CN101199033A - 掺锰的钛酸钡薄膜组合物、电容器和它们的制造方法 - Google Patents
掺锰的钛酸钡薄膜组合物、电容器和它们的制造方法 Download PDFInfo
- Publication number
- CN101199033A CN101199033A CNA200680021826XA CN200680021826A CN101199033A CN 101199033 A CN101199033 A CN 101199033A CN A200680021826X A CNA200680021826X A CN A200680021826XA CN 200680021826 A CN200680021826 A CN 200680021826A CN 101199033 A CN101199033 A CN 101199033A
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- Prior art keywords
- dielectric
- barium titanate
- capacitor
- manganese
- composition
- 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.)
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- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 48
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000011572 manganese Substances 0.000 title claims abstract description 44
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 239000003990 capacitor Substances 0.000 title claims description 42
- 238000000034 method Methods 0.000 title claims description 31
- 239000010409 thin film Substances 0.000 title abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 229910052788 barium Inorganic materials 0.000 claims abstract description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 238000000137 annealing Methods 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims 1
- 238000010304 firing Methods 0.000 abstract 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000011889 copper foil Substances 0.000 description 24
- 239000010408 film Substances 0.000 description 22
- 239000010410 layer Substances 0.000 description 22
- 239000002243 precursor Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 16
- 238000009740 moulding (composite fabrication) Methods 0.000 description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 238000000224 chemical solution deposition Methods 0.000 description 10
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 7
- 229940043237 diethanolamine Drugs 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- 239000002019 doping agent Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical class [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000006259 organic additive Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- -1 3-monoethanolamine Chemical class 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- WCMHZFHLWGFVCQ-UHFFFAOYSA-N [Ba].[Mn] Chemical compound [Ba].[Mn] WCMHZFHLWGFVCQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- MTZOKGSUOABQEO-UHFFFAOYSA-L barium(2+);phthalate Chemical compound [Ba+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O MTZOKGSUOABQEO-UHFFFAOYSA-L 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZBSCCQXBYNSKPV-UHFFFAOYSA-N oxolead;oxomagnesium;2,4,5-trioxa-1$l^{5},3$l^{5}-diniobabicyclo[1.1.1]pentane 1,3-dioxide Chemical compound [Mg]=O.[Pb]=O.[Pb]=O.[Pb]=O.O1[Nb]2(=O)O[Nb]1(=O)O2 ZBSCCQXBYNSKPV-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000010363 phase shift Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- 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
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- 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
- H01G4/10—Metal-oxide dielectrics
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- 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
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- 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
- 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
- H01G4/33—Thin- or thick-film capacitors
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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
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- 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
- H01L21/02337—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 gas or vapour
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- 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
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/16—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor
- H05K1/162—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor incorporating printed capacitors
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
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- H05K2201/0175—Inorganic, non-metallic layer, e.g. resist or dielectric for printed capacitor
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0179—Thin film deposited insulating layer, e.g. inorganic layer for printed capacitor
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/43—Electric condenser making
- Y10T29/435—Solid dielectric type
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49117—Conductor or circuit manufacturing
- Y10T29/49124—On flat or curved insulated base, e.g., printed circuit, etc.
- Y10T29/4913—Assembling to base an electrical component, e.g., capacitor, etc.
