CN86108656A - 耐久的金属合金氧化物溅射薄膜 - Google Patents
耐久的金属合金氧化物溅射薄膜 Download PDFInfo
- Publication number
- CN86108656A CN86108656A CN86108656.2A CN86108656A CN86108656A CN 86108656 A CN86108656 A CN 86108656A CN 86108656 A CN86108656 A CN 86108656A CN 86108656 A CN86108656 A CN 86108656A
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- Prior art keywords
- film
- metal
- oxide
- metal oxide
- goods according
- 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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- 229910001092 metal group alloy Inorganic materials 0.000 title claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000005540 biological transmission Effects 0.000 claims abstract description 11
- 239000010410 layer Substances 0.000 claims description 47
- 239000011701 zinc Substances 0.000 claims description 40
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 38
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 36
- 229910044991 metal oxide Inorganic materials 0.000 claims description 34
- 150000004706 metal oxides Chemical class 0.000 claims description 31
- 229910052725 zinc Inorganic materials 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 24
- 230000008021 deposition Effects 0.000 claims description 20
- 239000011521 glass Substances 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- 229910052709 silver Inorganic materials 0.000 claims description 14
- 239000004332 silver Substances 0.000 claims description 14
- 229910052718 tin Inorganic materials 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 239000011241 protective layer Substances 0.000 claims description 7
- 229910052738 indium Inorganic materials 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- 230000003667 anti-reflective effect Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims 2
- 229910052755 nonmetal Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 67
- 238000000034 method Methods 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 22
- 238000004544 sputter deposition Methods 0.000 description 22
- 238000000151 deposition Methods 0.000 description 18
- 230000000977 initiatory effect Effects 0.000 description 18
- 229910001128 Sn alloy Inorganic materials 0.000 description 16
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 13
- 229910001297 Zn alloy Inorganic materials 0.000 description 13
- 238000002834 transmittance Methods 0.000 description 12
- 239000011135 tin Substances 0.000 description 11
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 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
