WO2011077157A1 - Coated substrate - Google Patents
Coated substrate Download PDFInfo
- Publication number
- WO2011077157A1 WO2011077157A1 PCT/GB2010/052193 GB2010052193W WO2011077157A1 WO 2011077157 A1 WO2011077157 A1 WO 2011077157A1 GB 2010052193 W GB2010052193 W GB 2010052193W WO 2011077157 A1 WO2011077157 A1 WO 2011077157A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- coating
- substrate
- coated
- float glass
- glass
- Prior art date
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 94
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000005329 float glass Substances 0.000 claims abstract description 23
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006124 Pilkington process Methods 0.000 claims abstract 3
- 238000000576 coating method Methods 0.000 claims description 115
- 239000011248 coating agent Substances 0.000 claims description 97
- 239000011521 glass Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 30
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 21
- 239000012530 fluid Substances 0.000 claims description 19
- 239000007800 oxidant agent Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 15
- 230000008021 deposition Effects 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910001887 tin oxide Inorganic materials 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 229910003437 indium oxide Inorganic materials 0.000 claims description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 19
- 229910052681 coesite Inorganic materials 0.000 abstract description 6
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 6
- 229910052682 stishovite Inorganic materials 0.000 abstract description 6
- 229910052905 tridymite Inorganic materials 0.000 abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract 1
- 230000000903 blocking effect Effects 0.000 abstract 1
- 238000009792 diffusion process Methods 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 description 15
- 230000032798 delamination Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000003570 air Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000005137 deposition process Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000001066 destructive effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052752 metalloid Inorganic materials 0.000 description 2
- 150000002738 metalloids Chemical class 0.000 description 2
- 238000006748 scratching Methods 0.000 description 2
- 230000002393 scratching effect Effects 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000012505 colouration Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/453—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating passing the reaction gases through burners or torches, e.g. atmospheric pressure CVD
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/123—Spraying molten metal
-
- 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
-
- 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
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/73—Anti-reflective coatings with specific characteristics
- C03C2217/732—Anti-reflective coatings with specific characteristics made of a single layer
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/90—Other aspects of coatings
- C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/152—Deposition methods from the vapour phase by cvd
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/365—Coating different sides of a glass substrate
Definitions
- This invention relates to coated substrates comprising a coating on at least one surface with a transparent conductive coating on at least one other surface.
- the invention also relates to processes for the production of such coated substrates.
- sol gel type deposition processes have been proposed in EP 1429997, DE 10146687, EP 1328483 and USP 6918957 in which a silica sol is coated on to the surface of a substrate and heated at elevated temperature so as to drive off organic material resulting in the production of a silica coating.
- deposition processes include chemical vapour deposition where a vapour of a precursor is directed at the substrate surface, often at elevated temperature.
- Deposition processes may involve directing the precursor through a flame on to the substrate surface.
- USPA 2006/003108 discloses a process for depositing a coating on to the surface of a glass substrate in which a silicon containing precursor is decomposed with a flame and the substrate is introduced into the flame so as to apply the precursor to the substrate directly from the gas phase.
- WO-A-2009/00745 also discloses flame pyrolysis processes for deposition of coatings upon the surface of a continuous glass ribbon.
- Deposition processes for deposition of transparent conductive coatings include those processes used to deposit conductive oxides such as indium tin oxide, doped tin oxide, doped zinc oxide and doped cadmium oxide. These processes may include chemical vapour deposition, flame pyrolysis, sputtering (or other types of physical vapour deposition) and other processes.
- conductive oxides such as indium tin oxide, doped tin oxide, doped zinc oxide and doped cadmium oxide.
- These processes may include chemical vapour deposition, flame pyrolysis, sputtering (or other types of physical vapour deposition) and other processes.
- One of the uses of transparent conductive coatings is in photovoltaic (PV) modules.
- PV photovoltaic
- PV photovoltaic
- substrates may be coated with a transparent conductive coating and then further layers, as components of the PV cells, may be deposited on the conductive coating.
- the transparent conductive coatings may occasionally delaminate from the substrate surface which causes failure of PV cells and may cause the whole module to fail.
- the present invention accordingly provides, in a first aspect, a coated substrate comprising a substrate having a first surface and a second surface, a transparent conductive coating on the first surface and a second coating on the second surface.
- the second coating is an antireflection coating, preferably, with a refractive index of 1.25 to 1.4. This is particularly advantageous when the substrate is a transparent (or substantially transparent or translucent) substrate because it increases transmission of light. If the coated substrate is to be used in PV modules this can be a very significant improvement because an increase in transmission of just 1 to 3% can have a beneficial effect on the efficiency of a PV module.
- the thickness of the coating is preferably that which will result in destructive interference between the light reflected from the surface of the coating and the surface of the glass (if the substrate is glass).
- the length of the optical path in the coating should be equal to one half of the wavelength of the light. This thickness can be calculated from the equation where t is the thickness of the coating, ⁇ is the wavelength of the incident light and n is the refractive index of the coating.
