CN1020639C - 制备含锡/锌合金氧化物涂层的高透射率、低辐射率制品的方法 - Google Patents
制备含锡/锌合金氧化物涂层的高透射率、低辐射率制品的方法 Download PDFInfo
- Publication number
- CN1020639C CN1020639C CN85109342A CN85109342A CN1020639C CN 1020639 C CN1020639 C CN 1020639C CN 85109342 A CN85109342 A CN 85109342A CN 85109342 A CN85109342 A CN 85109342A CN 1020639 C CN1020639 C CN 1020639C
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- CN
- China
- Prior art keywords
- zinc
- sputter
- tin
- oxide
- layer
- 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.)
- Expired - Lifetime
Links
- 239000011248 coating agent Substances 0.000 title claims description 41
- 238000000576 coating method Methods 0.000 title claims description 41
- 229910001297 Zn alloy Inorganic materials 0.000 title claims description 31
- 229910001128 Sn alloy Inorganic materials 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 229910052709 silver Inorganic materials 0.000 claims abstract description 31
- 239000004332 silver Substances 0.000 claims abstract description 31
- 238000004544 sputter deposition Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims description 55
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 53
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 33
- 238000000151 deposition Methods 0.000 claims description 33
- 230000008021 deposition Effects 0.000 claims description 28
- 229910052725 zinc Inorganic materials 0.000 claims description 28
- 239000011521 glass Substances 0.000 claims description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 20
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 15
- 229910052718 tin Inorganic materials 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 10
- 229910052738 indium Inorganic materials 0.000 claims description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 229910001369 Brass Inorganic materials 0.000 claims 4
- 239000010951 brass Substances 0.000 claims 4
- NDYFZEOTGYVXNJ-UHFFFAOYSA-N [Zn].[Zn][Sn] Chemical compound [Zn].[Zn][Sn] NDYFZEOTGYVXNJ-UHFFFAOYSA-N 0.000 claims 1
- 229910000765 intermetallic Inorganic materials 0.000 claims 1
- 229910052755 nonmetal Inorganic materials 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 24
- 150000004706 metal oxides Chemical class 0.000 abstract description 24
- 230000003667 anti-reflective effect Effects 0.000 abstract description 2