- 239000007789 gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000011253 protective coating Substances 0.000 description 3
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000005546 reactive sputtering Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 239000010409 thin film 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
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 1
- 230000004520 agglutination Effects 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
- 239000010974 bronze Substances 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- DPDORTBBLUCNJG-UHFFFAOYSA-N calcium tin Chemical compound [Ca].[Sn] DPDORTBBLUCNJG-UHFFFAOYSA-N 0.000 description 1
- HNQGTZYKXIXXST-UHFFFAOYSA-N calcium;dioxido(oxo)tin Chemical compound [Ca+2].[O-][Sn]([O-])=O HNQGTZYKXIXXST-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- -1 metal oxide compound Chemical class 0.000 description 1
- 238000001465 metallisation Methods 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
- 238000012856 packing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
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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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
-
- 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
-
- 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
- G02B1/116—Multilayers including electrically conducting layers
-
- 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
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
-
- 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
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/73—Anti-reflective coatings with specific characteristics
-
- 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
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
-
- 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
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12597—Noncrystalline silica or noncrystalline plural-oxide component [e.g., glass, 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
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Abstract
本发明公开一种多层高透光率,低发射率镀层制品,由于氧化钛外保护层的存在,改善了其耐化学腐蚀性能。
Description
这一申请是美国F.Howard Gillery 1984年12月19日提出的美国序号No.683,458的部分继续申请。
概括地讲,本发明涉及金属氧化物薄膜的阴极溅射技术,特别与多层金属及金属氧化物薄膜的磁控溅射技术有关。
Gillery等人在美国专利4,094,763中公开了生产透明、导电薄膜制品阴极溅射方法,即在温度为400°F以上,氧含量可控的低气压条件下,把诸如锡和铟之类的金属溅射在耐热的基板(如玻璃)上。
在美国专利4,113,599中Gillery提出了用于反应沉积氧化铟的阴极溅射技术。在这种方法中调节氧气的流速为一恒定的放射气流,与此同时使溅射室中氩气的流速保持在恒定压力下。
