CA1192773A - Non-iridescent glass structures - Google Patents
Non-iridescent glass structuresInfo
- Publication number
- CA1192773A CA1192773A CA000411270A CA411270A CA1192773A CA 1192773 A CA1192773 A CA 1192773A CA 000411270 A CA000411270 A CA 000411270A CA 411270 A CA411270 A CA 411270A CA 1192773 A CA1192773 A CA 1192773A
- Authority
- CA
- Canada
- Prior art keywords
- infra
- red
- interlayer
- reflective coating
- refractive index
- 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
Links
- 239000011521 glass Substances 0.000 title abstract description 40
- 238000000576 coating method Methods 0.000 claims abstract description 89
- 239000011248 coating agent Substances 0.000 claims abstract description 76
- 239000011229 interlayer Substances 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000010410 layer Substances 0.000 claims description 64
- 230000003287 optical effect Effects 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 33
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 27
- 229910001887 tin oxide Inorganic materials 0.000 claims description 24
- 239000004065 semiconductor Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 9
- 238000013461 design Methods 0.000 claims description 9
- 230000006870 function Effects 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 7
- -1 bromofluoro methane compound Chemical class 0.000 claims description 2
- 230000006872 improvement Effects 0.000 claims description 2
- 239000000306 component Substances 0.000 claims 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 230000002829 reductive effect Effects 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 description 33
- 239000010408 film Substances 0.000 description 29
- 239000003086 colorant Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 241000206607 Porphyra umbilicalis Species 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 6
- 230000001629 suppression Effects 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 235000019642 color hue Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- 229910003437 indium oxide Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 241000282337 Nasua nasua Species 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000004456 color vision Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- QUZPNFFHZPRKJD-UHFFFAOYSA-N germane Chemical compound [GeH4] QUZPNFFHZPRKJD-UHFFFAOYSA-N 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 229910052986 germanium hydride Inorganic materials 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 239000012780 transparent material Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910005091 Si3N Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- KZZFGAYUBYCTNX-UHFFFAOYSA-N diethylsilicon Chemical compound CC[Si]CC KZZFGAYUBYCTNX-UHFFFAOYSA-N 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- UTUAUBOPWUPBCH-UHFFFAOYSA-N dimethylsilylidene(dimethyl)silane Chemical compound C[Si](C)=[Si](C)C UTUAUBOPWUPBCH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001803 electron scattering Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 229910000078 germane Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007775 late Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000004447 silicone coating Substances 0.000 description 1
- 230000002226 simultaneous effect Effects 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- VIPCDVWYAADTGR-UHFFFAOYSA-N trimethyl(methylsilyl)silane Chemical compound C[SiH2][Si](C)(C)C VIPCDVWYAADTGR-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
-
- 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
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
-
- 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
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide 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
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3482—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising silicon, hydrogenated silicon or a silicide
-
- 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
-
- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
-
- 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
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/261—In terms of molecular thickness or light wave length
Abstract
ABSTRACT OF THE DISCLOSURE
This disclosure describes transparent glass window structures of the type bearing a coating of infra-red reflective material which is advantageously less than about 0.85 microns in thickness and wherein the obser-vance of iridescence resulting from such a reflective coating is markedly reduced by provision of a very thin coating system beneath said infra-red reflective coating.
The thin coating system forms means to reflect and re-fract light to interfere with the observation of iride-scence. A particular advantage of the invention is the ability of the thin coating system to be coated in a fraction of the time presently required to coat anti-iridescent interlayers of the prior art.
This disclosure describes transparent glass window structures of the type bearing a coating of infra-red reflective material which is advantageously less than about 0.85 microns in thickness and wherein the obser-vance of iridescence resulting from such a reflective coating is markedly reduced by provision of a very thin coating system beneath said infra-red reflective coating.
The thin coating system forms means to reflect and re-fract light to interfere with the observation of iride-scence. A particular advantage of the invention is the ability of the thin coating system to be coated in a fraction of the time presently required to coat anti-iridescent interlayers of the prior art.
Description
~ 7~
TITLE
Mon-Iridescent C,lass C,tructures BACKGRO~ND OF TH~ INVENTI~N
This invention re:Lates to qlass structure.s bearing a thin, functional, inorganic coating (e.g. a coatina of tin oxide forming rneans to prornote reflectivity of infra-red light) which structures have improved an,r)ear-ance as a consecluence of reduced iridescence historically associated ~ith said thin coatinqs, and, also, to methods for achieving the aforesaid structures.
Glass and other transDarent materials can be coated with transparent semiconductor films such as tin oxide, indium oxide or cadmium stannate, in order to reflect infra-red radiation. Such materials are useful in pro-viding windows with enhanced insulating value (lower heat transport) in ovens, architectural windows, etc. Coat-in~s of these same materials also conduct electricity, and are emploved as resistance heaters to heat windows in vehicles in order to remove fog or ice.
~ne oblectionable feature of these coated windows is that ~hey show interference colors (iridescence) in re-flected light, and, to a lesser extent, in transmitted lighto This iridescence has heen a serious barrier to wides~read use of these coated windows (See, for example, American Institute of Ph~tsics Conference Proceedinq ~o.
25, New York, 1975, Paqe 28).
In some circumstances, i.e. when the qlass is quite dark in tone ~say, having a liqht transmittance of less than about 25~) this iridescence is muted and can be to-lerated. However, in most architectural wall and window ~ applications, the iridescent effect normally associated with coatings of less than about 0.75 microns is aesthe-tically unacceptable to many peoole (~ee, for exam~le, U~SO Patent 3,710,n74 to Stewart).
Iridescent colors are quite a yeneral phenorn~non in transparent Eilrns in the thickness range of about 0.1 to 1 micron especial]y at thicknesses helow about 0.~5 mi-crons. Unfortunately, it is precisely this range of thickness which is of practical importance in rnost corn-mercial applications. ~emiconductor coatinqs thinner than about 0.1 micron do not show interference colors, but such thin coatings have a markedly inferior reflec-tance of infra-red licht, and a markedly reduced capacity to conduct electricity.
Coatinas thicker than about 1 micron also do not show visible iridescence, in daylight illumination, hut such thick coatings are much more expensive to make, since larger amounts of coatinq materials are reauired, and the time necessary to deposit the coating is corre-spondingly lonqer. Furthermore, films thicker than 1 micron have a tendency to show haze, which arises frorn light scatterinq from surface irreaularities, which are larger on such films. Also, such films show a qreater tendency to crack, under thermal stress, because of dif-ferential thermal expansion.
As a result of these technical and economic con-straints, almost all present commercial production of such coated glass articles comprise films in the thick-ness ranqe of about 0.1 to 0.3 microns, which displav pronounced iridescent colors. A]most no architectural use of this coated glass is made at present, despite the fact that it would be cost-effective in conserving energv ~D ~ ~
~L ~ Y ~0 -to do so. I'or exclrrlE:~:Le, heat loss by infra--r-ed radiation through t'he glass areas Or a heated bullding can approx:i.rndte a'r,out onc~-half o:E -the heat loss through uncoate~cl w:i.ndows. 'J'rlfe ~:,r~-.serlcc Or iridescent co]o:rs on -t}l(-se coated gl.ass p:roducts :i.s a m.ljor rerl-on :[or the~ :fai~llre -to ernp]oy these coati.ngs.
'I:'he~ Eirst successfu:l. solution -to tnese prob1.errls is dl.sc]osed in United S-ta-tec; Patents 4,187,336 and 4,205,252. 'I'hese patents disclose methods and processes whereby th:in, usual.]y ]/4-wave]ength coatings of selec-ted refrac-tive index or gradient coat-i.nys of similar optical thickness were coated over -the glass sub-stra-te and beneath the infra-red reflective tin oxide. However, i-t became desirable to reduce the -to-tal. time necessary -to produce such coa-tings. The preserlt inven-tion arose out Or work directed to such reduction oE coating time.
SUMMARY OF 'I'HE INVENTION
It is one object of -the present invention to provide means to eliminate the visible iridescence from semiconducting thin film coatings on glass, while maintaining their desirable proper-ties of visible transparency, infra-red reflectivity, and electri-cal conductivity. These above goals can now be achieved withoutincreasing the cost of production significantly over -the cost of using ordinary iridescent, infra-red reflective films, and by a process which is continuous and fully compatible with modern manu-facturing processes in the glass industry.
The inven-tion provides a process fo:r making a non-iridescen-t, transparent, s-tructure of the type comprising a) a transpa-rent substra-te, b) an infra-red reflec-ti.ve coating thereon and c) an iridescence-suppressing i.nter:layer be-tween said substrate '773 and i.nfra-recl-re:flec-tive coati.ng, said process comprisi.ncJ the s-teps o.t :form:ing, be~tweell said intra-rec'~-rc-~rlec-tive~ coa t:i ng clnd said -transE)arerlt substrate, an in-te:r:Layer by ]) coat:inCJ n~;.arer to said substrate a firs-t interl,ayer component of re:l,ative:Ly h:i,gh reEractive inclex ma-terial; 2) coat:ing over sa:id relat:iv~-.,1y nigh refractive index material, a second in-terlayer component of rel,a--tively low re:trac-tive index material, and 3) terminating each of said -two inter:Layel- components at such a -thickness tha-t the com-bined in-terlayer components form said iridescence suppressing rneans and the to-tal optical thickness of said in-terlayer components is about l/6th o:f a 500 nanometer design wavelength.
The invention also provides in a non-iridescen-t, -trans-parent, sheet structure of the type comprising a) a transparent substrate, b) an infra-red reflective coating and c) an iridescence-suppressing in-terlayer means between said subs-tra-te and in:fra-red-reflective coa-ting, the improvement whereby said structure com-prises, between said infra-red-reflective coating anc'l said trans-parent substrate, an interlayer comprising 1) a firs-t in-terlayer component of relatively high refractive index material, nearer to said substrate; 2) over said relatively high refractive index material, a second interlayer component of relatively low refrac-tive index material, and 3) the combined interlayer components for said iridescence-suppressing means having a total optical thickness of abou-t l/6th of a 500 nanometer design wavelength.
