US20130065064A1 - Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same - Google Patents
Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same Download PDFInfo
- Publication number
- US20130065064A1 US20130065064A1 US13/670,538 US201213670538A US2013065064A1 US 20130065064 A1 US20130065064 A1 US 20130065064A1 US 201213670538 A US201213670538 A US 201213670538A US 2013065064 A1 US2013065064 A1 US 2013065064A1
- Authority
- US
- United States
- Prior art keywords
- coating
- layer
- glass substrate
- capping layer
- silica
- 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.)
- Abandoned
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 117
- 239000011248 coating agent Substances 0.000 title claims abstract description 99
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 230000003667 anti-reflective effect Effects 0.000 title abstract description 6
- 239000010410 layer Substances 0.000 claims abstract description 101
- 239000011521 glass Substances 0.000 claims abstract description 98
- 239000000758 substrate Substances 0.000 claims abstract description 62
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 239000011247 coating layer Substances 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 18
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008119 colloidal silica Substances 0.000 claims abstract description 14
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000077 silane Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 21
- 238000000151 deposition Methods 0.000 claims description 18
- 238000010304 firing Methods 0.000 claims description 17
- 238000004381 surface treatment Methods 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- 238000007761 roller coating Methods 0.000 claims description 4
- 238000012360 testing method Methods 0.000 description 33
- 230000005540 biological transmission Effects 0.000 description 24
- 230000008859 change Effects 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 230000007613 environmental effect Effects 0.000 description 14
- -1 hydrogen ions Chemical class 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 11
- 239000010408 film Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000003086 colorant Substances 0.000 description 8
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000006121 base glass Substances 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000006117 anti-reflective coating Substances 0.000 description 4
- 239000006066 glass batch Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000000040 green colorant Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- VSIKJPJINIDELZ-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octakis-phenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VSIKJPJINIDELZ-UHFFFAOYSA-N 0.000 description 2
- KMPBCFZCRNKXSA-UHFFFAOYSA-N 2,2,4,4,6,6-hexaethyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound CC[Si]1(CC)O[Si](CC)(CC)O[Si](CC)(CC)O1 KMPBCFZCRNKXSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- YTEISYFNYGDBRV-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)oxy-dimethylsilyl]oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)(C)O[Si](C)C YTEISYFNYGDBRV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- WRHICBQGUKUJPR-UHFFFAOYSA-N dichloro-[[dimethyl(trimethylsilyloxy)silyl]oxy-dimethylsilyl]oxy-methylsilane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(Cl)Cl WRHICBQGUKUJPR-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229940035429 isobutyl alcohol Drugs 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- SWGZAKPJNWCPRY-UHFFFAOYSA-N methyl-bis(trimethylsilyloxy)silicon Chemical compound C[Si](C)(C)O[Si](C)O[Si](C)(C)C SWGZAKPJNWCPRY-UHFFFAOYSA-N 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- QHAHOIWVGZZELU-UHFFFAOYSA-N trichloro(trichlorosilyloxy)silane Chemical compound Cl[Si](Cl)(Cl)O[Si](Cl)(Cl)Cl QHAHOIWVGZZELU-UHFFFAOYSA-N 0.000 description 2
- WILBTFWIBAOWLN-UHFFFAOYSA-N triethyl(triethylsilyloxy)silane Chemical compound CC[Si](CC)(CC)O[Si](CC)(CC)CC WILBTFWIBAOWLN-UHFFFAOYSA-N 0.000 description 2
- HFMRLLVZHLGNAO-UHFFFAOYSA-N trimethylsilyloxysilicon Chemical compound C[Si](C)(C)O[Si] HFMRLLVZHLGNAO-UHFFFAOYSA-N 0.000 description 2
- IVZTVZJLMIHPEY-UHFFFAOYSA-N triphenyl(triphenylsilyloxy)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)O[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 IVZTVZJLMIHPEY-UHFFFAOYSA-N 0.000 description 2
- IGJPWUZGPMLVDT-UHFFFAOYSA-N tris(ethenyl)-tris(ethenyl)silyloxysilane Chemical compound C=C[Si](C=C)(C=C)O[Si](C=C)(C=C)C=C IGJPWUZGPMLVDT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000013545 self-assembled monolayer Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/006—Anti-reflective 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
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
-
- 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
- C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31609—Particulate metal or metal compound-containing
- Y10T428/31612—As silicone, silane or siloxane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Definitions
- Certain example embodiments of this invention relate to a method of making a low-index silica coating having an overcoat or capping layer.
- the coating may comprise an antireflective (AR) coating supported by a glass substrate for use in a photovoltaic device or the like in certain example embodiments.
- the capping or overcoat layer may include siloxane(s) and/or hydrofluoroether(s).
- Glass is desirable for numerous properties and applications, including optical clarity and overall visual appearance.
- certain optical properties e.g., light transmission, reflection and/or absorption
- reduction of light reflection from the surface of a glass substrate may be desirable for storefront windows, display cases, photovoltaic devices (e.g., solar cells), picture frames, other types of windows, greenhouses, and so forth.
- Photovoltaic devices such as solar cells (and modules therefor) are known in the art. Glass is an integral part of most common commercial photovoltaic modules, including both crystalline and thin film types.
- a solar cell/module may include, for example, a photoelectric transfer film made up of one or more layers located between a pair of substrates. One or more of the substrates may be of glass, and the photoelectric transfer film (typically semiconductor) is for converting solar energy to electricity.
- Example solar cells are disclosed in U.S. Pat. Nos. 4,510,344, 4,806,436, 6,506,622, and 5,977,477, the disclosures of which are hereby incorporated herein by reference.
- Substrate(s) in a solar cell/module are sometimes made of glass.
- Incoming radiation passes through the incident glass substrate of the solar cell before reaching the active layer(s) (e.g., photoelectric transfer film such as a semiconductor) of the solar cell. Radiation that is reflected by the incident glass substrate does not make its way into the active layer(s) of the solar cell, thereby resulting in a less efficient solar cell. In other words, it would be desirable to decrease the amount of radiation that is reflected by the incident substrate, thereby increasing the amount of radiation that makes its way to the active layer(s) of the solar cell.
- the power output of a solar cell or photovoltaic (PV) module may be dependant upon the amount of light, or number of photons, within a specific range of the solar spectrum that pass through the incident glass substrate and reach the photovoltaic semiconductor.
- the power output of the module may depend upon the amount of light within the solar spectrum that passes through the glass and reaches the PV semiconductor, certain attempts have been made in an attempt to boost overall solar transmission through the glass used in PV modules.
- One attempt is the use of iron-free or “clear” glass, which may increase the amount of solar light transmission when compared to regular float glass, through absorption minimization.
- porous silica as an antireflective coating on glass substrate.
- the environmental durability of AR coatings derived from porous silica may be an issue if the coating is cast on the glass substrate at high humidity and/or temperature.
- an ion exchange process may begin, in which sodium ions in the glass are displaced by hydrogen ions from the water.
- the immediate outcome can be the hydration, or dealkalization, of the glass and depletion of the hydrogen ions from the water.
- This process can be accompanied by a shift in the aqueous equilibrium to produce more H + and OH ⁇ ions (i.e., H 2 O ⁇ H + +OH ⁇ ).
- This ion exchange process may be temperature and humidity dependent. If this process occurs over a sufficiently long period of time, there may be degradation in the surface quality due to alkali attack on the glass silicate network. This degradation may manifest itself in one or more forms, such as: (1) A distinctive milky white haze, which may be seen in all the glass (with or without a coating) after reaction in high humidity and/or freezing conditions; and/or (2) Microscopic pitting of glass occurs, wherein the pits may develop into tiny crevices that grow and eventually undercut the surface, forming islands of glass which can exfoliate from the underlying bulk material.
- this invention relates to use of a capping layer, such as, an antifog coating on a temperable AR coating on glass substrate, and possibly a minimization of reduction in transmittance after the exposure of high humidity and temperature conditions (such as, for example, thermal and dampness/wetness testing).