- the thickness of the second coating is preferably in the range 10 to 1100 nm. It is preferred if the thickness of the second coating is 25 nm or greater, 40 nm or greater, 50 nm or greater, 80 nm or greater or 100 nm or greater. The more preferred thickness is 105 to 500 nm, most preferably 105 to 200 nm.
- the second coating may have a porous portion and/or a dense portion. If a dense portion is present it is preferably in contact with the substrate surface.
- the advantage of the porous portion of the second coating is that is tends to reduce the refractive index of the second coating.
- At least a part of the dense portion preferably has a thickness in the range 10 to 150 nm, more preferably 10 to 95 nm, most preferably 15 to 80 nm.
- At least a part of the porous portion preferably has a thickness in the range 50 to 1000 nm, more preferably 50 to 600 nm, most preferably 60 to 250 nm.
- the second coating comprises a silicon oxide, for example silicon oxynitride (SiNO), silicon oxycarbide (SiCO) or silicon dioxide (silica).
- the preferred material of the second coating is silicon dioxide.
- the substrate will usually comprise glass, preferably float glass or rolled glass.
- the glass may be a soda lime float glass, a low iron float glass or a body tinted float glass comprising a higher proportion of iron, cobalt or selenium which may have a green, grey or blue colouration.
- the glass has an iron content of 0.015% by weight or lower.
- the glass substrate may have a thickness of from 0.5 mm to 25 mm preferably of from 2 mm to 20 mm and a visible light transmission of from 10.0% to 90.0%.
- the coated glass where the second coating is an antireflection coating, may have a visible light transmission which is from 1% to 3.5% greater than the glass before the coating was applied.
- the glass is float glass it is preferred that the second surface of the glass is the tin side surface and the first surface of the glass is the gas side surface. This is advantageous because subsequent processing (including of deposition of other layers on the conductive coating) is usually preferred by PV producers to be on the gas side surface (also known as the air side surface).
- the transparent conductive coating is preferably a transparent conductive oxide coating.
- Preferred oxides are selected from tin oxide, zinc oxide, copper oxide, indium oxide, a mixed oxide and/or mixtures thereof.
- the most preferred oxide is doped tin oxide (in particular fluorine doped tin oxide).
- the coated substrate may comprise one or more further coatings which may be deposited under or above the second coating and/or under or above the transparent conductive coating.
- Typical further coating include coatings comprising one or more layers of a metal oxide or a silicon oxide.
- the present invention provides a process for the deposition of a second coating on a substrate, the process comprising providing a substrate having a transparent conductive coating on a first surface, passing a fluid mixture comprising a coating precursor through a flame, and contacting at least a second surface of the substrate with the coating precursor during or after its passage through the flame, thereby depositing the second coating.
- Flame pyrolysis deposition processes usually comprise the steps of forming a fluid mixture comprising a precursor of an oxide of a metal or a metalloid, an oxidant and optionally a comburant. This fluid mixture may then be ignited at a point which is adjacent to the surface of the substrate.
- the precursor for the oxide may be any compound of a metal or metalloid which may be dispersed in the fluid mixture and which will decompose to form an oxide when the mixture is ignited.
- Processes in which the precursor is in the vapour phase are commonly termed combustion chemical vapour deposition processes (often known as CCVD processes).
- CCVD processes combustion chemical vapour deposition processes
- the processes of this aspect of the invention are CCVD processes.
- precursors which may be used in the formation of silica coatings include compounds having the general formula SiX 4 wherein the groups X which may be the same or different represent a halogen atom especially a chlorine atom or a bromine atom, a hydrogen atom, an alkoxy group having the formula -OR or an ester group having the formula -OOCR wherein R represents an alkyl group comprising from 1 to 4 carbon atoms.
- Particularly preferred precursors for use in the present invention include tetraethoxysilane (TEOS), hexamethyldisiloxane (HMDSO) and silane.
- the thermal output of the burners useful in the processes of this invention may be from 0.5 to 10 kW/10cm 2 , preferably from 1 to 5 kW/10cm 2 .
- the concentration of precursor in the fluid mixture which is delivered to the burner is typically from 0.05 to 25 vol%, preferably from 0.05 to 5 vol% gas phase concentration.
- the process may be carried out by passing the fluid mixture to a burner which is positioned above or below the surface of the substrate.
- One burner or a series of smaller burners may be used to coat the substrate evenly.
- the burner is preferably positioned by the substrate in close proximity to the second surface.
- the distance between the burner and the surface will typically be in the range of from 2 to 20 mm and preferably in the range 5.0 to 15.0 mm.
- Such close proximity results in a coating having improved properties possibly because it minimises the amount of recombination between the species produced by burning the precursor before they are deposited upon the surface of the substrate. It may be necessary to adjust the distance between the burner and the surface in order to optimise the properties of the desired coating.
- the process, whether off line or on line may be carried out at a range of relative speeds of the substrate (relative to the burner or burners). Typically relative speeds are 1 to 25 m/min, preferably 2 to 20 m/min.