The struc-ture provi.des p:roduc-ts which are durable and stable to light, chernicals and mechanical, abrasion while using rna-terials which are sufficien-tly abundant and readi.ly available to perrnit widespread use.
~1 ~1 ~t~
JLII~ ~J~ fr br ~3 ~P' The invention util.izes -thin f i l.ms -to suppress i,r;,df.?.;crer)t effec-ts without re~sor-t to Films or- light-abso:rpi-i~/e Inet-ll lic ma-terials such as gold, aluminuml copper, si,:lve:r and the ],iki-.
':L'he present inventi.on can prodllce t-,he :i.r:idescfent-frefe s-truc-turf-~s a-t a h.igher coat:i.ng .rate than was possih:Le with col,or suppression layers pre~iousl.y disc:losed :in United States Patent ~,187,336, using less raw material, since -thinner layers are used.
A wi,der choice o:E raw rnateriaLs can be used for forming -the required coatings by avoiding those systems which require l.0 selec-tion of reac-tants which are compa-tible in simul-taneous deposi-ti.on of mixed reaction products for providing adjustable or vari-able refractive index.
The invention can provide a glass structure comprising a compound wherein an outer coating is formed o-f an infra-red reflect-ing surface of about 0.7 microns or less and wherein an inner coat-ing forms means for (a) reducing haze on the coated glass and, simultaneously and independently (b) reducing the iridescence of the glass structure by means of coherent addition of reflected light.
The invention can provide a glass structure having the non-iridescen-t characteristics referred to above which structure is characterized by a s-tep-wise, or a graduated, change in coating composition between glass and air.
rL'he invention utilizes the formation of t~Jo or more very thin layers of transparent material between the glass and -the semi-conductor :ilm. This in-terlayer :is much -thinner -than those pre-viously di,sclosed to have iridescence-suppressi,ng utility. These layers form an i.ntermediate, i,ridescence--suppressing i.nterlayer.
-5a-With suitable choices of -thickness and re~fractjve index va:luec;, :it has been discc)vered, the iridescent colors can be maci( to-, f',l-i,nt Eor most human observers to detect, and certainly too Lairlt, to interf'ere with wi,despread commercial us.e even in archit,,ectural applications. Sui-table rnaterials for these interrnediate layers are also clisclosed hereirl, as well as processes for the forrnation of these layers.
Ln the embodiments of the invention disc]osed herein, the intermediate layer closer to the glass surface has a hiyher refractive index, while the intermediate layer fur-ther from the glass surface has a lower reErac-tive index. This order of refrac-tive index is the reverse of the order used in the color suppres-sion layers disclosed previously in United States Patent 4,187,336.
By reversing the order, I have made the surprising discovery that color suppression can be ach:ieved using -thinner layers than required by -the previous designs.
In one preferred embodiment of this invention, I use two intermediate layers, each of optical thickness ap-proximately one twelfth (1/12) of a visible wavelenqth of about 5000 ~nqstroms in vacuum. The first inter~ediate layer, the layer closer to the alass, has a hi~h re~rac-tive index of ahout the same value as the functiona:L
semiconcluctor coatin~ (say of tin oxirle). Indee-.l, this layer closest to the glass can be tin oxide. The next intermediate layer between that first intermediate layer and the functional, semiconductor coatinq, has a low refractive index about equal to that of glass (n=1.5).
The total optical thickness of the two intermediate lay-ers is thus about one sixth (1/6) of a visible wave-lengthc "Optical Thickness" is the thic~ness of the material mu].tiplied by its index of refraction.
The previously disclosed desians for co].or sup~res-sion re~uired a minimum of one quarter (1/~) of a visihle wavelenqth, and some re~uired one half (1/2) or more.
Thus the present design increases production speed by at least 50~, and decreases raw material usage hy at least 33~.
In another emhodiment of this invention, the refrac-tive index of the intermediate layer closer to the qlass is substantiallv higher than that of the functional semi-conductor coatin~. The total o~tical thickness of thetwo intermediate layers is then even less than about one sixth (1/6) of a visible wavelength.
In still another embodiment, the refractive index of the intermediate ].ayer closer to the functional coating is substantially lower than that of the alass. The total optical thickness of the two intermediate layers is also less than about one sixth (1/6) of a visible wavelen-~th~
By "substantially higher" an~ "su~,stantia11~ 1ower"
in the foregoing two paragraE~hs is meant a ~leyiation ~rom the refractive index of the semiconductor coatinq ~7hich makes it practical to vary the total real thickness of the coatin~ in response to the different re~racti~e in-dices. Thus, for example "suhstantially the sarne" re-fractive index can he taken as plus or minus 0~1 refrac-tive index unlts, while deviations from this norm ma~ be described as substantiallv lower or substantially hiqher.
"About 1/6 wavelenath" defined an irre~ular and varyin~ zone (best exemplified by ref~rence to Figure 2) which is substantially less than 1/4 wavelength in thick-ness. In practice, the actual thickness of the inter-layer coating will conveniently range fro~ ahout 30 to ~0 nanometers dependinq on the svstem used and the color index which is acceptable.
In a less preferred embodiment, the intermediate lavers are both intermediate in refractive index between those of -the glass and the functional coatinq. The total optical thickness in this case is still less than about one fourth (1/4) of a visible wavelength~
Approximate formulas for the optical thicknesses of the intermediate lavers are given bv the followina:
The optical thickness of the intermediate layer closer to the glass is approximately dl -- (l/720)cos 1 [(rl2-~ r22- r32)/2rlr2], in units of a visible waelength (0.5 microns), where the Fresnel reflection amplitudes are aiven by rl = (n1-nq)/(n1+ng) r2 = (n1-n2)/(n1-~n2) r3 = (nC-n2 )/ (nC'~n2 ) in terms of the refractive indices-ng = refractive in~ex oE the glass, n1 = refractive index of the intermediate layer closer to the qlass, n2 = refractive index of the intermediate layer closer to the functional semiconductor coatinq, and nc = refractive index of the functional semicon-ductor coating. These formulas assume the inverse cosine function is in deqrees.
The optical thickness of the intermediate layer closer to the functional semiconductor coating is given approximately by d2 = (1/720) cos 1[(r22-~ r32- rl2)/2r2r3].
The two layer thicknesses predicted by these simple formula.s are only approximate, since they neglect such effects as optical dispersion, surface roughness, multi-ple reflections, and the non-linear nature of color vi-sion. Numerical calculations can include these effects, and thus provide more realistic predictions of optimum coating thicknesses. The quantitative basis ror these numerical evaluations is disclosed in the next section, and some numerical results are given in the following section.
A unifying aspect of these various embo-liments is that they all utilize a thin semiconductor coatinq ar-ranged congruently with a second coating which for7r,s means to substantially diminish iridescence by providing at least two additional interfaces forming means, with the mass of the second coating, to reflect and refract light in such a way that it markedly interferes with the observation of any iridescent colors.
MET~ODS A~n ASS7JMPTION~
It is believed desirable, because of the subjective nature of color perception, to provide a discussion of the methods and assumptions which have been used to eval-uate the invention disclosed herein. It should be real-iæed that the application of much of the theory discussed below is retrospective in nature hecause the information necessarily is being provided in hindsight, i.e. by one having a knowledge of the invention disclosed herein.
In order to make a suitable quantitative evallJation of various possible constructions ~7hich suppress iride-scent colors, the intensities of such colors were calcu-lated using optical data and color perception data. In this discussion, film layers are assumed to be planar, with uniform thickness and uniform refractive index with-in each layer. The refractive index changes are taken to be abrupt at the planer interfaces between ad~acent film layers. Real refractive indices are used, corresponding to neg]igible ahsor~tion losses within the layers. The reflection coefficients are evaluated for normally inci-dent plane light waves.
Using the above assumptions, the amplitudes for reflection and transmission from each interface ar2 - l o -calculated from Fresnel's formulae~ Then these ampli-tudes are summed, taking into accoltnt the phase differen~
ces produced by propagation through the relevant lavers.
These results have been found to be equivalent to the Airy formulae (see, for example, Optics o Thin Films, by F. Knittl, ~iley and ~ons, New York, 1976) for multiple reflection and interference in thin films, when those formulae are a~plied to the same cases I considered.
The calculated i.ntensity of reflected li~ht has been observed to vary with ~avelength, and thu~ is enhance-3 in certain colors more than in others. To calculate the reflected color .seen by an observer, it is clesirahle first to specify the spectral distribution of the inci~
dent light. For this purpose, one mav use the Interna-ti.onal Commission on Illumination Standard Illumin~nt C,which approximates norma~ dayliaht illuminati.on. The spectral ~istribution of the reflected liaht is the pro-duct of the calculated reflection coefficient and the spectrum of Illuminant C. The color hue and color satu~
ration as seen in reflection by a human observer, are then calculated from this reflected spectrum, usina the uniform color scales such as those known to the art. One useful scale is that disclosed by Hunter in Food Techno-loqy, Vol. 21, ~ages 100-105, 1967. This scale has been used in derivin~ the relationship now to be disclosed.
The results of calculations, for each combination of refractive indices ~nd thickne.sses of the lavers, are a pair of numbers, i.e. "a" and "b". "a" represents red (if positive) or green (if negative) color hue, while "b"
describes a yellow (if positive) or blue (ir negative) hue. These color-hue results are useful in checking the calculations a~ainst the observable co]ors of .samples including those of the lnventlon. A single number, "c", represents the "color saturation": c=(a2 ~ b2)l/2 This color saturation index, "c", is clirectly relatec1 to the a~ility of the e~e to detect the trouble.some iride-scent color hues. When the saturation index is below a certain value, one ls not able to see any color ln the reflectecl li~ht. The numerical value of this threshold saturation for observahillty depends on the partlcular unlform color scale used, and on the viewing conditions and level of illumlnation (see, for example, R..~,. Hunter, The Measurement of Appearance, ~lley and Sons, New York, 1975, for a recent review of numerical color scales).
