CN110699668A - Composite coating body, preparation method and application thereof, and solar cell - Google Patents
Composite coating body, preparation method and application thereof, and solar cell Download PDFInfo
- Publication number
- CN110699668A CN110699668A CN201910986983.3A CN201910986983A CN110699668A CN 110699668 A CN110699668 A CN 110699668A CN 201910986983 A CN201910986983 A CN 201910986983A CN 110699668 A CN110699668 A CN 110699668A
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- CN
- China
- Prior art keywords
- silicon dioxide
- dioxide layer
- composite coating
- super
- silane coupling
- Prior art date
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Links
- 239000002131 composite material Substances 0.000 title claims abstract description 144
- 238000000576 coating method Methods 0.000 title claims abstract description 132
- 239000011248 coating agent Substances 0.000 title claims abstract description 130
- 238000002360 preparation method Methods 0.000 title abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 333
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 101
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 97
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 63
- 230000003075 superhydrophobic effect Effects 0.000 claims abstract description 59
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 54
- 239000000413 hydrolysate Substances 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 29
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 67
- 238000000151 deposition Methods 0.000 claims description 66
- 230000008021 deposition Effects 0.000 claims description 61
- 239000000126 substance Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 29
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 26
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 26
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 23
- 239000011521 glass Substances 0.000 claims description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 229910001868 water Inorganic materials 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- -1 polyethylene Polymers 0.000 claims description 12
- 239000000741 silica gel Substances 0.000 claims description 12
- 229910002027 silica gel Inorganic materials 0.000 claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 7
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 7
- DFJDZTPFNSXNAX-UHFFFAOYSA-N ethoxy(triethyl)silane Chemical compound CCO[Si](CC)(CC)CC DFJDZTPFNSXNAX-UHFFFAOYSA-N 0.000 claims description 7
- 239000000499 gel Substances 0.000 claims description 7
- 239000010445 mica Substances 0.000 claims description 7
- 229910052618 mica group Inorganic materials 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 238000004528 spin coating Methods 0.000 claims description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 6
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 6
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 5
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 5
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 claims description 4
- 238000000038 ultrahigh vacuum chemical vapour deposition Methods 0.000 claims description 4
- 229920000491 Polyphenylsulfone Polymers 0.000 claims description 3
- 239000005388 borosilicate glass Substances 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- KWUXODGLFDJGBS-UHFFFAOYSA-N dimethoxy-[3-(oxiran-2-ylmethoxy)butoxy]-propylsilane Chemical compound CCC[Si](OC)(OC)OCCC(C)OCC1CO1 KWUXODGLFDJGBS-UHFFFAOYSA-N 0.000 claims description 3
- 239000005361 soda-lime glass Substances 0.000 claims description 3
- 239000012495 reaction gas Substances 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 13
- 230000007774 longterm Effects 0.000 abstract description 10
- 239000010410 layer Substances 0.000 description 107
- 238000003756 stirring Methods 0.000 description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 description 12
- 239000002585 base Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 238000001132 ultrasonic dispersion Methods 0.000 description 11
- 239000011247 coating layer Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920012287 polyphenylene sulfone Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
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- 239000002352 surface water Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C16/402—Silicon dioxide
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
-
- 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
-
- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
-
- 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
Abstract
The invention relates to the field of solar cells, and particularly provides a composite coating body, a preparation method and application thereof, and a solar cell. The tape composite coating body includes: the composite coating comprises a substrate and a composite coating formed on the surface of the substrate, wherein the composite coating comprises: the nano silicon dioxide layer is formed on the surface of the base material by adopting a chemical vapor deposition method; the super-hydrophobic silicon dioxide layer is arranged opposite to the nano silicon dioxide layer; the nano silicon dioxide layer is connected with the super-hydrophobic silicon dioxide layer through a silicon-oxygen bond; wherein, the nano silicon dioxide layer and the super-hydrophobic silicon dioxide layer respectively contain hydroxyl and are condensed with a hydrolysate of a silane coupling agent to form a silicon-oxygen bond. The composite coating body with the composite coating has the advantages of stable and firm structure, good hydrophobicity, excellent stain resistance and high transparency, and can keep good super-hydrophobic property and light transmittance under the condition of long-term use in severe outdoor environment, so that the photoelectric efficiency of the solar cell is not lost.
Description
Technical Field
The invention relates to the field of solar cells, in particular to a composite coating body, a preparation method and application thereof and a solar cell.
Background
With the increasing population and the increasing demand for energy, green and renewable energy sources have great significance for the sustainable development of society. Solar cells have become a research hotspot in the field of renewable energy sources as a clean, low-cost energy device.
However, the power generation efficiency of a solar photovoltaic module used for power generation is generally affected by many environmental factors, such as available solar radiation, wind speed, wind direction, ambient temperature, humidity, and atmospheric dust. Particularly in desert regions, due to frequent occurrence of sand storms, the dust on the surface of the solar module is accumulated too much, and finally the power generation efficiency of the solar cell is remarkably reduced.