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
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- Engineering & Computer Science (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
本发明涉及电容器用的电介质薄膜组合物,该组合物包含:(1)一种或多种含钡/钛添加剂,选自:(a)钛酸钡,(b)能够在焙烧时形成钛酸钡的任何组合物和(c)它们的混合物;(2)有机介质;所述(1)添加剂能溶解在(2)有机介质中;其中所述薄膜组合物掺有0.002-0.05原子%的含锰添加剂。
Description
技术领域
本发明涉及薄膜电容器,具体地说,涉及在铜箔上形成薄膜电容器,这种电容器能够嵌入印刷线路板(PWB),为安装在该印刷线路板封装件上的集成电路模块进行去耦和电压控制提供电容。
背景技术
由于包含集成电路(IC)的半导体器件需要在高频率、高数据处理速度和低电压下工作,电源和接地线(回线)中的噪音以及提供足够的电流以适应快速的电路转换操作已成为日益重要的问题,要求在电源分配系统中的低阻抗。为了向IC提供低噪音、稳定的电源,通过使用以并联的方式互连的外加式表面装配工艺(SMT)的电容器来减少传统电路中的阻抗。工作频率越高(IC转换速率越高)意味着对IC的电压响应时间越快。低工作电压要求容许电压变化(脉动)和噪音变得较小。例如,当微处理器进行开关和开始工作时,需要电源来支持对电路的开关。如果电压供应的响应时间太慢,微处理器会遭遇电压下降即功率下降,导致超过容许的脉动电压和噪音的限度,并且IC会触发假闸门(falsegeat)。此外,随IC的功率上升,响应时间慢会导致功率过冲。必须使用足够靠近IC的电容器,在适当的响应时间内提供和吸收功率,而将功率下降或过冲控制在允许的范围之内。用电容器在适当的响应时间内提供或吸收功率的方式可以将功率下降和过冲维持在容许的范围之内。
用于去耦和衰减功率下降或过冲的电容器一般放置在尽可能靠近IC的位置,以提高它们的性能。传统的设计使表面安装在印刷线路板(PWB)上的电容器聚集在IC周围。在这种情况下,大量的电容器需要复杂的电路接线,这些电路接线产生电感。随着频率增加和工作电压持续下降,功率增加,因此必须以更低的电感水平提供更高的电容。一种解决问题的方法是在其上安装有IC的PWB封装件中加入高电容密度的薄膜陶瓷电容器。直接装配在IC下面的单层陶瓷电容器将电感尽可能减小到最低,高电容密度则提供了满足IC要求的电容。PWB中的这种电容器能够以明显加快的响应时间和较低的电感水平提供电容。
在印刷线路板中嵌入陶瓷电容器膜的方法是众所周知的。首先在金属箔上形成电容器,其方法是在箔上沉积电容器的电介质材料并在高温下对材料进行退火。在电介质上形成顶部电极,以在金属箔构件上形成焙烧过的电容器。然后将金属箔与有机层压构件接合在一起产生一块内层片,其中,电容器嵌埋在该内层片中。然后将这些内层片重叠起来并用互连电路连接,叠层的内层片形成了多层印刷线路板。
采用具有高电容率即介电常数(K)的电介质和薄电介质可以获得高电容密度的电容器。众所周知铁电体陶瓷为高介电常数的。具有高介电常数的铁电体电介质材料包括通式为ABO3的钙钛矿,式中A位和B位可以为一种或多种不同金属所占据。例如,已知钛酸钡晶体(BT)、锆钛酸铅(PZT)、锆钛酸铅镧(PLZT)、铌酸铅镁(PMN)和钛酸钡锶(BST)具有高介电常数,这些材料常用于表面装配部件的器件。钛酸钡基组合物因具有高介电常数且不含铅而特别有用。