In order to establish a hasls for comparison of structures a first series of calculations was carried out to simulate a single semiconductor layer on glass. The refractive index of the semiconductor layer was taken as
TITLE
Mon-Iridescent C,lass C,tructures BACKGRO~ND OF TH~ INVENTI~N
This invention re:Lates to qlass structure.s bearing a thin, functional, inorganic coating (e.g. a coatina of tin oxide forming rneans to prornote reflectivity of infra-red light) which structures have improved an,r)ear-ance as a consecluence of reduced iridescence historically associated ~ith said thin coatinqs, and, also, to methods for achieving the aforesaid structures.
Glass and other transDarent materials can be coated with transparent semiconductor films such as tin oxide, indium oxide or cadmium stannate, in order to reflect infra-red radiation. Such materials are useful in pro-viding windows with enhanced insulating value (lower heat transport) in ovens, architectural windows, etc. Coat-in~s of these same materials also conduct electricity, and are emploved as resistance heaters to heat windows in vehicles in order to remove fog or ice.
~ne oblectionable feature of these coated windows is that ~hey show interference colors (iridescence) in re-flected light, and, to a lesser extent, in transmitted lighto This iridescence has heen a serious barrier to wides~read use of these coated windows (See, for example, American Institute of Ph~tsics Conference Proceedinq ~o.
25, New York, 1975, Paqe 28).
In some circumstances, i.e. when the qlass is quite dark in tone ~say, having a liqht transmittance of less than about 25~) this iridescence is muted and can be to-lerated. However, in most architectural wall and window ~ applications, the iridescent effect normally associated with coatings of less than about 0.75 microns is aesthe-tically unacceptable to many peoole (~ee, for exam~le, U~SO Patent 3,710,n74 to Stewart).
Iridescent colors are quite a yeneral phenorn~non in transparent Eilrns in the thickness range of about 0.1 to 1 micron especial]y at thicknesses helow about 0.~5 mi-crons. Unfortunately, it is precisely this range of thickness which is of practical importance in rnost corn-mercial applications. ~emiconductor coatinqs thinner than about 0.1 micron do not show interference colors, but such thin coatings have a markedly inferior reflec-tance of infra-red licht, and a markedly reduced capacity to conduct electricity.
Coatinas thicker than about 1 micron also do not show visible iridescence, in daylight illumination, hut such thick coatings are much more expensive to make, since larger amounts of coatinq materials are reauired, and the time necessary to deposit the coating is corre-spondingly lonqer. Furthermore, films thicker than 1 micron have a tendency to show haze, which arises frorn light scatterinq from surface irreaularities, which are larger on such films. Also, such films show a qreater tendency to crack, under thermal stress, because of dif-ferential thermal expansion.
As a result of these technical and economic con-straints, almost all present commercial production of such coated glass articles comprise films in the thick-ness ranqe of about 0.1 to 0.3 microns, which displav pronounced iridescent colors. A]most no architectural use of this coated glass is made at present, despite the fact that it would be cost-effective in conserving energv ~D ~ ~
~L ~ Y ~0 -to do so. I'or exclrrlE:~:Le, heat loss by infra--r-ed radiation through t'he glass areas Or a heated bullding can approx:i.rndte a'r,out onc~-half o:E -the heat loss through uncoate~cl w:i.ndows. 'J'rlfe ~:,r~-.serlcc Or iridescent co]o:rs on -t}l(-se coated gl.ass p:roducts :i.s a m.ljor rerl-on :[or the~ :fai~llre -to ernp]oy these coati.ngs.
'I:'he~ Eirst successfu:l. solution -to tnese prob1.errls is dl.sc]osed in United S-ta-tec; Patents 4,187,336 and 4,205,252. 'I'hese patents disclose methods and processes whereby th:in, usual.]y ]/4-wave]ength coatings of selec-ted refrac-tive index or gradient coat-i.nys of similar optical thickness were coated over -the glass sub-stra-te and beneath the infra-red reflective tin oxide. However, i-t became desirable to reduce the -to-tal. time necessary -to produce such coa-tings. The preserlt inven-tion arose out Or work directed to such reduction oE coating time.
SUMMARY OF 'I'HE INVENTION
It is one object of -the present invention to provide means to eliminate the visible iridescence from semiconducting thin film coatings on glass, while maintaining their desirable proper-ties of visible transparency, infra-red reflectivity, and electri-cal conductivity. These above goals can now be achieved withoutincreasing the cost of production significantly over -the cost of using ordinary iridescent, infra-red reflective films, and by a process which is continuous and fully compatible with modern manu-facturing processes in the glass industry.
The inven-tion provides a process fo:r making a non-iridescen-t, transparent, s-tructure of the type comprising a) a transpa-rent substra-te, b) an infra-red reflec-ti.ve coating thereon and c) an iridescence-suppressing i.nter:layer be-tween said substrate '773 and i.nfra-recl-re:flec-tive coati.ng, said process comprisi.ncJ the s-teps o.t :form:ing, be~tweell said intra-rec'~-rc-~rlec-tive~ coa t:i ng clnd said -transE)arerlt substrate, an in-te:r:Layer by ]) coat:inCJ n~;.arer to said substrate a firs-t interl,ayer component of re:l,ative:Ly h:i,gh reEractive inclex ma-terial; 2) coat:ing over sa:id relat:iv~-.,1y nigh refractive index material, a second in-terlayer component of rel,a--tively low re:trac-tive index material, and 3) terminating each of said -two inter:Layel- components at such a -thickness tha-t the com-bined in-terlayer components form said iridescence suppressing rneans and the to-tal optical thickness of said in-terlayer components is about l/6th o:f a 500 nanometer design wavelength.
The invention also provides in a non-iridescen-t, -trans-parent, sheet structure of the type comprising a) a transparent substrate, b) an infra-red reflective coating and c) an iridescence-suppressing in-terlayer means between said subs-tra-te and in:fra-red-reflective coa-ting, the improvement whereby said structure com-prises, between said infra-red-reflective coating anc'l said trans-parent substrate, an interlayer comprising 1) a firs-t in-terlayer component of relatively high refractive index material, nearer to said substrate; 2) over said relatively high refractive index material, a second interlayer component of relatively low refrac-tive index material, and 3) the combined interlayer components for said iridescence-suppressing means having a total optical thickness of abou-t l/6th of a 500 nanometer design wavelength.
The struc-ture provi.des p:roduc-ts which are durable and stable to light, chernicals and mechanical, abrasion while using rna-terials which are sufficien-tly abundant and readi.ly available to perrnit widespread use.
~1 ~1 ~t~
JLII~ ~J~ fr br ~3 ~P' The invention util.izes -thin f i l.ms -to suppress i,r;,df.?.;crer)t effec-ts without re~sor-t to Films or- light-abso:rpi-i~/e Inet-ll lic ma-terials such as gold, aluminuml copper, si,:lve:r and the ],iki-.
':L'he present inventi.on can prodllce t-,he :i.r:idescfent-frefe s-truc-turf-~s a-t a h.igher coat:i.ng .rate than was possih:Le with col,or suppression layers pre~iousl.y disc:losed :in United States Patent ~,187,336, using less raw material, since -thinner layers are used.
A wi,der choice o:E raw rnateriaLs can be used for forming -the required coatings by avoiding those systems which require l.0 selec-tion of reac-tants which are compa-tible in simul-taneous deposi-ti.on of mixed reaction products for providing adjustable or vari-able refractive index.
The invention can provide a glass structure comprising a compound wherein an outer coating is formed o-f an infra-red reflect-ing surface of about 0.7 microns or less and wherein an inner coat-ing forms means for (a) reducing haze on the coated glass and, simultaneously and independently (b) reducing the iridescence of the glass structure by means of coherent addition of reflected light.
The invention can provide a glass structure having the non-iridescen-t characteristics referred to above which structure is characterized by a s-tep-wise, or a graduated, change in coating composition between glass and air.
rL'he invention utilizes the formation of t~Jo or more very thin layers of transparent material between the glass and -the semi-conductor :ilm. This in-terlayer :is much -thinner -than those pre-viously di,sclosed to have iridescence-suppressi,ng utility. These layers form an i.ntermediate, i,ridescence--suppressing i.nterlayer.
-5a-With suitable choices of -thickness and re~fractjve index va:luec;, :it has been discc)vered, the iridescent colors can be maci( to-, f',l-i,nt Eor most human observers to detect, and certainly too Lairlt, to interf'ere with wi,despread commercial us.e even in archit,,ectural applications. Sui-table rnaterials for these interrnediate layers are also clisclosed hereirl, as well as processes for the forrnation of these layers.
Ln the embodiments of the invention disc]osed herein, the intermediate layer closer to the glass surface has a hiyher refractive index, while the intermediate layer fur-ther from the glass surface has a lower reErac-tive index. This order of refrac-tive index is the reverse of the order used in the color suppres-sion layers disclosed previously in United States Patent 4,187,336.
By reversing the order, I have made the surprising discovery that color suppression can be ach:ieved using -thinner layers than required by -the previous designs.
In one preferred embodiment of this invention, I use two intermediate layers, each of optical thickness ap-proximately one twelfth (1/12) of a visible wavelenqth of about 5000 ~nqstroms in vacuum. The first inter~ediate layer, the layer closer to the alass, has a hi~h re~rac-tive index of ahout the same value as the functiona:L
semiconcluctor coatin~ (say of tin oxirle). Indee-.l, this layer closest to the glass can be tin oxide. The next intermediate layer between that first intermediate layer and the functional, semiconductor coatinq, has a low refractive index about equal to that of glass (n=1.5).
The total optical thickness of the two intermediate lay-ers is thus about one sixth (1/6) of a visible wave-lengthc "Optical Thickness" is the thic~ness of the material mu].tiplied by its index of refraction.
The previously disclosed desians for co].or sup~res-sion re~uired a minimum of one quarter (1/~) of a visihle wavelenqth, and some re~uired one half (1/2) or more.