Dust on the surface of the solar photovoltaic module reduces the transmittance of the glass cover and prevents incident light photons from reaching the working part of the solar cell, thereby reducing the output power. A number of studies report the effect of dust deposition on solar panel efficiency: adinoyi et al report that if a solar photovoltaic module is not clean for more than 6 months, its photoelectric conversion efficiency will decrease by 50%; also, in the same manner as above,hee et al found that for bare glass samples, the transmission rate decreased despite heavy rain on singapore lasting several months. After 33 days, the transmittance of the common glass slide is reduced from 90.7 percent to 87.6 percent; paudyal et al reported that the dust deposition density on the surface of the solar cell panel was from 0.1047g/m for 5 months outdoor exposure2Raised to 9.6711g/m2Resulting in a solar panel efficiency of only 29.76%. Therefore, how to improve the long-term contamination resistance of the solar cell panel is the key to ensure the conversion efficiency of the solar cell.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first object of the present invention is to provide a composite coating with a high bonding strength, in which a nano-silica layer is firmly bonded to a substrate, and the layers in the composite coating are bonded to each other by chemical bonds, so that the composite coating is not easily separated from the surface of the substrate, and has super-strong hydrophobicity, contamination resistance and good light transmittance, thereby preventing the photoelectric conversion efficiency of a solar cell from being reduced after the composite coating with a high bonding strength is used for a long time.
The second objective of the invention is to provide a preparation method of the composite coating body, the method has scientific process, the composite coating body obtained by the method has stable structure, the composite coating is not easy to separate from the surface of the base material, and has super-strong hydrophobicity, stain resistance and good light transmission, and the composite coating body can not reduce the photoelectric conversion efficiency of the solar cell after long-term use.
The third purpose of the invention is to provide the application of the composite coating in the preparation of the solar cell.
A fourth object of the present invention is to provide a solar cell.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the present invention provides a coated composite body comprising: the composite coating comprises a substrate and a composite coating formed on the surface of the substrate, wherein the composite coating comprises:
the nano silicon dioxide layer is formed on the surface of the base material by adopting a chemical vapor deposition method;
the super-hydrophobic silicon dioxide layer is arranged opposite to the nano silicon dioxide layer;
the nano silicon dioxide layer is connected with the super-hydrophobic silicon dioxide layer through a silicon-oxygen bond; wherein, the nano silicon dioxide layer and the super-hydrophobic silicon dioxide layer respectively contain hydroxyl and are condensed with a hydrolysate of a silane coupling agent to form a silicon-oxygen bond.
As a further preferred technical solution, the substrate comprises glass, silicon wafer, mica sheet or polymer sheet;
preferably, the glass comprises quartz glass, high borosilicate glass or soda lime glass, preferably quartz glass;
preferably, the polymeric sheet comprises a polyethylene sheet, a polyvinyl chloride sheet, a polypropylene sheet, a polycarbonate sheet, a polymethylmethacrylate sheet or a polyphenylsulfone sheet;
preferably, the thickness of the nano silicon dioxide layer is 200-800 nm; an intermediate connecting layer is formed between the nano silicon dioxide layer and the super-hydrophobic silicon dioxide layer, and the thickness of the intermediate connecting layer is 0.5-1 mu m; the thickness of the super-hydrophobic silicon dioxide layer is 200-600 nm;
preferably, the particle size of the silicon dioxide in the nano silicon dioxide layer is 10-20 nm;
preferably, the silane coupling agent includes at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (2, 3-glycidoxypropyl) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, or gamma-aminopropylmethyldiethoxysilane.
In a second aspect, the present invention provides a method for producing a body with a composite coating layer, including the steps of:
(a) providing a base material, and depositing a nano silicon dioxide layer on the surface of the base material by adopting a chemical vapor deposition method;
(b) providing a hydrolysate of a silane coupling agent;
(c) providing a super-hydrophobic silica suspension;
(d) and sequentially coating the hydrolysate of the silane coupling agent and the super-hydrophobic silica suspension on the surface of the nano silica layer, and curing to obtain the composite coating body.
In a further preferred embodiment, the chemical vapor deposition method includes a plasma enhanced chemical vapor deposition method, an ultra-high vacuum chemical vapor deposition method, or a low temperature chemical vapor deposition method, and is preferably a plasma enhanced chemical vapor deposition method.
As a further preferred embodiment, the reaction gas source for chemical vapor deposition comprises SiH4And N2O；
Preferably, SiH4And N2The volume ratio of O is 1: 0.1 to 5, preferably 1: 0.1 to 2;
preferably, the deposition conditions of the chemical vapor deposition method include at least one of the following conditions:
the deposition temperature is 30-300 ℃, preferably 150-250 ℃, and more preferably 150-180 ℃;
the radio frequency power is 20-200W, preferably 60-80W, and further preferably 65-75W;
the deposition pressure is 10-150Pa, preferably 80-100Pa, and more preferably 85-95 Pa;
the deposition time is 1-10min, preferably 5-10min, and more preferably 6-9 min.