- 238000002834 transmittance Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 47
- 239000010408 film Substances 0.000 description 40
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 239000007789 gas Substances 0.000 description 18
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 12
- 239000011135 tin Substances 0.000 description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 7
- 229910000416 bismuth oxide Inorganic materials 0.000 description 5
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002310 reflectometry Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000005477 sputtering target Methods 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- CSBHIHQQSASAFO-UHFFFAOYSA-N [Cd].[Sn] Chemical compound [Cd].[Sn] CSBHIHQQSASAFO-UHFFFAOYSA-N 0.000 description 1
- 229910002064 alloy oxide Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- BEQNOZDXPONEMR-UHFFFAOYSA-N cadmium;oxotin Chemical compound [Cd].[Sn]=O BEQNOZDXPONEMR-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Classifications
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
- G02B1/115—Multilayers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3613—Coatings of type glass/inorganic compound/metal/inorganic compound/metal/other
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3652—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the coating stack containing at least one sacrificial layer to protect the metal from oxidation
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
- C03C17/366—Low-emissivity or solar control coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3681—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating being used in glazing, e.g. windows or windscreens
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
-
- 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
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Abstract
具有对可见波长光有高透射率和低红外辐射率的透明制品是通过在含氧气氛中溅射锌/锡金属合金靶从而所沉淀的锌/锡金属合金氧化物涂覆在所述透明制品上制备的,该类制品可用于制备用于窗户的玻璃。
Description
本发明涉及阴极溅射金属氧化物薄膜的工艺,更具体地说,涉及电磁溅射多层金属和其氧化物的薄膜。
美国专利4094763(Cillery et al)公开了透明的电导性制品的生产,它是在200°以上,在含有可控制量的氧气低气压中,用将锡和铟等金属阴极溅射到诸如玻璃之类的耐火基体上。
美国专利4113599(Cillery)论述了铟的氧化物的反应性沉积的阴极溅射技术,其中说,要调节氩气的流速使溅射室内保持恒定的压力,并且同时调节氧气的流速使排放气流保持恒定。
美国专利4166018(Chapin)叙述了溅射装置,在该装置中,磁场在紧接二维溅射表面处形成,磁场由溅射表面的封闭环形腐蚀区上方的弧形磁通量线表示。
美国专利4201649(Cillery)公开了制造低电阻铟氧化物膜的方法,在用常规高溅射温度阴极溅射法沉积铟氧化物导电主层的基体加热之前,先在较低的温度沉积很薄的第一层铟氧化物。
