oligomer and an organic solvent; depositing the solution on a
substrate; removing at least part of the organic solvent from the
solution on the substrate; and thermally treating the substrate for
converting the metal oxide oligomer into the corresponding metal
oxide film.
The present invention provides, in a second aspect thereof,
a method for preparing a metal oxide film including the steps of:
dissolving a metal salt into an organic solvent; adding a water-alcohol
solution to the organic solvent to form a solution
containing a complex including a metal oxide oligomer and the
organic solvent; depositing the solution on a substrate; removing
at least part of the organic solvent from the solution on the
substrate; and thermally treating the substrate for converting the
metal oxide oligomer into the corresponding metal oxide film.
In accordance with the present invention, at least part of
the solvent in the complex containing the metal oxide oligomer
and the organic solvent (hereinafter referred to as "oligomer-solvent
complex") is removed before converting the metal oxide
oligomer into the metal oxide film by means of the thermal
treatment. Thereby, the diffusion of component between the
substrate and in the metal oxide oligomer is prevented to provide
a crack-free homogeneous metal oxide film on the substrate.
The above and other objects, features and advantages of the
present invention will be more apparent from the following
description.
Based on the fact that the immediate heating of the
substrate on which the oligomer-solvent complex is formed
induces the diffusion of component between the metals in the
substrate and in the metal oxide oligomer, the present inventors
have investigated a technique for holding the metal oxide
oligomer on the surface of the substrate while maintaining the
structure of the metal oligomer as much as possible, which is once
prepared in the oligomer-solvent complex and is homogeneous and
substantially crack-free, to reach to the present invention.
In the present invention, an organic solvent is used as a
solvent for forming, together with the metal oxide oligomer, the
oligomer-solvent complex. The organic solvent includes an
unsaturated organic solvent and a saturated organic solvent.
The unsaturated organic compound in the solvent includes
an aromatic compound having one or more 6-membered rings
consisting of carbons, a heterocyclic aromatic compound, an
aliphatic or an alicyclic hydrocarbon compound having a carbon-carbon
double bond or a carbon-carbon triple bond, a heterocyclic
compound having a carbon-carbon double bond or a carbon-hetero
atom double bond and an alcohol compound having not less than
three carbon atoms and a carbon-carbon double bond.
More concretely, the unsaturated organic compound includes
benzene, ethylbenzene, ethoxybenzene, nitrobenzene, toluene,
xylene, aniline, dimethylaniline, acetophenone, methylbenzoate,
ethylbenzoate, pyridine, picoline, furan, thiophene oxazole,
thiazale, 2-methylpyridine, hexene, 1-butene, 2-methyl-1,3-pentadiene,
cyclopentene, pyran, 1-buten-3-ol and ethyl acetate.
The saturated organic compound includes an aliphatic
hydrocarbon compound, an alicyclic hydrocarbon compound, a
heterocyclic compound, and an alcohol compound having not less
than three carbon atoms, a carbon-carbon double bond and a
halogenated aliphatic hydrocarbon compound.
More concretely, the saturated organic compound includes
hexane, cyclohexane, petroleum ether, n-butanol, diethyl ether,
dioxane, tetrahydrofuran, diethylmercaptane, carbon
tetrachloride, chloroform and carbon tetrafluoride.
Although the solvent employable in the present invention is
not restricted thereto, the solvent is desirably liquid at room
temperature and easily removable in a solvent removing step
described later.
The form of a metal salt includes an alkoxide, an organic
salt and an inorganic salt. The alkoxide includes ethoxide, n-propoxide,
iso-propoxide, n-butoxide, iso-butoxide, sec-butoxide,
and tert-butoxide. The organic salt includes a phenolate, a
carboxylate, and a 1, 3-diketone-type salt. The inorganic salt
includes a chloride, a sulfate and a nitrate.
When the chloride is used as the metal salt, hydrogen
chloride may be produced in one or more of the subsequent steps.
The hydrogen chloride may deteriorate the metal oxide film. The
use of a basic aromatic solvent such as aniline, pyridine and
nitrobenzene excludes the hydrogen chloride or chloride ion by
means of the coordination with its nitrogen atom. Accordingly, the
basic aromatic solvent is preferably used when the metal chloride
is used as the metal salt.
The metal in the metal salt includes Mg, Al, Si, Ca, Sc, Ti, V,
Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Cr, Sr, Y, Zr, Nb, Mo, In, Sn, Sb, Cs,
Ba, Ta, W, Ru, Os, Ir, Pb Bi, La, Ce and Gd.
At first, the oligomer-solvent complex is prepared by using
the unsaturated or the saturated organic solvent.