As a further preferred embodiment, the step (b) comprises: under the alkaline condition, the silane coupling agent is subjected to hydrolysis reaction in an aqueous solution of alcohol to obtain a hydrolysate of the silane coupling agent;
preferably, step (b) comprises: firstly, uniformly mixing a silane coupling agent with an aqueous solution of alcohol, and then uniformly mixing the silane coupling agent with an alkaline substance to obtain a hydrolysate of the silane coupling agent;
preferably, the time of the hydrolysis reaction is 10-60min, preferably 20-40 min;
preferably, the alcohol comprises a C1-C4 alcohol;
preferably, the C1-C4 alcohol comprises at least one of methanol, ethanol, isopropanol, n-butanol, propylene glycol, or glycerol;
preferably, the mass ratio of alcohol to water in the aqueous alcohol solution is 1: 0.01 to 5, preferably 1: 0.05 to 1;
preferably, the alkaline substance includes an organic alkaline substance and/or an inorganic alkaline substance;
preferably, the organic basic substance includes an organic amine;
preferably, the organic amine comprises an aliphatic amine;
preferably, the fatty amine comprises at least one of decylamine, dodecylamine, hexadecylamine, or octadecylamine;
preferably, the inorganic alkaline substance comprises ammonia and/or sodium carbonate.
As a further preferred embodiment, the step (c) comprises: carrying out surface grafting reaction on the silica gel obtained by the sol-gel method and a low surface energy modifier to obtain a super-hydrophobic silica suspension;
preferably, a silicon source, a catalyst and a solvent are mixed, and silica gel is obtained after sol-gel reaction;
preferably, the silicon source comprises a silicate;
preferably, the silicate comprises at least one of methyl orthosilicate, tetraethyl orthosilicate, tetrapropyl silicate, or butyl orthosilicate;
preferably, the solvent comprises an aqueous solution of an alcohol;
preferably, the catalyst comprises ammonia, hydrochloric acid, acetic acid or carbon dioxide;
preferably, the low surface energy modifying agent comprises at least one of hexamethyldisilazane, trimethylmethoxysilane, or triethylethoxysilane.
As a further preferred technical solution, the coating comprises blade coating, spray coating or spin coating;
preferably, the curing temperature is 20-200 ℃, preferably 50-100 ℃; and/or the curing time is 1-60min, preferably 10-30 min.
In a third aspect, the present invention provides a use of the above-described coated composite body or the coated composite body obtained by the above-described method for producing a coated composite body in the production of a solar cell.
In a fourth aspect, the present invention provides a solar cell including the above-described composite coated body or the composite coated body with tape obtained by the above-described method for producing a composite coated body with tape.
Compared with the prior art, the invention has the beneficial effects that:
the composite coating body comprises a base material and a composite coating formed on the surface of the base material, wherein a nano silicon dioxide layer in the composite coating is formed on the surface of the base material by adopting a chemical vapor deposition method, the chemical vapor deposition method is good in film forming quality, and a plated film is thin, and the nano silicon dioxide layer is formed independently, so that the nano silicon dioxide layer can be firmly combined with the base material; in addition, the surface of the nano silicon dioxide layer formed by the chemical vapor deposition method has a large number of active hydroxyl groups, which is beneficial to being connected with the active hydroxyl groups in the hydrolysate of the silane coupling agent to form silicon-oxygen bonds, so that the connection strength of the nano silicon dioxide layer and the hydrolysate of the silane coupling agent is improved; active hydroxyl in the hydrolysis condensation product of the silane coupling agent can be connected with active hydroxyl in the super-hydrophobic silica layer to form a silicon-oxygen bond, so that the connection strength between the super-hydrophobic silica layer and the hydrolysis product of the silane coupling agent (the two ends of the hydrolysis product both contain hydroxyl) is improved (the hydrolysis product of the silane coupling agent is condensed with the nano silica layer and the super-hydrophobic silica layer to form an intermediate connection layer).
Therefore, in the composite coating body with the specific structure, the composite coating can be firmly connected with the substrate, and the layers of the composite coating are connected through chemical bonds, so that the connection strength is high, the composite coating is not easy to separate from the surface of the substrate, and the structure of the composite coating body with the specific structure is stable. In addition, due to the existence of the super-hydrophobic silica layer, the super-hydrophobic silica layer has super hydrophobicity and stain resistance, and the hydrolysate of the silane coupling agent has high transparency, so that the super-hydrophobic silica layer can ensure good light transmission.
Therefore, the composite coating body with the super-hydrophobic property and the light transmittance can be kept well even if the composite coating body with the super-hydrophobic property is applied to packaging of the surface of a solar cell and used outdoors for a long time, and the photoelectric efficiency of the solar cell is guaranteed not to be lost.
Drawings
FIG. 1 is a schematic view of the structure of a composite coated body obtained in example 28;
FIG. 2 is a light transmission UV (ultraviolet and visible spectrum) spectrum of a blank glass, an intermediate bonding layer and the resulting composite coated body of example 28;
fig. 3 is a graph comparing the photoelectric conversion efficiency of the composite coated body-packaged solar cell and the bare glass-packaged solar cell obtained in example 28 during outdoor use for 60 days.