美国专利4327967(Groth)公开了中性彩色外观的热反射板材,它由玻璃板,玻璃表面上的折射率大于2的干涉膜,干涉膜上的热反射金膜和铬、铁、镍、钛或它们的合金的中性氧化薄膜组成。
美国专利4349425(Miyakeetal)公开了在氩和氧混合气体中镉锡合金的d-c反应性溅射,以形成透明度高、电阻低的镉-锡氧化物膜。
美国专利4462883(Hart)公开了低辐射率层,它用阴极溅射法在诸如玻璃之类的基底上溅射一层银,少量的非银金属。和金属氧化物的抗-反射层生产。抗-反射层可以是氧化锡、氧化钛、氧化锌、氧化铟、氧化铋、或氧化锆。
再公告号27473(Mauer)公开一种多层透明制品,它由一薄层金或铜夹在两层透明材料如多种金属、氧化钛、氧化铅、或氧化铋之间组成。
改善能量效率的双玻璃窗的使用中,希望在玻璃的表面之上,提供由减少辐射热而提高隔热能力的涂层。因此涂层必须在红外波长区有较低的辐射。实际应用要求涂层在可见光区有高透明度。涂层对光线的反射作用应当低,最好基本无色。
如上所述,高透射率、低辐射率的涂层,通常由反射红外光且低辐射的薄金属层夹在用以减少可见光反射的金属氧化物的不导电层中组成。这些多层膜典型的生产方法是阴极溅射,特别是电磁溅射。金属层可是金或铜,通常是银。在先有技术中述及的金属氧化物层,包括氧化锡、氧化铟、氧化钛、氧化铋、氧化锌、氧化锆和氧化铝。有时,氧化物中也掺入少量其它金属,如:镁掺在氧化铋中;在氧化锡中掺铟;或反过来在氧化铟中掺加锡,在氧化镁中掺加铋,以克服诸如耐久性差,或边界辐射之类的缺陷。但是所有这些氧化物都有不足之处。
虽然使用中可将涂层保持在双玻璃窗的内表面,这就能使涂层免于受到使它失效的物质和环境的作用,但是,非常希望耐久有效的涂层能够在制造和安装中间,经受得住所遇到的处理、包装、冲洗和其它加工过程。另外,除了提供机械耐久的硬度、提供化学耐久的隋性以及对玻璃层和金属层的粘着性外,金属氧化物还应有下述性质。
金属氧化物必须具有相当高的折射率,最好要大于2.0,以减少金属的反射,加强涂层产品的透射率。它吸收的光能必须小,以使产品透射率最大,从工业化上考虑,它应该价格合适且有较快的磁溅射沉积速率,应该无毒。
可能最重要的是,也是最难使人满意的要求是;涉及金属氧化物与金属膜之间的相互作用,金属氧化物薄膜必须空隙少,以使下面的金属膜与外面的物质隔离;并且必须对金属的扩散性低以保持分层的完整。最后,最重要的是,金属氧化物层必须对沉积金属层提供良好的聚结表面,以保证具有最小的电阻和最大的透光作用的连续金属膜沉积,连续和非连续银薄膜的特性在美国专利4462884中已有叙述,其中公开内容可在此处作为参考。
常用的金属氧化物薄膜中,氧化锌和氧化铋耐久性不足,溶于酸性和碱性物质,会因手印而降低功效,在盐、二氧化硫和潮汽试验中被破坏。最好在氧化铟中掺上锡,以使耐久性较好;但铟的溅射慢且价格较高。在氧化锡中可掺铟或锑,以使它有较长的耐久性,但是它不能为沉积银提供适用的表面,结果,产品的电阻高、透射率差。在没有做出能使银沉积薄膜适当聚结的特征性金属膜之前,用上述金属氧化物已经广泛地实践了试验一一失败的过程。
本发明提供金属合金氧化物的新型薄膜组合物,同时也为高透光低辐射的涂层提供金属和金属合金氧化物层的新型多层薄膜。本发明也用能改进金属和金属氧化物层之间结合能力的底涂层提高了上述涂层的耐久性。
由金属合金的氧化物组成的新型薄膜组合物是以用阴极溅射法沉极为好,最好是用电磁溅射。阴极靶制成含有要求比例的合金元素。然后,靶在反应性气氛中溅射,最好含有氧气以便在基底表面沉积合金氧化物。
根据本发明,适用的合金氧化物是含有锌和锡的合金氧化物。按照本发明,锌/锡合金氧化膜可用阴极溅射沉积,最好用电磁场加强。按照本发明,对于沉积高透射率、低辐射率薄膜,阴极溅射法也是优先选取的。这样的薄膜典型是多层膜,由一层高反射性的金属,如:金、银或铜夹在抗一反射性的金属氧化物层,如氧化铟或氧化钛中组成较为理想。按照本发明,抗一反射性金属氧化物层最好由锌和锡合金氧化物组成,并且以由锡酸锌组成最好。当涉及到与金属膜层结合后构成高透射、低辐射率涂层的性能时,合金氧化物薄膜的特性不能总是予先可指出,可进行多种试验以确定它的耐久性,以及更为重要的关于银膜层聚结的效果性。
对于耐久性,可进行热试验,通过测量涂层的透射率、反射率和颜色的改变,用以表示长期稳定性;通过加快气候的变化和暴露试验,来测量环境条件:如紫外线辐射、潮湿和盐(手印或海岸环境)的影响;通过二氧化硫试验用以确定涂层对酸性气体污染危害的敏感性;以及确定涂层是否受到常规玻璃清洗剂、酸性或碱性洗涤剂的破坏。
更重要的是,可以进行估价合金氧化物对如银之类金属的沉积效果的聚结试验。将一层合金氧化物沉积到基底的表面上。指定的单位基底表面的银量沉积到氧化物膜上。最后,将第二层合金氧化物沉积到银层。首先要估价的效果是由于银层沉积而导致的透射率降低,透射率降低越少,光吸收越少,则聚结作用越好。第二是多层涂层的表面电阻,电阻越低聚结得越好。第三是多层涂层的最后透射率,透射率越高聚结作用越好。
多种合金都可以溅射形成合金氧化物膜,按本发明为了产生适用的高透射、低辐射率多层薄膜,最好用锌和锡的合金。具体适用的合金含锡10~90%,含锌10~90%。较好的锌/锡合金含锌30~60%,较好的锌/锡比例为40/60~60/40。最好是锡对锌的比例在46∶54~50∶50。锌/锡合金阴极在氧化气氛中溅射反应,结果沉积成含锌、锡和氧的金属氧化物层,最好是锡酸锌的形成:Zn2Sno4。
在常规的电磁溅射工艺中,基体放在溅射室内,面对有要溅射材料的靶表面的阴极:适用的基体有玻璃、陶瓷和塑料,这些材料不会受到溅射工艺操作条件的损害。