厚度小于1μm的薄膜电容器电介质是人们所熟知的。可以通过溅射、激光烧蚀、化学气相沉积和化学溶液沉积等方法在基材上沉积薄膜。最初的沉积物依据沉积条件或是非晶形的或是结晶体。非晶形组合物具有低K(约20)并且必须在高温下进行退火以诱导结晶和产生所需的高K相。在钛酸钡基电介质中的高K相只有在颗粒尺寸超过0.1μm的情况下才能获得,因此可以采用高达900℃的退火温度。
化学溶液沉积(CSD)工艺常被用来在金属箔上形成薄膜电容器。CDS工艺因为简便和低成本而是合意的。在诸如铜或镍之类的基底金属箔上形成的钛酸钡CSD薄膜进行的高温退火需要低氧分压,以避免金属氧化。但低氧分压往往因电介质材料还原而导致钛酸钡基组合物在施加偏压下出现高漏电流(电流密度)的情况。在最糟糕的情况下,电容器可能短路并且无法测出电介质性能。这可以用随后在较低温度下进行的再氧化工序来解释,在该工序中电介质和金属箔暴露在较高的氧分压下,但这导致基底金属箔氧化。
美国国家专利申请第10/621,796(美国专利公开号2005-001185)揭示了一种钛酸钡CSD组合物。该组合物特别适用于在铜箔上形成高电容密度的陶瓷膜。该前体组合物包括以下化学物质:
乙酸钡 2.6g
异丙氧化钛 2.9ml
乙酰丙酮 2.0ml
乙酸 10.0ml
甲醇 15ml
但是,在氧分压为约10-11大气压中于900℃进行退火时,该薄膜是导电的,而且有必要进行再氧化过程,以产生从中可以获取电学性能数据的部件。该工序使金属箔氧化,未必产生最佳电容器性能,特别是偏压下的漏电流密度。况且在独立的步骤中对电介质进行再氧化成本效率不高。因此,如果能在低氧分压退火加工后,立即掺入钛酸钡组合物以产生良好的电学性能,尤其是偏压下的低漏电流密度的话,则是有益的。
发明概述
本发明涉及电介质薄膜组合物,该组合物包括:(1)一种或多种含钡/钛的添加剂,选自:(a)钛酸钡,(b)能够在焙烧时形成钛酸钡的任何组合物和(c)它们的混合物;(2)有机介质;所述(1)添加剂能溶解于(2)有机介质中;其中所述薄膜组合物掺有0.002至0.05原子%的含锰添加剂。
本方面还涉及一种包含上述薄膜组合物的电容器,其中所述薄膜组合物已在还原环境中进行焙烧而不需要再氧化。此外,本发明还涉及一种内层片和包括这种电容器的印刷线路板。
在一个实施方式中,本发明涉及一种制造电容器的方法,该方法包括:提供金属箔;在金属箔上形成电介质,其中形成电介质的步骤包括:在金属箔上形成电介质层,其中电介质层是由上述组合物形成的;对电介质层进行退火;在电介质上形成导电层,其中金属箔、电介质和导电层形成电容器。
附图的简要说明
参考以下附图进行详细描述,附图中相同的数字指相同的元件,其中:
图1所示是不需要再氧化工序来形成电介质的前体溶液的制备方法的框图。
图2所示是在铜箔上制造电容器的方法的框图。
图3所示是纯钛酸钡再氧化后的电容密度和损耗角正切作为电压函数的变量图。
图4所示是未掺杂的纯钛酸钡再氧化后的漏电流密度作为电压变量的曲线图。
图5所示是不进行再氧化但掺有0.01原子%锰的钛酸钡的电容密度和损耗角正切作为电压变量的曲线图。
图6所示是说明不进行再氧化但掺有0.02原子%锰的钛酸钡的漏电流密度作为电压变量的曲线图。
图7所示是不进行再氧化但掺有0.02原子%数锰的钛酸钡的电容密度和损耗角正切作为电压变量的曲线图。
图8所示是不进行再氧化掺有0.02原子%锰的钛酸钡的漏电流密度作为电压变量的曲线图。
图9所示是不进行再氧化但掺有0.04原子%锰的钛酸钡的电容密度和损耗角正切作为电压变量的曲线图。
图10所示不进行再氧化但掺有0.04原子%锰的钛酸钡的漏电流密度作为电压变量的曲线图。