- a method of making a low-index silica based coating comprising: forming a silica precursor comprising a silica sol comprising a silane and/or a colloidal silica; depositing the silica precursor on a glass substrate to form a coating layer; curing and/or firing the coating layer in an oven at a temperature of from about 550 to 700° C. for a duration of from about 1 to 10 minutes; depositing a capping layer composition on the coating layer; wherein the capping layer composition comprises an antifog composition including a hydrofluoroether and curing and/or firing the surface treatment composition to form a capping layer.
- the method may result in a coating having improved durability after exposure to high humidity and high temperature and/or low humidity and low temperature when compared to a coating not including the capping layer.
- deposition may occur using at least one of the following: flow-coating, spin-coating, roller-coating, and spray-coating.
- the antifog composition comprises a siloxane.
- the antifog composition comprises a hydrofluoroether and may corresponds to the formula R f (OR h ) n , wherein R f is a perfluorinated alkyl group, wherein R h is an alkyl group, and n is a number ranging from 1 to 3, and wherein a number of carbon atoms contained in R f is greater than a total number of carbon atoms contained in all R h groups.
- R f comprises between 2 and 8 carbon atoms and is a linear or branched perfluoroalkyl group.
- a photovoltaic device comprising a photoelectric transfer film, at least one electrode, and the low-index coating
- the method of making the photovoltaic device comprises making a low-index coating comprising a capping layer including a siloxane and/or hydrofluoroether, and wherein the low-index coating is provided on a light incident side of a front glass substrate of the photovoltaic device.
- a method of making a photovoltaic device including a low-index silica based coating used in an antireflective coating comprising: forming a silica precursor comprising a silica sol comprising a silane and/or a colloidal silica; depositing the silica precursor on a glass substrate to form a coating layer; curing and/or firing the coating layer in an oven at a temperature of from about 550 to 700° C.
- the capping layer composition comprises an antifog composition including a siloxane and/or hydrofluoroether; curing and/or firing the surface treatment composition to form a capping layer; the method resulting in a coating having improved durability after exposure to high humidity and high temperature and/or low humidity and low temperature when compared to a coating not including the capping layer; using the glass substrate with the low-index silica based coating thereon as a front glass substrate of the photovoltaic device so that the low-index silica based coating is provided on a light incident side of the glass substrate.
- a photovoltaic device comprising: a photovoltaic film, and at least a glass substrate on a light incident side of the photovoltaic film; an antireflection coating provided on the glass substrate; wherein the antireflection coating comprises at least a layer provided directly on and contacting the glass substrate, the layer produced using a method comprising the steps of: forming a silica precursor comprising a silica sol comprising a silane and/or a colloidal silica; depositing the silica precursor on a glass substrate to form a coating layer; curing and/or firing the coating layer in an oven at a temperature of from about 550 to 700° C.
- the capping layer composition comprises an antifog composition including a hydrofluoroether; curing and/or firing the surface treatment composition to form a capping layer; wherein the layer has an improved durability after exposure to high humidity and high temperature and/or low humidity and low temperature when compared to a layer not including the capping layer.
- a coated article comprising: a glass substrate; an antireflection coating provided on the glass substrate; wherein the antireflection coating comprises at least a layer provided directly on and contacting the glass substrate, the layer produced using a method comprising the steps of: forming a silica precursor comprising a silica sol comprising a silane and/or a colloidal silica; depositing the silica precursor on a glass substrate to form a coating layer; curing and/or firing the coating layer in an oven at a temperature of from about 550 to 700° C.
- the capping layer composition comprises an antifog composition including a siloxane and/or hydrofluoroether; curing and/or firing the surface treatment composition to form a capping layer; wherein the layer has an improved durability after exposure to high humidity and high temperature and/or low humidity and low temperature when compared to a layer not including the capping layer.
- deposition may occur using at least one of the following: flow-coating, spin-coating, roller-coating, and spray-coating.
- the antifog composition comprises a siloxane.
- Suitable siloxanes may, for example, include hexaethylcyclotrisiloxane, hexaethyl disiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, hexamethylcyclotrisiloxane, hexavinyldisiloxane, hexaphenyldisiloxane, octaphenylcyclotetrasiloxane, hexachlorodisiloxane, dichlorooctamethyltetrasiloxane, 2-methoxy(polyethyleneoxy)propyl)heptamethyl trisiloxane, 3 acryloxypropyl tris trimethyl siloxysilane, methylacryloxypropyl heptacyclopentyl-T8silsesquioxane, octakis(dimethylsiloxy)o
- the antifog composition comprises a hydrofluoroether and may corresponds to the formula R f (OR h ) n , wherein R f is a perfluorinated alkyl group, wherein R h is an alkyl group, and n is a number ranging from 1 to 3, and wherein a number of carbon atoms contained in R f is greater than a total number of carbon atoms contained in all R h groups.
- R f comprises between 2 and 8 carbon atoms and is a linear or branched perfluoroalkyl group.
- FIG. 1 is a cross sectional view of a coated article including an antireflective (AR) coating made in accordance with an example embodiment of this invention (this coated article of FIG. 1 may be used in connection with a photovoltaic device or in any other suitable application in different embodiments of this invention).
- AR antireflective
- FIG. 2 is a cross sectional view of a photovoltaic device that may use the AR coating of FIG. 1 .
- This invention relates to antireflective (AR) coatings that may be provided for in coated articles used in devices such as photovoltaic devices, storefront windows, display cases, picture frames, greenhouses, other types of windows, and the like.
- the AR coating may be provided on either the light incident side or the other side of a substrate (e.g., glass substrate), such as a front glass substrate of a photovoltaic device.
- the AR coatings described herein may be used in the context of sport and stadium lighting (as an AR coating on such lights), and/or street and highway lighting (as an AR coating on such lights).
- an improved anti-reflection (AR) coating is provided on an incident glass substrate of a solar cell or the like.
- This AR coating may function to reduce reflection of light from the glass substrate, thereby allowing more light within the solar spectrum to pass through the incident glass substrate and reach the photovoltaic semiconductor so that the solar cell can be more efficient.
- such an AR coating is used in applications other than photovoltaic devices (e.g., solar cells), such as in storefront windows, display cases, picture frames, greenhouse glass/windows, solariums, other types of windows, and the like.
- the glass substrate may be a glass superstrate or any other type of glass substrate in different instances.
- FIG. 1 is a cross sectional view of a coated article according to an example embodiment of this invention.
- the coated article of FIG. 1 includes a glass substrate 1 and an AR coating 3 .
- the AR coating includes a first layer 3 a and an overcoat layer 3 b.
- the antireflective coating 3 includes first layer 3 a comprising a silane and/or a colloidal silica.
- the first layer 3 a may be any suitable thickness in certain example embodiments of this invention. However, in certain example embodiments, the first layer 3 a of the AR coating 3 has a thickness of approximately 500 to 4000 ⁇ after firing.
- the AR coating 3 also includes a capping layer 3 b of or including siloxane(s) and/or hydrofluoroether(s), which is provided over the first layer 3 a in certain example embodiments of this invention as shown in FIG. 1 . It is possible to form other layer(s) between layers 3 a and 3 b , and/or between glass substrate 1 and layer 3 a , in different example embodiments of this invention.
- high transmission low-iron glass may be used for glass substrate 1 in order to further increase the transmission of radiation (e.g., photons) to the active layer of the solar cell or the like.
- the glass substrate 1 may be of any of the glasses described in any of U.S. patent application Ser. Nos. 11/049,292 and/or 11/122,218, the disclosures of which are hereby incorporated herein by reference.
- additional suitable glasses include, for example (i.e., and without limitation): standard clear glass; and/or low-iron glass, such as Guardian's ExtraClear, UltraWhite, or Solar.
- certain embodiments of anti-reflective coatings produced in accordance with the present invention may increase transmission of light to the active semiconductor film of the photovoltaic device.
- Certain glasses for glass substrate 1 (which or may not be patterned in different instances) according to example embodiments of this invention utilize soda-lime-silica flat glass as their base composition/glass.
