TWI423927B - Composite oxide film and its manufacturing method, composite and manufacturing method thereof, dielectric material, piezoelectric material, capacitor, piezoelectric element and electronic machine - Google Patents
Composite oxide film and its manufacturing method, composite and manufacturing method thereof, dielectric material, piezoelectric material, capacitor, piezoelectric element and electronic machine Download PDFInfo
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- TWI423927B TWI423927B TW095149508A TW95149508A TWI423927B TW I423927 B TWI423927 B TW I423927B TW 095149508 A TW095149508 A TW 095149508A TW 95149508 A TW95149508 A TW 95149508A TW I423927 B TWI423927 B TW I423927B
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- Prior art keywords
- composite
- oxide film
- titanium
- composite oxide
- producing
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- 239000002131 composite material Substances 0.000 title claims description 100
- 238000004519 manufacturing process Methods 0.000 title claims description 39
- 239000000463 material Substances 0.000 title claims description 25
- 239000003990 capacitor Substances 0.000 title claims description 23
- 239000003989 dielectric material Substances 0.000 title claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 40
- 239000000758 substrate Substances 0.000 claims description 31
- 229910052684 Cerium Inorganic materials 0.000 claims description 24
- -1 cerium ions Chemical class 0.000 claims description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims description 22
- 150000004706 metal oxides Chemical class 0.000 claims description 22
- 239000010936 titanium Substances 0.000 claims description 21
- 229910052719 titanium Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 18
- 229910052746 lanthanum Inorganic materials 0.000 claims description 12
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 11
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 10
- 238000002048 anodisation reaction Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 8
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000000859 sublimation Methods 0.000 claims description 4