阴极可以是任何常规的结构,较好的是长方形结构,连结电压源。并且最好结合使用磁场以加强溅射。至少一个阴极靶表面由合金组成,如锌/锡合金,合金在反应性气氛中溅射形成合金氧化物膜。阳极最好是对称结构的,装配位置如美国后续专利571406所述该专利1984,1、17日提交(Cillery at al),其中内容在此处参考。
在本发明较好的具体实施中,用阴极溅射沉积了多层薄形成高透射低辐射率的涂层。除了合金靶之外,至少另一个阴极靶表面由要溅射的形成反射性金属层的金属组成。具有反射金属层与抗一反射合金氧化物的结合的多涂层的生产如下文所述。
将清洗后的玻璃基体放入真空涂层室,以小于0.013Pa为好,最好小于0.003Pa。选定的惰性和反应性气体,氧气和氩气适用,在涂层室中的压力为0.065-1.3Pa之间。在要涂覆的基底的表面上方操作带有锌/锡合金靶表面的阴极。溅射靶金属,在室中与气体反应使在玻璃表面沉积锡/锌合金氧化物层。
锌/锡合金氧化物的初始层沉积之后,抽空涂层室;用惰性气体,如纯氩气使室内压力为0.065-1.3Pa在锌/锡合金氧化物涂层表面上方操作具有银靶面的阴极。溅射靶金属,在涂复锌/锡合金氧化物的玻璃表面上,沉积具有反射性、传导性的金属层。在基本上与沉积第一锌/锡合金氧化物层相同的条件下,在银层上沉积第二锌/锡合金氧化物层。
最好是,至少一个另加的阴极靶面是由沉积后作为底涂层的金属组成。具有反射性的金属薄膜和抗一反射性合金氧化物薄膜结合在一起的耐久多层涂层的生产过程如下,使用底涂层改善金属和金属氧化物之间的结合能力。
把清洁的玻璃基体放入真空涂层室,压力低于0.013Pa,最好低于0.003Pa。选定的惰性和反应气体,以氩气和氧气为好,在室内压力应为0.065-1.3Pa。在要涂覆的基底表面上方操作具有锌/锡合金靶面的阴极。溅射靶金属,在该室内与气体
反应以在玻璃表面沉积锌/锡合金氧化物涂层。
锌/锡合金氧化物的初始层沉积后,抽空涂覆室,加入惰性气体,如纯氩气,使室内压力为0.065-1.3Pa毫米汞柱。溅射有金属(如铜)靶表面的阴极,使锌/锡合金氧化物层上沉积一层底涂层。然后溅射有银靶面的阴极,使银反射层沉积到能改善银膜对下面的金属氧化物膜层的结合能力的底涂层上。接着,用溅射金属(如铜)的方法将另加的底涂层沉积到银反射层上,以改善银层与后面沉积的金属氧化物层间的结合力。最后,在与沉积第一锌/锡氧化物层同样的条件下,在第二底涂层上沉积第二锌/锡合金氧化物层。
在本发明的大多数实施方案中,都在最后的金属氧化物层上沉积保护性表面层。最好也是用溅射法沉积,在金属氧化物膜上沉积一层金属,如1983、9、9提交的美国后续专例530570(Gillery et al)所述。适用的保护性外涂层的金属有铁或镍的合金,如:不锈钢或因康镍合金。由于钛的高透光性,它是最适用的外保护层。
本发明将从下述具体实施例中得到进一步的理解,在实施例中,虽然薄膜组合物不需要是精确的Zn2Sno4,锌/锡合金氧化膜最好是酸锌。
实例1
固定阴极的尺寸为5×17英寸(12.7×43.2厘米),由52.4%(重量)的锌和47.6%锡的合金溅射表面构成。将钠-钙-硅玻璃(Soda-lime-Silica ylass)基底放入涂层室,并抽成真空后,涂层室中压力维持在0.5Pa氩气和氧气均占各半。在玻璃以2.8米/分钟的速度通过溅射表面
时,磁场中阴极以1.7千瓦的功率溅射。在玻璃表面沉积一层锡酸锌薄膜。三次操作产生约340埃厚的薄膜,由于涂覆了锡酸锌薄膜,结果使透射率为90%的玻璃的透射率减少到81%。
实例2
在钠-钙-硅玻璃上沉积多层薄膜以生产高透射、低辐射率的涂层产品。首先,按例1沉积锡酸锌层。然后,在0.5Pa的氩气中,用溅射银阴极靶的方法在锡酸锌上面沉积银层。基体通过阴极靶的速度与例1相同,二次操作使每平方厘米的表面沉积11微克银,相当于银层厚约90埃,使透射率从81%减少到72%。最好在银层上涂覆一层锌/锡合金以改进结合性能,并且能在最后沉积抗一反射的锡酸锌层之前保护银层。因为合金层会进一步减少透射率,所以它的厚度应当尽量薄。这层的沉积是在0.5Pa压力的氩气中,以最小的功率溅射锌/锡合金靶而形成的。一次操作后样品的透射率减少到60%。最后按照例1,在氧化气氛中溅射锌/锡合金阴极靶以产生锡酸锌薄膜。以2.8米/分钟的速度进行四次操作,产生薄膜的厚度约为430埃,使涂层产品的透射率从60%增加到87%。最后产品的表面电阻为10欧姆/100平方,产品两面都有轻微的浅兰色反射,有涂层的一面光反射为5%,无涂层面为6%。
实例3
在钠-钙-硅玻璃上沉积多层薄膜以生产高透射低辐射率的涂层产品。12.7×43.2(厘米)的固定阴极是由52.4%(重量)的锌和47.6%的锡合金的溅射面组成。玻璃基体放入抽成真空后又维持在0.5Pa压力、氧气和氩气各占一半的涂层室中。在
玻璃以2.8米分钟的速度通过溅射表面时,磁场中阴极以1.7千瓦的功率溅射。在玻璃表面沉积一层锡酸锌。三次操作后产生约340埃厚的薄膜,该薄膜使玻璃基体的透射率从90%减少到83%。溅射铜靶固定阴极使锡酸锌上沉积铜底涂层,铜底涂层使透射率减到约80.6%然后,在0.5Pa的氩气中溅射银阴极靶,使铜底层上沉积一层银。以同样速度使基底通过银阴极靶下,需要二次操作使每平方厘米沉积11微克银,相当于90埃的银膜厚度,其结果使涂层后的基体的透射率减少到约70.3%。在银层上溅射第二铜底涂层以后改进结合力,并且在沉积最后的抗一反射锡酸锌层之前保护了银层。因铜底层减少透射率,故其厚度应当尽量小。铜底层是用在0.5Pa的氩气中以最小功率溅射铜靶的方式沉积。沉积第二铜底层之后,样品的透射率降底到68.3%。最后,在氧化性气氛中溅射锌/锡合金阴极靶以产生锡酸锌薄膜。以2.8米/分钟的速度进行四次操作,产生的膜层厚约为430埃,使产品透射率从68.3%增加到83.2%。最终产品的表面电阻为10欧姆/100平方,并且两面都有轻微淡兰色的反射性,有涂层的一面光线反射率约为5%,未涂层一面光线反射率约为6%。