Thus the present design increases production speed by at least 50~, and decreases raw material usage hy at least 33~.
In another emhodiment of this invention, the refrac-tive index of the intermediate layer closer to the qlass is substantiallv higher than that of the functional semi-conductor coatin~. The total o~tical thickness of thetwo intermediate layers is then even less than about one sixth (1/6) of a visible wavelength.
In still another embodiment, the refractive index of the intermediate ].ayer closer to the functional coating is substantially lower than that of the alass. The total optical thickness of the two intermediate layers is also less than about one sixth (1/6) of a visible wavelen-~th~
By "substantially higher" an~ "su~,stantia11~ 1ower"
in the foregoing two paragraE~hs is meant a ~leyiation ~rom the refractive index of the semiconductor coatinq ~7hich makes it practical to vary the total real thickness of the coatin~ in response to the different re~racti~e in-dices. Thus, for example "suhstantially the sarne" re-fractive index can he taken as plus or minus 0~1 refrac-tive index unlts, while deviations from this norm ma~ be described as substantiallv lower or substantially hiqher.
"About 1/6 wavelenath" defined an irre~ular and varyin~ zone (best exemplified by ref~rence to Figure 2) which is substantially less than 1/4 wavelength in thick-ness. In practice, the actual thickness of the inter-layer coating will conveniently range fro~ ahout 30 to ~0 nanometers dependinq on the svstem used and the color index which is acceptable.
In a less preferred embodiment, the intermediate lavers are both intermediate in refractive index between those of -the glass and the functional coatinq. The total optical thickness in this case is still less than about one fourth (1/4) of a visible wavelength~
Approximate formulas for the optical thicknesses of the intermediate lavers are given bv the followina:
The optical thickness of the intermediate layer closer to the glass is approximately dl -- (l/720)cos 1 [(rl2-~ r22- r32)/2rlr2], in units of a visible waelength (0.5 microns), where the Fresnel reflection amplitudes are aiven by rl = (n1-nq)/(n1+ng) r2 = (n1-n2)/(n1-~n2) r3 = (nC-n2 )/ (nC'~n2 ) in terms of the refractive indices-ng = refractive in~ex oE the glass, n1 = refractive index of the intermediate layer closer to the qlass, n2 = refractive index of the intermediate layer closer to the functional semiconductor coatinq, and nc = refractive index of the functional semicon-ductor coating. These formulas assume the inverse cosine function is in deqrees.
The optical thickness of the intermediate layer closer to the functional semiconductor coating is given approximately by d2 = (1/720) cos 1[(r22-~ r32- rl2)/2r2r3].
The two layer thicknesses predicted by these simple formula.s are only approximate, since they neglect such effects as optical dispersion, surface roughness, multi-ple reflections, and the non-linear nature of color vi-sion. Numerical calculations can include these effects, and thus provide more realistic predictions of optimum coating thicknesses. The quantitative basis ror these numerical evaluations is disclosed in the next section, and some numerical results are given in the following section.
A unifying aspect of these various embo-liments is that they all utilize a thin semiconductor coatinq ar-ranged congruently with a second coating which for7r,s means to substantially diminish iridescence by providing at least two additional interfaces forming means, with the mass of the second coating, to reflect and refract light in such a way that it markedly interferes with the observation of any iridescent colors.
MET~ODS A~n ASS7JMPTION~
It is believed desirable, because of the subjective nature of color perception, to provide a discussion of the methods and assumptions which have been used to eval-uate the invention disclosed herein. It should be real-iæed that the application of much of the theory discussed below is retrospective in nature hecause the information necessarily is being provided in hindsight, i.e. by one having a knowledge of the invention disclosed herein.
In order to make a suitable quantitative evallJation of various possible constructions ~7hich suppress iride-scent colors, the intensities of such colors were calcu-lated using optical data and color perception data. In this discussion, film layers are assumed to be planar, with uniform thickness and uniform refractive index with-in each layer. The refractive index changes are taken to be abrupt at the planer interfaces between ad~acent film layers. Real refractive indices are used, corresponding to neg]igible ahsor~tion losses within the layers. The reflection coefficients are evaluated for normally inci-dent plane light waves.
Using the above assumptions, the amplitudes for reflection and transmission from each interface ar2 - l o -calculated from Fresnel's formulae~ Then these ampli-tudes are summed, taking into accoltnt the phase differen~
ces produced by propagation through the relevant lavers.
These results have been found to be equivalent to the Airy formulae (see, for example, Optics o Thin Films, by F. Knittl, ~iley and ~ons, New York, 1976) for multiple reflection and interference in thin films, when those formulae are a~plied to the same cases I considered.
The calculated i.ntensity of reflected li~ht has been observed to vary with ~avelength, and thu~ is enhance-3 in certain colors more than in others. To calculate the reflected color .seen by an observer, it is clesirahle first to specify the spectral distribution of the inci~
dent light. For this purpose, one mav use the Interna-ti.onal Commission on Illumination Standard Illumin~nt C,which approximates norma~ dayliaht illuminati.on. The spectral ~istribution of the reflected liaht is the pro-duct of the calculated reflection coefficient and the spectrum of Illuminant C. The color hue and color satu~
ration as seen in reflection by a human observer, are then calculated from this reflected spectrum, usina the uniform color scales such as those known to the art. One useful scale is that disclosed by Hunter in Food Techno-loqy, Vol. 21, ~ages 100-105, 1967. This scale has been used in derivin~ the relationship now to be disclosed.
The results of calculations, for each combination of refractive indices ~nd thickne.sses of the lavers, are a pair of numbers, i.e. "a" and "b". "a" represents red (if positive) or green (if negative) color hue, while "b"
describes a yellow (if positive) or blue (ir negative) hue. These color-hue results are useful in checking the calculations a~ainst the observable co]ors of .samples including those of the lnventlon. A single number, "c", represents the "color saturation": c=(a2 ~ b2)l/2 This color saturation index, "c", is clirectly relatec1 to the a~ility of the e~e to detect the trouble.some iride-scent color hues. When the saturation index is below a certain value, one ls not able to see any color ln the reflectecl li~ht. The numerical value of this threshold saturation for observahillty depends on the partlcular unlform color scale used, and on the viewing conditions and level of illumlnation (see, for example, R..~,. Hunter, The Measurement of Appearance, ~lley and Sons, New York, 1975, for a recent review of numerical color scales).
In order to establish a hasls for comparison of structures a first series of calculations was carried out to simulate a single semiconductor layer on glass. The refractive index of the semiconductor layer was taken as
2.0, which is a value apProximatina tin oxi~e or indium oxide films, either of which could be functional semicon-ductor films used in the present invention. The valuel.52 was used for the glass substrate; this is a value typical of commercial window glass. The calculated coloration saturation values are plotted in Figure l as a function of the semiconductor film thickness. The color saturation is found to be high for reflections from films in the thickness range O.l to 0.5 microns. For films thicker than 0.5 microns, the color saturation ~ecreases i with increasing thickness. These results are in accord with qualltative observations of actual films. The pro-nounced osclllations are due to the varying sensitivity of the e~e to different spectral wavelenqths. ~ach of the peaks corresponds to a particular color, a.s ~arked on the curve (R=red, Y=yellow, G=green, ~=hlue).
Using the.se results, the minimum observable value of color saturation was estahlished by the following experi-ment: Tin oxide films with continuously var~ing thick-ness, up to about 1.5 microns, were deposited on glass plates, by the oxidation of tetramethyltin vapor. The thickness profile was established by a temperature varia-tion ~Erom about 450C to 500C across the qlass surface.
The thi~kness profile was then measured by observinq the interference frinqes under monochromatic light. ~hen ob-served under diffuse daylight, the films showed interfer-ence colors at the correct positions shown in Figure 1.
The portions of the films with thicknesses qreater than 0.85 micron showed no observable interference colors in diffuse daylight. The qreen peak calculated to lie at a thickness of 0.88 micron could not he seen. Therefore, the threshold of observability is above 8 of these color units. Likewise, the calculated blue Peak at 0.03 micron - 20 could not be seen, so the threshold is above 11 colorunits, the calclllatd value for this peak. ~owever, a faint red peak at 0.81 micron could be seen under ~ood viewing conditions, e.g. using a black velvet background and no colored objects in the field of view beinq reElec-ted, so that threshold is below the 13 color units calcu-lated for this color. We conclude fro~ these studies that the threshold for observation of reElected color is between 11 and 13 color units on this scale, an~ there-fore we have adopted a value of 12 units to represent the threshold for observabillity of reflected color under daylight viewing conditions. In other words, a color ~ a~%~3 satt~ration of more than 12 units appears as a visih]~
colored iridescence, while a color sat~ration of less than 12 units is seen as a neutral.
It is believed that there will be little ob~ection to commercialization of products havinq color satura~ion values oE 13 or below. However, it is much preferred that the value be 12 or ~elow and, as will appear in more detail hereinaEter, there appears to be no practical reason why the most advantageous products according to the invention, e.g. those characterized hy wholly color-free surEaces, i.e. below about 8, cannot be made economically. Indeed, color saturation values below 5 can be obtained by practice of the invention.
A value of 12 or less is indicative of a reflection which does not distort the color of a reflected image in an observable way. This threshold value of 12 units is taken to he a quantitative standard with which one can evaluate the success or failure of various multilayer designs, in sllppressing the iridescence colors.
SUITABLE ~.ATERIALS
A wide ranqe of transparent materials can be selec-ted to make products meetinq the aforesaid criteria hy forming anti-iridescent undercoat layers. Various metal oxides and nitride~s, and their mixtures have the correct optical properties of transparency and refractive index.