- a colorant portion may be provided in order to achieve a glass that is fairly clear in color and/or has a high visible transmission.
- An exemplary soda-lime-silica base glass includes the following basic ingredients: SiO 2 , 67-75% by weight; Na 2 O, 10-20% by weight; CaO, 5-15% by weight; MgO, 0-7% by weight; Al 2 O 3 ,0-5% by weight; K 2 O, 0-5% by weight; Li 2 O, 0-1.5% by weight; and BaO, 0-1%, by weight.
- glass herein may be made from batch raw materials silica sand, soda ash, dolomite, limestone, with the use of sulfate salts such as salt cake (Na 2 SO 4 ) and/or Epsom salt (MgSO 4 ⁇ 7H 2 O) and/or gypsum (e.g., about a 1:1 combination of any) as refining agents.
- sulfate salts such as salt cake (Na 2 SO 4 ) and/or Epsom salt (MgSO 4 ⁇ 7H 2 O) and/or gypsum (e.g., about a 1:1 combination of any) as refining agents.
- soda-lime-silica based glasses herein include by weight from about 10-15% Na 2 O and from about 6-17% CaO, by weight.
- the glass batch includes materials (including colorants and/or oxidizers) which cause the resulting glass to be fairly neutral in color (slightly yellow in certain example embodiments, indicated by a positive b* value) and/or have a high visible light transmission. These materials may either be present in the raw materials (e.g., small amounts of iron), or may be added to the base glass materials in the batch (e.g., cerium, erbium and/or the like). In certain example embodiments of this invention, the resulting glass has visible transmission of at least 75%, more preferably at least 80%, even more preferably of at least 85%, and most preferably of at least about 90% (Lt D65).
- the glass and/or glass batch comprises or consists essentially of materials as set forth in Table 1 below (in terms of weight percentage of the total glass composition):
- the total iron content of the glass is more preferably from 0.01 to 0.06%, more preferably from 0.01 to 0.04%, and most preferably from 0.01 to 0.03%.
- the colorant portion is substantially free of other colorants (other than potentially trace amounts).
- amounts of other materials e.g., refining aids, melting aids, colorants and/or impurities may be present in the glass in certain other embodiments of this invention without taking away from the purpose(s) and/or goal(s) of the instant invention.
- the glass composition is substantially free of, or free of, one, two, three, four or all of: erbium oxide, nickel oxide, cobalt oxide, neodymium oxide, chromium oxide, and selenium.
- substantially free means no more than 2 ppm and possibly as low as 0 ppm of the element or material. It is noted that while the presence of cerium oxide is preferred in many embodiments of this invention, it is not required in all embodiments and indeed is intentionally omitted in many instances. However, in certain example embodiments of this invention, small amounts of erbium oxide may be added to the glass in the colorant portion (e.g., from about 0.1 to 0.5% erbium oxide).
- the total amount of iron present in the glass batch and in the resulting glass, i.e., in the colorant portion thereof, is expressed herein in terms of Fe 2 O 3 in accordance with standard practice. This, however, does not imply that all iron is actually in the form of Fe 2 O 3 (see discussion above in this regard). Likewise, the amount of iron in the ferrous state (Fe +2 ) is reported herein as FeO, even though all ferrous state iron in the glass batch or glass may not be in the form of FeO.
- iron in the ferrous state (Fe 2+ ; FeO) is a blue-green colorant
- iron in the ferric state (Fe 3+ ) is a yellow-green colorant
- the blue-green colorant of ferrous iron is of particular concern, since as a strong colorant it introduces significant color into the glass which can sometimes be undesirable when seeking to achieve a neutral or clear color.
- the light-incident surface of the glass substrate 1 may be flat or patterned in different example embodiments of this invention.
- FIG. 2 is a cross-sectional view of a photovoltaic device (e.g., solar cell), for converting light to electricity, according to an example embodiment of this invention.
- the solar cell of FIG. 2 uses the AR coating 3 and glass substrate 1 shown in FIG. 1 in certain example embodiments of this invention.
- the incoming or incident light from the sun or the like is first incident on capping layer 3 b of the AR coating 3 , passes therethrough and then through layer 3 a and through glass substrate 1 and front transparent electrode 4 before reaching the photovoltaic semiconductor (active film) 5 of the solar cell.
- the solar cell may also include, but does not require, a reflection enhancement oxide and/or EVA film 6 , and/or a back metallic contact and/or reflector 7 as shown in example FIG. 2 .
- a reflection enhancement oxide and/or EVA film 6 and/or a back metallic contact and/or reflector 7 as shown in example FIG. 2 .
- Other types of photovoltaic devices may of course be used, and the FIG. 2 device is merely provided for purposes of example and understanding.
- the AR coating 3 reduces reflections of the incident light and permits more light to reach the thin film semiconductor film 5 of the photovoltaic device thereby permitting the device to act more efficiently.
- AR coatings 3 discussed above are used in the context of the photovoltaic devices/modules, this invention is not so limited. AR coatings according to this invention may be used in other applications such as for picture frames, fireplace doors, greenhouses, and the like. Also, other layer(s) may be provided on the glass substrate under the AR coating so that the AR coating is considered on the glass substrate even if other layers are provided therebetween. Also, while the first layer 3 a is directly on and contacting the glass substrate 1 in the FIG. 1 embodiment, it is possible to provide other layer(s) between the glass substrate and the first layer in alternative embodiments of this invention.
- Silanes containing short organic chains such as methyl trichlorosilane may be used to produce monolayers of coatings (e.g., first layer 3 a ) on glass surface.
- Dilute solutions or dispersions of coating materials in aqueous or non-aqueous media may be applied by any conventional wet application techniques.
- a preferred method involves application of a dilute coating formulation by spray process on the AR coating surface immediately after the coated glass emerges from a tubular furnace such as tempering line, etc. Concentration of spray coating formulation and the dwell time of the wet coating on the AR coating surface may be varied to get maximum packing density of monolayers. In addition thermal energy may be applied to further enhance coating process.
- Exemplary embodiments of this invention provide a new method to produce a low index silica coating for use as the AR coating 3 , with appropriate light transmission properties.
- Exemplary embodiments of this invention provide a method of making a coating containing a stabilized colloidal silica for use in coating 3 .
- the coating may be based, at least in part, on a silica sol comprising two different silica precursors, namely (a) a stabilized colloidal silica including or consisting essentially of particulate silica in a solvent and (b) a polymeric solution including or consisting essentially of silica chains.
- suitable solvents may include, for example, n-propanol, isopropanol, other well-known alcohols (e.g., ethanol), and other well-known organic solvents (e.g., toluene).
- silica precursor materials may be optionally combined with solvents, anti-foaming agents, surfactants, etc., to adjust rheological characteristics and other properties as desired.
- use of reactive diluents may be used to produce formulations containing no volatile organic matter.
- Some embodiments may comprise colloidal silica dispersed in monomers or organic solvents.
- the weight ratio of colloidal silica and other silica precursor materials may be varied.
- the weight percentage of solids in the coating formulation may be varied.
- the uncured coating may be deposited in any suitable manner, including, for example, not only by spin-coating but also roller-coating, spray-coating, and any other method of depositing the uncured coating on a substrate.
- the firing may occur in an oven at a temperature ranging preferably from 550 to 700° C. (and all subranges therebetween), more preferably from 575 to 675° C. (and all subranges therebetween), and even more preferably from 600 to 650° C. (and all subranges therebetween).
- the firing may occur for a suitable length of time, such as between 1 and 10 minutes (and all subranges therebetween) or between 3 and 7 minutes (and all subranges therebetween).
- the capping layer composition comprises siloxane(s) and/or hydrofluoroether(s).