本发明的底涂层改善了金属和金属氧化物之间的结合力,因此改善了涂层制品的耐久性。这些很容易用简单的摩擦试验证明,可以用湿布擦洗涂层表面试验。按本发明,无底涂层的锡酸锌/银/锡酸锌涂层表面在用湿布擦揩几次之后,反射性从约6%增加到约18%,这表明最表面的锡酸锌和它下面的银层都有脱落。相反,本发明带有底涂层的锡酸锌/铜/银/铜/锡酸锌涂复的制品,在经受更长时间
的强烈湿布摩擦之后,没有发现变化。
提出上述实例,是为了说明本发明。还可以有产品和工艺上的多种变化,例如,本发明范围内的其它涂层组合物。当溅射锌/锡合金时,根据锌和锡的比例,除了锡酸锌之外,涂层可以含有在很大范围内改变的氧化锌和氧化锡的量。因为工艺过程不要求很高温度,除玻璃之外的基体,如多种塑料都可涂层。对于固定的基体,可以使用扫描式阴极,或阴极和基体都可以固定。工艺参数,如压力和气体浓度都可以在很大范围内改变。根据本发明,用底涂层的手段可以改善多种金属和金属氧化膜之间的结合力。底涂层也可以是其它金属,如铟,或者是氧化物,例如:氧化铜、氧化铟。本发明的范围由下述权利要求所限定。
Claims (12)
1、制备含透明底物和复合层的高透射率,低辐射率制品的方法,所述复合层是通过将溅射阴极靶得到的锡和锌氧化物沉淀在透明底物上形成的,其特征在于:阴极靶是锡和锌的金属合金,溅射是在含氧反应气氛中进行的。
2、按照权利要求1所述的方法,其中所述的溅射过程用磁场加强。
3、按照权利要求1所述的方法,其特征在于:通过在惰性气氛中首先溅射银阴极靶。随后在含氧反应活性气氛中进一步溅射锌和锡合金,沉积出其它层。
4、按照权利要求1所述的方法,其中在溅射锌和锡合金后,首先溅射铜靶,在锡和锌合金氧化物薄膜上沉淀出第一层,然后在惰性气氛中溅射银靶,随后再溅射铜靶沉积出第二层,最后于含氧的反应活性气氛中溅溅含锡和锌合金的阴极靶。
5、按照权利要求4所述的方法,其中所说的铜靶溅射是在含氧的反应活性气氛中进行的。
6、沉积耐久性薄膜的方法,其特征在于包括下述步骤:
(1)在含氧的反应性气氛中,溅射锡、锌合金阴极靶,在基本表面沉积锡锌合金氧化物薄膜;
(2)在上述锡锌合金氧化物薄膜上溅射选自铜,铟及它们的氧化物的底层;
(3)在上述底层上溅射反射性金属薄膜;
(4)在上述反射性薄膜上溅射选自铜,铟及它们的氧化物的第二底层;
(5)在上述第二底层上溅射第二层锡锌合金氧化物薄膜。
7、按照权利要求6所述的方法,其中的基体是玻璃。
8、按照权利要求6所述的方法,其中的金属合金氧化物薄膜中含有锡酸锌。
9、用权利要求1所述的方法得到高透射率、低辐射率制品,该制品组成如下:
a.透明的非金属基体,
b.沉积在上述基体表面上的锡锌合金氧化物组成的第一层透明薄膜。
c.沉积在上述锡锌金属氧化物薄膜上的第一透明底涂层,
d.沉积在上述底涂层上的透明金属薄膜。
e.沉积在上述反射性金属薄膜上的第二透明底涂层。
f.沉积在上述第二低涂层上的锡锌合金氧化物组成的第二层透明薄膜。
10、按照权利要求9所述的制品,其中存在锌和锡的氧化物层,且该层中的金属化合物中含有30~60%的锌。
11、按照权利要求10所述的制品,其中锌和锡的氧化物混合在一起时,以锡酸锌的形式存在。
12、按照权利要求9-11中任一项所述的制品,其中至少存在一层底层,且该底层的组成选自铜,铟及它们的氧化物。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/665,680 US4610771A (en) | 1984-10-29 | 1984-10-29 | Sputtered films of metal alloy oxides and method of preparation thereof |
US665,680 | 1984-10-29 | ||
US68345884A | 1984-12-19 | 1984-12-19 | |
US683,458 | 1984-12-19 |
Publications (2)
Publication Number | Publication Date |
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CN85109342A CN85109342A (zh) | 1986-10-08 |
CN1020639C true CN1020639C (zh) | 1993-05-12 |
Family
ID=27099265
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN85109342A Expired - Lifetime CN1020639C (zh) | 1984-10-29 | 1985-10-28 | 制备含锡/锌合金氧化物涂层的高透射率、低辐射率制品的方法 |
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Country | Link |