- the burner is preferably associated with means for extracting the exhaust gases from the area adjacent to the surface of the substrate.
- at least one means for extraction is positioned adjacent to each burner.
- the extraction means is typically a conduit associated with a fan which produces an updraft at the mouth of the conduit.
- Each extraction means is preferably provided with control means whereby the draft provided may be adjusted.
- the extraction means are controlled so as to isolate the burner flames (if there are a plurality of burners) from each other, to control the direction of the flame so as to optimise the impingement of the flame over the surface and to efficiently remove the by-products which are generated by the combustion.
- a single conduit is associated with a burner it is preferably positioned upstream of the conduit but in the preferred embodiments exhaust conduits are provided both upstream and downstream of each burner head.
- the quality of the coating which is deposited can be improved by extracting the exhaust gases in a manner which causes the tail of the flame to be positioned above the surface of the substrate i.e. when the burner is located above the surface the tail of the flame is also located above the surface and when the burner is located below the surface the tail of the flame is also below the surface. Extracting the gases in this way has been found to reduce powder formation and to improve the uniformity of the coating. These are significant advantages especially in an on line coating process where a high deposition speed is advantageous.
- the temperature of the flame varies with the choice of comburant. Any gas which can be burnt to generate a sufficiently high flame temperature to decompose the precursor is potentially useful. Generally the comburant will be one which generates a flame temperature of at least 1700°C.
- the preferred comburants include hydrocarbons such as propane, acetylene, methane and natural gas or hydrogen.
- the temperature of deposition may be at a substrate temperature of 20 to 650°C, preferably 100 to 450°C, more preferably 100 to 300°C and most preferably 100 to 250°C.
- the fluid mixture preferably further comprises a carrier fluid, preferably a carrier gas, and/or an oxidant and optionally a comburant.
- the comburant may be burnt in any gas which comprises a source of oxygen. Typically the comburant will be mixed with and burnt in air.
- the ratio of comburant to air may be adjusted so that the flame is either oxygen rich or oxygen deficient.
- the use of an oxygen rich flame favours the production of a fully oxidised coating whereas the use of an oxygen deficient flame favours the production of a coating which is less than fully oxidised.
- the amount of oxidant in the fluid mixture is such that the parameter ⁇ 0X idant,
- a ox idant is the amount of oxidant
- Aoxcomburant is the amount of oxidant necessary to fully oxidise the comburant
- Aa Ixprecursor is the amount of oxidant necessary to fully oxidise the coating precursor.
- the amount of oxidant is in this range, it has been surprisingly discovered that the anti-reflection properties of the coated substrate are good especially at the relatively low temperature used in the process according to the first aspect of the invention.
- the amount of oxidant oxygen
- the amount of oxidant should preferably be greater such that ⁇ 5.
- ox idaiit is less than 1.3, more preferably less than 1.2 and most preferably 1 or lower.
- Values of ox idaiit in this range are advantageous because they result in improved anti reflection properties of the second coating, even at relatively low deposition temperatures.
- Coated substrates according to the first aspect of the invention may be used in many areas of industry.
- coated substrates according to the invention may be used as substrates in photovoltaic modules.
- the present invention provides a photovoltaic module comprising a coated substrate according to the first aspect of the invention.
- the invention is illustrated by the following Figures in which:
- Figure 1 is a scanning electron micrograph of a second coating according to the invention.
- Figure 2 is a graph of transmission (%) against wavelength for Example 5 (higher transmission curve) compared to the TCO coated substrate (lower transmission curve) without the second coating.
- Figure 3 is a graph of transmission (%) against wavelength for Example 1 (higher transmission curve) compared to the TCO coated substrate (lower transmission curve) without the second coating.
- Figure 1 illustrates a silica coating deposited on the tin side of TCO coated float glass.
- the silica coating is deposited as described in the Examples with 6 passes under the coater.
- the coating comprises two portions: a relatively dense portion against the substrate surface approximately 100 nm thick, and a porous portion above the dense portion approximately 540 nm thick.
- SIMS analysis indicates that the dense portion is silica, relatively high in sodium.
- Coatings comprising silica were deposited on the tin side of float glass with a transparent conductive oxide (TCO) coating deposited by on line CVD on the air side.
- TCO transparent conductive oxide
- the layers and thicknesses of the TCO coating for each Example were as indicated in table 1.
- a fluid mixture comprising propane, air and hexamethyldisiloxane (HMDSO) was fed to a burner for flame deposition of silica coatings.
- the deposition conditions for the silica coatings were: glass temperature 180 °C, propane flow rate 3.5 standard litres/minute, air 75 standard litres/minute.
- Six coating passes were made for each coating.
- the flow rate of HMDSO (liquid) was 3.3 cm 3 /hour
- the flow rate of HMDSO (liquid) was 12 cm 3 /hour.
- the silica coatings were deposited across about 85 mm width of the substrate. The substrate was moved at about 3 m/min relative to the burner.
- T v i s values were calculated from the spectra of the samples (according to ISO9050 and EN410/673). The values are given in Table 2 for the substrates (carrying a TCO coating on the first surface) and the Examples (i.e. substrates after coating with the second coating on the second surface).