Icon: 1-a substrate; 2-composite coating; 201-a nano-silica layer; 202-a superhydrophobic silicon dioxide layer; 203-intermediate connection layer.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.
According to an aspect of the present invention, there is provided a coated composite body comprising: the composite coating comprises a substrate and a composite coating formed on the surface of the substrate, wherein the composite coating comprises:
the nano silicon dioxide layer is formed on the surface of the base material by adopting a chemical vapor deposition method;
the super-hydrophobic silicon dioxide layer is arranged opposite to the nano silicon dioxide layer;
the nano silicon dioxide layer is connected with the super-hydrophobic silicon dioxide layer through a silicon-oxygen bond; wherein, the nano silicon dioxide layer and the super-hydrophobic silicon dioxide layer respectively contain hydroxyl and are condensed with a hydrolysate of a silane coupling agent to form a silicon-oxygen bond.
The existing hydrophobic coating is mainly formed by adding a hydrophobic material with low surface energy into a coating and then coating the coating on the surface of an object, for example, by adopting a dip-dyeing method and the like. However, the coating formed by the method has the characteristics of poor adhesion and unstable super-hydrophobic property. The inventor finds out through research that: on the one hand, conventional coating methods such as dip dyeing dry the resulting coating to a substrate have poor adhesion; on the other hand, the hydrophobic material is mixed with other components of the coating, the binding force is poor, and a stable hydrophobic surface cannot be fully formed on the surface of the hydrophobic material; on the other hand, the existing multi-component coating containing hydrophobic materials is obviously incapable of forming a coating layer by a chemical vapor deposition method.
In view of the above, the present invention provides a composite coating body with the above structure, which has the advantages of stable and firm structure, good hydrophobicity, excellent stain resistance, and high transparency, and the long-term service performance is not deteriorated, so that the composite coating body with the above structure is applied to the packaging of the surface of a solar cell, and can maintain good super-hydrophobic property and light transmittance even under the long-term use in severe outdoor environment, thereby ensuring that the photoelectric efficiency of the solar cell is not lost.
It should be noted that:
the "nano-silica layer" mentioned above means a coating layer mainly composed of nano-scale silica, and the nano-scale silica means silica having a particle diameter ranging from 1 to 100 nm.
The super-hydrophobic silica layer is a coating formed by surface-modified silica, the surface-modified silica has super-strong hydrophobicity, the contact angle of water on the surface of the silica exceeds 140 degrees, and the sliding angle of the silica is less than 10 degrees.
In a preferred embodiment, the substrate comprises glass, silicon wafer, mica sheet or polymer sheet. The polymer sheet means a sheet material made of a polymer. The light transmission of the glass, the mica sheet and the polymer sheet is high, and the silicon wafer has high photoelectric conversion efficiency. The above substrate has good transparency and is not easily deformed or damaged during deposition.
Preferably, the glass comprises quartz glass, high borosilicate glass or soda lime glass, preferably quartz glass. The quartz glass has high spectral transmission, can transmit ultraviolet rays and infrared rays, and cannot be damaged by radiation rays.
Preferably, the polymer sheet comprises a polyethylene sheet, a polyvinyl chloride sheet, a polypropylene sheet, a polycarbonate sheet, a polymethylmethacrylate sheet or a polyphenylsulfone sheet. Polyethylene sheet refers to a sheet material made of polyethylene. The polyvinyl chloride sheet is a sheet material made of polyvinyl chloride. The polypropylene sheet refers to a sheet material made of polypropylene. Polycarbonate sheet refers to a sheet material made of polycarbonate. The polymethyl methacrylate sheet refers to a sheet material made of polymethyl methacrylate. The polyphenylene sulfone sheet is a sheet material made of polyphenylene sulfone.
Preferably, the thickness of the nano silicon dioxide layer is 200-800 nm; an intermediate connecting layer is formed between the nano silicon dioxide layer and the super-hydrophobic silicon dioxide layer, and the thickness of the intermediate connecting layer is 0.5-1 mu m; the thickness of the super-hydrophobic silicon dioxide layer is 200-600 nm. The thickness of the aforementioned nanosilica layer is typically, but not limited to, 200, 300, 400, 500, 600, 700 or 800 nm; the thickness of the above-mentioned intermediate tie layer is typically, but not limited to, 0.5, 0.6, 0.7, 0.8, 0.9 or 1 μm; the thickness of the aforementioned superhydrophobic silicon dioxide layer is typically, but not limited to, 200, 300, 400, 500, or 600 nm. When the thicknesses of the nano silicon dioxide layer, the middle connecting layer and the super-hydrophobic silicon dioxide layer are in the ranges, the mechanical property and the light transmittance of the nano silicon dioxide layer are optimal.
Preferably, the particle size of the silicon dioxide in the nano silicon dioxide layer is 10-20 nm. The above particle size is typically, but not limited to, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 nm. When the particle size of the silicon dioxide is in the range, the mechanical property of the nano silicon dioxide layer is higher, and the cracking phenomenon is not easy to occur after long-term use, so that the service life of the composite coating is longer.