The metal salt is dissolved into or suspended in the organic
solvent such that the metal ion concentration in the solvent is
adjusted to be between 0.01 and 3 mol/liter. If the metal ion
concentration is below 0.01 mol/liter, the distance between the
adjacent metals is so large that the metal oxide oligomer cannot be
smoothly formed in a step mentioned below. On the other hand, if
the metal ion concentration exceeds 3 moL/liter, the distance
between the adjacent metals is so small that the three-dimensional
growth of the metal oxide oligomer cannot be
suppressed in the step mentioned below, thereby hardly providing
the planar metal oxide oligomer.
Then, a water-alcohol mixed solution (aqueous alcohol) is
desirably added to the solution including the organic solvent and
the metal salt dissolved or suspended therein, thereby subjecting
the metal salt to hydrolysis and dehydration condensation to
prepare the metal oxide oligomer formed by a plurality of units
"Me-O (metal-oxygen)". The addition is preferably conducted at a
temperature between 0 and 100 °C followed by heating at a
temperature between 0 and 200 °C for effecting the hydrolysis and
the dehydration condensation. The reactions proceed
insufficiently at a temperature below 0 °C, and the control of the
formation of the oligomer-solvent complex is hardly achieved at a
temperature exceeding 200 °C because the reactions proceed too
rapidly. The reactions may be conducted under pressure.
In this manner, the oligomer-solvent complex is prepared.
However, the oligomer-solvent complex may be prepared by an
alternative process.
The alcohol used in the water-alcohol mixed solution is not
especially restricted, and includes ethyl alcohol, propyl alcohol,
butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl
alcohol, nonyl alcohol, decyl alcohol and glycerin.
The exemplified alcohols have a role of controlling the
activity of the water for decreasing the hydrolysis reaction rate,
thereby gradually growing the metal oxide oligomer. Accordingly,
the ratio of the water in the water-alcohol mixed solution
significantly affects the hydrolysis reaction rate. When the
reaction rate is too rapid, the metal oxide oligomer produced by
the hydrolysis has a disturbed arrangement. Conversely, when the
reaction rate is too slow, a longer period of time is required to
complete the reaction thereby reducing the efficiency though the
arrangement is not disturbed.
Accordingly, the ratio of the water in the water-alcohol
mixed solution is preferably between 0.1 and 20 % in weight.
When the ratio of the water is below 0.1 % in weight, the
hydrolysis proceeds so slowly that the economical operations
cannot be attained. On the other hand, when the ratio exceeds
20 % in weight, the hydrolysis proceeds so abruptly that the
hydrous metal oxide particles may be agglomerated.
The water-alcohol mixed solution is desirably added to the
metal salt such that 0.1 to 3 mol/liter of the water is present per 1
mol/liter of the metal salt. When the volume of the water is below
0.1 mol/liter, the hydrolysis proceeds so slowly that the economical
operations cannot be attained. On the other hand, when the
volume of the water exceeds 3 mol/liter, the hydrolysis proceeds so
rapidly that the three-dimensional growth of the metal oxide
oligomer cannot be suppressed in the step mentioned below,
thereby hardly providing the planar metal oxide oligomer.
In view of the performance of the alcohol, optimum liquid
mixed with the water in the mixed solution is an alcohol. However,
another solvent may be used with or in place of the alcohol.
When the unsaturated organic solvent is used, the double
bond of the solvent coordinates to the metal ion of the metal salt
and metal oxide oligomer during the hydrolysis and the
dehydration condensation. Especially, when the solvent is the
aromatic compound or the heterocyclic aromatic compound, the
dehydration condensation of the metal hydroxide proceeds along
the aromatic ring to form the complex having a planar structure
formed by the metal oxide oligomer and the aromatic compound
solvent.
In the metal oxide oligomer prepared in this manner, it is
assumed that the unsaturated organic solvent makes a bond to
the metal oxide oligomer by coordinating the π-electron to the
metal oxide oligomer, thereby forming the three-layered sandwich
structure essentially consisting of (the unsaturated organic
solvent) - (the metal oxide oligomer) - (the unsaturated organic
solvent).
In the present invention, the saturated organic solvent
having no π -electron may be used with or in place of the
unsaturated organic solvent. Since the saturated organic solvent
is also highly hydrophobic and the water is hardly dissolved in the
saturated organic solvent, the attack of the water to the metal salt
is suppressed to decrease the hydrolysis reaction rate, thereby
forming a metal oxide oligomer having a homogeneous network.
The solution containing the oligomer-solvent complex was
stable even after the solution was stored for one year in a cold
dark place.