- Figures 2 and 3 illustrate the % transmission against wavelength for Examples 5 and 1 compared to TCO coated substrates without the tin side (second) coating.
- the optical properties of the other Examples are similar. In each case the second coatings significantly increase T v i s . The durability of the coatings was also good.
- the % improvement of weighted transmission values were calculated for standard photovoltaic cells of varying types. The results of this calculation are described in Table 2.
- the silica coatings of Examples 1 to 5 significantly improve the transmission of light into PV cells with consequent improvement in efficiency.
- c-Si refers to crystalline silicon PV cell, CdTe to a cadmium telluride PV cell, a-Si to amorphous silicon PV cell, uc-Si to microcrystalline silicon PV cell and CIGS to copper indium gallium selenide PV cell.
- ECDL Electro-chemical delamination
- the scratching generates a path for water vapor to reach the TCO-glass interface, and it also creates a mechanical defect that helps to initiate the delamination in a damaged coating. If no delamination occurs within 15 min after the scratching is applied, it suggests the TCO coating has a good adhesion to the glass substrate, indicating less risk of delamination in use.
- the results of the ECDL test for Example 3 are described in Table 3 and compared to the results for the same TCO coated glass without the tin side coating (Comparative Example).
- Example 3 2/2 Approx. 67.9 43.9 39.1 35.2 32.3 30.6
- the inventors have discovered that the dense silica layer or dense silica layer with a porous top coat significantly reduces / eliminates this increased reflection / loss of transmission. This effect can be seen when coating on the bottom surface of float glass but is of a further benefit when a TCO is coated on the top surface.
- dense silica layers are regarded as layers having a density of the same order of magnitude as the glass substrate and porous top coats are regarded as coats which substantially allow for fluid communication between opposing surfaces or interfaces due to porosity.
- a coating having a dense portion and a porous portion refers to any coating having two portions, one of which has a greater density than the other.
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Abstract
Substrate with TCO on one surface and SiO2 underlayer on other. Underlayer has dense portion and porous portion providing for alkali blocking and RI matching respectively. A second aspect provides a float glass substrate having and antireflection layer on the tin side surface of the substrate. The antireflection layer may comprise a dense region or a dense region and a porous region and eliminates or reduces unwanted reflections associated with tin diffusion to the substrate during the float glass process.
Description
COATED SUBSTRATE
This invention relates to coated substrates comprising a coating on at least one surface with a transparent conductive coating on at least one other surface. The invention also relates to processes for the production of such coated substrates.
It is known to deposit coating on substrates for various purposes. For example, sol gel type deposition processes have been proposed in EP 1429997, DE 10146687, EP 1328483 and USP 6918957 in which a silica sol is coated on to the surface of a substrate and heated at elevated temperature so as to drive off organic material resulting in the production of a silica coating.
Other types of deposition processes include chemical vapour deposition where a vapour of a precursor is directed at the substrate surface, often at elevated temperature. Deposition processes may involve directing the precursor through a flame on to the substrate surface. USPA 2006/003108 discloses a process for depositing a coating on to the surface of a glass substrate in which a silicon containing precursor is decomposed with a flame and the substrate is introduced into the flame so as to apply the precursor to the substrate directly from the gas phase. WO-A-2009/00745 also discloses flame pyrolysis processes for deposition of coatings upon the surface of a continuous glass ribbon.
Deposition processes for deposition of transparent conductive coatings include those processes used to deposit conductive oxides such as indium tin oxide, doped tin oxide, doped zinc oxide and doped cadmium oxide. These processes may include chemical vapour deposition, flame pyrolysis, sputtering (or other types of physical vapour deposition) and other processes. One of the uses of transparent conductive coatings is in photovoltaic (PV) modules.
In photovoltaic (PV) modules, substrates may be coated with a transparent conductive coating and then further layers, as components of the PV cells, may be deposited on the conductive coating. In use, however, the transparent conductive coatings may occasionally delaminate from the substrate surface which causes failure of PV cells and may cause the whole module to fail.
It is an aim of the present invention to address the delamination problem.
The present invention accordingly provides, in a first aspect, a coated substrate comprising a substrate having a first surface and a second surface, a transparent conductive coating on the first surface and a second coating on the second surface.
This is advantageous because, surprisingly, the presence of the second coating on the second surface reduces the potential for delamination of the conductive coating on the first surface.
It is preferred if the second coating is an antireflection coating, preferably, with a refractive index of 1.25 to 1.4. This is particularly advantageous when the substrate is a transparent (or substantially transparent or translucent) substrate because it increases transmission of light. If the coated substrate is to be used in PV modules this can be a very significant improvement because an increase in transmission of just 1 to 3% can have a beneficial effect on the efficiency of a PV module.
The thickness of the coating is preferably that which will result in destructive interference between the light reflected from the surface of the coating and the surface of the glass (if the substrate is glass). For optimum destructive interference the length of the optical path in the coating should be equal to one half of the wavelength of the light. This thickness can be calculated from the equation where t is the thickness of the coating, λ is the wavelength of the incident light and n is the refractive index of the coating.