图11所示是不进行再氧化但掺有0.01原子%锰的钛酸锶钡的电容密度和损耗角正切作为电压变量的曲线图。
图12所示是不进行再氧化但掺有0.01原子%锰的钛酸锶钡的漏电流密度作为电压变量的曲线图。
发明详述
公开了高电容密度的薄膜电介质及其制造方法。
根据本发明,掺杂锰的钛酸钡电介质具有与经过再氧化的不掺杂的钛酸钡基本相同的电容密度和损耗角正切。但是在不采用再氧化工序进行处理时,掺杂锰的钛酸钡电介质偏压下的漏电流密度比经过再氧化的纯钛酸钡低得多。
BaTiO3是形成本发明的高电容密度电介质的优选的核心材料。但是,在MO2氧化物化学计量式中的金属阳离子也可以用来部分地或基本上取代钛(如Zr、Hf、Sn和它们的混合物)。虽然术语“部分地”和“基本上”并不意味着具体的限定,但仍有各种优选的实施方式。在一个实施方式中,“部分地”定义为最多及包括10摩尔%的钛。在一个实施方式中,“基本上”定义为最多及包括50摩尔%的钛。通过使BaTiO3的三相转变“收缩”(相移)而在温度空间相互接近,这些增加了在居里温度下电介质的电容对温度的依赖性。具有MO氧化物化学计量式的金属阳离子(如Pb、Ca、Sr和它们的混合物)也可以用来部分地或基本上取代钡。虽然术语“部分地”和“基本上”并不意味着具体的限定,所以可以存在各种优选的实施方式。在一个实施方式中,“部分地”在本文定义为最多及包括10摩尔%的钡。在一个实施方式中,“基本上”定义为最多及包括50摩尔%的钡。根据所用的材料,这些阳离子将电介质的居里点转移到更高或更低的温度。
根据第一实施方式,公开了一种高电容密度的薄膜CSD电介质组合物,该实施方式取消了在小于约10-8大气压的低氧分压和约800~1050℃温度条件下对电介质层进行退火后进行再氧化工序的需求。在一个实施方式中,公开一种高电容密度的薄膜CSD电介质组合物,该实施方式取消了在小于约10-11大气压的低氧分压和约900℃的条件下对电介质层进行退火后进行再氧化工序的需求。
按照上述方法制成的电容器可以嵌入内层片中,而内层片又可以被结合到印刷线路板中。这些电容器具有高电容密度、低损耗角正切和在偏压下的低漏电流密度。此外本发明的方法可以不需要采用再氧化处理,而使用符合环境需要的材料进行实施。
本领域的技术人员在结合下列附图阅读了对实施方式的详细说明后,会了解本发明的上述优点,以及各种其他实施方式的其他优点和益处。
按照常规实践,以下讨论的附图的各特征不必按比例绘制。图中各种特征和要素可以放大或缩小,以便更清楚地说明本发明的实施方式。
在此讨论的电容器实施方式中,电介质的厚度在约0.4~1.0μm范围,电容密度为约2.5μF/cm2。在这一电容密度范围的电容器的击穿电压超过约20V。
在本说明书所讨论的容电器实施方式中,使用掺杂锰的结晶钛酸钡制成高电容率的电介质膜或电介质层。掺杂锰的结晶钛酸钡膜可以用来制造高电容密度的部件。采用物理上结实的厚度,优选0.4~1.0μm之间的电介质可以获得高电容密度。可以使用掺入少到250ppm的锰来形成高介电常数的电介质,这种电介质可以没有采用再氧化工序进行处理的电介质相比。
可以采用化学溶液沉积技术(CSD)来形成电介质。CSD技术因为简便和低成本而是合意的。用来制备掺杂锰的BaTiO3的化学前体溶液优选含有乙酸钡、异丙氧化钛、乙酰丙酮、乙酸、甲醇、二乙醇胺和四水合乙酸锰。
为制备稳定的前体溶液,上述化学品应不含水。水使前体组合物不稳定,产生氧化钛沉淀。因此重要的是在相对湿度较低的环境,如小于约40%的相对湿度环境中制备和沉积前体溶液。一旦前体溶液完全沉积在金属箔上并干燥,它对湿度的敏感性就较低。