Then, after the solution containing the oligomer-solvent
complex is concentrated depending on necessity, the solution is
applied on a substrate, on which the metal oxide film is to be
formed, by means of brush painting, spray coating, spin coating,
and dip coating. Since the existence of the excess water is not
preferable in the subsequent steps, the solvent containing the
complex in which the water may remain can be replaced with a
non-aqueous solvent.
The substrate employable in the present invention is not
especially restricted, and may be appropriately selected
depending on a purpose and a usage. The material of the substrate
includes a single crystal such as silicon wafer, polycrystal glass, a
metal, a polymer and ceramic, and the shape may be a thick plate,
a small fragment, a bead, a ring, a cylinder, a fiber or a chain.
The concentration of the oligomer-solvent complex applied to
the substrate is desirably between 0.01 and 5 mol/liter. When the
concentration is out of the range, the solution is concentrated or
diluted before the complex is applied on the substrate.
The applying procedure can be conducted preferably in a
solvent atmosphere including hydrophobic solvent vapor. The
solvent may be the same as or different from that used for forming
the complex. When different, any organic compound other than
the solvent in the oligomer-solvent complex can be used, including
an unsaturated organic compound and a saturated organic
compound, for example, aliphatic hydrocarbon, heterocyclic
hydrocarbon, alicyclic hydrocarbon containing a hetero atom and
an alcohol having a relatively longer carbon chain the number of
which is three or more.
The thickness of the metal oxide film prepared in this
manner on the substrate in a single film forming process is
generally between 0.01 and 5 µm. The film thickness is mainly
controlled by the concentration and volume of the metal oxide
oligomer in the solution containing the oligomer-solvent complex
prepared in the previous step.
The above procedure may be repeated for obtaining a
thicker metal oxide film.
Then, the oligomer-solvent complex thus prepared is
thermally treated to form the metal oxide film on the substrate. In
the film forming step different from the prior art, the heating is
performed after at least part of the solvent containing the
oligomer-solvent complex on the substrate is removed. The partial
removal of the solvent prevents the diffusion and mixing between
the substrate and the metal oxide oligomer, thereby forming the
homogeneous and substantially crack-free metal oxide film on the
substrate. A preferable removal rate is between 20 and 80 %.
The solvent removal can be conducted by any process in
which the diffusion and the mixing between the substrate and the
metal oxide oligomer do not occur, for example, by heating the
substrate to a temperature at which the diffusion does not take
place in an inert gas atmosphere, in the air, or by placing the
substrate under a reduced pressure without heating, or by
indirectly irradiating, on the surface of the substrate, infrared ray
from an infrared lamp or ultraviolet ray from an ultraviolet lamp
after the substrate is placed in a vessel saturated with organic
solvent vapor.
The infrared ray provides the thermal effect on the solvent
at least part of which is removed from the substrate by means of
vaporization. On the other hand, when the ultraviolet ray having
no or little thermal effect is applied to the solvent on the substrate,
the ultraviolet ray decomposes at least part of the solvent.
The solvent fragments having a smaller molecular size
formed by the solvent decomposition easily leave the substrate
without heating.
The solvent used for the irradiation may be the same as or
different from that used for the complex formation or the
application to the substrate.
Then, the substrate having the metal oxide oligomer and
the organic solvent at least part of which is removed is thermally
treated to form the metal oxide film on the surface of the
substrate.
The thermal treatment is preferably conducted at a
temperature between 100 and 1300 °C to form the metal oxide film.
The heating out of the temperature range may invite unfavorable
results. The heating below 100 °C sometimes makes it difficult to
crystallize the metal oxide film, and the heating exceeding 1300 °C
sometimes precipitates unwanted crystals in addition to the
desired ones.
The metal oxide film prepared in this manner is
homogenous and substantially crack-free because the metal oxide
oligomer is thermally treated after at least part of the solvent is
removed.
The substrate having the homogeneous and crack-free
metal oxide film thereon is useful as an optical material, a
photoelectric converter material, an electronic material and a
surface protection film, and more concretely, these include a
capacitor, a piezoelectric element, an SAW filter, a ferroelectric
material and a ferroelectric memory.
The present invention includes, other than the metal oxide
film formation on the substrate, formation of an oligomer-solvent
complex solution containing a metal oxide oligomer and an
organic solvent, and formation of metal oxide powders.
The oligomer-solvent complex solution employable for the
application to the substrate is also used in other usage.
The metal oxide powders having the desired homogeneous
structure may be prepared by removing at least part of the organic
solvent from the metal oxide oligomer-solvent complex solution
followed by the thermal treatment.
Although Examples of the preparation of the metal oxide
film by using metal oxide oligomer in accordance with the present
invention will be described, the present invention shall not be
restricted thereto.