Preferably, the silane coupling agent includes at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (2, 3-glycidoxypropyl) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, or gamma-aminopropylmethyldiethoxysilane. The above silane coupling agents include, but are not limited to, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (2, 3-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane, a combination of gamma-aminopropyltriethoxysilane and gamma-glycidoxypropyltrimethoxysilane, a combination of gamma- (2, 3-glycidoxypropyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane, a combination of gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane and gamma-mercaptopropyltriethoxysilane, or a combination of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and gamma-aminopropylmethyldiethoxysilane, and the like.
According to another aspect of the present invention, there is provided a method for preparing the above-mentioned composite coated body, comprising the steps of:
(a) providing a base material, and depositing a nano silicon dioxide layer on the surface of the base material by adopting a chemical vapor deposition method;
(b) providing a hydrolysate of a silane coupling agent;
(c) providing a super-hydrophobic silica suspension;
(d) and sequentially coating the hydrolysate of the silane coupling agent and the super-hydrophobic silica suspension on the surface of the nano silica layer, and curing to obtain the composite coating body.
The method has the advantages that the process is scientific and reasonable, the obtained composite coating body with the composite coating layer is stable in structure, the composite coating layer is not easy to separate from the surface of the base material, the composite coating layer has super-strong hydrophobicity, stain resistance and good light transmission, and the photoelectric conversion efficiency of the solar cell cannot be reduced after the composite coating body with the composite coating layer is used for a long time.
The "basic substance" refers to a substance having an ability to donate electrons or an ability to accept protons. The alkaline substance can be divided into organic base and inorganic base according to the material characteristics; the proton-absorbing material can be divided into monobasic alkali, binary alkali, ternary alkali, polybasic alkali and the like according to the quantity of protons accepted by the material; the alkaline substances can be classified into strong alkali and weak alkali according to their alkalinity.
In a preferred embodiment, the chemical vapor deposition method comprises plasma enhanced chemical vapor deposition, ultra high vacuum chemical vapor deposition or low temperature chemical vapor deposition, preferably plasma enhanced chemical vapor deposition. The ultra-high vacuum chemical vapor deposition method is below 10 deg.C-6Chemical vapor deposition in a pressure atmosphere of Pa. The Plasma Enhanced Chemical Vapor Deposition (PECVD) method has the advantages of low basic Deposition temperature, high Deposition rate, good film forming quality, less pinholes and difficult cracking.
In a preferred embodiment, the reactant gas source for chemical vapor deposition comprises SiH4And N2O。
Preferably, SiH4And N2The volume ratio of O is 1: 0.1 to 5, preferably 1: 0.1-2. The above volume ratio is typically, but not limited to, 1: 0.1, 1: 0.5, 1: 1. 1: 1.5, 1: 2. 1: 2.5, 1: 3. 1: 3.5, 1: 4. 1: 4.5 or 1: 5. when the volume ratio of the two is within the above range, the surface of the obtained nano silica layer is relatively flat, and the molar ratio of Si to O is closer to the theoretical value.
In a preferred embodiment, the deposition conditions of the chemical vapor deposition process include at least one of the following conditions:
the deposition temperature is 30-300 deg.C, preferably 150-250 deg.C, and more preferably 150-180 deg.C. The deposition temperature is typically, but not limited to, 30, 50, 100, 150, 200, 250, or 300 ℃. When the deposition temperature is within the above range, the reaction for generating silicon dioxide is favorably and smoothly carried out, the deposition speed is high, and the reaction is difficult to realize or the bonding force between the coating and the substrate is poor due to the excessively high or excessively low deposition temperature.
The radio frequency power is 20-200W, preferably 60-80W, and more preferably 65-75W. The rf power is typically, but not limited to, 20, 40, 60, 80, 100, 120, 140, 160, 180, or 200W. When the radio frequency power is within the range, the thickness of the obtained nano silicon dioxide layer is more reasonable, and the number of active hydroxyl groups on the surface of the nano silicon dioxide layer is more, so that the number of binding points with the active hydroxyl groups of the hydrolysate of the silane coupling agent is more, and the connection strength between the two layers is higher. If the radio frequency power is too low, the thickness of the nano silicon dioxide layer is too small, and the number of active groups on the surface is too small, so that the strength of the nano silicon dioxide layer is not improved; if the radio frequency power is too high, the thickness of the nano silicon dioxide layer is too large, so that the whole thickness of the composite coating is too large, and light cannot penetrate through the composite coating easily.
The deposition pressure is 10 to 150Pa, preferably 80 to 100Pa, and more preferably 85 to 95 Pa. The deposition pressure is typically, but not limited to, 10, 20, 40, 60, 80, 100, 120, 140, or 150 Pa. The deposition pressure may also be referred to as the working pressure or the reaction pressure. When the deposition pressure is within the above range, the deposition rate is high and the continuity of the resulting film is strong. If the deposition pressure is too low, the film has poor continuity and low deposition rate; if the deposition pressure is too high, the particle size of the silicon dioxide in the nano silicon dioxide layer is too large, which may affect the light transmittance.