- 230000008022 sublimation Effects 0.000 claims description 4
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 description 87
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000004408 titanium dioxide Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 6
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 6
- 229910002113 barium titanate Inorganic materials 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 150000007514 bases Chemical class 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000000873 masking effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 229920006015 heat resistant resin Polymers 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- NTWSIWWJPQHFTO-AATRIKPKSA-N (2E)-3-methylhex-2-enoic acid Chemical compound CCC\C(C)=C\C(O)=O NTWSIWWJPQHFTO-AATRIKPKSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000408939 Atalopedes campestris Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 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
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000000866 electrolytic etching Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02197—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides the material having a perovskite structure, e.g. BaTiO3
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/47—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on strontium titanates
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
- H01L21/02258—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by anodic treatment, e.g. anodic oxidation
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02343—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a liquid
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31691—Inorganic layers composed of oxides or glassy oxides or oxide based glass with perovskite structure
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
- H01L28/40—Capacitors
- H01L28/55—Capacitors with a dielectric comprising a perovskite structure material
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/093—Forming inorganic materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/616—Liquid infiltration of green bodies or pre-forms
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Description
本發明係關於一種複合氧化物膜及其製造方法、複合體及其製造方法、介電材料、壓電材料、電容器、壓電元件及電子機器。更詳而言之,係關於一種介電常數高之複合氧化物膜及其製造方法、含有該複合氧化物膜之複合體及其製造方法、含有上述複合氧化物膜或複合體之介電材料或壓電材料、含有於高耐電壓化有利之複合氧化物膜之電容器及具備該等之電子機器。
近年來,作為小型電容器而言,層合陶瓷電容器、鉭電解電容器、鋁電解電容器已實用化。其中,層合陶瓷電容器使用介電常數大的鈦酸鋇或耐電壓大的鈦酸鍶等複合氧化物作為介電體。
由於靜電容量比與介電常數的比例與介電常數的厚度為反比例,希望可均勻地製膜薄且具有高介電常數的介電體層。
介電體層的製膜方法而言,日本專利特開昭60-116119號公報(專利文獻1)及日本專利特開昭61-30678號公報(專利文獻2)中,揭示於含有鋇離子之強鹼性水溶液中,以化成處理金屬鈦基材,而形成鈦酸鋇薄膜的技術。日本專利特開平5-124817號公報(專利文獻3;相關申請案US 5328718)中,揭示以烷氧金屬鹽(alkoxide)法於基材上形成鈦酸鋇薄膜的技術。
再者,日本特開2003-206135號公報(專利文獻4;相關申請案EP 1445348)中,揭示將金屬鈦基體於鹼金屬的水溶液中處理,於基體表面形成鹼金屬之鈦酸鹽後,以含有鍶、鈣等金屬離子之水溶液處理,使鹼金屬置換為鍶、鈣等金屬而形成複合鈦氧化被膜的技術。再者,日本專利特開平11-172489號公報(專利文獻5)中,揭示以電化學的手法於基板上形成鈦氧化物被膜,該被膜於鋇水溶液中以陽極氧化而製造鈦酸鋇被膜的方法。
[專利文獻1]特開昭60-116119號公報[專利文獻2]特開昭61-30678號公報[專利文獻3]特開平5-124817號公報[專利文獻4]特開2003-206135號公報[專利文獻5]特開平11-172489號公報
然而,根據本發明者們的研究,專利文獻1至5所揭示之方法,可知介電體層厚度的調控困難,所製得電容器之耐電壓的調控困難。因此,本發明的課題係提供不使用複雜大體積的設備,介電常數高,膜厚度任意調控,具有高耐電壓之複合氧化物膜及其製造方法,含有該複合氧化物膜之複合體及其製造方法、含有上述複合氧化物膜或複合體之介電材料或壓電材料、含有於高耐電壓化有利之複合氧化物膜之電容器及具備該等之電子機器
有鑑於上述課題致力研究的結果,本發明者們致力於研究。其結果發現以下之手段而完成本發明。
亦即,本發明如下述者。
(1)一種複合氧化物膜之製造方法,該複合氧化物膜含有鈦元素及鍶元素,該製造方法包括形成含有鈦元素之金屬氧化物膜之第一步驟,以及使含有鍶離子的溶液於該金屬氧化物膜上反應之第二步驟。
(2)如(1)之複合氧化物膜之製造方法,其中,該含有鍶離子的溶液為pH11以上的鹼性溶液。
(3)如上述(1)或(2)之複合氧化物膜之製造方法,其中,該第二步驟中含有鍶離子的溶液為40℃以上。
(4)如上述(1)至(3)中任一項之複合氧化物膜之製造方法,其中,該含有鍶離子的溶液含有於大氣壓下或減壓下,以蒸發、昇華及/或熱分解之至少一種手段而成為氣體之鹼性化合物。
(5)如上述(4)之複合氧化物膜之製造方法,其中,該鹼性化合物為鹼性有機化合物。
(6)如上述(5)之複合氧化物膜之製造方法,其中,該鹼性有機化合物為氫氧化四甲基銨。
(7)一種複合氧化物膜,其係以上述(1)至(6)中任一項之製造方法所製得者。
(8)一種複合體之製造方法,該複合體於基體表面具有含鈦元素以及鍶元素之複合氧化物層,該製造方法包含於基體表面形成含有鈦元素之金屬氧化物膜之第一步驟,以及使含有鍶離子的溶液於該金屬氧化物膜上反應之第二步驟。
(9)如上述(8)之複合體之製造方法,其中,該基體係由金屬鈦或含鈦合金所成者。
(10)如上述(8)或(9)之複合體之製造方法,其中,該第一步驟包含陽極氧化基體表面的步驟。
(11)如上述(8)至(10)中任一項之複合體之製造方法,其中,該基體為厚度5至300 μm的箔。
(12)如上述(8)至(11)中任一項之複合體之製造方法,其中,該基體為平均粒徑0.1至20 μm的粒子所燒結者。
(13)一種複合體,其係含有由金屬鈦或含鈦合金所成之層,以及於該層表面所形成之藉由上述(1)至(6)中任一項之製造方法所製得之複合氧化物層而成者。
(14)一種複合體,其係藉由上述(8)至(12)中任一項之製造方法所製得者。
(15)如上述(13)或(14)之複合體,其中,該複合氧化物層含有鈣鈦鑛。
(16)一種介電材料,其係含有上述(7)之複合氧化物膜。
(17)一種介電材料,其係含有上述(13)至(15)中任一項之複合體。
(18)一種電容器,其係含有上述(16)或(17)之介電材料。