After titanium-n-butoxide acting as a metal salt was
dissolved in benzene acting as an unsaturated organic solvent at a
concentration of 1 mol/liter and stirred in an ice bath, aqueous
butanol (water-butanol mixed solution) having 4.0 molar
concentration was added dropwise to the titanium-n-butoxide
solution such that 1.6 moles of the butanol per 1 mole of the
titanium ion existed in the solution. After the solution was stirred
for additional 1 hour in the ice bath, the bath temperature was
elevated to 80 to 90 °C. The solution was concentrated by using an
evaporator and then diluted such that the titanium ion
concentration was adjusted to be 1 mol/liter.
After a titanium substrate polished with alumina having an
average particle diameter of about 1 µm was washed with a
neutral detergent, the detergent was rinsed out with ion exchange
water. After the ultrasonic cleansing was conducted to the
substrate in a mixed solution containing pure water, acetone and
butanol for five minutes, the substrate was dipped in the titanium
oxide oligomer-solvent complex solution in an atmosphere
saturated with benzene vapor.
After the substrate was pulled up from the solution at a rate
of 0.15 mm/sec. by using a stepping motor and place in a glass
vessel, infrared ray from an infrared lamp was indirectly
irradiated through the wall of the glass vessel to the substrate in
the benzene atmosphere separated from the lamp by about 20 cm
for 15 minutes for drying followed by the further drying at 120 °C
for 30 minutes.
After the substrate was thermally treated at 580 °C for 1
hour, the substrate was allowed to stand for cooling until the
temperature thereof reached to room temperature, thereby
forming a metal oxide film on the substrate. The thickness of the
metal oxide film thus obtained was measured by using EPMA
(electron probe microanalysis) to be about 0.6 µm.
A microphotograph taken with a scanning electron
microscope (SEM) showing the surface of the metal oxide film thus
obtained is shown in Fig.1. The microphotograph shows the
formation of a substantially crack-free metal oxide film.
A metal oxide film was prepared using the same procedures
as those of Example 1 except that titanium-n-butoxide was
dissolved in benzene at a concentration of 0.5 mol/liter and stirred
at 5 °C, and a water-butanol mixed solution containing 1.5
mol/liter of water was added dropwise to the titanium-n-butoxide
solution such that 0.2 mole of the water per 1 mole of the
titanium-n-butoxide existed in the solution followed by the
stirring for 1 hour at 5 °C, thereby adjusting the final
concentration of the titanium ion to be 0.5 mol/liter. The thickness
of the metal oxide film thus obtained was about 0.1 µm. The
observation of the surface state of the substrate revealed that the
substrate was homogeneous and crack-free.
A metal oxide film was prepared using the same procedures
as those of Example 1 except that, in place of the indirect
irradiation of the infrared ray, the substrate was heated at a
temperature range between 40 and 60 °C under a reduced
pressure (133 h Pa). The thickness of the metal oxide film thus
obtained was about 0.6 µm. The observation of the surface state
of the substrate revealed that the substrate was homogeneous and
crack-free.
A metal oxide film was prepared using the same procedures
as those of Example 1 except that acetophenone was employed as
the unsaturated organic solvent in place of the benzene. The
thickness of the metal oxide film thus obtained was about 0.4 µm.
The observation of the surface state of the substrate revealed that
the substrate was homogeneous and crack-free.
A metal oxide film was prepared using the same procedures
as those of Example 1 except that pyridine was employed in place
of the benzene. The thickness of the metal oxide film was about
0.5 µm. The observation of the surface state of the substrate
revealed that the substrate was homogeneous and crack-free.
A metal oxide film was prepared using the same procedures
as those of Example 1 except that α-picoline was employed in
place of the benzene. The thickness of the metal oxide film was
about 0.5 µm. The observation of the surface state of the substrate
revealed that the substrate was homogeneous and crack-free.
A metal oxide film was prepared using the same procedures
as those of Example 1 except that cyclohexene was employed in
place of the benzene. The thickness of the metal oxide film was
about 0.4 µm. The observation of the surface state of the
substrate revealed that the substrate was homogeneous and
crack-free.
A metal oxide film was prepared using the same procedures
as those of Example 1 except that 1-buten-3-ol was employed in
place of the benzene. The thickness of the metal oxide film was
about 0.6 µm. The observation of the surface state of the substrate
revealed that the substrate was homogeneous and crack-free.
A metal oxide film was prepared using the same procedures
as those of Example 1 except that n-hexane was employed in place
of the benzene. The thickness of the metal oxide film was about
0.6 µm. The observation of the surface state of the substrate
revealed that the substrate was homogeneous and crack-free.