- Suitable siloxanes may, for example, include hexaethylcyclotrisiloxane, hexaethyl disiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, hexamethylcyclotrisiloxane, hexavinyldisiloxane, hexaphenyldisiloxane, octaphenylcyclotetrasiloxane, hexachlorodisiloxane, dichlorooctamethyltetrasiloxane, 2-methoxy(polyethyleneoxy)propyl)heptamethyl trisiloxane, 3 acryloxypropyl tris trimethyl siloxysilane, methylacryloxypropyl heptacyclopentyl-T8silsesquioxane, oc
- the hydrofluoroether may correspond to the following general formula: R f (OR h ) n , where R f is a perfluorinated alkyl group; R h is an alkyl group; and n is a number ranging from 1 to 3; and where the number of carbon atoms contained in R f is greater than the total number of carbon atoms contained in all R h groups.
- R f comprises between 2 and 8 carbon atoms and is selected from the group consisting of a linear or branched perfluoroalkyl group (such as, for example, described in PCT Pub. No. WO/1999/019707, the entirety of which is incorporated herein by reference).
- a primer layer prior to application and formation of the capping layer.
- the primer layer may promote adhesion of the capping layer to the coating.
- Suitable primer layers include layers comprising alcohols, such as isopropanol, ethanol, and isobutyl alcohol, and/or well-known solvent(s).
- the resulting capping layer may vary from 2 ⁇ m to 50 ⁇ m, and all subranges therebetween.
- AR coating 3 may be made according to certain example non-limiting embodiments of this invention.
- the silica sol was prepared as follows.
- a polymeric component of silica was prepared by using 64% wt of n-propanol (available from Chem Central), 24% wt of glycydoxylpropyltrimethoxysilane (glymo) (available from Gelest, Inc.), 7% wt of water and 5% wt of hydrochloric acid (available from VWR International). These ingredients were used and mixed for 24 hrs.
- the coating solution was prepared by using 21% wt of polymeric solution, 7% wt colloidal silica in methyl ethyl ketone supplied by Nissan Chemicals Inc, and 72% wt n-propanol. This was stirred for 2 hrs to give silica sol.
- the final solution is referred to as a silica sol.
- the silica coating was fabricated using the spin coating method with 1000 rpm for 18 secs. The coating was heat treated in furnace at 625° C. for three and a half minutes. This coating does not have any barrier layer. The environmental durability of the coating was done under following conditions for high humidity and freezing.
- the transmission measurements were done using PerkinElmer UV-VIS Lambda 950 before and after the environmental testing.
- the change in % T after testing is shown in the Table 2, i.e., 13.39.
- Example #2 a bottom layer was made as mentioned in Example #1 and then followed the heat treatment.
- a primer layer based on isopropyl alcohol and isobutyl alcohol (commercially available as SP-22 from Exxene Corporation) was applied on the AR coating by flow method.
- the coating was dried at 120° C. for 5 minutes.
- the coating was cooled down to room temperature.
- antifog coating based on modified siloxane in organic solvent (diacetone alcohol) commercially available Exxene HCAF-424 antifog solution
- the coating was dried at 125° C. for 5 minutes.
- the coatings were subjected to the environmental testing as illustrated in the Example #1. Transmission was measured before and after the environmental testing and result shown in Table 2. The change in % T after testing is 3.65.
- Example #3 is same as Example #2 except the antifog coatings are based on a hydrofluoroether (FogTech supplied by MotoSolutions, Calif.). The antifog coating was applied by flow coating method and dried at room temperature. The coatings were subjected to the environmental testing as illustrated in the Example #1. Transmission was measured before and after the environmental testing and result is shown in Table 2. The change in % T after testing is 0.45.
- Example #4 is the same as Example #1 except the coating was exposed to thermal cycle ( ⁇ 40 to +85 C) with condensation minimization and air circulation for 20 days per IEC 61215, which is incorporated herein by reference. Transmission was measured before and after the environmental testing and the result is shown in Table 2. The change in % T after testing is 1.31.
- Example #5 is the same as Example #2 except the antifog coating was exposed to thermal cycle ( ⁇ 40 to +85 C) with condensation minimization and air circulation for 20 days per IEC 61215. Transmission was measured before and after the environmental testing and result shown in Table 2. The change in % T after testing is 0.70.
- Example #6 is the same as Example #3 except the antifog coating was exposed to thermal cycle ( ⁇ 40 to +85 C) with condensation minimization and air circulation for 20 days per IEC 61215. Transmission was measured before and after the environmental testing and result shown in Table 2. The change in % T after testing is 0.03.
- Example #7 is the same as Example #1 except the coating was exposed to damp testing (85 C and 85% RH) for 40 days per IEC61215. Transmission was measured before and after the environmental testing and the result is shown in Table 2. The change in % T after testing is 3.06.
- Example #8 is the same as Example #2 except the antifog coating was exposed to damp testing (85 C and 85% RH) for 40 days per IEC61215. Transmission was measured before and after the environmental testing and the result is shown in Table 2. The change in % T after testing is 1.78.
- Example #9 is the same as Example #3 except the antifog coating was exposed to damp testing (85 C and 85% RH) for 40 days per IEC61215. Transmission was measured before and after the environmental testing and the result is shown in Table 2. The change in % T after testing is 0.27.
- the durability of temperable antireflecting coatings can be enhanced for high humidity and freeze conditions using an antifog coating as a capping layer.
- the change in % T after high humidity and freeze condition may become 4% if the modified siloxane based antifog is used as capping layer on AR coating in comparison to a 14% change without capping layer.
- the change in % T after high humidity and freeze condition may become 1.5% if the hydrofluoroether based antifog is used on AR coating in comparison to a 14% change without capping layer.
- the durability of temperable antireflecting coatings can be enhanced for thermal testing conditions using antifog coating as capping layer.
- the change in % T after thermal testing may become 0.70% if the modified siloxane based antifog is used as capping layer on AR coating in comparison to a 1.31% change without capping layer.
- the change in % T after thermal testing may become 0.03% if the hydrofluoroether based antifog is used on AR coating in comparison to a 1.31% change without capping layer.
- the durability of temperable antireflecting coatings may be enhanced for damp testing conditions using antifog coating as capping layer.
- the change in % T after damp testing may become 1.78% if the modified siloxane based antifog is used as capping layer on AR coating in comparison to a 3.86% change without capping layer.
- the change in % T after damp testing may became 0.27% if the hydrofluoroether based antifog is used on AR coating in comparison to a 3.86% change without capping layer.
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Abstract
A low-index silica coating may be made by forming silica sol comprising a silane and/or a colloidal silica. The silica precursor may be deposited on a substrate (e.g., glass substrate) to form a coating layer. The coating layer may then be cured and/or fired using temperature(s) of from about 550 to 700° C. A capping layer composition comprising an antifog composition including a siloxane and/or hydrofluororether may be formed, deposited on the coating layer, then cured and/or fired to form a capping layer The capping layer improves the durability of the coating. The low-index silica based coating may be used as an antireflective (AR) film on a front glass substrate of a photovoltaic device (e.g., solar cell) or any other suitable application in certain example instances.
Description
- Certain example embodiments of this invention relate to a method of making a low-index silica coating having an overcoat or capping layer. In certain example embodiments, the coating may comprise an antireflective (AR) coating supported by a glass substrate for use in a photovoltaic device or the like in certain example embodiments. The capping or overcoat layer may include siloxane(s) and/or hydrofluoroether(s).
- Glass is desirable for numerous properties and applications, including optical clarity and overall visual appearance. For some example applications, certain optical properties (e.g., light transmission, reflection and/or absorption) are desired to be optimized. For example, in certain example instances, reduction of light reflection from the surface of a glass substrate may be desirable for storefront windows, display cases, photovoltaic devices (e.g., solar cells), picture frames, other types of windows, greenhouses, and so forth.
- Photovoltaic devices such as solar cells (and modules therefor) are known in the art. Glass is an integral part of most common commercial photovoltaic modules, including both crystalline and thin film types. A solar cell/module may include, for example, a photoelectric transfer film made up of one or more layers located between a pair of substrates. One or more of the substrates may be of glass, and the photoelectric transfer film (typically semiconductor) is for converting solar energy to electricity. Example solar cells are disclosed in U.S. Pat. Nos. 4,510,344, 4,806,436, 6,506,622, and 5,977,477, the disclosures of which are hereby incorporated herein by reference.