(19)一種電子機器,其係具備上述(18)之電容器。
(20)一種壓電材料,其係含有上述(7)之複合氧化物膜。
(21)一種壓電材料,其係含有上述(13)至(15)中任一項之複合體。
(22)一種壓電元件,其係含有上述(20)或(21)之壓電材料。
(23)一種電子機器,其係具備上述(22)之壓電元件。
根據本發明之複合氧化物膜之製造方法,以極簡單的方法,可形成含有鈦元素及鍶元素之複合氧化物膜。為此,不必要複雜的大型設備,可以低成本的製造複合氧化物膜。
根據本發明之製造方法所製得之含有鈦元素及鍶元素之複合氧化物膜的厚度,由於清楚使用材料與製造條件之間的相關關係,可容易地進行膜厚的調控。
使用金屬鈦或含鈦合金作為基體時,該基體於陽極氧化時可容易地製得膜厚度經調控的鈦氧化物膜,將該鈦氧化物膜於含鍶離子的溶液中反應,可容易地形成膜厚度經調控之耐電壓高的介電體膜。
本文中,使用pH為11以上的鹼性溶液作為含鍶離子的溶液,可形成結晶性高的介電體膜,獲得高介電常數。作為該鹼性溶液之鹼成份,使用於大氣壓下或減壓下,以蒸發、昇華及/或熱分解中至少一種手段而成為氣體之有機鹼,可抑制複合氧化物膜中鹼成份殘存所造成之膜的特性降低,可製得具有經安定之特性之複合氧化物膜。又,溶液溫度為40℃以上,可更確實進行反應。
此方式所製得之複合氧化物膜,具有高耐電壓。使用厚度5至300μm或平均粒徑0.1至20μm之金屬鈦或含鈦之合金微粒子燒結體作為基體,可增加複合氧化物相對於基體之比例,適合做為電容器等電子零件使用,使電子零件的小型化,進一步使含有該等電子零件之電子機器的小型化、輕量化成為可能。
以下,以本發明之實施形態例示說明本發明。
本發明之含鈦元素及鍶元素之複合氧化物膜的製造方法,係包含形成含有鈦元素之金屬氧化物膜之第一步驟,以及使含有鍶離子的溶液於該金屬氧化物膜上反應之第二步驟。又,於本發明之基體表面具有含鈦元素及鍶元素之複合氧化物膜之複合體的製造方法,係包含於基體表面形成含有鈦元素之金屬氧化物膜之第一步驟,以及使含有鍶離子的溶液於該金屬氧化物膜上反應之第二步驟。
第一步驟中係形成含鈦元素之金屬氧化物膜。形成該金屬氧化物膜的方法並無特別限制,本發明中,較佳方法為使用基體,於其表面形成含鈦元素之金屬氧化物層之金屬氧化物膜。
基體的材質雖無特別限制,但因應用途可使用導電體、半導體或絕緣體。作為電容器用途之較佳材質之例,可列舉為導電體之金屬鈦或含鈦合金。於導電體表面形成介電體之複合氧化物膜所得之複合體,可直接使用作為電容器之電極。
基體的形狀並無特別限制,板狀者、箔狀者、甚至是表面不為平滑者皆可適用。於電容器用途中,由小型、輕量化的觀點,以及由毎基體質量之表面積越大,複合氧化物膜相對於基體之比例增加有優勢的觀點而言,較佳為箔狀者,厚度為5至300 μm,再較佳厚度為5至100 μm,更較佳厚度為5至30 μm的箔。
作為基體使用之箔,進行以氟酸等化學蝕刻或電解蝕刻等蝕刻,於表面形成凹凸,表面積增加的箔較為適合。
同樣地,為了增加複合氧化物膜相對於基體的比例,以平均粒徑0.1至20 μm的粒子燒結者,較佳以平均粒徑1至10 μm的粒子燒結者作為基體較為適合。
含鈦元素之金屬氧化物,只要為含鈦元素者即可,並無特別限制,較佳為鈦氧化物。此鈦氧化物為以一般式TiOx.nH2
O(0.5≦x≦2,0≦n≦2)表示之化合物。
金屬氧化物層的厚度,可根據所欲之複合氧化物膜的厚度加以適宜調整,較佳為1至4000nm的範圍,更佳為5至2000nm的範圍。
含鈦元素之金屬氧化物層的形成方法並無特別限定,使用鈦金屬或鈦合金以外的金屬或合金時,例如雖可使用濺鍍法或電漿蒸鍍法等乾式製程,但由低成本製造的觀點而言,以溶膠-凝膠法、電解電鍍法等濕式製程之形成方法較佳。
使用鈦金屬或鈦合金作為基體時,可適用上述同樣方法,可以基體表面之自然氧化、熱氧化、陽極氧化等方法而形成。。本發明中,由經電壓可容易調控層厚度的觀點而言,較佳為陽極氧化。
陽極氧化中,係將鈦金屬或鈦合金所成之基體的既定區域,浸漬於電解液,以既定的電壓電流密度進行處理。此時,為使電解液的浸漬液面程度安定化,冀望於既定位置塗佈遮罩材而實施化成。遮罩材的材料並無限定。遮罩材,例如可使用一般的耐熱性樹脂,較佳為於溶劑中可溶或可膨潤之耐熱性樹脂或其前驅物、無機質微粉與纖維素系樹脂所成之組成物(日本專利特開平11-80596號公報)等。遮罩材所使用材料之更具體例,可列舉聚苯碸(PPS)、聚醚碸(PES)、氰酸酯樹脂、氟樹脂(四氟乙烯、四氟乙烯 全氟烷基乙烯醚共聚物)、聚醯胺及其等之衍生物等。該等可溶解或分散於有機溶劑,容易地調製適合塗佈操作之任意固形分濃度(從而之黏度)之溶液或分散液。
電解液為酸及/或其鹽之溶液,例如可列舉含有磷酸、硫酸、草酸、硼酸、己二酸及其鹽之至少一種之溶液。電解液中的酸及/或其鹽之濃度通常為0.1至30質量%,較佳為1至20質量%。電解液的溫度通常為0至90℃,較佳為20至80℃。
基體於電解液浸漬後,通常先進行定電流化成,到達既定電壓後,進行定電壓化成。定電流化成及定電壓化成,通常以電流密度0.1至1000mA/cm2