图1示出按照本发明方法制备用来形成电介质的前体溶液的方法的框图。在步骤S110中,异丙氧化钛与乙酰丙酮预混合并加热。该预混合过程可以在例如PYREX容器中进行,加热可以在表面温度为约90℃的热板上进行。在步骤S120中,将乙酸加入到异丙氧化钛/乙酰丙酮的混合物中。在步骤S130中,将乙酸钡和四水合乙酸锰加入该容器中,进行搅拌直至它们溶解。在步骤S140中,对溶液于90℃加热约1小时的同时进行搅拌。在步骤S150中,将甲醇加入到该溶液中,达到约0.3摩尔的浓度。至此,前体溶液可用于沉积。
图2示出按照本发明形成电容器的方法框图。采用参考图1所示的方法制成的前体溶液来形成最终电容器的电介质。也可以使用上述前体溶液中甲醇和乙酰丙酮等组分的变体。例如,甲醇可以被乙酸替代。甲醇也可以被乙醇、异丙醇、丙酮、丁醇和其他醇替代。乙酰丙酮可以被诸如3-乙醇胺、二乙醇胺或单乙醇胺等乙醇胺替代。异丙氧化钛也可以被丁氧化钛取代。
图2所示的沉积工艺为旋涂。其他涂布方法也是可行的,如浸涂或喷涂。在步骤S210中,对金属箔进行清洁。清洁工作并非总是必需的,而是可取的。金属箔可以用铜制成。铜箔因为其低成本和易于处理而是合意的。铜箔将用作在其上制造电容器的基材。铜箔也可以用作成品电容器中的电容器“底”电极。在一个实施方式中,基材为18μm厚的无电裸铜箔。其他未经处理的金属箔,如1盎司(oz)铜箔也是适用的。适用的清洁条件包括在盐酸的氯化铜稀溶液中对金属箔进行30秒的蚀刻。蚀刻溶液可以是其浓缩液形式稀释约10,000倍后的溶液。清洁步骤去除了金属箔上的过量氧化层、指印和其他积累的外来物质。如果来自供应商或其他来源的铜箔为基本清洁的状况,并且经过仔细处理并很快使用的话,则不必采用推荐的清洁工序。
铜箔最好不用有机添加剂进行处理。有时使用有机添加剂是为了改善金属基材与环氧树脂的粘合性。但是有机添加剂会使电介质膜在退火时发生降解。
在步骤S220中,将参见图1所述制成的前体溶液沉积在铜箔基材的转鼓面(即“光滑面”)上。前体溶液可以采用例如塑料注射器进行施涂。
在步骤S230中,旋转基材以便进行旋涂。适用的旋转时间和速率分别为30秒和每分钟3000转。在步骤S240中,对基材进行热处理。热处理例如可以在250℃温度下进行5~10分钟。热处理用于通过蒸发前体溶液中的溶剂对前体溶液进行干燥。热处理后,干燥的电介质前体层厚约150nm。可以采用连续旋涂步骤,涂覆铜箔基材至所需的厚度。例如可以采用三道旋涂步骤,使最终干燥电介质前体的厚度达到约0.5μm。
在S250中,对涂覆后的基材进行退火。退火步骤首先去除了残留的有机物,然后对干燥的电介质前体进行烧结、致密化和结晶。退火可以在高温、低氧分压的环境中进行。合适的总压环境为约1个大气压。合适的氧分压为约10-10~10-11大气压。
在S250中,低氧分压可以通过使高纯度的氮气鼓泡通过控制温度的水浴来获得。也可采用其他混合气体。在一个实施方式中,炉温度为至少约900℃,氧分压为约10-11个大气压。水浴的温度可以为约25℃。可以将涂覆的金属箔基材插入温度在250℃以下的炉中进行退火。然后以约30℃/min的速率使炉温、上升到最高为900℃。炉温在900℃下保持30分钟。
在步骤S260中,使箔基材冷却。冷却可以利用牛顿分布(Newtonian profile)来加以调节,例如,只是简单地关闭加热炉产生的分布曲线。或者,炉温可以以特定的速率下降。当炉温达到约450℃时,可以从炉中安全取出箔基材而不会有对铜箔产生不需要的氧化作用的风险。或者,在将铜箔基材从加热炉中取出之前,允许炉温回落到室温。
在低氧分压退火方法中,铜箔没有被氧化成Cu2O或CuO。存在这种抗氧化性的原因在于低氧分压和高处理温度。电介质也没有被还原并保持良好的电学性能,尤其是在偏压下的低漏电流密度。存在这种抗还原性的原因在于锰受体的掺混。通过掺杂锰,导电电子被锰捕获,因而耐绝缘性的下降和介电损失的增加受到抑制。