The thickness of the second coating is preferably in the range 10 to 1100 nm. It is preferred if the thickness of the second coating is 25 nm or greater, 40 nm or greater, 50 nm or greater, 80 nm or greater or 100 nm or greater. The more preferred thickness is 105 to 500 nm, most preferably 105 to 200 nm.
The second coating may have a porous portion and/or a dense portion. If a dense portion is present it is preferably in contact with the substrate surface. The advantage of the porous portion of the second coating is that is tends to reduce the refractive index of the second coating. At least a part of the dense portion preferably has a thickness in the range 10 to 150 nm, more preferably 10 to 95 nm, most preferably 15 to 80 nm. At least a part of the porous portion preferably has a thickness in the range 50 to 1000 nm, more preferably 50 to 600 nm, most preferably 60 to 250 nm.
Preferably, the second coating comprises a silicon oxide, for example silicon oxynitride (SiNO), silicon oxycarbide (SiCO) or silicon dioxide (silica). The preferred material of the second coating is silicon dioxide.
The substrate will usually comprise glass, preferably float glass or rolled glass. The glass may be a soda lime float glass, a low iron float glass or a body tinted float glass comprising a higher proportion of iron, cobalt or selenium which may have a green, grey or blue colouration. In a preferred embodiment the glass has an iron content of 0.015% by weight or lower.
The glass substrate may have a thickness of from 0.5 mm to 25 mm preferably of from 2 mm to 20 mm and a visible light transmission of from 10.0% to 90.0%.
The coated glass, where the second coating is an antireflection coating, may have a visible light transmission which is from 1% to 3.5% greater than the glass before the coating was applied.
If the glass is float glass it is preferred that the second surface of the glass is the tin side surface and the first surface of the glass is the gas side surface. This is advantageous because subsequent processing (including of deposition of other layers on the conductive coating) is usually preferred by PV producers to be on the gas side surface (also known as the air side surface).
The transparent conductive coating is preferably a transparent conductive oxide coating. Preferred oxides are selected from tin oxide, zinc oxide, copper oxide, indium oxide, a mixed oxide and/or mixtures thereof. The most preferred oxide is doped tin oxide (in particular fluorine doped tin oxide).
The coated substrate may comprise one or more further coatings which may be deposited under or above the second coating and/or under or above the transparent conductive coating. Typical further coating include coatings comprising one or more layers of a metal oxide or a silicon oxide.
In a second aspect the present invention provides a process for the deposition of a second coating on a substrate, the process comprising providing a substrate having a transparent conductive coating on a first surface, passing a fluid mixture comprising a coating precursor through a flame, and contacting at least a second surface of the substrate with the coating precursor during or after its passage through the flame, thereby depositing the second coating.
Flame pyrolysis deposition processes usually comprise the steps of forming a fluid mixture comprising a precursor of an oxide of a metal or a metalloid, an oxidant and optionally a comburant. This fluid mixture may then be ignited at a point which is adjacent to the surface of the substrate. The precursor for the oxide may be any compound of a metal or metalloid which may be dispersed in the fluid mixture and which will decompose to form an oxide when the mixture is ignited. Processes in which the precursor is in the vapour phase are commonly termed combustion chemical vapour deposition processes (often known as CCVD processes). In a preferred embodiment the processes of this aspect of the invention are CCVD processes.
Examples of precursors which may be used in the formation of silica coatings include compounds having the general formula SiX4 wherein the groups X which may be the same or different represent a halogen atom especially a chlorine atom or a bromine atom, a hydrogen atom, an alkoxy group having the formula -OR or an ester group having the formula -OOCR wherein R represents an alkyl group comprising from 1 to 4 carbon atoms. Particularly preferred precursors for use in the present invention include tetraethoxysilane (TEOS), hexamethyldisiloxane (HMDSO) and silane.
The thermal output of the burners useful in the processes of this invention may be from 0.5 to 10 kW/10cm2, preferably from 1 to 5 kW/10cm2. The concentration of precursor in the fluid mixture which is delivered to the burner is typically from 0.05 to 25 vol%, preferably from 0.05 to 5 vol% gas phase concentration.
The process may be carried out by passing the fluid mixture to a burner which is positioned above or below the surface of the substrate. One burner or a series of smaller burners may be used to coat the substrate evenly. The burner is preferably positioned by the substrate in close proximity to the second surface. The distance between the burner and the surface will typically be in the range of from 2 to 20 mm and preferably in the range 5.0 to 15.0 mm. Such close proximity results in a coating having improved properties possibly because it minimises the amount of recombination between the species produced by burning the precursor before they are deposited upon the surface of the substrate. It may be necessary to adjust the distance between the burner and the surface in order to optimise the properties of the desired coating.
The process, whether off line or on line, may be carried out at a range of relative speeds of the substrate (relative to the burner or burners). Typically relative speeds are 1 to 25 m/min, preferably 2 to 20 m/min.