Chapin在美国专利4,166,018中描述了一种溅射装置,在此装置中,邻近平的溅射表面形成一个磁场,即在此溅射表面上,形成一个包括遍布闭合环路不整齐区的拱形磁力线的磁场。
在美国专利4,201,649中,Gillery公开了一种制备低阻氧化铟薄膜的方法,所用的方法是首先沉积一层非常薄的氧化铟初始膜,这一步骤是在加热基板之前在低温条件下进行的,从而用阴极溅射法沉积较大厚度的氧化铟导电薄膜时应在典型的高阴极溅射温度下进行。
Groth在美国专利4,327,967中公开了一种外观为灰色热反射面板,由一块玻璃板,及在此玻璃板表面上涂上折射率大于2的干涉膜所构成,在此干涉膜之上是热反射金膜,和在金膜之上的铬、铁、镍、钛或其合金的中和膜。
Miyake等在美国专利4,349,425中公开了在氩-氧混合气体中钙-锡合金的直流反应溅射法,以形成具有低电阻高透光率的钙-锡氧化物薄膜。
在美国专利4,462,883中,Hart公开了一种低发射率镀层。它的制法是在一块透明基板(如玻璃)上,阴极溅射一层银膜,一层除银外的少量其它金属膜和一层金属氧化物的抗反射膜,该抗反射膜可以是氧化锡、氧化钛、氧化锌、氧化铟、氧化铋或氧化锆。
Mauer在再颁专利27,473中,公开了一种具有金或铜薄层的多层透明制品,这种薄层是夹在两层透明材料如各种金属、氧化钛、氧化铅或氧化铋之间的夹层。
为了改善双层玻璃窗的能量效率,在玻璃的一个表面上镀一种涂层是很理想的,它可以降低辐射热的传递,从而提高玻璃窗的热绝缘性能。因此,这种涂层在该辐射光谱的红外波长区域内必须具有低发射率。由于实用上的原因,该涂层在可见光波长区域内必须具有高透光率。从美学上考虑,它应该是不耀眼反射,而最好是基本无色的。
如上所述的高透光率,低发射率镀层一般是一种反射红外光及低发射率金属薄层,它作为夹层存在于用来减少可见光反射的金属氧化物介电层之间。这类多层结构的薄膜一般用阴极溅射法,特别是用磁控溅射法制造。金属层可以是金或铜,但一般是银。上述方法中所说的金属氧化物层包括氧化锡、氧化铟、氧化钛、氧化铋、氧化锌、氧化锆和氧化铅。在一些场合,这些氧化物中要掺入少量其它金属,如:在氧化铋中掺入锰,氧化锡中加铟,反之亦然。其目的是为了克服存在的某些缺点,如;耐久性低或免强够格的发射系数。但是,所有这些金属氧化物都存在一些不足。
虽然使用时这些镀层可以被置于双层玻璃窗内表面上,这样可以保护其免受那些来自窗零部件及环境中能引起其性能劣化的介质所带来的损害,但还是特别希望有一种耐久、有效的,能够经受住在制造和安装中所遇到的运输、包装、洗涤和其它制造加工处理的镀层。金属氧化物就具有这些特征。然而,除保证一定的机械耐久性所要求的硬度,化学稳定性所要求的惰性,以及对玻璃和金属镀层都有好的密着性能之外,这些金属氧化物还应该具有以下各种特性。
此金属氧化物必须具有足够高的折射率,最好大于2.0,以便能降低其金属膜层的反射,从而增加该镀膜制品的透光率。金属氧化物也必须具有最小的光吸收率以充分增大镀膜制品的透光率。从商业角度考虑,这类金属氧化物的价格应该适中,用磁控溅射时有相当快的沉积速率,并且应是无毒的。
可能最重要的也是最难满足的要求是金属氧化物薄膜与金属膜的相互作用问题。此类金属氧化物薄膜应该具有低气孔率,以防止外部介质影响基底的金属薄膜,它还应有低扩散系数以使金属层保持各自的完整性。最后,也是最重要的,此类金属氧化物必须具有金属层沉积的优良成核表面,以使一种连续的电阻极小透光率最高的金属薄膜能沉积其上。连续的和不连续的银膜特性在美国专利4,462,884中由Gillery进行了说明,此处引用作考虑。
在一般使用的金属氧化物多层薄膜中,氧化锌和氧化铋薄膜不太耐久,这些氧化物在酸和碱介质中可溶。指纹会使这种多层膜劣化,并且在盐、二氧化硫和湿度试验时被破坏。氧化铟最好掺入锡,这将使基底的金属层更牢固和有保护作用。但是,铟溅射速度较慢,而且相当昂贵。氧化锡可以与铟或锑掺杂,也较为耐久并对基底的金属层有保护作用,但并不能产生一个适于银膜成核的表面,从而导至了高电阻低透光率。适合于接续沉积银膜,具有适当的成核作用的金属氧化物膜的特点还未被确定,但是,试探性实验已用如上所述的金属氧化物进行了广泛的摸索。
由Gilley1984年10月29日申请的美国序列号665,680中公开了一种金属合金氧化物新型薄膜组成,还介绍了一种新型的用作高透光率、低发射率镀层的金属和金属合金氧化物层的多层薄膜。
本发明改善了多层薄膜,特别是由金属和/或金属合金氧化物层以及金属(如银)层构成的多层膜的耐久性,这是借助加上一种特殊的耐化学浸蚀的材料(如氧化钛)做外保护层来实现的。
薄膜的组成最好是一种金属或金属合金氧化物,薄膜的形成最好用阴极溅射尤其是磁控溅射方法沉积而成。阴极靶由所希望的金属或金属合金制成,而阴极靶的溅射是在一种反应气氛中进行的,气氛中最好含有氧以便在基板的表面上沉积金属或金属合金氧化物薄膜。
根据本发明,理想的金属合金氧化物最好是含锌和锡的合金氧化物。按本发明,锌/锡合金氧化物薄膜可以用阴极溅射法沉积,最好是用磁控增强。依据本发明,阴极溅射法对高透光率低发射率薄膜的沉积也是一种优先采用的方法。这类薄膜一般是多层结构,最好有一层高反射金属(如金或银)层,此高反射金属层是在抗反射金属氧化物(如氧化铟或氧化钛)层之间的夹层,或最好是一种锌和锡合金的氧化物,其中最好还包含锡酸锌。
根据本发明,为了制成一种最佳的高透光率低发射率的多层膜,虽然很多种金属合金都可以用作溅射金属合金氧化物薄膜,但是锡和锌的合金是最佳的。一种优先选用的锌-锡合金的优选组成比是10%到90%的锌和90%到10%的锡。更优的锌/锡合金组成比是含30%到60%的锌,最优锌/锡比是从40∶60到60∶40,最佳组成比是46∶54到50∶50(以锡对锌的重量比计)。锌/锡合金阴极在氧化气氛中被反应溅射而形成了包括锌、锡和氧,最好是含有锡酸锌Zn2SnO4的金属氧化物沉积层。