Table A lists some materials which have high refractive indices suitable for forming the intermediate layer clo-ser to the glass. Table s lists some ~aterials which have low refractive indices suitable for forming the in-termediate layer closer to the functional semiconductorcoating. Film refractive indices vary somewhat with deposition method and conditions employed~
Table A
Coatin~ Materials with Hi~h Refractive Index Material Formula Refractive Index tin oxide SnO2 2.0 silicon nitride ~Ci3~4 2.0 silicon monoxide SiO ~bollt 2 zinc oxide ZnO 2.0 indium oxide In203 2.0 niobium oxide Nb25 2.1 tantalum oxide Ta25 2.1 hafnium oxide HfO2 2.1 zirconium oxide ZrO2 2.1 cerium oxide CeO2 2.2 zinc sulfide Zn~ 2.3 titanium oxide TiO2 2.5 ~2~
Table B
Coatinq Materials with Low Refractive Index Material Formula Refractive Index silicon dioxide SiO2 1.46 silicone polymer [(cH3)~si~n 1.4 magnesium flouri~e MgF2 1.38 cryolite Na3A1~6 1.33 Numerical Calculations of Color Suppression An example of the intensity of reflected cc,l.ors, as a function of total intermediate layer thickne.ss, and of functional tin oxide thickness, is shown in Figllre 2.
Total intermediate layer thickness is listed belo~ a point in Figure 2, and the functional tin oxide thickness is listed to the left of that Point. If the color satll-ration index is larger than 12, then white light, after reflection, takes on the color indicated by the letter code (R=red, Y=yellow, G=green, and R=blue). If the color saturation index is 12 or less, then the coated glass is colorless, in the sense that white light reflec-ted from the surface still appears white; no letter code appears in Figure 2 for these cornbinations of thicknes-ses, for which the iridescent color is successfully sup-pressed. The particular color chart in Figure 2 is cal-culated assuming that the intermediate layer closer to the glass has a refractive index of 2.0, and the interme-diate layer further from the glass has a refractive index of 1.45, and that the optical thickness of the two ].avers 0 remain in the ration 0.89:1.0 as the total intermediate layer thickness is varied over the figure. (A haze~
inhibiting layer of refractive index 1~45 is also assumed to be dePosited first on the glass, ~ith optical thick-ness of 0.14 relative to the total intermediate laYer.
However, this haze-inhibiting layer has only a small e-Efect on the color suppression desian, since its refrac-tive index is so close to that of the base glass. The thickness of this ha~e-inhibitinq layer is included in the total intermediate layer thickness in Figure 2).
~ ~ ~a2~
~,~
-l7-From this color chart in Fi~ure 2, one may conclude, for example, that a functional tin oxide coatina 0.2 mi-crons thick may be made colorless by the use of a total intermediate layer thickness anywhere between .034 and .055 microns. Similarly, for a functional tir~ o~i~3e coating 0.3 micron thick, effective intermediate la~ers~
range from .050 to .064 micron in thickness. For a 0.~, micron tin oxide thickness, the broader range of .034 to 0~
to ~8 microns in intermediate la~er thickness, produces `~ lO color suppression. Any intermediate layer beti~een .050 and .055 microns thick suppresses the color for all func-tional tin oxide thicknesses qreater than 0.14 microns.
PROCESS FOR FORMING FILMS
All of these films can be formed by simultaneous vacuum evaporation of the appropriate materials of an ap-propriate mixture. For coatina of large areas, such as window glass, chemical vanor deposition ~CVD) at normal atmospheric pressure is more convenient and less expen-sive. However, the CVD metho~ reauires suitable volatile compounds for forming each material. The most convenient sources for CVD are aases at room tem~erature. Silicon and ~ermanium can be deposited by CVD from ~ases such as silane, SiH4, dimethylsilane lCE13)2~iH2, and ger-mane (GeH4). Liquids which are sufficiently volatile at room temperature are almost as convenient as qases;
tetramethyltin is such a source for CVD of tin compounds, while (C2Els)2SiE12 and SiCl~ are volatile liauid sources for silicon. Similarly, trimethyl aluminum and dimetllyl zinc, and their higher alkyl homoloas, furnish volatile sources for these ~etals. Less convenient, but still useful, sources for CVD are solids or li~uids which 7~3 -18~
are volatile at some temperature above room temperature but still below the temperature at which they react to deposit films. Examples of this latter category are the acetylacetonates of aluminum, aallium, inclium and zinc (also called 2, ~ pentanedionates), aluminum alkoxides such as aluminum isopropoxide and aluminum ethyla~e, and zinc propionate. ~or magnesium, no convenient co~pounds are known which are volatile below deposition tempera ture, so CVD Processes are not believed to be a~plicahle to the preparation of magnesium flouride films.
Typical conditions under which metal oxide films have been successfully formed hy chemical vapor deposi-tion are summarized in Table C. Typically, the organome-tallic vaPor is present in about one percent (by volume) in air. The films thus formed show good adhesion to both the glass substrate, and to subsequently deposited layers of tin oxide or indium oxide. The refractive indices of the mi~od films are measured conveniently by taking the visible reflection s~ectra as a function of wavelength.
The positions and heiahts of the maxima and minima in the reflected intensity can then be related to the refractive index of the deposited film.
27~3 Table C
Some Volati].e Oxi~lizahle Orqanometallic Compounds ,Suitable for Depositinq Metal Oxi.de Lavers, and Mi~ed Metal Qxide Lavers with Oxidizing Gases Such as 2 or Volatization ~eposition Compound Tem~3erature (C) Temperature(C) 1 SiH4 gas at 20 300-500 2 (CH3)2SiH2 gas at 20 400-600
Using the.se results, the minimum observable value of color saturation was estahlished by the following experi-ment: Tin oxide films with continuously var~ing thick-ness, up to about 1.5 microns, were deposited on glass plates, by the oxidation of tetramethyltin vapor. The thickness profile was established by a temperature varia-tion ~Erom about 450C to 500C across the qlass surface.
The thi~kness profile was then measured by observinq the interference frinqes under monochromatic light. ~hen ob-served under diffuse daylight, the films showed interfer-ence colors at the correct positions shown in Figure 1.
The portions of the films with thicknesses qreater than 0.85 micron showed no observable interference colors in diffuse daylight. The qreen peak calculated to lie at a thickness of 0.88 micron could not he seen. Therefore, the threshold of observability is above 8 of these color units. Likewise, the calculated blue Peak at 0.03 micron - 20 could not be seen, so the threshold is above 11 colorunits, the calclllatd value for this peak. ~owever, a faint red peak at 0.81 micron could be seen under ~ood viewing conditions, e.g. using a black velvet background and no colored objects in the field of view beinq reElec-ted, so that threshold is below the 13 color units calcu-lated for this color. We conclude fro~ these studies that the threshold for observation of reElected color is between 11 and 13 color units on this scale, an~ there-fore we have adopted a value of 12 units to represent the threshold for observabillity of reflected color under daylight viewing conditions. In other words, a color ~ a~%~3 satt~ration of more than 12 units appears as a visih]~
colored iridescence, while a color sat~ration of less than 12 units is seen as a neutral.
It is believed that there will be little ob~ection to commercialization of products havinq color satura~ion values oE 13 or below. However, it is much preferred that the value be 12 or ~elow and, as will appear in more detail hereinaEter, there appears to be no practical reason why the most advantageous products according to the invention, e.g. those characterized hy wholly color-free surEaces, i.e. below about 8, cannot be made economically. Indeed, color saturation values below 5 can be obtained by practice of the invention.
A value of 12 or less is indicative of a reflection which does not distort the color of a reflected image in an observable way. This threshold value of 12 units is taken to he a quantitative standard with which one can evaluate the success or failure of various multilayer designs, in sllppressing the iridescence colors.
SUITABLE ~.ATERIALS
A wide ranqe of transparent materials can be selec-ted to make products meetinq the aforesaid criteria hy forming anti-iridescent undercoat layers. Various metal oxides and nitride~s, and their mixtures have the correct optical properties of transparency and refractive index.
Table A lists some materials which have high refractive indices suitable for forming the intermediate layer clo-ser to the glass. Table s lists some ~aterials which have low refractive indices suitable for forming the in-termediate layer closer to the functional semiconductorcoating. Film refractive indices vary somewhat with deposition method and conditions employed~
Table A
Coatin~ Materials with Hi~h Refractive Index Material Formula Refractive Index tin oxide SnO2 2.0 silicon nitride ~Ci3~4 2.0 silicon monoxide SiO ~bollt 2 zinc oxide ZnO 2.0 indium oxide In203 2.0 niobium oxide Nb25 2.1 tantalum oxide Ta25 2.1 hafnium oxide HfO2 2.1 zirconium oxide ZrO2 2.1 cerium oxide CeO2 2.2 zinc sulfide Zn~ 2.3 titanium oxide TiO2 2.5 ~2~
Table B
Coatinq Materials with Low Refractive Index Material Formula Refractive Index silicon dioxide SiO2 1.46 silicone polymer [(cH3)~si~n 1.4 magnesium flouri~e MgF2 1.38 cryolite Na3A1~6 1.33 Numerical Calculations of Color Suppression An example of the intensity of reflected cc,l.ors, as a function of total intermediate layer thickne.ss, and of functional tin oxide thickness, is shown in Figllre 2.
Total intermediate layer thickness is listed belo~ a point in Figure 2, and the functional tin oxide thickness is listed to the left of that Point. If the color satll-ration index is larger than 12, then white light, after reflection, takes on the color indicated by the letter code (R=red, Y=yellow, G=green, and R=blue). If the color saturation index is 12 or less, then the coated glass is colorless, in the sense that white light reflec-ted from the surface still appears white; no letter code appears in Figure 2 for these cornbinations of thicknes-ses, for which the iridescent color is successfully sup-pressed. The particular color chart in Figure 2 is cal-culated assuming that the intermediate layer closer to the glass has a refractive index of 2.0, and the interme-diate layer further from the glass has a refractive index of 1.45, and that the optical thickness of the two ].avers 0 remain in the ration 0.89:1.0 as the total intermediate layer thickness is varied over the figure. (A haze~
inhibiting layer of refractive index 1~45 is also assumed to be dePosited first on the glass, ~ith optical thick-ness of 0.14 relative to the total intermediate laYer.