The deposition time is 1-10min, preferably 5-10min, and more preferably 6-9 min. Deposition times are typically, but not limited to, 1, 2,3, 4, 5, 6, 7, 8, 9, or 10 min. The influence of the deposition time on the nano silicon dioxide layer is similar to the influence of the radio frequency power on the nano silicon dioxide layer, and when the deposition time is within the range, the thickness of the obtained nano silicon dioxide layer is more reasonable. The thickness of the nano silicon dioxide layer is too large due to too long time, the thickness of the nano silicon dioxide layer is too small due to too short time, and the two conditions are not favorable for forming a good nano silicon dioxide layer.
In a preferred embodiment, step (b) comprises: under alkaline conditions, the silane coupling agent is subjected to hydrolysis reaction in an alcohol aqueous solution to obtain a hydrolysate of the silane coupling agent. The "alkaline condition" mentioned above means a condition of pH more than 7.
Preferably, step (b) comprises: firstly, uniformly mixing a silane coupling agent and an alcohol aqueous solution, and then uniformly mixing the silane coupling agent and an alkaline substance to obtain a hydrolysate of the silane coupling agent. According to the preferred embodiment, the hydrolysate of the silane coupling agent is obtained by mixing the silane coupling agent with the aqueous solution of the alcohol and then mixing the silane coupling agent with the alkaline substance, so that the hydrolytic condensation of the silane coupling agent is quicker and more thorough, and the active hydroxyl in the hydrolysate of the silane coupling agent is more, thereby being beneficial to further improving the connection strength between layers in the composite coating.
Optionally, the mixing means comprises stirring and/or ultrasonic dispersion.
Preferably, the mixing reaction time is 10-60min, preferably 20-40 min. The above mixing reaction time is typically, but not limited to, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60 min. When the mixing reaction time is within the above range, the silane coupling agent can be completely hydrolyzed and condensed, and active hydroxyl groups in the silane coupling agent can be completely released, which is beneficial to improving the utilization rate of the silane coupling agent and the connecting force between the silane coupling agent and the rest layers.
Preferably, the alcohol comprises a C1-C4 alcohol. The C1-C4 alcohol refers to an alcohol having 1, 2,3 or 4 carbon atoms. The alcohol has reasonable carbon chain length, excessive carbon number, overlong carbon chain and increased boiling point, and is not beneficial to the volatilization of later alcohol solvent; meanwhile, when the number of carbon atoms is increased, the alcohol becomes solid and unusable.
Preferably, the C1-C4 alcohol comprises at least one of methanol, ethanol, isopropanol, n-butanol, propylene glycol, or glycerol. The C1-C4 alcohols include, but are not limited to, ethanol, isopropanol, methanol, n-butanol, propylene glycol, glycerol, a combination of ethanol and isopropanol, a combination of methanol and n-butanol, a combination of propylene glycol and glycerol, a combination of ethanol, isopropanol, and methanol, or a combination of n-butanol, propylene glycol, and glycerol, and the like.
Preferably, the mass ratio of alcohol to water in the aqueous alcohol solution is 1: 0.01 to 5, preferably 1: 0.05-1. The above mass ratio is typically, but not limited to, 1: 0.01, 1: 0.5, 1: 1. 1: 1.5, 1: 2. 1: 2.5, 1: 3. 1: 3.5, 1: 4. 1: 4.5 or 1: 5. the alcohol has better compatibility as a solvent, and the addition of water can promote the hydrolysis process, and when the mass ratio of the alcohol to the water is in the range, the reaction is more favorably carried out.
Preferably, the basic substance includes an organic basic substance and/or an inorganic basic substance. The alkaline substance includes an organic alkaline substance, an inorganic alkaline substance, or a combination of an organic alkaline substance and an inorganic alkaline substance. The organic alkaline substance refers to a substance that is alkaline in organic substances. The inorganic alkaline substance refers to a substance that is alkaline in inorganic substances.
Preferably, the organic basic substance includes an organic amine.
Preferably, the organic amine comprises an aliphatic amine.
Preferably, the fatty amine comprises at least one of decylamine, dodecylamine, hexadecylamine, or octadecylamine. Such fatty amines include, but are not limited to, decylamine, dodecylamine, hexadecylamine, octadecylamine, a combination of decylamine and dodecylamine, a combination of hexadecylamine and octadecylamine, a combination of decylamine, dodecylamine, and hexadecylamine, or a combination of dodecylamine, hexadecylamine, and octadecylamine, and the like.
Preferably, the inorganic alkaline substance comprises ammonia and/or sodium carbonate. The inorganic alkaline substance includes but is not limited to ammonia, sodium carbonate, or a combination of ammonia and sodium carbonate, etc.