、電壓2至400V、時間1毫秒至400分鐘的條件,較佳以電流密度1至400mA/cm2
、電壓5至70V、時間1秒至300分鐘的條件進行。
接著之第二步驟中,係使含有鍶離子之溶液於第一步驟所形成之含鈦元素之金屬氧化物層上反應。
經此反應,含鈦元素之金屬氧化物層變化為含鈦元素及鍶元素之複合氧化物膜。含鈦元素及鍶元素之複合氧化物膜較佳為含鈣鈦礦化合物。
含鍶離子之溶液只要為含有鍶離子者即可,並無特別限制。含鍶離子之溶液,除了鍶離子外,例如亦可以比鍶離子為更少的濃度(mol/l)含有鈣、鋇等鹼土族金屬或鉛。
該溶液較佳為水溶性者,可使用氫氧化物、硝酸鹽、醋酸鹽、氯化物等金屬化合物之水溶液。再者,該等金屬化合物可1種類單獨使用,亦可2種以上以任意比率混合使用。具體而言可使用氯化鈣、硝酸鈣、醋酸鈣、氯化鍶、硝酸鍶、氫氧化鋇、氯化鋇、硝酸鋇、醋酸鋇、硝酸鉛、醋酸鉛等。再者,亦可將含有由Sn、Zr、La、Ce、Mg、Bi、Ni、Al、Si、Zn、B、Nb、W、Mn、Fe、Cu及Dy所成組群中選出至少一種元素之化合物,以反應後的複合氧化物膜中,該等元素含量未達5莫耳%的方式添加。
本發明中所使用之含鍶離子之溶液中的鍶離子量(莫耳),以相對於上述含鈦元素之金屬氧化物層的物質量(莫耳)為1至1000倍的方式加以調製為較佳。
該溶液較佳為鹼性溶液。具體而言,溶液的pH較佳為11以上,再較佳為13以上,特佳為14以上。提高pH可製造結晶性高的複合氧化物膜。此乃因期望結晶性越高,膜的耐電壓越高。
溶液係添加例如鹼性化合物,較佳為鹼性有機化合物,使pH為11以上的鹼性為較佳。所添加之鹼性化合物雖無特別限制,但以於後述之乾燥或煅燒時的溫度以下,且於大氣壓下或減壓下,以蒸發、昇華及/或熱分解中至少一種手段而成為氣體之鹼性化合物較佳,例如可列舉TMHA(氫氧化四甲基銨)、氫氧化四乙基銨、膽鹼等。由於添加氫氧化鋰、氫氧化鈉、氫氧化鉀等鹼金屬氫氧化物,所製得之複合氧化物膜中有鹼金屬的殘存,作為製品時的介電材料、壓電材料等機能性材料的特性有變差的可能性。由反應後去除的容易性、pH調整的容易性而言,較佳為添加氫氧化四甲基銨等鹼性有機化合物。
此方式所調製之溶液,於攪拌之同時於常壓中,通常加熱保持於40℃至溶液沸點,較佳為80℃至溶液沸點的範圍的溫度,與上述含鈦金屬的氧化物被膜接觸而反應。反應時間通常為10分鐘以上,較佳為1小時以上。
上述反應後,必要時可使用相應之電透析、離子交換、水洗、滲透膜等方法,由反應部位去除雜質離子。接著進行乾燥。乾燥通常於室溫至150℃進行1至24小時。乾燥的環境並無特別限制,可於大氣中或減壓中進行。
根據以上的方法,可得含鈦元素及鍶元素之複合氧化物膜,或具有基體與含鈦元素及鍶元素之複合氧化物膜之複合體。
本發明之複合氧化物膜或複合體,可使用作為介電材料、壓電材料。
本發明之電容器為含有上述介電材料者。具體而言,本發明之複合體使用於電容器之陽極。由於使用於陽極,通常,複合體的表面附著碳糊料(carbon paste)以降低電阻,再附著銀糊料以導通外部導線。此時,於電容器的陰極使用氧化錳、導電性高分子、鎳等金屬。
本發明之壓電元件為含有上述壓電材料者。因此,該等電容器及壓電元件可配備於電子機器中。
本發明之複合體(介電材料)為介電體層之複合氧化物膜厚度為薄且均一。再者,該介電體層為介電常數高。其結果,含有本發明之複合體(介電材料)之電容器,為以小型持有高靜電容量者。此方式之小型高容量的電容器,可適用於電子機器類,特別是行動電話為主的攜帶型機器的零件。
以下,根據實施例、比較例,具體說明本發明,但本發明不以該等實施例為限定。
將厚度20 μm之純度99.9%的鈦箔(Thank-Metal公司製造)切斷為3.3mm寬、切取各長度為13mm,將該薄片的一方的短邊部溶接固定於金屬製導向器。距上述鈦箔之末固定側之端為7mm處,以聚醯亞胺樹脂溶液(宇部興產公司製造)描繪0.8mm寬的線,於約180℃乾燥30分鐘後,加以遮罩。上述鈦箔之未固定側之端至遮罩部分為止的部份(成為單面約0.22cm2
),浸漬於5質量%之磷酸水溶液,以電流密度30mA/cm2
、陽極氧化電壓15V、溫度40℃、陽極氧化處理120分鐘,接著由磷酸水溶液取出,水洗、乾燥,於鈦箔表面形成二氧化鈦層。於此陽極氧化條件下所製得之二氧化鈦膜的平均膜厚為0.15 μm。所製得之二氧化鈦膜,每1cm2
的二氧化鈦的量係根據二氧化鈦的平均膜厚(0.15 μm)、二氧化鈦的密度(約4g/cm3
)、及二氧化鈦之化學式量(TiO2
=約80)求出為7.5×10-5
莫耳。
於20%氫氧化四甲基銨水溶液(Sachem昭和公司製造)中,溶解二氧化鈦層之物質量(莫耳)100倍莫耳之氫氧化鍶(高純度化學研究所公司製造)製得溶液。該溶液之pH為14。將上述形成有二氧化鈦層之箔於該溶液中,於100℃浸漬4小時而反應,形成複合氧化物膜。
複合氧化物膜以X設線繞射鑑定時,了解為立方晶體鈣鈦礦構造之鈦酸鍶。