上述为使沉积后的电介质致密化和结晶而在900℃高温进行的退火步骤产生了所需要的物理性质和电学性质。一种需要的物理性质是致密的微结构。另一个需要的物理性质是产生的颗粒粒度为0.1-0.2μm。由这种粒度的颗粒产生的一种所需要的电学性质是超过1μF/cm2的电容密度。另一个的需要的物理性质是低损耗角正切,可能低于2.5%。总之,当平均粒度小于0.1μm时,基于多晶BaTiO3的材料的介电常数明显下降,因此至少为这一量级的粒度是合要求的。
在步骤S270中,在所得电介质上形成顶电极。顶电极的可以采用例如以下方法形成:溅射、燃烧气相沉积、无电电镀、印刷或其他适用的沉积方法。在一个实施方式中,使用溅射的铂电极。其他适用于顶电极的材料包括镍、铜和钯。需要时,顶电极可以镀敷铜以增加厚度。
以下实施例说明了按照本发明方法制备的电介质的良好性能以及加入这种电介质的电容器。
实施例1
使用按美国国家专利申请10/621,796(美国专利公开第2005-001185)揭示的前体,在铜箔上制备未掺杂的纯钛酸钡薄膜。采用图2所示的方法在铜箔上涂覆电介质前体组合物。电介质前体的组成如下:
乙酸钡 2.6g
异丙氧化钛 2.9ml
乙酰丙酮 2.0ml
乙酸 10.0ml
甲醇 15ml
进行3次旋涂。涂覆后的铜箔在约10-11大气压的氧分压下,于900℃进行30分钟退火。退火后,将所述箔置于氧分压为约10-5托的气氛,温度为550℃的真空室中,对纯钛酸钡进行30分钟再氧化。选择上述条件是为了避免铜箔发生明显的氧化,同时仍能提供用于电介质再氧化的氧。再氧化后,在电介质上溅射铂顶电极,可测定电容、耗散因数和偏压下的漏电流密度。
如图3所示,在零偏压时,电容密度为约2.5μF/cm2,损耗角正切为约5%,但如图4所示,在10V偏压下,纯钛酸钡层显示达1安培/厘米2量级的高漏电流密度。
实施例2
在铜箔上制备掺杂有0.01原子%锰的钛酸钡薄膜。采用图2所示的方法,在所述铜箔上涂覆电介质前体组合物。所述电介质前体的组成如下:
乙酸钡 5.08g
异丙氧化钛 5.68ml
乙酰丙酮 3.86ml
乙酸 21ml
甲醇 24.26ml
乙酸锰 0.002g
二乙醇胺 0.54g
实施例1和实施例2之间无机物含量方面仅有的差异是锰。二乙醇胺是降低应力(stress reducing)的有机物,对最终的无机组合物没有影响。进行3次旋涂。涂覆后的铜箔在约10-11大气压的氧分压下,于900℃进行30分钟退火。在电介质上溅射铂顶电极,测定电容器的电学性质。
如图5所示,没有进行再氧化的掺杂锰的钛酸钡层显示出与经过再氧化的纯钛酸钡相似的电容密度和损耗角正切。但是如图6所示,没有经过再氧化的掺杂锰的钛酸钡在10V偏压下显示出约10微安/厘米2的低漏电流密度,即与经过再氧化的未掺杂锰的钛酸钡相比,漏电流量低了约10,000倍。
实施例3
按照与实施例1所述方式相类似的方式,使用下面所述的前体溶液,在铜箔上制备掺杂有0.02原子%锰的钛酸钡薄膜,除了重复进行6次涂覆/预烘焙处理之外。将Mn(OAc)2(0.2g)溶解在热乙酸(29.8g)中制成锰掺杂剂溶液:
乙酸钡 2.0g
异丙氧化钛 2.22g
乙酰丙酮 1.56g
乙酸 17.0g
二乙醇胺 0.21g
锰掺杂剂溶液 0.17g
没有进行再氧化的掺杂锰的钛酸钡层的电容密度和损耗角正切示于图7。在零伏偏压下电容密度为约1.4μF/cm2,损耗角正切小于5%,耗散因数在偏压下没有降低。与实施例1和实施例2相比,电容密度较低的原因是涂覆次数为两倍,产生明显增厚的电介质层的结果。如图8所示,没有进行氧化工序的掺杂0.02原子%锰的钛酸钡在10V偏压下显示出约10微安/厘米2的低漏电流密度,即与经过再氧化的未掺杂锰的钛酸钡相比,漏电流量低了约1,000,000倍。