In a preferred embodiment, step (c) comprises: reacting the silica gel obtained by the sol-gel method with a low surface energy modifier to obtain a silica suspension. The silica gel obtained by the sol-gel method has strong size controllability, and is beneficial to improving the light transmittance of the super-hydrophobic silica layer. The above-mentioned "low surface energy modifier" means a silane coupling agent having a functional group with a low chemical surface energy on the surface, such as hexamethyldisilazane, trimethylmethoxysilane, etc.
Preferably, the silicon source comprises a silicate. "silicate ester" refers to esters which, upon hydrolysis, yield silicic acid (or silica) and various organic alcohols.
Preferably, the silicate comprises at least one of methyl orthosilicate, tetraethyl orthosilicate, tetrapropyl silicate, or butyl orthosilicate. Such silicates include, but are not limited to, methyl orthosilicate, tetraethyl orthosilicate, tetrapropyl silicate, butyl orthosilicate, a combination of methyl orthosilicate and tetraethyl orthosilicate, a combination of tetrapropyl silicate and butyl orthosilicate, or a combination of methyl orthosilicate, tetraethyl orthosilicate, and tetrapropyl silicate, and the like.
Tetraethyl orthosilicate is also called ethyl silicate, tetraethyl orthosilicate, tetraethyl silicate or tetraethoxysilane and has the chemical formula C8H20O4Si。
Preferably, the solvent comprises an aqueous solution of an alcohol.
Preferably, the catalyst comprises ammonia, hydrochloric acid, acetic acid or carbon dioxide.
Preferably, the low surface energy modifying agent comprises at least one of hexamethyldisilazane, trimethylmethoxysilane, or triethylethoxysilane. Such low surface energy modifiers include, but are not limited to, hexamethyldisilazane, trimethylmethoxysilane, triethylethoxysilane, a combination of hexamethyldisilazane and trimethylmethoxysilane, a combination of trimethylmethoxysilane and triethylethoxysilane, a combination of hexamethyldisilazane and triethylethoxysilane, or a combination of hexamethyldisilazane, trimethylmethoxysilane and triethylethoxysilane, and the like.
In a preferred embodiment, the coating comprises knife coating, spray coating or spin coating.
Preferably, the curing temperature is 20-200 ℃, preferably 50-100 ℃; and/or the curing time is 1-60min, preferably 10-30 min. The above curing temperature is typically, but not limited to, 20, 50, 80, 100, 120, 150, 170, or 200 ℃; the above curing time is typically, but not limited to, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60 min. In the curing temperature and the curing time, the hydrolysate of the silane coupling agent and the silica suspension can be completely cured, and the layers of the composite coating are tightly connected and have strong firmness. If the curing temperature is too low or the curing time is too short, the curing is incomplete, the connection among layers is unstable, and the layers are easy to fall off; if the curing temperature is too high or the curing time is too long, the time cost and energy cost of curing are increased, and unnecessary cracks are easily generated in the coating at high temperature, which affects the functionality of the coating.
The light transmittance of the composite coating body is up to 96%, the static water contact angle on the surface of the composite coating body is 153 degrees, the composite coating body has excellent water resistance and sand impact resistance, and the composite coating body still keeps excellent super-hydrophobic self-cleaning performance after being soaked in extreme conditions such as strong acid, strong alkali, salt water and the like. The photovoltaic efficiency of the solar cell is tested after the composite coated body is applied to the surface of the solar cell and stored outdoors for 2 months, and the result shows that the efficiency of the solar cell with the composite coated body is kept at 14.21 percent, while the efficiency of the solar cell without the coating is only 13.01 percent.
According to another aspect of the present invention, there is provided a use of the above-described body with a composite coating for producing a solar cell. The composite coating body with the function of improving the stain resistance of the solar cell can be effectively improved when the composite coating body is applied to the preparation of the solar cell, and the high photoelectric efficiency of the solar cell can be still kept under the condition of long-term outdoor use.
According to another aspect of the present invention, there is provided a solar cell including the above ribbon composite coating body. The solar cell comprises the composite coating body, so that the solar cell has the advantages of good stain resistance and high photoelectric conversion efficiency after long-term use.
It should be noted that, the specific application mode of the composite coated body in the preparation of the solar cell and the specific position (connection relationship with other components or assemblies) in the solar cell are not particularly limited, and the common methods in the art can be adopted.
The present invention will be described in further detail with reference to examples and comparative examples.
Example 1
A preparation method of a body with a composite coating comprises the following steps:
(a) depositing a nano silicon dioxide layer on the surface of the mica sheet by adopting a low-temperature chemical vapor deposition method; the gas source is a gas source with the volume ratio of 1: SiH of 64And N2O; the thickness of the nano silicon dioxide layer is 1 mu m, and the particle size of the silicon dioxide is 30 nm; the deposition temperature is 330 ℃, the radio frequency power is 15W, the deposition pressure is 200Pa, and the deposition time is 15 min;
(b) mixing gamma-aminopropyltriethoxysilane with an aqueous solution of ammonia water for reaction for 70min to obtain a hydrolysate of a silane coupling agent;
(c) mixing silicon dioxide and trimethyl methoxy silane for reaction to obtain a silicon dioxide suspension;
(d) and sequentially spraying a hydrolysate of a silane coupling agent and the silica suspension on the surface of the nano silica layer, and respectively forming an intermediate connecting layer (the thickness is 1.2 mu m) and a super-hydrophobic silica layer (the thickness is 650nm) after curing to obtain the composite coating, wherein the curing temperature is 220 ℃ and the curing time is 65 min.