- Substrate(s) in a solar cell/module are sometimes made of glass. Incoming radiation passes through the incident glass substrate of the solar cell before reaching the active layer(s) (e.g., photoelectric transfer film such as a semiconductor) of the solar cell. Radiation that is reflected by the incident glass substrate does not make its way into the active layer(s) of the solar cell, thereby resulting in a less efficient solar cell. In other words, it would be desirable to decrease the amount of radiation that is reflected by the incident substrate, thereby increasing the amount of radiation that makes its way to the active layer(s) of the solar cell. In particular, the power output of a solar cell or photovoltaic (PV) module may be dependant upon the amount of light, or number of photons, within a specific range of the solar spectrum that pass through the incident glass substrate and reach the photovoltaic semiconductor.
- Because the power output of the module may depend upon the amount of light within the solar spectrum that passes through the glass and reaches the PV semiconductor, certain attempts have been made in an attempt to boost overall solar transmission through the glass used in PV modules. One attempt is the use of iron-free or “clear” glass, which may increase the amount of solar light transmission when compared to regular float glass, through absorption minimization.
- Another attempt to boost overall solar transmission involves the use of porous silica as an antireflective coating on glass substrate. But the environmental durability of AR coatings derived from porous silica may be an issue if the coating is cast on the glass substrate at high humidity and/or temperature. When water contacts glass, an ion exchange process may begin, in which sodium ions in the glass are displaced by hydrogen ions from the water. The immediate outcome can be the hydration, or dealkalization, of the glass and depletion of the hydrogen ions from the water. This process can be accompanied by a shift in the aqueous equilibrium to produce more H+ and OH− ions (i.e., H2O→H++OH−).
- This ion exchange process may be temperature and humidity dependent. If this process occurs over a sufficiently long period of time, there may be degradation in the surface quality due to alkali attack on the glass silicate network. This degradation may manifest itself in one or more forms, such as: (1) A distinctive milky white haze, which may be seen in all the glass (with or without a coating) after reaction in high humidity and/or freezing conditions; and/or (2) Microscopic pitting of glass occurs, wherein the pits may develop into tiny crevices that grow and eventually undercut the surface, forming islands of glass which can exfoliate from the underlying bulk material.
- These defects may lead to a reduction in transmissivity of an antireflecting coating after the high humidity and temperature variation. Therefore, there may be a need to minimize the reduction in transmission to maintain the performance of the antireflecting coatings in the environmental conditions such as high humidity and temperature conditions.
- In one aspect of the present invention, there is a capping layer on antireflecting coatings that may minimizes the direct contact of water to the coating and substrate. It may lead to an environmentally durable AR coating. Accordingly, in one embodiment, this invention relates to use of a capping layer, such as, an antifog coating on a temperable AR coating on glass substrate, and possibly a minimization of reduction in transmittance after the exposure of high humidity and temperature conditions (such as, for example, thermal and dampness/wetness testing).
- In certain example embodiments of this invention, there is provided a method of making a low-index silica based coating, the method comprising: forming a silica precursor comprising a silica sol comprising a silane and/or a colloidal silica; depositing the silica precursor on a glass substrate to form a coating layer; curing and/or firing the coating layer in an oven at a temperature of from about 550 to 700° C. for a duration of from about 1 to 10 minutes; depositing a capping layer composition on the coating layer; wherein the capping layer composition comprises an antifog composition including a hydrofluoroether and curing and/or firing the surface treatment composition to form a capping layer. The method may result in a coating having improved durability after exposure to high humidity and high temperature and/or low humidity and low temperature when compared to a coating not including the capping layer.
- In certain embodiments, deposition may occur using at least one of the following: flow-coating, spin-coating, roller-coating, and spray-coating. In preferred embodiments, the antifog composition comprises a siloxane. In other preferred embodiments, the antifog composition comprises a hydrofluoroether and may corresponds to the formula Rf(ORh)n, wherein Rf is a perfluorinated alkyl group, wherein Rh is an alkyl group, and n is a number ranging from 1 to 3, and wherein a number of carbon atoms contained in Rf is greater than a total number of carbon atoms contained in all Rh groups. In certain embodiments, Rf comprises between 2 and 8 carbon atoms and is a linear or branched perfluoroalkyl group.
- In certain embodiments, there is a method of making a photovoltaic device comprising a photoelectric transfer film, at least one electrode, and the low-index coating, wherein the method of making the photovoltaic device comprises making a low-index coating comprising a capping layer including a siloxane and/or hydrofluoroether, and wherein the low-index coating is provided on a light incident side of a front glass substrate of the photovoltaic device.
- In certain embodiments, there is a method of making a photovoltaic device including a low-index silica based coating used in an antireflective coating, the method comprising: forming a silica precursor comprising a silica sol comprising a silane and/or a colloidal silica; depositing the silica precursor on a glass substrate to form a coating layer; curing and/or firing the coating layer in an oven at a temperature of from about 550 to 700° C. for a duration of from about 1 to 10 minutes; depositing a capping layer composition on the coating layer; wherein the capping layer composition comprises an antifog composition including a siloxane and/or hydrofluoroether; curing and/or firing the surface treatment composition to form a capping layer; the method resulting in a coating having improved durability after exposure to high humidity and high temperature and/or low humidity and low temperature when compared to a coating not including the capping layer; using the glass substrate with the low-index silica based coating thereon as a front glass substrate of the photovoltaic device so that the low-index silica based coating is provided on a light incident side of the glass substrate.
- In certain embodiments, there is a photovoltaic device comprising: a photovoltaic film, and at least a glass substrate on a light incident side of the photovoltaic film; an antireflection coating provided on the glass substrate; wherein the antireflection coating comprises at least a layer provided directly on and contacting the glass substrate, the layer produced using a method comprising the steps of: forming a silica precursor comprising a silica sol comprising a silane and/or a colloidal silica; depositing the silica precursor on a glass substrate to form a coating layer; curing and/or firing the coating layer in an oven at a temperature of from about 550 to 700° C. for a duration of from about 1 to 10 minutes; depositing a capping layer composition on the coating layer, wherein the capping layer composition comprises an antifog composition including a hydrofluoroether; curing and/or firing the surface treatment composition to form a capping layer; wherein the layer has an improved durability after exposure to high humidity and high temperature and/or low humidity and low temperature when compared to a layer not including the capping layer.
- In certain embodiments, there is a coated article comprising: a glass substrate; an antireflection coating provided on the glass substrate; wherein the antireflection coating comprises at least a layer provided directly on and contacting the glass substrate, the layer produced using a method comprising the steps of: forming a silica precursor comprising a silica sol comprising a silane and/or a colloidal silica; depositing the silica precursor on a glass substrate to form a coating layer; curing and/or firing the coating layer in an oven at a temperature of from about 550 to 700° C. for a duration of from about 1 to 10 minutes; depositing a capping layer composition on the coating layer, wherein the capping layer composition comprises an antifog composition including a siloxane and/or hydrofluoroether; curing and/or firing the surface treatment composition to form a capping layer; wherein the layer has an improved durability after exposure to high humidity and high temperature and/or low humidity and low temperature when compared to a layer not including the capping layer.
- In certain embodiments, deposition may occur using at least one of the following: flow-coating, spin-coating, roller-coating, and spray-coating.
- In certain embodiments, the antifog composition comprises a siloxane. Suitable siloxanes may, for example, include hexaethylcyclotrisiloxane, hexaethyl disiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, hexamethylcyclotrisiloxane, hexavinyldisiloxane, hexaphenyldisiloxane, octaphenylcyclotetrasiloxane, hexachlorodisiloxane, dichlorooctamethyltetrasiloxane, 2-methoxy(polyethyleneoxy)propyl)heptamethyl trisiloxane, 3 acryloxypropyl tris trimethyl siloxysilane, methylacryloxypropyl heptacyclopentyl-T8silsesquioxane, octakis(dimethylsiloxy)octaprismosilsesquioxane, and octaviny-T8-silsesquioxane.