在传统的磁控溅射工艺中,基板被置于镀层室中,并面向着表面为待溅射材料的阴极靶。按本发明,优先采用的基板包括玻璃、陶瓷和塑料等,这些材料不会受镀层工艺条件的不利影响。
该阴极可以是任意的、传统的设计,最好是细长矩形的与电源相连接的形式,并且为了增强溅射过程最好与一磁场配合使用。至少有一个阴极靶表面包含金属合金(如锌/锡)。该合金在反应气氛中被溅射而形成一种金属合金氧化物膜。阳极最好按对称形式设计并按Gillery等在美国专利4478702中公开的并在此处引用作参考的方法布置。
在本发明所优先采用的方法中,高透光率、低发射率的多层薄膜是用阴极溅射法制成的。除金属合金靶外,至少还有另外一个阴极靶的表面由一种用于溅射形成反射金属层的金属构成。至少有一个附加的阴极靶表面的金属是用于沉积形成初始层的。生产一种耐久的,与金属合金氧化物抗反射膜相配合,并具有反射金属膜层的多层结构薄膜,所采用的办法是:利用初始层改善金属和金属氧化物膜厚之间的密着性能。
清洁的玻璃基板被置于已抽空的镀膜真空室中,真空度要低于10-4乇,最好低于2×10-5乇。在此真空室中充以经选择的惰性和反应气体(最好是氩和氧),使室内气压在约5×10-4和10-2乇之间。将具有锌/锡靶表面的金属合金阴极放在要镀膜的基板表面上。溅射该靶的金属,并与真空中的气体相反应,从而在玻璃表面上沉积成一层锌/锡合金氧化物镀层。
在锌/锡合金氧化物初始层沉积之后,把镀层室抽空,并充入惰性气体(如纯氩),使气压约在5×10-4乇和10-2乇之间。将具有金属(如铜)靶面的阴极进行溅射,在锌/锡合金氧化物层上沉积一层初始层。接着溅射银靶面的阴极,在初始层的上面沉积一层金属银的反射层。该初始层改善了银膜与底层金属氧化物膜的密着力。随后,在反射的银层之上溅射一种金属(如铜)层作为另一初始层,用以改善银膜与接着沉积的复盖金属氧化物之间的密着力。最后,第二层锌/锡合金氧化物被沉积在该第二初始层上。所使用的沉积条件与沉积第一层锌/锡合金氧化物层基本相同。
本发明最优选采用的实施方案是在最后的金属氧化物薄膜上面沉积一层外保护层。该外保护层最好是通过在该金属氧化物薄膜上溅射一种金属层的方法来实现。如由Gillery等人在1983年9月9日于美国序列号530,570中所公开,优先采用的外保护层金属材料包括有铁或镍合金,如不锈钢或铬镍铁合金。由于钛具有高透光率,因而成为最优先采用的外保护层材料。
根据本发明,多层膜的化学稳定性是通过在该多层膜之上沉积一层氧化钛保护层而得到巨大改善的。该氧化钛保护层最好是在相当高沉积速率和较低气压(最好在3毫乇左右)条件下用阴极溅射法沉积的。氧化钛构成的保护层可以在充分氧化性气氛中用溅射钛的方法直接沉积氧化钛膜。本发明中的另一个实施例中,氧化钛的保护层可以在惰性气氛中用溅射钛的方法直接沉积氧化钛膜。本发明中的另一个实施例中,氧化钛的保护层可以在惰性气氛中用溅射钛的方法沉积成一层含钛的薄膜,随后将该薄膜暴露在氧化气氛(如空气)中进行氧化,从而生成氧化钛薄膜。
从如下的具体实例中,可以进一步的理解本发明。在该例中,锌/锡合金氧化物薄膜被认为是锡酸锌Zn2SnO4,但该薄膜的组成不必是精确的。
实例:
在钠-钙-硅玻璃基板上沉积多层膜可以制成高透光率,低发射率镀层制品。一个大小为5×17英寸(12.7×43.2cm)溅射面构成锌/锡合金组成的固定式阴极,锌/锡合金之重量百分数为52.4%的锌和47.6%的锡。钠-钙-硅玻璃基板被置于真空度为4毫乇,氩/氧为50/50的镀层室中。阴极在一电源功率为1.7KW的磁场中溅射。此时,玻璃基板以每分钟110英寸(2.8M)的速度移动通过溅射表面。从而在玻璃表面上沉积一层锡酸锌薄膜。通过三次便制成厚度约为340
的薄膜,结果可使玻璃基板的透光率从90%降到83%(锡酸锌镀膜的玻璃基板)。随后,带有铜靶的固定阴极被溅射,在锡酸锌膜之上生成一层铜初始层,致使透光率降低约80.6%。
其次,在压力为4毫乇的氩气氛中,通过溅射银阴极靶在铜初始膜上沉积一银层。由于基板以同样的速度在银阴极靶下通过,因此为使每平方厘米上沉积10微克银(大约等于90
厚)就需要通过二次。这样镀层后的基板的透光率大约降到70.3%。将第二铜初始层溅射在银层之上以改善密着力,并且在锡酸锌抗反射膜最终被沉积之前,它起保护银膜的作用。由于铜初始层降低透光率,因此,它们的厚度应尽量薄。在最小的电源功率及4毫乇压力的氩气氛中,用铜靶溅射的方法沉积铜初始层。在第二层铜初始层沉积之后,样品的透光率降到了68.3%。其次,锌/锡合金阴极靶在氧化气氛中被溅射而生成一锡酸锌薄膜。以每分钟110时(2.8M)速度通过四次镀膜厚度可达约为430
,制品的透光率因此可从68.3%增加到83.2%。多层膜表面电阻为10欧姆/口并从两侧显有少量淡兰色反射光,从玻璃的镀膜一侧发光反射为5%,从非镀膜一侧反射为6%。最后,大小为5×17英寸(12.7×43.2cm)的固定式钛阴极在功率为10KW,等体积的氩和氧气氛中,气压为3毫乇条件下溅射,基板以每分钟110英寸(2.8M)速度通过两次,溅射沉积出大约15到20
厚的氧化钛镀层。氧化钛保护层并不过于影响多层膜的电阻和反射特性,对透光率引起的变化大约不会超过1%。
由于本发明中初始层的作用,镀层制品耐久性的改善可以通过金属与金属氧化物膜厚之间密着力的改善而实现,这一改进由一简单的密着力试验很容易地被证明。检验方法是用一块湿布擦试镀层表面。根据本发明,用锡酸锌/银/锡酸锌镀敷且不具有初始层的表面,当用湿布擦几次后其反射率从约6%增加到约18%,这表明,不论上部的锡酸锌膜还是基底的银膜都被擦掉了。相反,对本发明中包括初始层的用锡酸锌/铜/银/铜/锡酸锌镀层的制品,既使用力擦,也并未产生明显的变化。