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EP (2) | EP0343695B1 (zh) |
JP (1) | JPH0662319B2 (zh) |
KR (1) | KR920007499B1 (zh) |
CN (1) | CN1020639C (zh) |
AT (1) | ATE70818T1 (zh) |
AU (1) | AU561315B2 (zh) |
DE (2) | DE3585025D1 (zh) |
DK (1) | DK169758B1 (zh) |
ES (1) | ES8609505A1 (zh) |
FI (1) | FI854214L (zh) |
HK (1) | HK91192A (zh) |
NO (1) | NO172065C (zh) |
NZ (1) | NZ213849A (zh) |
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- 1985-10-24 EP EP89113298A patent/EP0343695B1/en not_active Expired - Lifetime
- 1985-10-24 DE DE8585113488T patent/DE3585025D1/de not_active Expired - Lifetime
- 1985-10-24 EP EP85113488A patent/EP0183052B1/en not_active Expired - Lifetime
- 1985-10-24 AT AT85113488T patent/ATE70818T1/de not_active IP Right Cessation
- 1985-10-24 DE DE8989113298T patent/DE3587078T2/de not_active Expired - Fee Related
- 1985-10-25 NO NO854274A patent/NO172065C/no not_active IP Right Cessation
- 1985-10-28 ES ES548274A patent/ES8609505A1/es not_active Expired
- 1985-10-28 DK DK494185A patent/DK169758B1/da not_active IP Right Cessation
- 1985-10-28 JP JP60241231A patent/JPH0662319B2/ja not_active Expired - Fee Related
- 1985-10-28 FI FI854214A patent/FI854214L/fi not_active Application Discontinuation
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-
1992
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Also Published As
Publication number | Publication date |
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DK494185A (da) | 1986-04-30 |
NO854274L (no) | 1986-04-30 |
CN85109342A (zh) | 1986-10-08 |
KR860005049A (ko) | 1986-07-16 |
EP0343695B1 (en) | 1993-02-03 |
AU4839085A (en) | 1986-06-12 |
ES8609505A1 (es) | 1986-07-16 |
DE3585025D1 (de) | 1992-02-06 |
DE3587078D1 (de) | 1993-03-18 |
ES548274A0 (es) | 1986-07-16 |
NO172065C (no) | 1993-06-02 |
FI854214L (fi) | 1986-04-30 |
DK494185D0 (da) | 1985-10-28 |
ATE70818T1 (de) | 1992-01-15 |
HK91192A (en) | 1992-11-27 |
EP0183052A3 (en) | 1987-05-27 |
NZ213849A (en) | 1990-03-27 |
JPS61111940A (ja) | 1986-05-30 |
FI854214A0 (fi) | 1985-10-28 |
EP0183052B1 (en) | 1991-12-27 |
EP0183052A2 (en) | 1986-06-04 |
KR920007499B1 (ko) | 1992-09-04 |
AU561315B2 (en) | 1987-05-07 |
EP0343695A1 (en) | 1989-11-29 |
DE3587078T2 (de) | 1993-07-15 |
NO172065B (no) | 1993-02-22 |
JPH0662319B2 (ja) | 1994-08-17 |
DK169758B1 (da) | 1995-02-20 |
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