The burner is preferably associated with means for extracting the exhaust gases from the area adjacent to the surface of the substrate. In the preferred embodiments at least one means for extraction is positioned adjacent to each burner. The extraction means is typically a conduit associated with a fan which produces an updraft at the mouth of the conduit. Each extraction means is preferably provided with control means whereby the draft provided may be adjusted. In the preferred embodiments of the invention the extraction means are controlled so as to isolate the burner flames (if there are a plurality of burners) from each other, to control the direction of the flame so as to optimise the impingement of the flame over the surface and to efficiently remove the by-products which are generated by the combustion. Where a single conduit is associated with a burner it is preferably positioned upstream of the conduit but in the preferred embodiments exhaust conduits are provided both upstream and downstream of each burner head.
The Applicants have discovered that the quality of the coating which is deposited can be improved by extracting the exhaust gases in a manner which causes the tail of the flame to be positioned above the surface of the substrate i.e. when the burner is located above the surface the tail of the flame is also located above the surface and when the burner is located below the surface the tail of the flame is also below the surface. Extracting the gases in this way has been found to reduce powder formation and to improve the uniformity of the coating. These are significant advantages especially in an on line coating process where a high deposition speed is advantageous.
The temperature of the flame varies with the choice of comburant. Any gas which can be burnt to generate a sufficiently high flame temperature to decompose the precursor is potentially useful. Generally the comburant will be one which generates a flame temperature of at least 1700°C. The preferred comburants include hydrocarbons such as propane, acetylene, methane and natural gas or hydrogen.
The temperature of deposition may be at a substrate temperature of 20 to 650°C, preferably 100 to 450°C, more preferably 100 to 300°C and most preferably 100 to 250°C.
The fluid mixture preferably further comprises a carrier fluid, preferably a carrier gas, and/or an oxidant and optionally a comburant. The comburant may be burnt in any gas which comprises a source of oxygen. Typically the comburant will be mixed with and burnt in air. The ratio of comburant to air may be adjusted so that the flame is either oxygen rich or oxygen deficient. The use of an oxygen rich flame favours the production of a fully oxidised coating whereas the use of an oxygen deficient flame favours the production of a coating which is less than fully oxidised.
It is preferred if the amount of oxidant in the fluid mixture is such that the parameter λ 0Xidant,
wherein Aoxidant is the amount of oxidant, Aoxcomburant is the amount of oxidant necessary to fully oxidise the comburant and Aa Ixprecursor is the amount of oxidant necessary to fully oxidise the coating precursor.
When the amount of oxidant is in this range, it has been surprisingly discovered that the anti-reflection properties of the coated substrate are good especially at the relatively low temperature used in the process according to the first aspect of the invention. Previously (in for example WO-A-2009/00745) it was thought that the amount of oxidant (oxygen) should preferably be greater such that
·5.
It is preferred if oxidaiit is less than 1.3, more preferably less than 1.2 and most preferably 1 or lower.
Values of oxidaiit in this range are advantageous because they result in improved anti reflection properties of the second coating, even at relatively low deposition temperatures.
Coated substrates according to the first aspect of the invention may be used in many areas of industry. In particular coated substrates according to the invention may be used as substrates in photovoltaic modules.
Thus, in a third aspect the present invention provides a photovoltaic module comprising a coated substrate according to the first aspect of the invention.
The invention is illustrated by the following Figures in which:
Figure 1 is a scanning electron micrograph of a second coating according to the invention.
Figure 2 is a graph of transmission (%) against wavelength for Example 5 (higher transmission curve) compared to the TCO coated substrate (lower transmission curve) without the second coating.
Figure 3 is a graph of transmission (%) against wavelength for Example 1 (higher transmission curve) compared to the TCO coated substrate (lower transmission curve) without the second coating.
Figure 1 illustrates a silica coating deposited on the tin side of TCO coated float glass. The silica coating is deposited as described in the Examples with 6 passes under the coater. The coating comprises two portions: a relatively dense portion against the substrate surface approximately 100 nm thick, and a porous portion above the dense portion approximately 540 nm thick. SIMS analysis indicates that the dense portion is silica, relatively high in sodium.
Examples
The invention is further illustrated by the following Examples.
Coatings comprising silica were deposited on the tin side of float glass with a transparent conductive oxide (TCO) coating deposited by on line CVD on the air side. The TCO coating were deposited on the glass during the float glass production process in the tin bath and/or lehr gap.
The layers and thicknesses of the TCO coating for each Example were as indicated in table 1.