根據FIB裝置以穿透式電子顯微鏡(TEM)觀察剖面加工之樣品,了解平均厚度為0.15 μm。於該複合氧化物膜上,以電子線蒸鍍而形成膜厚0.2 μm之鎳蒸鍍膜,製得負極。使用此負極測定耐電壓為9V之大的值。
將厚度20 μm之純度99.9%的鈦箔(Thank-Metal公司製造)切斷為3.3mm寬、切取各長度為13mm,將該薄片的一方的短邊部溶接固定於金屬製導向器。距上述鈦箔之未固定側之端為7mm處,以聚醯亞胺樹脂溶液(宇部興產公司製造)描繪0.8mm寬的線,於約180℃乾燥30分鐘後,加以遮罩。上述鈦箔之未固定側之端至遮罩部分為止的部份,浸漬於5質量%之磷酸水溶液,以電流密度30mA/cm2
、陽極氧化電壓15V、溫度40℃、陽極氧化處理120分鐘,接著由磷酸水溶液取出,水洗、乾燥,於鈦箔表面形成二氧化鈦層。
將0.1莫耳之硝酸鋇Ba(NO3
)2
與1莫耳之氫氧化鉀KOH溶解於1000毫升水中製得溶液。將上述形成有二氧化鈦層之箔於該溶液中,於100℃浸漬0.5小時而反應,形成複合氧化物膜。複合氧化物膜以X設線繞射鑑定時,了解為立方晶體鈣鈦礦構造之鈦酸鈣。
根據FIB裝置以穿透式電子顯微鏡(TEM)觀察剖面加工之樣品,了解平均厚度為0.04 μm。於該複合氧化物膜上,以電子線蒸鍍而形成膜厚0.2 μm之鎳蒸鍍膜,製得負極。使用此負極測定耐電壓為0.5V的值。咸信由於薄膜不均勻地附著,使耐電壓低。
本實施例雖使用複合氧化物膜作為介電體層説明電容器之一例,但該複合氧化物膜亦可使用作為壓電元件的壓電材料。
Claims (20)
- 一種複合氧化物膜之製造方法,該複合氧化物膜含有鈦元素及鍶元素,該製造方法包括藉由陽極氧化形成含有鈦元素之金屬氧化物膜之第一步驟,以及使含有鍶離子的溶液於該金屬氧化物膜上反應之第二步驟,其中該含有鍶離子的溶液含有於大氣壓下或減壓下,以蒸發、昇華及/或熱分解之至少一種手段而成為氣體之鹼性有機化合物。
- 如申請專利範圍第1項之複合氧化物膜之製造方法,其中,該含有鍶離子的溶液為pH11以上的鹼性溶液。
- 如申請專利範圍第1項之複合氧化物膜之製造方法,其中,該第二步驟中含有鍶離子的溶液為40℃以上。
- 如申請專利範圍第1項之複合氧化物膜之製造方法,其中,該鹼性有機化合物為氫氧化四甲基銨。
- 一種複合氧化物膜,其係以申請專利範圍第1至4項中任一項之製造方法所製得者。
- 一種複合體之製造方法,該複合體於基體表面具有含鈦元素以及鍶元素之複合氧化物層,該製造方法包含於基體表面藉由陽極氧化形成含有鈦元素之金屬氧化物膜之第一步驟,以及使含有鍶離子的溶液於該金屬氧化物膜上反應之第二步驟,其中該含有鍶離子的溶液含有於大氣壓下或減壓下,以蒸發、昇華及/或熱分解之至少一種手段而成為氣體之鹼性 有機化合物。
- 如申請專利範圍第6項之複合體之製造方法,其中,該基體係由金屬鈦或含鈦合金所成者。
- 如申請專利範圍第6項之複合體之製造方法,其中,該基體為厚度5至300μm的箔。
- 如申請專利範圍第6項之複合體之製造方法,其中,該基體為平均粒徑0.1至20μm的粒子所燒結者。
- 一種複合體,其係含有由金屬鈦或含鈦合金所成之層,以及於該層表面所形成之藉由申請專利範圍第1至4項中任一項之製造方法所製得之複合氧化物層而成者。
- 一種複合體,其係藉由申請專利範圍第6至8項中任一項之製造方法所製得者。
- 如申請專利範圍第10或11項之複合體,其中,該複合氧化物層含有鈣鈦鑛。
- 一種介電材料,其係含有申請專利範圍第5項之複合氧化物膜。
- 一種介電材料,其係含有申請專利範圍第10至12項中任一項之複合體。
- 一種電容器,其係含有申請專利範圍第13或14項之介電材料。
- 一種電子機器,其係具備申請專利範圍第15項之電容器。
- 一種壓電材料,其係含有申請專利範圍第5項之複合氧化物膜。
- 一種壓電材料,其係含有申請專利範圍第10至12項中任一項之複合體。
- 一種壓電元件,其係含有申請專利範圍第17或18項之壓電材料。
- 一種電子機器,其係具備申請專利範圍第19項之壓電元件。
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EP1975127B1 (en) * | 2005-12-28 | 2017-03-01 | Showa Denko K.K. | Complex oxide film and method for producing same, composite body and method for producing same, dielectric material, piezoelectric material, capacitor and electronic device |
JP5747480B2 (ja) * | 2010-11-08 | 2015-07-15 | 株式会社村田製作所 | 複合酸化物被覆金属粉末、その製造方法、導電性ペーストおよび積層セラミック電子部品 |
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