However, this haze-inhibiting layer has only a small e-Efect on the color suppression desian, since its refrac-tive index is so close to that of the base glass. The thickness of this ha~e-inhibitinq layer is included in the total intermediate layer thickness in Figure 2).
~ ~ ~a2~
~,~
-l7-From this color chart in Fi~ure 2, one may conclude, for example, that a functional tin oxide coatina 0.2 mi-crons thick may be made colorless by the use of a total intermediate layer thickness anywhere between .034 and .055 microns. Similarly, for a functional tir~ o~i~3e coating 0.3 micron thick, effective intermediate la~ers~
range from .050 to .064 micron in thickness. For a 0.~, micron tin oxide thickness, the broader range of .034 to 0~
to ~8 microns in intermediate la~er thickness, produces `~ lO color suppression. Any intermediate layer beti~een .050 and .055 microns thick suppresses the color for all func-tional tin oxide thicknesses qreater than 0.14 microns.
PROCESS FOR FORMING FILMS
All of these films can be formed by simultaneous vacuum evaporation of the appropriate materials of an ap-propriate mixture. For coatina of large areas, such as window glass, chemical vanor deposition ~CVD) at normal atmospheric pressure is more convenient and less expen-sive. However, the CVD metho~ reauires suitable volatile compounds for forming each material. The most convenient sources for CVD are aases at room tem~erature. Silicon and ~ermanium can be deposited by CVD from ~ases such as silane, SiH4, dimethylsilane lCE13)2~iH2, and ger-mane (GeH4). Liquids which are sufficiently volatile at room temperature are almost as convenient as qases;
tetramethyltin is such a source for CVD of tin compounds, while (C2Els)2SiE12 and SiCl~ are volatile liauid sources for silicon. Similarly, trimethyl aluminum and dimetllyl zinc, and their higher alkyl homoloas, furnish volatile sources for these ~etals. Less convenient, but still useful, sources for CVD are solids or li~uids which 7~3 -18~
are volatile at some temperature above room temperature but still below the temperature at which they react to deposit films. Examples of this latter category are the acetylacetonates of aluminum, aallium, inclium and zinc (also called 2, ~ pentanedionates), aluminum alkoxides such as aluminum isopropoxide and aluminum ethyla~e, and zinc propionate. ~or magnesium, no convenient co~pounds are known which are volatile below deposition tempera ture, so CVD Processes are not believed to be a~plicahle to the preparation of magnesium flouride films.
Typical conditions under which metal oxide films have been successfully formed hy chemical vapor deposi-tion are summarized in Table C. Typically, the organome-tallic vaPor is present in about one percent (by volume) in air. The films thus formed show good adhesion to both the glass substrate, and to subsequently deposited layers of tin oxide or indium oxide. The refractive indices of the mi~od films are measured conveniently by taking the visible reflection s~ectra as a function of wavelength.
The positions and heiahts of the maxima and minima in the reflected intensity can then be related to the refractive index of the deposited film.
27~3 Table C
Some Volati].e Oxi~lizahle Orqanometallic Compounds ,Suitable for Depositinq Metal Oxi.de Lavers, and Mi~ed Metal Qxide Lavers with Oxidizing Gases Such as 2 or Volatization ~eposition Compound Tem~3erature (C) Temperature(C) 1 SiH4 gas at 20 300-500 2 (CH3)2SiH2 gas at 20 400-600
3 (C2H5)2SiH2 20 400-600
4 (CH3)2SiHSiH(CH3)2 20 400-600 GeH4 gas at 20 300-450 6 (C 3)3 20 400-650 7 Al(OC2H5)3 200-300 400-650 8 Al(OC3H7)3 200-220 400-600 9 Al(C5H7O2)3 200-220 500-650 10 Ga(C5H7O2)3 200-220 350-650 11 In(C5H7O2)3 200-220 300-600 12 (C 3)2Zn 20 100-600 13 Zn(C3H5O2)2 200-250 450-650 14 (C 3)4 20 450-650 ( 4 9)5 150-250 400-600 16 Ti(OC3H7)4 100-150 400-600 17 Zr(OC4Hg)4 200-250 400-600 18 Hf(OC4H9)4 200-250 400-600 t7~73 Thc techniques of coa-ting of hot glass with this inorganic coati11g are disclosed ;n lJ.S. Patents ~,187,336 and ~,265,97~, a1ld elxewhere in the prior art. Ihe coatings applied by tne processes disclosed hereiil can be apl)Lied using the same procedures except for the necessity of controlling the coating times to achieve the rela-tiveLy thin coatings used hereiJ1.
TIIE LIAZE PROBLEM
When these same depositions were -tried on ordinary window glass ("soda-lime" or "soft" glass) many of the resulting coatings showed considerable haze or scattered light. When the layer first de-posited on soft glass is amorphous and consists of SiO2, Si3N~, or GeO2 or mixtures thereof, the coating is free of haze, no matter what the subsequent layers are. Al2O3 also gives clear coatings, provided it is deposited in the amorphous form, advantageously below a tempera-ture of about 550 C. If the initial layer contains large proportions of Ga2O3, ZnO, In2O3, or SnO2, then haze formulation is likely.
The first anti-iridescence layer to be deposited OTI a window glass surface is advantageously amorphous, ratl1er than crystalline, in structure. Subsequently, deposited layers can be of a polycrystal-line form, without causing any haze.
ILLUSTRATIVE EXAMPLES OF TLIE INVENTION
In this application and accompanying drawings there is shown and described a preferred embodiment of the invention and suggested various alternatives and modifications thereof, but it is to be under-stood that these are not intended to be exhaustive and that other changes and modifications can be made within the scope of the inven-tion. These s~ggestions herein are selected and included for purposes of illustration in order that others skilled in the art will more fully understand the invention and the principles thereof and will be able to modify it and embody it in a variety of forms, each as may be best suited in the condition of a particular case.
With the very thin coatinqs of the invention, it is difficult to achieve precise planar cutoffs of the vari-ous interlayer components. Consequently, in many embodi-ments of the invention, the resulting coating is much like a step-wise or qradient coating with the higher-refractive-index concentration being nearer the glass.
For the purposes of this invention therefore such gradi-ent and stepwise interlayer systems, the reverse (with respect to refractive index qradient) of those tauqht in the prior art ~.~. Patents 4,1~7,336 and 4,205,252 to Gordon, may be considered mechanical and optical equiva-lents of the two-interlayer-component systems describe~
hereln.
The silica-silicone terminology in the following examples is used to describe some thin lavers only he-cause analysis by ESCA (electron-scattering for chemical analysis) techni~ues and Auqer analytical techniques show the presence of carbon in the coating. This suggests that some of the silicon-carbon bonds believed to be present during the coating process remain in the coatina.
Rowever, the presence of the carbon is not to be believed to be functionally important. A silica coating of the proper refractive index and thickness is the optical and ~2~
mechanical equivalent of those coatings describe-l herein as silica~silicone coatings.
It also should be noted that the flourine-hearing gas used in the Eormation of the tin-oxide inter:layer coating is not utilized for the purpose of imparting electrical conductivity to that coating because that function is not usually required for the principal archi-tectural use for which the procluct is intended. ~Jever~
theless, it has ~een found that the rate of deposition of the tin oxide is substantially greater when the Freon-type gas is used~
IN THE DRAWINC.S
Figure 1 is a graph illustrating the variation of calculated color intensity of various colors with semi-conductor film thickne.ss.
Figure 2 illustrates graphically the iridescent character, or lack thereof, for various coating thickness of tin oxide (as an intermediate layer nearer the glass) in a system such as described in ~xample 2.
Figure 3 illustrates a window 36 constructed of a semiconductor film 2fi, glass 22 and two intermediate coatings as follows: Coating 30 which is 0.018 microns thick and has a high refractive index of about 2Ø
Coating 32 is about 0.028 microns and has a low refrac-tive index of about 1.45. Coatinq 30 is formed of any of the materials disclosed in Tahle A. Coating 32 is formed of any of the materials disclosed in Table B.
~2~
Example 1 By heating pyrex glass (refractive index about ].47 to about fiOOC, and passing reactant gas mixtures over it, the glass was coated with the followi~y la~ers:
a) A layer of tin oxide about 18 nanometers thick was deposited usinq a ~ixture containing 1.~ tetrame-thyltin, 3.0~ bromotriEluoromet:hane and halance dr~ air, for about one second.
b) Then about 2~ nanometer of a silica-silicone mixture layer (refractive index about 1.45) was deposite-l using a gas mixture containinq 0.~ tetramethyldisilane and balance dry air, for about five seconds.
c) Finally a fluorine-doped tin oxide layer abo~t 200 nanometers thick was deposited usin~ the same gas mixture as in deposition a), but with an exposure time of about 10 seconds.
The sample thus prepared has a suhstantially color-less appearance in reflected and in transmitted li~ht.
Example 2 The process of example 1 is carried out on a sample of soda-lime float glass, with the additional step of first coating the glass with a thin layer (about lO nano-meters thick) of a silica-tetramethyldisilane in air, for about one second. ~esults similar to Example 1 are ob-tained. When this first protective layer is omitted, soda-lime glass samples coated according to Example l have a hazy appearance.
Figure 2 further indicates how variations in tin oxide thickness will affect the optical performance of the interlayer. The type of profile as shown in Figure 2 is typical of interlayer systems of the present inven-tion.
27'7~3 Examples 3 ancl 4 Titanium dioxide (refractive index about 2.5) is used in place of the intermediate tin oxide coating in Examp]es 1 and 2. ~eposition a) is replaced b~/ the fo]lowing:
a) a layer of titanium dioxide ahout 8 nanometers thlck is deposited from a gas rnixture containinq 0.2%
titanium isopropoxide vapor in dry nitrogen carrier ~as, for five seconds.
Results for Examples 3 and 4 eauivalent to Example.s 1 and 2, respectively, were obtained.
Example 5 Silicon nitride (refractive index about 2.0) is used in place of the intermediate tin oxide coating in Example 1. Deposition a) is replaced by the following:
a) a layer of silicon nitride about 18 nanometers thick is deposited from a aas mixture containing 0.2%
silane, 1.5~ hydrazine, and halance nitro~en, for about twenty seconds.