Example Substrates: nature of TCO Coating
1 Glass/Sn02(25 nm)/Si02(25 nm)/SnO2:F(340 nm)
2 Glass/SnO2(60nm)/SiO2(25 nm)/SnO2:F(630 nm)
3 Glass/Sn02(25 nm)/Si02(25 nm)/SnO2:F(420
nm)/Sn02(75 nm)
4 Low iron glass (600 ppm)/Sn02(25 nm)/Si02(25
nm)/SnO2:F(420 nm)/Sn02(75 nm)
5 Glass/Sn02 (40-80nm)/SiO2 (10-20nm)/SnO2:F(700- 850nm)
Table 1
A fluid mixture comprising propane, air and hexamethyldisiloxane (HMDSO) was fed to a burner for flame deposition of silica coatings. The deposition conditions for the silica coatings were: glass temperature 180 °C, propane flow rate 3.5 standard litres/minute, air 75 standard litres/minute. Six coating passes were made for each coating. In Example 1 the flow rate of HMDSO (liquid) was 3.3 cm3/hour, for Examples 2 to 5 the flow rate of HMDSO (liquid) was 12 cm3/hour. The silica coatings were deposited across about 85 mm width of the substrate. The substrate was moved at about 3 m/min relative to the burner.
The optical properties of the Examples were analysed. Tvis values were calculated from the spectra of the samples (according to ISO9050 and EN410/673). The values are given in Table 2 for the substrates (carrying a TCO coating on the first surface) and the Examples (i.e. substrates after coating with the second coating on the second surface). Figures 2 and 3 illustrate the % transmission against wavelength for Examples 5 and 1 compared to TCO coated substrates without the tin side (second) coating. The optical properties of the other Examples are similar. In each case the second coatings significantly increase Tvis. The durability of the coatings was also good.
The % improvement of weighted transmission values were calculated for standard photovoltaic cells of varying types. The results of this calculation are described in Table
2. The silica coatings of Examples 1 to 5 significantly improve the transmission of light into PV cells with consequent improvement in efficiency.
Table 2.
In Table 2, c-Si refers to crystalline silicon PV cell, CdTe to a cadmium telluride PV cell, a-Si to amorphous silicon PV cell, uc-Si to microcrystalline silicon PV cell and CIGS to copper indium gallium selenide PV cell.
The effect of the second (tin) side coatings on delamination of the TCO coatings were investigated using the Electro-chemical delamination (ECDL) test. ECDL is an accelerated screening test using a hot plate and voltage source to rapidly drive Na+ ion from the glass substrate to the TCO layer to generate stress, which eventually results in cracking and peeling of the coatings. In the test, the glass side of the sample is positively biased under 100 V, at 185°C for 15 minutes. The sample is then removed from the heat and bias, and kept within a humidity chamber (50%HR) to allow water vapour to diffuse to the interface and initiate the delamination process. After 5 min of storage in the humidity ambient air, the TCO is scratched with a razor blade. The scratching generates a path for water vapor to reach the TCO-glass interface, and it also creates a mechanical defect that helps to initiate the delamination in a damaged coating. If no delamination occurs within 15 min after the scratching is applied, it suggests the TCO coating has a good adhesion to the glass substrate, indicating less risk of delamination in use.
The results of the ECDL test for Example 3 are described in Table 3 and compared to the results for the same TCO coated glass without the tin side coating (Comparative Example).
ECDL current (μΑ)
Result Time to t=0 t=3 t=6 t=9 t=12 t=15
(#pass at 15 failure min min min min min min
min / total
tested)
Comparative 2/2 Approx. 82.7 69.9 66 62.2 59.5 56.9
Example 18 min
Example 3 2/2 Approx. 67.9 43.9 39.1 35.2 32.3 30.6
18
hours
Table 3
During the manufacture of float glass it is inherent in the production process that some of the molten tin which the glass is floated on diffuses into the bottom surface of the glass. This is known to have a detrimental impact on the optical quality of the glass by increasing the reflection from this bottom surface and thus resulting in reduced transmission.
The inventors have discovered that the dense silica layer or dense silica layer with a porous top coat significantly reduces / eliminates this increased reflection / loss of transmission. This effect can be seen when coating on the bottom surface of float glass but is of a further benefit when a TCO is coated on the top surface.
In this context, dense silica layers are regarded as layers having a density of the same order of magnitude as the glass substrate and porous top coats are regarded as coats which substantially allow for fluid communication between opposing surfaces or interfaces due to porosity.
A coating having a dense portion and a porous portion refers to any coating having two portions, one of which has a greater density than the other.
Claims
1. A coated substrate comprising a substrate having a first surface and a second surface, a transparent conductive coating on the first surface and a second coating on the second surface.
2. A coated substrate as claimed in claim 1, wherein the second coating is an anti reflection coating, preferably having a refractive index in the range 1.25 to 1.4.
3. A coated substrate as claimed in either claim 1 or claim 2, wherein the second coating comprises a porous portion.
4. A coated substrate as claimed in any one of the preceding claims, wherein the second coating comprises a dense portion.
5. A coated substrate as claimed in claim 4, wherein the dense portion is in contact with the substrate surface.
6. A coated substrate as claimed in either claim 4 or claim 5 wherein the dense portion has a thickness in the range 10 to 150 nm.
7. A coated substrate as claimed in any one of the preceding claims, wherein the second coating comprises a silicon oxide.
8. A coated substrate as claimed in any one of the preceding claims, wherein the thickness of the second coating is 10 to 500nm, preferably 105 to 200nm.