- In certain embodiments, the antifog composition comprises a hydrofluoroether and may corresponds to the formula Rf(ORh)n, wherein Rf is a perfluorinated alkyl group, wherein Rh is an alkyl group, and n is a number ranging from 1 to 3, and wherein a number of carbon atoms contained in Rf is greater than a total number of carbon atoms contained in all Rh groups. In certain embodiments, Rf comprises between 2 and 8 carbon atoms and is a linear or branched perfluoroalkyl group.
-
FIG. 1 is a cross sectional view of a coated article including an antireflective (AR) coating made in accordance with an example embodiment of this invention (this coated article ofFIG. 1 may be used in connection with a photovoltaic device or in any other suitable application in different embodiments of this invention). -
FIG. 2 is a cross sectional view of a photovoltaic device that may use the AR coating ofFIG. 1 . - Referring now more particularly to the accompanying drawings in which like reference numerals indicate like parts throughout the several views.
- This invention relates to antireflective (AR) coatings that may be provided for in coated articles used in devices such as photovoltaic devices, storefront windows, display cases, picture frames, greenhouses, other types of windows, and the like. In certain example embodiments (e.g., in photovoltaic devices), the AR coating may be provided on either the light incident side or the other side of a substrate (e.g., glass substrate), such as a front glass substrate of a photovoltaic device. In other example embodiments, the AR coatings described herein may be used in the context of sport and stadium lighting (as an AR coating on such lights), and/or street and highway lighting (as an AR coating on such lights).
- In certain example embodiments of this invention, an improved anti-reflection (AR) coating is provided on an incident glass substrate of a solar cell or the like. This AR coating may function to reduce reflection of light from the glass substrate, thereby allowing more light within the solar spectrum to pass through the incident glass substrate and reach the photovoltaic semiconductor so that the solar cell can be more efficient. In other example embodiments of this invention, such an AR coating is used in applications other than photovoltaic devices (e.g., solar cells), such as in storefront windows, display cases, picture frames, greenhouse glass/windows, solariums, other types of windows, and the like. The glass substrate may be a glass superstrate or any other type of glass substrate in different instances.
-
FIG. 1 is a cross sectional view of a coated article according to an example embodiment of this invention. The coated article ofFIG. 1 includes aglass substrate 1 and anAR coating 3. The AR coating includes afirst layer 3 a and anovercoat layer 3 b. - In the
FIG. 1 embodiment, theantireflective coating 3 includesfirst layer 3 a comprising a silane and/or a colloidal silica. Thefirst layer 3 a may be any suitable thickness in certain example embodiments of this invention. However, in certain example embodiments, thefirst layer 3 a of theAR coating 3 has a thickness of approximately 500 to 4000 Å after firing. - The
AR coating 3 also includes acapping layer 3 b of or including siloxane(s) and/or hydrofluoroether(s), which is provided over thefirst layer 3 a in certain example embodiments of this invention as shown inFIG. 1 . It is possible to form other layer(s) betweenlayers glass substrate 1 andlayer 3 a, in different example embodiments of this invention. - In certain example embodiments of this invention, high transmission low-iron glass may be used for
glass substrate 1 in order to further increase the transmission of radiation (e.g., photons) to the active layer of the solar cell or the like. For example and without limitation, theglass substrate 1 may be of any of the glasses described in any of U.S. patent application Ser. Nos. 11/049,292 and/or 11/122,218, the disclosures of which are hereby incorporated herein by reference. Furthermore, additional suitable glasses include, for example (i.e., and without limitation): standard clear glass; and/or low-iron glass, such as Guardian's ExtraClear, UltraWhite, or Solar. No matter the composition of the glass substrate, certain embodiments of anti-reflective coatings produced in accordance with the present invention may increase transmission of light to the active semiconductor film of the photovoltaic device. - Certain glasses for glass substrate 1 (which or may not be patterned in different instances) according to example embodiments of this invention utilize soda-lime-silica flat glass as their base composition/glass. In addition to base composition/glass, a colorant portion may be provided in order to achieve a glass that is fairly clear in color and/or has a high visible transmission. An exemplary soda-lime-silica base glass according to certain embodiments of this invention, on a weight percentage basis, includes the following basic ingredients: SiO2, 67-75% by weight; Na2O, 10-20% by weight; CaO, 5-15% by weight; MgO, 0-7% by weight; Al2O3,0-5% by weight; K2O, 0-5% by weight; Li2O, 0-1.5% by weight; and BaO, 0-1%, by weight.
- Other minor ingredients, including various conventional refining aids, such as SO3, carbon, and the like may also be included in the base glass. In certain embodiments, for example, glass herein may be made from batch raw materials silica sand, soda ash, dolomite, limestone, with the use of sulfate salts such as salt cake (Na2SO4) and/or Epsom salt (MgSO4×7H2O) and/or gypsum (e.g., about a 1:1 combination of any) as refining agents. In certain example embodiments, soda-lime-silica based glasses herein include by weight from about 10-15% Na2O and from about 6-17% CaO, by weight.
- in addition to the base glass above, in making glass according to certain example embodiments of the instant invention the glass batch includes materials (including colorants and/or oxidizers) which cause the resulting glass to be fairly neutral in color (slightly yellow in certain example embodiments, indicated by a positive b* value) and/or have a high visible light transmission. These materials may either be present in the raw materials (e.g., small amounts of iron), or may be added to the base glass materials in the batch (e.g., cerium, erbium and/or the like). In certain example embodiments of this invention, the resulting glass has visible transmission of at least 75%, more preferably at least 80%, even more preferably of at least 85%, and most preferably of at least about 90% (Lt D65). In certain example non-limiting instances, such high transmissions may be achieved at a reference glass thickness of about 3 to 4 mm. In certain embodiments of this invention, in addition to the base glass, the glass and/or glass batch comprises or consists essentially of materials as set forth in Table 1 below (in terms of weight percentage of the total glass composition):
-
TABLE 1 Example Additional Materials In Glass Ingredient General (Wt. %) More Preferred Most Preferred total iron (expressed 0.001-0.06% 0.005-0.04% 0.01-0.03% as Fe2O3): cerium oxide: 0-0.30% 0.01-0.12% 0.01-0.07% TiO2 0-1.0% 0.005-0.1% 0.01-0.04% Erbium oxide: 0.05 to 0.5% 0.1 to 0.5% 0.1 to 0.35% - In certain example embodiments, the total iron content of the glass is more preferably from 0.01 to 0.06%, more preferably from 0.01 to 0.04%, and most preferably from 0.01 to 0.03%. In certain example embodiments of this invention, the colorant portion is substantially free of other colorants (other than potentially trace amounts). However, it should be appreciated that amounts of other materials (e.g., refining aids, melting aids, colorants and/or impurities) may be present in the glass in certain other embodiments of this invention without taking away from the purpose(s) and/or goal(s) of the instant invention. For instance, in certain example embodiments of this invention, the glass composition is substantially free of, or free of, one, two, three, four or all of: erbium oxide, nickel oxide, cobalt oxide, neodymium oxide, chromium oxide, and selenium. The phrase “substantially free” means no more than 2 ppm and possibly as low as 0 ppm of the element or material. It is noted that while the presence of cerium oxide is preferred in many embodiments of this invention, it is not required in all embodiments and indeed is intentionally omitted in many instances. However, in certain example embodiments of this invention, small amounts of erbium oxide may be added to the glass in the colorant portion (e.g., from about 0.1 to 0.5% erbium oxide).
- The total amount of iron present in the glass batch and in the resulting glass, i.e., in the colorant portion thereof, is expressed herein in terms of Fe2O3 in accordance with standard practice. This, however, does not imply that all iron is actually in the form of Fe2O3 (see discussion above in this regard). Likewise, the amount of iron in the ferrous state (Fe+2) is reported herein as FeO, even though all ferrous state iron in the glass batch or glass may not be in the form of FeO. As mentioned above, iron in the ferrous state (Fe2+; FeO) is a blue-green colorant, while iron in the ferric state (Fe3+) is a yellow-green colorant; and the blue-green colorant of ferrous iron is of particular concern, since as a strong colorant it introduces significant color into the glass which can sometimes be undesirable when seeking to achieve a neutral or clear color.