实施例4
按照与实施例3所述方式相类似的方式,使用以下所述的前体溶液,在铜箔上制备杂掺0.04原子%锰的钛酸钡薄膜。涂覆/预烘焙处理重复6次。将Mn(OAc)2(0.2g)溶解在热乙酸(29.8g)中制成锰掺杂剂溶液:
乙酸钡 2.0g
异丙氧化钛 2.22g
乙酰丙酮 1.56g
乙酸 17.0g
二乙醇胺 0.21g
锰掺杂剂溶液 0.42g
没有进行再氧化的掺杂锰的钛酸钡层的电容密度和损耗角正切示于图9。0伏时电容密度为约1.3μF/cm2,损耗角正切小于等于8%,在偏压下耗散因数没有降低。与实施例3相似,电容密度较低是较厚的电介质所致。如图10所示,没有进行氧化工序的掺杂0.04原子%锰的钛酸钡在10V偏压下显示出约10微安/厘米2的低漏电流密度,即与经过再氧化的未掺杂锰的钛酸钡相比,漏电流量低了约1,000,000倍。
实施例5
按照与实施例3所述方式相类似的方式,使用下述前体溶液,在铜箔上制备掺杂0.01原子%锰的钛酸钡锶(Ba0.65Sr0.35TiO3)薄膜,除了在加入乙酸钡的同时还加入乙酸锶外。涂覆/预烘焙处理重复6次。将四水合乙酸锰(0.29g)溶解在乙酸(27.71g)和蒸馏水(2.0g)的混合液中制成锰掺杂剂溶液:
乙酸钡 7.45g
乙酸锶 3.17g
异丙氧化钛 12.67g
乙酰丙酮 8.93g
乙酸 94.3g
二乙醇胺 1.17g
锰掺杂剂溶液 0.63g
没有进行再氧化的掺杂锰的钛酸钡锶层的电容密度和损耗角正切示于图11。0伏时电容密度为约1.2μF/cm2,损耗角正切小于等于3%,偏压下耗散因数没有降低。与实施例3相似,电容密度较低是较厚的电介质所致。如图12所示,没有进行氧化工序的掺杂0.01原子%锰的钛酸钡锶在10V偏压下显示出约10微安/厘米2的低漏电流密度,即与经过再氧化的未杂掺的锰钛酸钡相比,漏电流量低了约1,000倍。
Claims (11)
1.一种电介质薄膜组合物,该组合物包含:
(1)一种或多种含钡/钛的添加剂,选自:(a)钛酸钡、(b)能够在焙烧时形成钛酸钡的任何组合物和(c)它们的混合物;
(2)有机介质;
所述添加剂溶解于有机介质中;
所述薄膜组合物掺杂有0.002-0.05原子%的含锰添加剂。
2.权利要求1所述的组合物,其特征在于,在所述含钡/钛的添加剂中的钡已部分或基本上全部被一种或多种氧化物化学计量式为MO的金属阳离子所替代,其中M选自:(a)锶、(b)铅、(c)钙、和(d)它们的混合物。
3.权利要求1所述的组合物,其特征在于,在所述含钡/钛的添加剂中的钛已部分或基本上被一种或多种氧化物化学计量式为MO2的金属阳离子所取代,其中M选自:(a)锆、(b)铪、(c)锡、和(d)它们的混合物。
4.一种包括权利要求1所述的薄膜组合物的电容器,所述薄膜组合物已在还原气氛中进行焙烧而不需要进行再氧化。
5.一种包括权利要求4所述的电容器的内层片。
6.一种包括权利要求4所述的电容器的印刷线路板。
7.一种制造电容器的方法,该方法包括:
提供金属箔;
在金属箔上形成电介质;所述形成电介质的步骤包括:
在金属箔上形成电介质层,所述电介质层是由权利要求1所述的组合物形成的;
对电解质层进行退火;和
在电介质上形成导电层,
所述金属箔、电介质和导电层形成所述电容器。
8.权利要求7所述的方法,其特征在于,退火步骤包括在约800~1050℃范围的温度下进行退火。
9.权利要求7所述的方法,其特征在于,退火步骤包括在低于约10-8个大气压的氧分压的环境中进行退火。