如上所述的实例具体解释了本发明的内容,包括了产品和工艺的各种改进方法。例如:其它镀层的组成也包括在本发明范围之内。当用锌/锡合金溅射时,根据锌和锡的比例,镀层中氧化锌、氧化锡以及锡酸锌的含量可在很广的范围内变化。各种金属和金属氧化物薄膜之间的密着力可以用本发明所说的初始层进行改进。由于本工艺方法不要求很高的温度,因此除玻璃外的其它基板,如各种塑料,也可以用作镀层基板。对于基板固定的场合可以采用扫描式的阴极。诸如气压和气体浓度一类的工艺参数可在很广的范围内变化。初始层可以用别的金属(如铟)或氧化物(如氧化铜或氧化铟)构成。其它耐化学腐蚀材料的保护镀层可以用金属或氧化物沉积而成。本发明的范围由所附权利要求确定。
Claims (10)
1、高透光率,低发射率制品包括:
a.透明的非金属基板;
b.在所述基板表面上沉积而成的金属氧化物构成的第一透明抗反射薄膜;
c.在所述第一抗反射金属氧化物薄膜之后沉积的透明红外反射金属薄膜;
d.在所述红外反射金属膜沉积后沉积的金属氧化物第二透明抗反射薄膜;以及
c.在所述第二抗反射金属氧化物薄膜之后沉积的金属氧化物外保护层。
2、根据权利要求1所述的制品,其中,基板是玻璃。
3、根据权利要求2所述的制品,其中,反射金属膜厚是银。
4、根据权利要求3所述的制品,其中,金属氧化物包括一种由锌和锡组成的合金的氧化反应产物。
5、根据权利要求4所述的制品,其中,由金属合金氧化反应产物构成的透明薄膜中包括锡酸锌。
6、根据权利要求1所述的制品,其中,进一步包括选自铜、铟和其氧化物的初始薄膜,该初始膜被沉积在反射金属膜与透明金属氧化物抗反射膜之间。
7、根据权利要求6所述的制品,其中,初始膜由铜构成。
8、根据权利要求1所述的制品,其中,外保护金属氧化物层中包括氧化钛。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US06/812,680 US4716086A (en) | 1984-12-19 | 1985-12-23 | Protective overcoat for low emissivity coated article |
US812,680 | 1985-12-23 |
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Publication Number | Publication Date |
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CN86108656A true CN86108656A (zh) | 1987-09-23 |
CN1019319B CN1019319B (zh) | 1992-12-02 |
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CN86108656A Expired CN1019319B (zh) | 1985-12-23 | 1986-12-23 | 耐久的高透光率低辐射率溅射薄膜制品 |
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US (1) | US4716086A (zh) |
EP (1) | EP0226993B2 (zh) |
JP (1) | JPH0745710B2 (zh) |
KR (1) | KR900003979B1 (zh) |
CN (1) | CN1019319B (zh) |
AT (1) | ATE54300T1 (zh) |
AU (1) | AU571380B2 (zh) |
CA (1) | CA1327294C (zh) |
DE (1) | DE3672462D1 (zh) |
DK (1) | DK166536B1 (zh) |
ES (1) | ES2015525T5 (zh) |
FI (1) | FI90050C (zh) |
GR (1) | GR3000824T3 (zh) |
HK (1) | HK67592A (zh) |
IN (1) | IN169768B (zh) |
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-
1985
- 1985-12-23 US US06/812,680 patent/US4716086A/en not_active Expired - Lifetime
-
1986
- 1986-12-02 NZ NZ218479A patent/NZ218479A/xx unknown
- 1986-12-03 ZA ZA869153A patent/ZA869153B/xx unknown
- 1986-12-11 CA CA000525076A patent/CA1327294C/en not_active Expired - Lifetime
- 1986-12-12 AU AU66549/86A patent/AU571380B2/en not_active Ceased
- 1986-12-12 IN IN1094/DEL/86A patent/IN169768B/en unknown
- 1986-12-15 AT AT86117415T patent/ATE54300T1/de not_active IP Right Cessation
- 1986-12-15 DE DE8686117415T patent/DE3672462D1/de not_active Expired - Lifetime
- 1986-12-15 EP EP86117415A patent/EP0226993B2/en not_active Expired - Lifetime
- 1986-12-15 ES ES86117415T patent/ES2015525T5/es not_active Expired - Lifetime
- 1986-12-19 DK DK618586A patent/DK166536B1/da not_active IP Right Cessation