A metal oxide film was prepared using the same procedures
as those of Example 1 except that tetrahydrofuran was employed
in place of the benzene. The thickness of the metal oxide film was
about 0.5 µm. The observation of the surface state of the substrate
revealed that the substrate was homogeneous and crack-free.
A metal oxide film was prepared using the same procedures
as those of Example 1 except that n-butanol was employed in
place of the benzene. The thickness of the metal oxide film was
about 0.4 µm. The observation of the surface state of the substrate
revealed that the substrate was homogeneous and crack-free.
A metal oxide film was prepared using the same procedures
as those of Example 1 except that zirconium-n-butoxide was
employed as a metal salt in place of the titanium-n-butoxide. The
thickness of the metal oxide film thus obtained was about 0.3 µm.
The observation of the surface state of the substrate revealed that
the substrate was homogeneous and crack-free.
Barium acetate was added to the solution containing the
titanium ion of 1 mol/liter prepared in Example 1 such that the
equimolar barium ion to the titanium ion was present. After the
bath temperature was raised to 80 to 90 °C and the reaction was
allowed to proceed for 8 hours, the solution was concentrated by
using an evaporator and diluted such that the barium titanate
concentration was adjusted to be 1 mol/liter.
The diluted solution was coated on a quartz glass plate
which had been degreased and cleaned by using a spin-coater.
After the quartz glass plate subjected to drying was sintered for 1
hour at 700 °C by using an electric furnace in the atmosphere, the
glass plate was spontaneously cooled to room temperature to form
a metal oxide film.
The metal oxide film thus obtained was analyzed by using
an X-ray diffraction apparatus, and an X-ray diffraction pattern
obtained by the analysis is shown in Fig.2. The formation of
barium titanate is confirmed by the X-ray diffraction pattern.
The solution prepared in Example 1 containing 0.96 mole of
the titanium ion, and the solution prepared in Example 12
containing 1.04 moles of the zirconium ion were mixed. After the
bath temperature was raised to 80 to 90 °C and the reaction was
allowed to proceed for 4 hours, equimolar lead acetate to the total
of the titanium ion and the zirconium ion was added to the mixed
solution. After the reaction was allowed to proceed for 8 hours at
the bath temperature of 80 to 90 °C, the solution was
concentrated by using an evaporator and diluted such that the
composite metal oxide concentration was adjusted to be 1
mol/liter.
The diluted solution was coated on a quartz glass plate
which had been degreased and cleaned by using a spin-coater.
After the quartz glass plate subjected to drying was sintered for 1
hour at 700 °C by using an electric furnace in the atmosphere, the
glass plate was spontaneously cooled to room temperature to form
a metal oxide film.
The metal oxide film thus obtained was analyzed by using
an X-ray diffraction apparatus, and an X-ray diffraction pattern
obtained by the analysis is shown in Fig.3. The formation of PZT is
confirmed by the X-ray diffraction pattern.
After 1 mole of titanium tetrachloride acting as a metal salt,
6 moles of n-butanol and 5 moles of aniline acting as a basic
aromatic solvent were mixed, the resulting solution was heated at
about 100 °C for 10 hours for effecting a titanium alkoxide forming
reaction, thereby preparing a solution containing a titanium
alkoxide-coordinated complex.
After the complex containing solution was added to benzene
acting as an aromatic solvent such that 0.5 mole of the titanium
existed in 1 liter of the benzene and heated at about 80 °C for 6
hours, aqueous butanol having a water concentration of 1.84
mol/liter was added dropwise to the complex containing solution
such that 0.4 mole of the water was added per 1 mole of the
titanium ion. After the solution was heated at about 80 °C for 12
hours for affecting hydrolysis of the titanium alkoxide to convert
the titanium alkoxide into titanium hydroxide and subsequent
dehydration condensation of the titanium hydroxide to produce
polymeric titanium oxide which was then coordinated to the
solvent, thereby forming a complex containing the polymeric
titanium oxide.
The resulting solution containing the complex was
concentrated by using an evaporator until the titanium ion
concentration became to 1.5 mol/liter to obtain a titanium oxide-containing
solution.
After a glass substrate which had been degreased and
cleansed was dipped in the titanium oxide-containing solution, the
substrate was pulled up from the solution at a rate of 0.15 mm/sec.
by using a stepping motor and spontaneously dried in air at about
25 °C for 1 hour. After a thermal treatment at 500 °C for 1 hour in
an electric furnace including air, the substrate was spontaneously
cooled down to room temperature.
The thickness of the metal oxide film measured with a film
thickness measuring apparatus (tradename: F20, available from
Filmetrics Corporation) was about 1.2 µm. The surface SEM
microphotograph revealed that the film had no cracks and was
homogeneous, flat and tight, and the adhesion with the glass
substrate was excellent.