9. A coated substrate as claimed in any one of the preceding claims, wherein the substrate comprises glass.
10. A coated substrate as claimed in any one of the preceding claims, wherein the glass is float glass or rolled glass.
11. A coated substrate as claimed in any one of the preceding claims, wherein the glass has an iron content of 0.015% by weight or lower.
12. A coated substrate as claimed in either claim 10 or claim 11, wherein the glass is float glass and the second surface of the glass is the tin side surface and the first surface of the glass is the gas side surface
13. A coated substrate as claimed in any one of the preceding claims, wherein the transparent conductive coating is a transparent conductive oxide coating and is preferably selected from a tin oxide, a zinc oxide, a copper oxide, an indium oxide, a mixed oxide and/or mixtures thereof.
14. A coated substrate as claimed in any one of the preceding claims, further comprising at least one further coating.
15. A process for the deposition of a coating on a substrate, the process comprising a) providing a substrate having a transparent conductive coating on a first surface,
b) passing a fluid mixture comprising a coating precursor through a flame, and
c) contacting at least a second surface of the substrate with the coating precursor during or after its passage through the flame thereby depositing a second coating on the second surface.
16. A process as claimed in claim 15, wherein the substrate temperature is 100 to 450°C.
17. A process as claimed in either claim 15 or claim 16, wherein the substrate temperature is 105 to 350°C, preferably 105 to 200°C.
18. A process as claimed in any one of claims 15 to 17, wherein the fluid mixture further comprises a carrier fluid, preferably a carrier gas, and/or an oxidant.
A process as claimed in any one of claims 15 to 18, wherein the amount of oxidant in the fluid mixture is such that the parameter λ oxidant,
^oxidant Aidant — 1 · 5
20. A photovoltaic module comprising a coated substrate as claimed in any one of claims 1 to 14.
21. A coated float glass substrate having a tin side surface, said tin side surface being a surface which contacted molten tin during the float glass process, characterised by an antireflection coating on the tin side surface.
22. A coated float glass substrate according to claim 21, wherein the coating has a refractive index in the range 1.25 to 1.4.
23. A coated float glass substrate according to claim 21 or 22 wherein the coating comprises a porous portion.
24. A coated float glass substrate according to any of claims 21 to 23 wherein the coating comprises a dense portion.
25. A coated float glass substrate wherein the dense portion is in contact with the substrate surface.
26. A coated float glass substrate as claimed in claim 24 or 25, wherein the dense portion has a thickness of 10 to 150nm.
27. A coated float glass substrate as claim in any of claims 21 to 26, wherein the coating comprises a silicon oxide.
28. A coated float glass substrate according to any of claims 21 to 27, where the thickness of the coating is 10 to 500nm, preferably 105 to 200nm.
29. A process for the deposition of a coating on a float glass substrate, the process comprising:
a) providing a float glass substrate having a tin side surface, said tin side surface being a surface which contacted molten tin during the float glass process;
b) passing a fluid mixture comprising a coating precursor through a flame and c) contacting at least the tin side surface of the substrate with the coating precursor during or after its passage through the flame, thereby depositing a coating on the tin side surface.
30. A process as claimed in claim 29, wherein the substrate temperature is 100 to 450°C.
31. A process as claimed in either claim 29 or claim 30, wherein the substrate temperature is 105 to 350°C, preferably 105 to 200°C.
32. A process as claimed in any one of claims 29 to 31, wherein the fluid mixture further comprises a carrier fluid, preferably a carrier gas, and/or an oxidant.
33. A process as claimed in any one of claims 15 to 18, wherein the amount of oxidant in the fluid mixture is such that the parameter λ oxidant,
^oxidant Aidant — 1.5
(Acomburarrf^Aprecui-soi-) wherein Aoxidant is the amount of oxidant, Ac0mbUrant is the amount of comburant and Aprecursor is the amount of coating precursor.
34. A photovoltaic module comprising a coated substrate as claimed in any one of claims 21 to 28.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0922407.2 | 2009-12-22 | ||
GBGB0922407.2A GB0922407D0 (en) | 2009-12-22 | 2009-12-22 | Coated substrate |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011077157A1 true WO2011077157A1 (en) | 2011-06-30 |
Family
ID=41717389
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB2010/052193 WO2011077157A1 (en) | 2009-12-22 | 2010-12-22 | Coated substrate |
Country Status (2)
Country | Link |
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GB (1) | GB0922407D0 (en) |
WO (1) | WO2011077157A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013014423A1 (en) | 2011-07-22 | 2013-01-31 | Pilkington Group Limited | Deposition process |
WO2016062768A3 (en) * | 2014-10-21 | 2016-06-16 | Dsm Ip Assets B.V. | Method of coating substrate |
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WO2016062768A3 (en) * | 2014-10-21 | 2016-06-16 | Dsm Ip Assets B.V. | Method of coating substrate |
Also Published As
Publication number | Publication date |
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GB0922407D0 (en) | 2010-02-03 |
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