This procedure is re~eated usinq soda-lime ~lass; a haze-free appearance is obtained even wlthout a silica-silicone protective layer.
It is also to be understood that the following claims are intended to cover all of the generic and spe-cific features of the invention herein described and all statements of the scope of the invention which might be said to fall therebetween.
TIIE LIAZE PROBLEM
When these same depositions were -tried on ordinary window glass ("soda-lime" or "soft" glass) many of the resulting coatings showed considerable haze or scattered light. When the layer first de-posited on soft glass is amorphous and consists of SiO2, Si3N~, or GeO2 or mixtures thereof, the coating is free of haze, no matter what the subsequent layers are. Al2O3 also gives clear coatings, provided it is deposited in the amorphous form, advantageously below a tempera-ture of about 550 C. If the initial layer contains large proportions of Ga2O3, ZnO, In2O3, or SnO2, then haze formulation is likely.
The first anti-iridescence layer to be deposited OTI a window glass surface is advantageously amorphous, ratl1er than crystalline, in structure. Subsequently, deposited layers can be of a polycrystal-line form, without causing any haze.
ILLUSTRATIVE EXAMPLES OF TLIE INVENTION
In this application and accompanying drawings there is shown and described a preferred embodiment of the invention and suggested various alternatives and modifications thereof, but it is to be under-stood that these are not intended to be exhaustive and that other changes and modifications can be made within the scope of the inven-tion. These s~ggestions herein are selected and included for purposes of illustration in order that others skilled in the art will more fully understand the invention and the principles thereof and will be able to modify it and embody it in a variety of forms, each as may be best suited in the condition of a particular case.
With the very thin coatinqs of the invention, it is difficult to achieve precise planar cutoffs of the vari-ous interlayer components. Consequently, in many embodi-ments of the invention, the resulting coating is much like a step-wise or qradient coating with the higher-refractive-index concentration being nearer the glass.
For the purposes of this invention therefore such gradi-ent and stepwise interlayer systems, the reverse (with respect to refractive index qradient) of those tauqht in the prior art ~.~. Patents 4,1~7,336 and 4,205,252 to Gordon, may be considered mechanical and optical equiva-lents of the two-interlayer-component systems describe~
hereln.
The silica-silicone terminology in the following examples is used to describe some thin lavers only he-cause analysis by ESCA (electron-scattering for chemical analysis) techni~ues and Auqer analytical techniques show the presence of carbon in the coating. This suggests that some of the silicon-carbon bonds believed to be present during the coating process remain in the coatina.
Rowever, the presence of the carbon is not to be believed to be functionally important. A silica coating of the proper refractive index and thickness is the optical and ~2~
mechanical equivalent of those coatings describe-l herein as silica~silicone coatings.
It also should be noted that the flourine-hearing gas used in the Eormation of the tin-oxide inter:layer coating is not utilized for the purpose of imparting electrical conductivity to that coating because that function is not usually required for the principal archi-tectural use for which the procluct is intended. ~Jever~
theless, it has ~een found that the rate of deposition of the tin oxide is substantially greater when the Freon-type gas is used~
IN THE DRAWINC.S
Figure 1 is a graph illustrating the variation of calculated color intensity of various colors with semi-conductor film thickne.ss.
Figure 2 illustrates graphically the iridescent character, or lack thereof, for various coating thickness of tin oxide (as an intermediate layer nearer the glass) in a system such as described in ~xample 2.
Figure 3 illustrates a window 36 constructed of a semiconductor film 2fi, glass 22 and two intermediate coatings as follows: Coating 30 which is 0.018 microns thick and has a high refractive index of about 2Ø
Coating 32 is about 0.028 microns and has a low refrac-tive index of about 1.45. Coatinq 30 is formed of any of the materials disclosed in Tahle A. Coating 32 is formed of any of the materials disclosed in Table B.
~2~
Example 1 By heating pyrex glass (refractive index about ].47 to about fiOOC, and passing reactant gas mixtures over it, the glass was coated with the followi~y la~ers:
a) A layer of tin oxide about 18 nanometers thick was deposited usinq a ~ixture containing 1.~ tetrame-thyltin, 3.0~ bromotriEluoromet:hane and halance dr~ air, for about one second.
b) Then about 2~ nanometer of a silica-silicone mixture layer (refractive index about 1.45) was deposite-l using a gas mixture containinq 0.~ tetramethyldisilane and balance dry air, for about five seconds.
c) Finally a fluorine-doped tin oxide layer abo~t 200 nanometers thick was deposited usin~ the same gas mixture as in deposition a), but with an exposure time of about 10 seconds.
The sample thus prepared has a suhstantially color-less appearance in reflected and in transmitted li~ht.
Example 2 The process of example 1 is carried out on a sample of soda-lime float glass, with the additional step of first coating the glass with a thin layer (about lO nano-meters thick) of a silica-tetramethyldisilane in air, for about one second. ~esults similar to Example 1 are ob-tained. When this first protective layer is omitted, soda-lime glass samples coated according to Example l have a hazy appearance.
Figure 2 further indicates how variations in tin oxide thickness will affect the optical performance of the interlayer. The type of profile as shown in Figure 2 is typical of interlayer systems of the present inven-tion.
27'7~3 Examples 3 ancl 4 Titanium dioxide (refractive index about 2.5) is used in place of the intermediate tin oxide coating in Examp]es 1 and 2. ~eposition a) is replaced b~/ the fo]lowing:
a) a layer of titanium dioxide ahout 8 nanometers thlck is deposited from a gas rnixture containinq 0.2%
titanium isopropoxide vapor in dry nitrogen carrier ~as, for five seconds.
Results for Examples 3 and 4 eauivalent to Example.s 1 and 2, respectively, were obtained.
Example 5 Silicon nitride (refractive index about 2.0) is used in place of the intermediate tin oxide coating in Example 1. Deposition a) is replaced by the following:
a) a layer of silicon nitride about 18 nanometers thick is deposited from a aas mixture containing 0.2%
silane, 1.5~ hydrazine, and halance nitro~en, for about twenty seconds.
This procedure is re~eated usinq soda-lime ~lass; a haze-free appearance is obtained even wlthout a silica-silicone protective layer.
It is also to be understood that the following claims are intended to cover all of the generic and spe-cific features of the invention herein described and all statements of the scope of the invention which might be said to fall therebetween.
Claims (33)
1) A process for making a non-iridescent, transparent, structure of the type comprising a) a transparent substrate, b) an infra-red reflective coating thereon and c) an iridescence-suppressing interlayer between said substrate and infra-red-reflective coating, said process comprising the steps of forming, between said infra-red-reflective coating and said transparent substrate, an interlayer by
1) coating nearer to said substrate a first interlayer component of relative-ly high refractive index material;
2) coating over said relatively high refractive index material, a second interlayer component of relatively low refractive index material, and 3) terminating each of said two interlayer componentS
at such a thickness that the combined interlayer components form said iride-scence suppressing means and the total optical thickness of said interlayer components is about 1/6th of a 500 nanometer design wavelength.
2) coating over said relatively high refractive index material, a second interlayer component of relatively low refractive index material, and 3) terminating each of said two interlayer componentS
at such a thickness that the combined interlayer components form said iride-scence suppressing means and the total optical thickness of said interlayer components is about 1/6th of a 500 nanometer design wavelength.
2) A process as defined in claim 1 wherein said infra-red-reflective coating and said first interlayer components are of about the same refractive index.
3) A process as defined in claim 2 wherein said infra-red reflective coating and said first interlayer component are both tin oxide based coat-ings.
4) A process as defined in claim 1 wherein said first interlayer component is of a refractive index substantially higher than the refractive index of the infra-red reflective coating.
5) A process as defined in claim 1 wherein said first interlayer component is of a refractive index substantially lower than the refractive index of the infra-red reflective coating.
6) A process as defined in claim 1 wherein said interlayer components are of refractive indices intermediate between the refractive index of the substrate and the infra-red reflective coating.
7) A process as defined in claim 1 wherein said optical thickness d1 of said interlayer com-ponent closer to the substrate is about (1/720) cos-1 [(r12 + r22 - r32)/2r1r2], wherein said optical thickness d2 of said inter-layer component closer to the infra-red reflective layer is about (1/720) cos 1[(r22+ r32- r12)/2r2r3]
for a design wavelength of 500 nanometers and where-in r1 = (n1-ng)/(n1+ng) r2 = (n1-n2)/(n1+n2) r3 = (nc-n2)/(nc+n2) and wherein ng = refractive index of the substrate n1 = refractive index of the interlayer component closer to the substrate n2 = refractive index of the interlayer component closer to the functional semiconductor coat-ing, and nc = refractive index of the infra-red reflective coating.
for a design wavelength of 500 nanometers and where-in r1 = (n1-ng)/(n1+ng) r2 = (n1-n2)/(n1+n2) r3 = (nc-n2)/(nc+n2) and wherein ng = refractive index of the substrate n1 = refractive index of the interlayer component closer to the substrate n2 = refractive index of the interlayer component closer to the functional semiconductor coat-ing, and nc = refractive index of the infra-red reflective coating.
8) A process as defined in any of Claims 1 or 3 wherein said refractive indices and optical thicknesses of said substrate, said interlayer components and said infra-red-reflective coating are selected to provide a color saturation value below about 12.
9) A process as defined in any of Claims 1 or 3 wherein said refractive indices and optical thicknesses of said substrate said inter-layer components and said infra-red reflective coat-ing are selected to provide a color saturation value below about 8.
10) In a non-iridescent, transparent, sheet structure of the type comprising a) a transparent substrate, b) an infra-red reflective coating and c) an iridescence-suppressing interlayer means between said substrate and infra-red-reflective coating, the improvement whereby said structure comprises, between said infra-red-reflective coating and said transparent substrate, an interlayer com-prising 1) a first interlayer component of relatively high refractive index material, nearer to said substrate;
2) over said relatively high refractive index material, a second interlayer component of relatively low refractive index material, and 3) the combined interlayer components for said iridescence-suppressing means having a total optical thickness of about 1/6th of a 500 nanometer design wavelength.