- It is noted that the light-incident surface of the
glass substrate 1 may be flat or patterned in different example embodiments of this invention. -
FIG. 2 is a cross-sectional view of a photovoltaic device (e.g., solar cell), for converting light to electricity, according to an example embodiment of this invention. The solar cell ofFIG. 2 uses theAR coating 3 andglass substrate 1 shown inFIG. 1 in certain example embodiments of this invention. In this example embodiment, the incoming or incident light from the sun or the like is first incident on cappinglayer 3 b of theAR coating 3, passes therethrough and then throughlayer 3 a and throughglass substrate 1 and fronttransparent electrode 4 before reaching the photovoltaic semiconductor (active film) 5 of the solar cell. Note that the solar cell may also include, but does not require, a reflection enhancement oxide and/orEVA film 6, and/or a back metallic contact and/orreflector 7 as shown in exampleFIG. 2 . Other types of photovoltaic devices may of course be used, and theFIG. 2 device is merely provided for purposes of example and understanding. As explained above, theAR coating 3 reduces reflections of the incident light and permits more light to reach the thinfilm semiconductor film 5 of the photovoltaic device thereby permitting the device to act more efficiently. - While certain of the
AR coatings 3 discussed above are used in the context of the photovoltaic devices/modules, this invention is not so limited. AR coatings according to this invention may be used in other applications such as for picture frames, fireplace doors, greenhouses, and the like. Also, other layer(s) may be provided on the glass substrate under the AR coating so that the AR coating is considered on the glass substrate even if other layers are provided therebetween. Also, while thefirst layer 3 a is directly on and contacting theglass substrate 1 in theFIG. 1 embodiment, it is possible to provide other layer(s) between the glass substrate and the first layer in alternative embodiments of this invention. - Long chain organic materials having reactive end groups based on silicon and phosphorous may form self-assembled monolayers on glass surfaces. Silanes containing short organic chains such as methyl trichlorosilane may be used to produce monolayers of coatings (e.g.,
first layer 3 a) on glass surface. - Dilute solutions or dispersions of coating materials in aqueous or non-aqueous media may be applied by any conventional wet application techniques. A preferred method involves application of a dilute coating formulation by spray process on the AR coating surface immediately after the coated glass emerges from a tubular furnace such as tempering line, etc. Concentration of spray coating formulation and the dwell time of the wet coating on the AR coating surface may be varied to get maximum packing density of monolayers. In addition thermal energy may be applied to further enhance coating process.
- Exemplary embodiments of this invention provide a new method to produce a low index silica coating for use as the
AR coating 3, with appropriate light transmission properties. Exemplary embodiments of this invention provide a method of making a coating containing a stabilized colloidal silica for use incoating 3. In certain example embodiments of this invention, the coating may be based, at least in part, on a silica sol comprising two different silica precursors, namely (a) a stabilized colloidal silica including or consisting essentially of particulate silica in a solvent and (b) a polymeric solution including or consisting essentially of silica chains. - In accordance with certain embodiments of the present invention, suitable solvents may include, for example, n-propanol, isopropanol, other well-known alcohols (e.g., ethanol), and other well-known organic solvents (e.g., toluene).
- In exemplary embodiments, silica precursor materials may be optionally combined with solvents, anti-foaming agents, surfactants, etc., to adjust rheological characteristics and other properties as desired. In a preferred embodiment, use of reactive diluents may be used to produce formulations containing no volatile organic matter. Some embodiments may comprise colloidal silica dispersed in monomers or organic solvents. Depending on the particular embodiment, the weight ratio of colloidal silica and other silica precursor materials may be varied. Similarly (and depending on the embodiment), the weight percentage of solids in the coating formulation may be varied.
- Several examples were prepared, so as to illustrate exemplary embodiments of the present invention. Although the examples describe the use of the spin-coating method, the uncured coating may be deposited in any suitable manner, including, for example, not only by spin-coating but also roller-coating, spray-coating, and any other method of depositing the uncured coating on a substrate.
- In certain exemplary embodiments, the firing may occur in an oven at a temperature ranging preferably from 550 to 700° C. (and all subranges therebetween), more preferably from 575 to 675° C. (and all subranges therebetween), and even more preferably from 600 to 650° C. (and all subranges therebetween). The firing may occur for a suitable length of time, such as between 1 and 10 minutes (and all subranges therebetween) or between 3 and 7 minutes (and all subranges therebetween).
- In certain exemplary embodiments, the capping layer composition comprises siloxane(s) and/or hydrofluoroether(s). Suitable siloxanes may, for example, include hexaethylcyclotrisiloxane, hexaethyl disiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, hexamethylcyclotrisiloxane, hexavinyldisiloxane, hexaphenyldisiloxane, octaphenylcyclotetrasiloxane, hexachlorodisiloxane, dichlorooctamethyltetrasiloxane, 2-methoxy(polyethyleneoxy)propyl)heptamethyl trisiloxane, 3 acryloxypropyl tris trimethyl siloxysilane, methylacryloxypropyl heptacyclopentyl-T8silsesquioxane, octakis(dimethylsiloxy)octaprismosilsesquioxane, and octaviny-T8-silsesquioxane.
- The hydrofluoroether may correspond to the following general formula: Rf (ORh)n, where Rf is a perfluorinated alkyl group; Rh is an alkyl group; and n is a number ranging from 1 to 3; and where the number of carbon atoms contained in Rf is greater than the total number of carbon atoms contained in all Rh groups. In certain preferred embodiments, Rf comprises between 2 and 8 carbon atoms and is selected from the group consisting of a linear or branched perfluoroalkyl group (such as, for example, described in PCT Pub. No. WO/1999/019707, the entirety of which is incorporated herein by reference).
- In certain embodiments that include a siloxane, it may be beneficial to use a primer layer prior to application and formation of the capping layer. The primer layer may promote adhesion of the capping layer to the coating. Suitable primer layers include layers comprising alcohols, such as isopropanol, ethanol, and isobutyl alcohol, and/or well-known solvent(s).
- In some embodiments, the resulting capping layer may vary from 2 μm to 50 μm, and all subranges therebetween.
- Set forth below is a description of how
AR coating 3 may be made according to certain example non-limiting embodiments of this invention. - The silica sol was prepared as follows. A polymeric component of silica was prepared by using 64% wt of n-propanol (available from Chem Central), 24% wt of glycydoxylpropyltrimethoxysilane (glymo) (available from Gelest, Inc.), 7% wt of water and 5% wt of hydrochloric acid (available from VWR International). These ingredients were used and mixed for 24 hrs. The coating solution was prepared by using 21% wt of polymeric solution, 7% wt colloidal silica in methyl ethyl ketone supplied by Nissan Chemicals Inc, and 72% wt n-propanol. This was stirred for 2 hrs to give silica sol. The final solution is referred to as a silica sol. The silica coating was fabricated using the spin coating method with 1000 rpm for 18 secs. The coating was heat treated in furnace at 625° C. for three and a half minutes. This coating does not have any barrier layer. The environmental durability of the coating was done under following conditions for high humidity and freezing.
-
- Ramp—Heat from room temperature (25° C.) to 85° C. @ 100 C/hr; Bring RH up to 85%.
-
Cycle 1—Dwell @ 85° C./85% RH for 1200 minutes. - Ramp—Cool from 85° C. to −40° C. @ 100 C/hr; Bring RH down to 0%.
- Cycle 2—Dwell @ −40° C./0% RH for 40 minutes.
- Ramp—Heat from −40° C. to 85° C. @ 100 C/hr; Bring the RH up to 85%.
- Repeat—Repeat for 10 cycles or 240 hrs.
- The transmission measurements were done using PerkinElmer UV-VIS Lambda 950 before and after the environmental testing. The change in % T after testing is shown in the Table 2, i.e., 13.39.