A metal oxide film was prepared by using a conventional
sol-gel method based on the method described in Yogyo Kyokaishi
95, 150 (1987).
After 0.1 mole of titanium isopropoxide and 0.4 mole of
dehydrated ethanol were mixed at room temperature, stirred and
cooled down to 0°C, a mixed solution containing 0.4 mole of
dehydrated ethanol, 0.1 mole of water and 0.008 mole of
hydrochloric acid was added dropwise to the titanium
isopropoxide solution under stirring to prepare oxide sol by means
of hydrolysis at room temperature. The oxide sol was stored in a
cold dark place for examining stability thereof. The oxide particles
agglomerated in the sol after a lapse of two months, and was not
used.
After a titanium substrate polished with alumina having an
average particle diameter of about 1 µm was dipped into the oxide
sol to which the concentration adjustment had been conducted,
the substrate was pulled up from the solution at a rate of 0.15
mm/sec. by using a stepping motor and air-dried. After a thermal
treatment at 580 °C for 1 hour for forming a metal oxide film, the
substrate was spontaneously cooled down to room temperature.
The thickness of the metal oxide film obtained was about 0.07 µm.
A microphotograph taken with a scanning electron
microscope (SEM) showing the surface of the metal oxide film thus
obtained is shown in Fig.2. The microphotograph shows the
formation of distinctive fine cracks scattered in the metal oxide
film formed by the sol in which the metal oxide particles were
dispersed.
After a titanium substrate pretreated by the same
procedures as those of Example 12 was dipped for 5 minutes in the
solution of which a concentration was adjusted similarly to
Example 12, the substrate was pulled up from the solution at a
rate of 0.15 mm/sec. by using a stepping motor and was
immediately heat-treated at 580 °C for 1 hour. After the heat
treatment, the substrate was spontaneously cooled down to room
temperature. The observation of the surface state of the substrate
thus obtained revealed that the titanium metal in the substrate
and the zirconium oxide in the metal oxide film were mutually
diffused to each other to form a mixed layer at an interface
thereof.
Since the above embodiments are described only for
examples, the present invention is not limited to the above
embodiments and various modifications or alternations can be
easily made therefrom by those skilled in the art without
departing from the scope of the present invention.
Claims (30)
- A method for preparing a metal oxide film comprising the steps of:characterized by removing at least part of the organic solvent from the solution on the substrate between the solution deposition step and the thermal treating step.forming a solution containing a complex including a metal oxide oligomer and an organic solvent;depositing the solution on a substrate; andthermally treating the substrate for converting the metal oxide oligomer into the corresponding metal oxide film.
- The method as defined in claim 1, wherein the metal of the metal oxide oligomer is one or more metals selected from the group consisting of Mg, Al, Si, Ca, Sc, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Cr, Sr, Y, Zr, Nb, Mo, In, Sn, Sb, Cs, Ba, Ta, W, Ru, Os, Ir, Pb Bi, La, Ce and Gd.
- The method as defined in claim 1, wherein at least part of the organic solvent is removed by irradiating infrared ray and/or ultraviolet ray on the substrate.
- The method as defined in claim 1, wherein at least part of the organic solvent is removed by heating the substrate at a temperature below that at which diffusion of component between the substrate and the metal oxide oligomer starts.
- The method as defined in claim 1, wherein at least part of the organic solvent is removed under a reduced pressure.
- The method as defined in claim 1, wherein at least part of the organic solvent is removed by irradiating infrared ray or ultraviolet ray.
- The method as defined in claim 1, wherein the organic compound is an unsaturated organic compound.
- The method as defined in claim 7, wherein the unsaturated organic compound is one or more compounds selected from the group consisting of an aromatic compound having one or more 6-membered rings consisting of carbons, a heterocyclic aromatic compound, an aliphatic or an alicyclic hydrocarbon compound having a carbon-carbon double bond or a carbon-carbon triple bond, a heterocyclic compound having a carbon-carbon double bond or a carbon-hetero atom double bond or an alcohol compound having not less than three carbon atoms and a carbon-carbon double bond.
- The method as defined in claim 7, wherein the unsaturated organic compound is one or more compounds selected from the group consisting of benzene, ethylbenzene, ethoxybenzene, nitrobenzene, toluene, xylene, aniline, dimethylanilin, acetophenone, methylbenzoate, ethylbenzoate, pyridine, picoline, furan, thiophene oxazole, thiazole, 2-methylpyridine, hexene, 1-butene, 2-methyl-1,3-pentadiene, cyclopentene, pyran and 1-buten-3-ol.