10.权利要求7所述的方法,其特征在于,退火步骤产生了包含结晶钛酸钡或结晶钛酸钡锶的电介质。
11.权利要求7所述的方法,其特征在于,电容器的电容密度为至少0.5μF/cm2。
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KR100631894B1 (ko) * | 2004-12-07 | 2006-10-09 | 삼성전기주식회사 | 유전체 세라믹용 졸 조성물, 이를 이용한 유전체 세라믹과적층세라믹 커패시터 |
US7795663B2 (en) * | 2005-06-21 | 2010-09-14 | E. I. Du Pont De Nemours And Company | Acceptor doped barium titanate based thin film capacitors on metal foils and methods of making thereof |
-
2005
- 2005-06-21 US US11/157,621 patent/US20060287188A1/en not_active Abandoned
-
2006
- 2006-06-21 JP JP2008518322A patent/JP2008547227A/ja not_active Withdrawn
- 2006-06-21 CN CNA200680021826XA patent/CN101199033A/zh active Pending
- 2006-06-21 WO PCT/US2006/024008 patent/WO2007002107A1/en active Application Filing
- 2006-06-21 KR KR1020087001432A patent/KR100949254B1/ko active IP Right Grant
- 2006-06-21 EP EP20060785199 patent/EP1897103A1/en not_active Withdrawn
- 2006-06-21 TW TW095122297A patent/TW200715324A/zh unknown
-
2007
- 2007-10-24 US US11/923,594 patent/US7572518B2/en active Active
- 2007-10-25 US US11/923,974 patent/US7601181B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
TW200715324A (en) | 2007-04-16 |
US7601181B2 (en) | 2009-10-13 |
JP2008547227A (ja) | 2008-12-25 |
WO2007002107A1 (en) | 2007-01-04 |
US7572518B2 (en) | 2009-08-11 |
EP1897103A1 (en) | 2008-03-12 |
KR100949254B1 (ko) | 2010-03-25 |
US20080044672A1 (en) | 2008-02-21 |
KR20080018272A (ko) | 2008-02-27 |
US20060287188A1 (en) | 2006-12-21 |
US20080047117A1 (en) | 2008-02-28 |
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