2) over said relatively high refractive index material, a second interlayer component of relatively low refractive index material, and 3) the combined interlayer components for said iridescence-suppressing means having a total optical thickness of about 1/6th of a 500 nanometer design wavelength.
11) A structure as defined in claim 10 wherein said infra-red-reflective coating and said first interlayer components are of about the same refractive index.
12) A structure as defined in claim 11 wherein said infra-red-reflective coating and said first interlayer component are both tin-oxide based coat-ings.
13) A structure as defined in claim 10 wherein said first interlayer component is of a refractive index substantially higher than the refractive index of the infra-red-reflective coating.
14) A structure as defined in claim 10 wherein said first interlayer component is of a refractive index substantially lower than the refractive index of the infra-red-reflective coating.
15) A structure as defined in claim 10 wherein said interlayer components are of refractive indices intermediate between the refractive index of the substrate and the infra-red-reflective coating.
16) A structure as defined in claim 10 wherein said optical thickness d1 of said interlayer com-ponent closer to the substrate is about (1/720) cos-1[(r12+ r22- r32)/2r1,r2]
wherein said optical thickness d1 of said inter-layer closer to the infra-red-reflective layer is about (1/720) cos-1 [(r22+ r33- r12)/2r2r3]
for a design wavelength of 500 nanometers and where-in r1 = (n1-ng)/(n1+ng) r2 = (n1-n2)/(n1+n2) r3 = (nc-n2)/(nc+n2) and wherein ng = refractive index of the substrate n1 = refractive index of the interlayer closer to the substrate n2 = refractive index of the interlayer closer to the functional semiconductor coating, and nc = refractive index of the infra-red reflective coating.
wherein said optical thickness d1 of said inter-layer closer to the infra-red-reflective layer is about (1/720) cos-1 [(r22+ r33- r12)/2r2r3]
for a design wavelength of 500 nanometers and where-in r1 = (n1-ng)/(n1+ng) r2 = (n1-n2)/(n1+n2) r3 = (nc-n2)/(nc+n2) and wherein ng = refractive index of the substrate n1 = refractive index of the interlayer closer to the substrate n2 = refractive index of the interlayer closer to the functional semiconductor coating, and nc = refractive index of the infra-red reflective coating.
17) A structure as defined in any of Claims 10, 11, or 12 wherein said refractive indices and optical thicknesses of said substrate, said interlayer components and said infra-red-reflective coating are selected to provide a color saturation value below about 12.
18) A structure as defined in any of Claims 10, 11, or 12, wherein said refractive indices and optical thicknesses of said substrate, said interlayer components and said infra-red-reflective coating are selected to provide a color saturation value below about 8.
19) A structure as defined in Claims 10, 11 or 12 which is free from any metallic component or colored component which func-tions primarily to absorb visible light
20) In a process as defined in Claim 1 wherein a said inter-layer is formed by a process including the step of depositing a tin oxide-bearing composition, said process including the step of adding a quantity of fluorine-bearing gas to a coating mixture containing an organotin and oxygen as a means to increase the deposition rate of tin oxide.
21) A process as defined in Claim 20 wherein said fluorinated gas is a bromofluoro methane compound.
22) The process of Claim 1 wherein said infrared reflective coating is electrically conductive.
23) The structure as defined in Claim 10 wherein said infra-red reflective coating is electrically conductive.
24. A process as defined in any of Claims 4, 5 or 6 wherein said refractive indices and optical thicknesses of said substrate, said interlayer components and said infra-red-reflective coating are selected to provide a color saturation value below about 12.
25. A process as defined in any of Claims 4, 5 or 6 wherein said refractive indices and optical thicknesses of said substrate, said interlayer components and said infra-red-reflective coating are selected to provide a color saturation value below about 8.
26. A process as defined in Claim 7 wherein said refractive indices and optical thicknesses of said substrate, said interlayer components and said infra-red-reflective coating are selected to provide a color saturation value below about 12.
27. A process as defined in Claim 7 wherein said refractive indices and optical thicknesses of said substrate, said interlayer components and said infra-red-reflective coating are selected to provide a color saturation value below about 8.
28. A structure as defined in any of Claims 13, 14 or 15 wherein said refractive indices and optical thicknesses of said substrate, said interlayer components and said infra-red-reflective coating are selected to provide a color saturation value below about 12.
29. A structure as defined in any of Claims 13, 14 or 15 wherein said refractive indices and optical thicknesses of said substrate, said interlayer components and said infra-red-reflective coating are selected to provide a color saturation value below about 8.
30. A structure as defined in Claim 16 wherein said refractive indices and optical thicknesses of said substrate, said interlayer components and said infra-red-reflective coating are selected to provide a color saturation value below about 12.
31. A structure as defined in Claim 16 wherein said refractive indices and optical thicknesses of said substrate, said interlayer components and said infra-red-reflective coating are selected to provide a color saturation value below about 8.
32. A structure as defined in Claim 13, 14 or 15 which is free from any metallic component or colored component which functions primarily to absorb visible light.
33. A structure as defined in Claim 16 which is free from any metallic component or colored component which functions pri-marily to absorb visible light.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/302,216 US4377613A (en) | 1981-09-14 | 1981-09-14 | Non-iridescent glass structures |
US06/302,216 | 1981-09-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1192773A true CA1192773A (en) | 1985-09-03 |
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ID=23166797
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000411270A Expired CA1192773A (en) | 1981-09-14 | 1982-09-13 | Non-iridescent glass structures |
Country Status (20)
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US (1) | US4377613A (en) |
JP (1) | JPS58501466A (en) |
AR (1) | AR228680A1 (en) |
AU (1) | AU560433B2 (en) |
BE (1) | BE894383A (en) |
BR (1) | BR8207855A (en) |
CA (1) | CA1192773A (en) |
CH (1) | CH656116A5 (en) |
DE (1) | DE3249017T1 (en) |
DK (1) | DK159876C (en) |
ES (1) | ES515680A0 (en) |
FI (1) | FI72961C (en) |
FR (1) | FR2512967B1 (en) |
GB (1) | GB2115315B (en) |
IE (1) | IE53556B1 (en) |
IT (1) | IT1201923B (en) |
MX (1) | MX159622A (en) |
NL (1) | NL193404C (en) |
NO (1) | NO153766C (en) |
WO (1) | WO1983001018A1 (en) |
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US20150122319A1 (en) * | 2011-07-28 | 2015-05-07 | David A. Strickler | Apcvd of doped titanium oxide and the coated article made thereby |
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US3710074A (en) * | 1970-10-08 | 1973-01-09 | Ppg Industries Inc | Electrically heated multiple glazed window having an iridescence masking film |
US3677814A (en) * | 1970-10-26 | 1972-07-18 | Ppg Industries Inc | Process for forming electroconductive tin oxide films by pyrolyzation of alkyl and aryl tin fluorides |
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DE2646513C2 (en) * | 1976-10-15 | 1984-10-04 | Bfg Glassgroup, Paris | Process for the production of a heat-reflecting soda-lime-silicate glass pane |
US4146657A (en) * | 1976-11-01 | 1979-03-27 | Gordon Roy G | Method of depositing electrically conductive, infra-red reflective, transparent coatings of stannic oxide |
US4187336A (en) * | 1977-04-04 | 1980-02-05 | Gordon Roy G | Non-iridescent glass structures |
US4206252A (en) * | 1977-04-04 | 1980-06-03 | Gordon Roy G | Deposition method for coating glass and the like |
US4308316A (en) * | 1977-04-04 | 1981-12-29 | Gordon Roy G | Non-iridescent glass structures |
CH640276A5 (en) * | 1978-10-20 | 1983-12-30 | Roy Gerald Gordon | Process for producing films of stannic oxide on a heated substrate |
FR2439167A1 (en) * | 1978-10-20 | 1980-05-16 | Gordon Roy Gerald | Anti-glare coating formed on glass - includes an inorganic coating which reflects IR radiation |
US4216259A (en) * | 1979-01-02 | 1980-08-05 | Bfg Glassgroup | Heat reflecting pane and a method of producing it |
-
1981
- 1981-09-14 US US06/302,216 patent/US4377613A/en not_active Expired - Lifetime
-
1982
- 1982-09-03 AU AU88010/82A patent/AU560433B2/en not_active Ceased
- 1982-09-09 BR BR8207855A patent/BR8207855A/en not_active IP Right Cessation
- 1982-09-09 DE DE823249017T patent/DE3249017T1/en active Granted
- 1982-09-09 CH CH2717/83A patent/CH656116A5/en not_active IP Right Cessation
- 1982-09-09 WO PCT/US1982/001219 patent/WO1983001018A1/en active Application Filing
- 1982-09-09 NL NL8220335A patent/NL193404C/en not_active IP Right Cessation
- 1982-09-09 GB GB08311441A patent/GB2115315B/en not_active Expired
- 1982-09-09 JP JP57502868A patent/JPS58501466A/en active Granted
- 1982-09-10 FR FR8215371A patent/FR2512967B1/en not_active Expired
- 1982-09-13 MX MX194370A patent/MX159622A/en unknown
- 1982-09-13 AR AR290635A patent/AR228680A1/en active
- 1982-09-13 CA CA000411270A patent/CA1192773A/en not_active Expired
- 1982-09-13 DK DK407782A patent/DK159876C/en active
- 1982-09-13 NO NO823104A patent/NO153766C/en unknown
- 1982-09-13 IE IE2235/82A patent/IE53556B1/en not_active IP Right Cessation
- 1982-09-13 BE BE0/209002A patent/BE894383A/en not_active IP Right Cessation
- 1982-09-13 ES ES515680A patent/ES515680A0/en active Granted
- 1982-09-13 FI FI823162A patent/FI72961C/en not_active IP Right Cessation
- 1982-09-13 IT IT68090/82A patent/IT1201923B/en active
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