- In Example #2, a bottom layer was made as mentioned in
Example # 1 and then followed the heat treatment. After cooling down to room temperature, a primer layer based on isopropyl alcohol and isobutyl alcohol (commercially available as SP-22 from Exxene Corporation) was applied on the AR coating by flow method. The coating was dried at 120° C. for 5 minutes. The coating was cooled down to room temperature. Then antifog coating based on modified siloxane in organic solvent (diacetone alcohol) (commercially available Exxene HCAF-424 antifog solution) was fabricated using flow coating method. The coating was dried at 125° C. for 5 minutes. The coatings were subjected to the environmental testing as illustrated in theExample # 1. Transmission was measured before and after the environmental testing and result shown in Table 2. The change in % T after testing is 3.65. -
Example # 3 is same as Example #2 except the antifog coatings are based on a hydrofluoroether (FogTech supplied by MotoSolutions, Calif.). The antifog coating was applied by flow coating method and dried at room temperature. The coatings were subjected to the environmental testing as illustrated in theExample # 1. Transmission was measured before and after the environmental testing and result is shown in Table 2. The change in % T after testing is 0.45. -
Example # 4 is the same asExample # 1 except the coating was exposed to thermal cycle (−40 to +85 C) with condensation minimization and air circulation for 20 days per IEC 61215, which is incorporated herein by reference. Transmission was measured before and after the environmental testing and the result is shown in Table 2. The change in % T after testing is 1.31. -
Example # 5 is the same as Example #2 except the antifog coating was exposed to thermal cycle (−40 to +85 C) with condensation minimization and air circulation for 20 days per IEC 61215. Transmission was measured before and after the environmental testing and result shown in Table 2. The change in % T after testing is 0.70. -
Example # 6 is the same asExample # 3 except the antifog coating was exposed to thermal cycle (−40 to +85 C) with condensation minimization and air circulation for 20 days per IEC 61215. Transmission was measured before and after the environmental testing and result shown in Table 2. The change in % T after testing is 0.03. -
Example # 7 is the same asExample # 1 except the coating was exposed to damp testing (85 C and 85% RH) for 40 days per IEC61215. Transmission was measured before and after the environmental testing and the result is shown in Table 2. The change in % T after testing is 3.06. - Example #8 is the same as Example #2 except the antifog coating was exposed to damp testing (85 C and 85% RH) for 40 days per IEC61215. Transmission was measured before and after the environmental testing and the result is shown in Table 2. The change in % T after testing is 1.78.
- Example #9 is the same as
Example # 3 except the antifog coating was exposed to damp testing (85 C and 85% RH) for 40 days per IEC61215. Transmission was measured before and after the environmental testing and the result is shown in Table 2. The change in % T after testing is 0.27. -
TABLE 2 Transmission of AR coatings with and without capping layer before and after high humidity and freeze testing. % Transmission Example Before Testing After Testing Change Example # 1 86.96 73.57 13.39 Example #2 84.54 80.89 3.65 Example # 385.25 84.80 0.45 Example # 486.96 85.65 1.31 Example # 586.67 85.97 0.70 Example # 685.04 85.01 0.03 Example # 786.98 83.12 3.86 Example #8 84.68 82.91 1.78 Example #9 84.96 84.69 0.27 - As shown in these exemplary embodiments, the durability of temperable antireflecting coatings can be enhanced for high humidity and freeze conditions using an antifog coating as a capping layer. For instance, the change in % T after high humidity and freeze condition may become 4% if the modified siloxane based antifog is used as capping layer on AR coating in comparison to a 14% change without capping layer. For another example, the change in % T after high humidity and freeze condition may become 1.5% if the hydrofluoroether based antifog is used on AR coating in comparison to a 14% change without capping layer.
- In yet another example, the durability of temperable antireflecting coatings can be enhanced for thermal testing conditions using antifog coating as capping layer. In a further example, the change in % T after thermal testing may become 0.70% if the modified siloxane based antifog is used as capping layer on AR coating in comparison to a 1.31% change without capping layer. In another example, the change in % T after thermal testing may become 0.03% if the hydrofluoroether based antifog is used on AR coating in comparison to a 1.31% change without capping layer.
- In yet a further example, the durability of temperable antireflecting coatings may be enhanced for damp testing conditions using antifog coating as capping layer. In one more example, the change in % T after damp testing may become 1.78% if the modified siloxane based antifog is used as capping layer on AR coating in comparison to a 3.86% change without capping layer. In another example, the change in % T after damp testing may became 0.27% if the hydrofluoroether based antifog is used on AR coating in comparison to a 3.86% change without capping layer.
- All described and claimed numerical values and ranges are approximate and include at least some degree of variation.
- While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims (6)
1-16. (canceled)
17. A method of making a low-index silica based coating, the method comprising:
forming a silica based precursor comprising a silica sol comprising a silane and/or a colloidal silica;
depositing the silica precursor on a glass substrate to form a coating layer;
curing and/or firing the coating layer in an oven at a temperature of from about 550 to 700° C. for a duration of from about 1 to 10 minutes;
depositing a capping layer composition on the coating layer, wherein the capping layer composition comprises an antifog composition including a siloxane;
curing and/or firing the surface treatment composition to form a capping layer; and
wherein the method results in a coating having durability after exposure to high humidity and high temperature, and/or low humidity and low temperature, when compared to a coating not including the capping layer, and wherein said capping layer is the outermost layer of the coating.
18. The method of claim 17 , wherein at least one of the steps of depositing comprises flow-coating, spin-coating, roller-coating, or spray-coating.
19. A method of making a photovoltaic device comprising a photoelectric transfer film, at least one electrode, and the low-index coating, wherein the method of making the photovoltaic device comprises making the low-index coating according to claim 17 , and wherein the low-index coating is provided on a light incident side of a front glass substrate of the photovoltaic device.
20. A photovoltaic device comprising:
a photovoltaic film, and at least a glass substrate on a light incident side of the photovoltaic film;
an antireflection coating provided on the glass substrate;
wherein the antireflection coating comprises at least a layer provided directly on and contacting the glass substrate, the layer produced using a method comprising the steps of forming a silica precursor comprising a silica sol comprising a silane and/or a colloidal silica; depositing the silica precursor on a glass substrate to form a coating layer; curing and/or firing the coating layer in an oven at a temperature or from about 550 to 700° C. for a duration of from about 1 to 10 minutes; depositing a capping layer composition on the coating layer, wherein the capping layer composition comprises an antifog composition including a siloxane; curing and/or firing the surface treatment composition to form a capping layer; wherein the layer has an improved durability after exposure to high humidity and high temperature and/or low humidity and low temperature when compared to a layer not including the capping layer.
21. A coated article comprising:
a glass substrate;
an antireflection coating provided on the glass substrate;
wherein the antireflection coating comprises at least a layer provided directly on and contacting the glass substrate, the layer produced using a method comprising the steps of: forming a silica precursor comprising a silica sol comprising a silane and/or a colloidal silica; depositing the silica precursor on a glass substrate to form a coating layer; curing and/or firing the coating layer in an oven at a temperature of from about 550 to 700° C. for a duration of from about 1 to 10 minutes; depositing a capping layer composition on the coating layer, wherein the capping layer composition comprises an antifog composition including a siloxane; curing and/or firing the surface treatment composition to form a capping layer; wherein the layer has an improved durability after exposure to high humidity and high temperature and/or low humidity and low temperature when compared to a layer not including the capping layer.
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US13/670,538 US20130065064A1 (en) | 2007-11-27 | 2012-11-07 | Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same |
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US11/987,129 US8319095B2 (en) | 2007-11-27 | 2007-11-27 | Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same |
US13/670,538 US20130065064A1 (en) | 2007-11-27 | 2012-11-07 | Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same |
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US11/987,129 Division US8319095B2 (en) | 2007-11-27 | 2007-11-27 | Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same |
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US11/987,129 Expired - Fee Related US8319095B2 (en) | 2007-11-27 | 2007-11-27 | Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same |
US13/670,538 Abandoned US20130065064A1 (en) | 2007-11-27 | 2012-11-07 | Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same |
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US20090133748A1 (en) | 2009-05-28 |
US8319095B2 (en) | 2012-11-27 |
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