- 1986-12-22 JP JP61306193A patent/JPH0745710B2/ja not_active Expired - Lifetime
- 1986-12-22 KR KR1019860011072A patent/KR900003979B1/ko not_active IP Right Cessation
- 1986-12-22 NO NO865236A patent/NO174286C/no unknown
- 1986-12-22 FI FI865262A patent/FI90050C/fi not_active IP Right Cessation
- 1986-12-23 CN CN86108656A patent/CN1019319B/zh not_active Expired
- 1986-12-23 MY MYPI86000236A patent/MY101707A/en unknown
-
1990
- 1990-07-18 GR GR90400491T patent/GR3000824T3/el unknown
-
1992
- 1992-09-10 HK HK675/92A patent/HK67592A/xx not_active IP Right Cessation
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CN102496729A (zh) * | 2005-07-12 | 2012-06-13 | 通用汽车环球科技运作公司 | 镀层钢双极板 |
CN102496729B (zh) * | 2005-07-12 | 2014-10-29 | 通用汽车环球科技运作公司 | 镀层钢双极板 |
CN101273238B (zh) * | 2005-08-02 | 2010-04-07 | 桑斯翠普有限公司 | 镍-氧化铝涂覆的太阳能吸收器 |
CN100595172C (zh) * | 2006-10-19 | 2010-03-24 | 林嘉宏 | 可钢化低辐射镀膜玻璃及其生产方法 |
CN105859156A (zh) * | 2009-05-08 | 2016-08-17 | Ppg工业俄亥俄公司 | 具有高的阳光得热系数的阳光控制涂层 |
CN105859156B (zh) * | 2009-05-08 | 2019-08-13 | Vitro可变资本股份有限公司 | 具有高的阳光得热系数的阳光控制涂层 |
US11198641B2 (en) | 2009-05-08 | 2021-12-14 | Vitro Flat Glass Llc | Solar control coating with high solar heat gain coefficient |
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CN102667545A (zh) * | 2009-11-18 | 2012-09-12 | 日东电工株式会社 | 红外线反射基板 |
CN102667545B (zh) * | 2009-11-18 | 2015-05-27 | 日东电工株式会社 | 红外线反射基板 |
Also Published As
Publication number | Publication date |
---|---|
ATE54300T1 (de) | 1990-07-15 |
DK618586D0 (da) | 1986-12-19 |
JPH0745710B2 (ja) | 1995-05-17 |
CA1327294C (en) | 1994-03-01 |
FI865262A0 (fi) | 1986-12-22 |
EP0226993B1 (en) | 1990-07-04 |
KR870006232A (ko) | 1987-07-10 |
HK67592A (en) | 1992-09-18 |
ZA869153B (zh) | 1988-06-03 |
JPS62196366A (ja) | 1987-08-29 |
ES2015525T5 (es) | 1996-01-16 |
EP0226993B2 (en) | 1995-11-29 |
NZ218479A (en) | 1990-03-27 |
NO865236L (no) | 1987-06-24 |
AU6654986A (en) | 1987-06-25 |
GR3000824T3 (en) | 1991-11-15 |
NO865236D0 (no) | 1986-12-22 |
KR900003979B1 (ko) | 1990-06-07 |
CN1019319B (zh) | 1992-12-02 |
NO174286B (no) | 1994-01-03 |
DE3672462D1 (de) | 1990-08-09 |
AU571380B2 (en) | 1988-04-14 |
NO174286C (no) | 1994-04-13 |
US4716086A (en) | 1987-12-29 |
MY101707A (en) | 1992-01-17 |
DK166536B1 (da) | 1993-06-07 |
IN169768B (zh) | 1991-12-21 |
FI90050C (fi) | 1993-12-27 |
ES2015525B3 (es) | 1990-09-01 |
DK618586A (da) | 1987-06-24 |
EP0226993A1 (en) | 1987-07-01 |
FI90050B (fi) | 1993-09-15 |
FI865262A (fi) | 1987-06-24 |
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