- The method as defined in claim 1, wherein the organic compound is a saturated organic compound.
- The method as defined in claim 10, wherein the saturated organic compound is one or more compounds selected from the group consisting of an aliphatic hydrocarbon compound, an alicyclic hydrocarbon compound, a heterocyclic compound, and an alcohol compound having not less than three carbon atoms and a carbon-carbon double bond.
- The method as defined in claim 10, wherein the saturated organic compound is one or more compounds selected from the group consisting of hexane, cyclohexane, petroleum ether, n-butanol, diethyl ether, dibuthyl ether, dioxane and tetrahydrofuran.
- The method as defined in claim 1, wherein the thermal treatment is conducted in a temperature range between 100 and 1300°C.
- A metal oxide film prepared in accordance with the method of claim 1.
- The metal oxide film as defined in claim 14, wherein the metal oxide in the metal oxide film is one or more composite metal oxides selected from the group consisting of Mg, Al, Si, Ca, Sc, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Cr, Sr, Y, Zr, Nb, Mo, In, Sn, Sb, Cs, Ba, Ta, W, Ru, Os, Ir, Pb Bi, La, Ce and Gd.
- A method for preparing a metal oxide film comprising the steps of:characterized by removing at least part of the organic solvent from the solution on the substrate between the solution deposition step and the thermal treating step.dissolving a metal salt into an organic solvent;adding a water-alcohol solution to the organic solvent to form a solution containing a complex including a metal oxide oligomer and the organic solvent;depositing the solution on a substrate; andthermally treating the substrate for converting the metal oxide oligomer into the corresponding metal oxide film;
- The method as defined in claim 16, wherein the metal of the metal salt is one or more metals selected from the group consisting of Mg, Al, Si, Ca, Sc, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Cr, Sr, Y, Zr, Nb, Mo, In, Sn, Sb, Cs, Ba, Ta, W, Ru, Os, Ir, Pb Bi, La, Ce and Gd.
- The method as defined in claim 16, wherein the metal salt is one or more salt selected from the group consisting of an alkoxide, an organic salt and an inorganic salt.
- The method as defined in claim 16, wherein the water-alcohol solution contains 0.23 to 9.2 mol/liter of the water and the alcohol has 1 to 10 carbon atoms.
- The method as defined in claim 16, wherein the concentration of the metal salt in the organic solvent is between 0.01 and 3 mol/liter, and the water-alcohol solution is added to the organic solvent such that 0.1 to 3 moles of the water is added per 1 mole of the metal salt.
- The method as defined in claim 16, wherein the complex formation is conducted by adding the water-alcohol solution to the organic solvent dissolving the metal salt at a temperature between 0 and 100°C followed by heating at a temperature between 0 and 200°C for effecting hydrolysis and dehydration condensation to form the complex.
- A metal oxide oligomer-containing solution prepared by adding a water-alcohol mixed solution to an organic solvent dissolving a metal salt to form a solution dissolving a complex containing a metal oxide oligomer and the organic solvent.
- The metal oxide oligomer-containing solution as defined in claim 22, wherein the metal of the metal salt is one or more metals selected from the group consisting of Mg, Al, Si, Ca, Sc, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Cr, Sr, Y, Zr, Nb, Mo, In, Sn, Sb, Cs, Ba, Ta, W, Ru, Os, Ir, Pb Bi, La, Ce and Gd.
- The metal oxide oligomer-containing solution as defined in claim 22, wherein the metal salt is one or more salt selected from the group consisting of an alkoxide, an organic salt and an inorganic salt.
- The metal oxide oligomer-containing solution as defined in claim 22, wherein the water-alcohol solution contains 0.5 to 20 % in weight of the water and the alcohol has 1 to 10 carbon atoms.
- The metal oxide oligomer-containing solution as defined in claim 22, wherein the concentration of the metal salt in the organic solvent is between 0.01 and 3 mol/liter, and the water-alcohol solution is added to the organic solvent such that 0.1 to 3 moles of the water is added per 1 mole of the metal salt.
- The metal oxide oligomer-containing solution as defined in claim 22, wherein the complex formation is conducted by adding the water-alcohol solution to the organic solvent dissolving the metal salt at a temperature between 0 and 100°C followed by heating at a temperature between 0 and 200°C for effecting hydrolysis and dehydration to form the complex.
- Metal oxide powders prepared by removing at least part of an organic solvent from a metal oxide oligomer―solvent complex solution and by converting the metal oxide oligomer into metal oxide by thermal treatment.
- A metal oxide-containing solution prepared by heating a solution containing a metal salt, an alcohol and a basic aromatic solvent to form a solution containing a complex having a coordinated metal alkoxide and by heating the complex-containing solution for converting the metal alkoxide into the metal oxide.
- The metal oxide-containing solution as defined in claim 29, wherein the metal salt is a metal chloride.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000162454 | 2000-05-31 | ||
| JP2000162454A JP3985887B2 (en) | 2000-05-31 | 2000-05-31 | Metal oxide precursor solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1164207A2 true EP1164207A2 (en) | 2001-12-19 |
| EP1164207A3 EP1164207A3 (en) | 2004-03-24 |
Family
ID=18666347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP00308173A Withdrawn EP1164207A3 (en) | 2000-05-31 | 2000-09-19 | Method for preparing metal oxide film |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1164207A3 (en) |
| JP (1) | JP3985887B2 (en) |
| KR (1) | KR20010096478A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009020633A3 (en) * | 2007-08-07 | 2009-08-06 | Harvard College | Metal oxide coating on surfaces |
| EP2181066A4 (en) * | 2007-08-22 | 2010-08-04 | Kwangju Inst Sci & Tech | WET-PROCESSED METAL OXIDE SOLUTION, METHOD FOR USING THE SAME, AND PHOTOVOLTAIC CELL USING SUCH A SOLUTION |
| US8802027B2 (en) | 2008-03-28 | 2014-08-12 | President And Fellows Of Harvard College | Surfaces, including microfluidic channels, with controlled wetting properties |
| CN109053462A (en) * | 2018-08-14 | 2018-12-21 | 浙江今晖新材料股份有限公司 | A kind of preparation method of para-fluoroaniline |
| CN119633436A (en) * | 2024-12-04 | 2025-03-18 | 北京理工大学 | A low temperature crystallization preparation method of sol-gel metal oxide film |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007070673A (en) * | 2005-09-06 | 2007-03-22 | Univ Of Tokyo | Antimony-containing tin oxide film formed on aluminum substrate |
| CN115624966B (en) * | 2022-10-13 | 2024-07-05 | 中国科学院深圳先进技术研究院 | Metal oxide composite material and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3743472B2 (en) * | 1998-02-06 | 2006-02-08 | 日本カーリット株式会社 | Electrode for electrolysis and method for producing the same |
| JP3007961B2 (en) * | 1998-03-13 | 2000-02-14 | 工業技術院長 | Method for producing metal oxide thin film |
-
2000
- 2000-05-31 JP JP2000162454A patent/JP3985887B2/en not_active Expired - Fee Related
- 2000-09-19 KR KR1020000055028A patent/KR20010096478A/en not_active Withdrawn
- 2000-09-19 EP EP00308173A patent/EP1164207A3/en not_active Withdrawn
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009020633A3 (en) * | 2007-08-07 | 2009-08-06 | Harvard College | Metal oxide coating on surfaces |
| US8883291B2 (en) | 2007-08-07 | 2014-11-11 | President And Fellows Of Harvard College | Metal oxide coating on surfaces |
| EP2181066A4 (en) * | 2007-08-22 | 2010-08-04 | Kwangju Inst Sci & Tech | WET-PROCESSED METAL OXIDE SOLUTION, METHOD FOR USING THE SAME, AND PHOTOVOLTAIC CELL USING SUCH A SOLUTION |
| US20110168249A1 (en) * | 2007-08-22 | 2011-07-14 | Gwangju Institute Of Science And Technology | Wet-processible metal oxide solution, method of using the same, and organic photovoltaic cell of using the same |
| CN101835709B (en) * | 2007-08-22 | 2012-12-19 | 光州科学技术院 | Wet-processable multifunctional metal oxide solution, method for producing same, and organic solar cell using same |
| US8529795B2 (en) * | 2007-08-22 | 2013-09-10 | Gwangju Institute Of Science And Technology | Wet-processible metal oxide solution, method of using the same, and organic photovoltaic cell of using the same |
| US8802027B2 (en) | 2008-03-28 | 2014-08-12 | President And Fellows Of Harvard College | Surfaces, including microfluidic channels, with controlled wetting properties |
| CN109053462A (en) * | 2018-08-14 | 2018-12-21 | 浙江今晖新材料股份有限公司 | A kind of preparation method of para-fluoroaniline |
| CN119633436A (en) * | 2024-12-04 | 2025-03-18 | 北京理工大学 | A low temperature crystallization preparation method of sol-gel metal oxide film |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20010096478A (en) | 2001-11-07 |
| EP1164207A3 (en) | 2004-03-24 |
| JP3985887B2 (en) | 2007-10-03 |
| JP2001342019A (en) | 2001-12-11 |
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