Examples 2 to 4
A method of producing a body with a composite coating, which is different from that of example 1, in examples 2 to 4, SiH4And N2The volume ratio of O is 1: 5. 1: 0.1 and 1: 2. the rest is the same as in example 1.
SiH in examples 2 to 44And N2The volume ratio of O is in the preferred range of the present invention, wherein SiH in examples 3-44And N2The volume ratio of O is within a further preferable range of the present invention.
Examples 5 to 6
A method for preparing a body with a composite coating, which is different from example 4, in examples 2 to 4, the thicknesses of the nano-silica layers were 200 and 800nm, the thicknesses of the intermediate connection layers were 0.5 and 1 μm, the thicknesses of the super-hydrophobic silica layers were 200 and 600nm, and the particle diameters of the silica were 10 and 20nm, respectively.
The thickness of the nano-silica layer, the thickness of the intermediate connection layer, the thickness of the super-hydrophobic silica layer, and the particle size of silica in examples 5 to 6 are all within the preferred ranges of the present invention.
Example 7
A method for preparing a body with a composite coating, which is different from example 4, in this example, a plasma enhanced chemical vapor deposition method is used to prepare a nano-silica layer.
Examples 8 to 10
A method for preparing a body with a composite coating, which is different from example 7, in examples 8 to 10, deposition temperatures were 30, 30 and 150 ℃.
The deposition temperatures in examples 8-10 are all within the preferred range of the present invention, with the deposition temperature in example 10 being within the further preferred range of the present invention.
Examples 11 to 13
A method for preparing a body with a composite coating, which is different from example 10, in examples 11 to 13, the RF power was 20, 200 and 70W, respectively.
The radio frequency power in examples 11-13 is within the preferred range of the present invention, with the radio frequency power in example 13 being within the further preferred range of the present invention.
Examples 14 to 16
A method of producing a body with a composite coating, which is different from example 13, in examples 14 to 16, deposition pressures were 10, 150 and 90Pa, respectively.
The deposition pressures in examples 14-16 are all within the preferred range of the present invention, with the deposition pressure in example 16 being within a further preferred range of the present invention.
Examples 17 to 19
A method for preparing a body with a composite coating, which is different from example 16, in examples 17 to 19, deposition times were 1, 10 and 8min, respectively.
The deposition times in examples 17-19 are all within the preferred range of the present invention, with the deposition time in example 19 being within the further preferred range of the present invention.
Examples 20 to 22
A method for preparing a body with a composite coating, which is different from example 19, in examples 20 to 22, the mixing reaction time in step (b) was 10, 60 and 30min, respectively.
The mixing reaction time in examples 20-22 is within the preferred range of the present invention, with the mixing reaction time in example 22 being within the further preferred range of the present invention.
Example 23
A method for producing a body with a composite coating, which is different from example 22 in that, in example 23, the step (b) comprises: firstly, uniformly mixing gamma-aminopropyltriethoxysilane with an aqueous solution of propylene glycol (the mass ratio of propylene glycol to water is 1: 1), and then uniformly mixing with ammonia water to obtain a hydrolysate of the silane coupling agent.
Step (b) in example 23 selects the preferred mode of the present invention.
Example 24
A method for producing a body with a composite coating, which is different from example 23, in example 24, the step (c) comprises: tetraethyl orthosilicate, hydrochloric acid and an aqueous solution of ethanol are mixed, silica gel is obtained after sol-gel reaction, and then the silica gel and trimethylmethoxysilane are mixed and reacted to obtain silica suspension.
Step (c) in example 23 selects the preferred mode of the present invention.
Examples 25 to 27
A method of producing a composite coated body, which is different from example 24, in examples 25 to 27, in the step (d), the curing temperatures were 20, 200 and 70 ℃ and the curing times were 60, 1 and 20min, respectively.
The curing temperature and curing time in examples 25-27 are within the preferred ranges of the present invention, with the curing temperature and curing time in example 27 being within the further preferred ranges of the present invention.
Example 28
A preparation method of a body with a composite coating comprises the following steps:
(a) cleaning the surface of a quartz glass substrate, putting the cleaned quartz glass substrate into a PECVD (plasma enhanced chemical vapor deposition) chamber, and carrying out SiH (hydrogen peroxide)4The gas flow rate was 80sccm, N2The flow rate of O is 150sccm, the deposition temperature is 150 ℃, the radio frequency power is 60W, the deposition pressure is 80Pa, the deposition time is 5min, and the nano SiO is prepared2And (4) coating.
(b) Adding 50mL of methanol and 10mL of deionized water into a 100mL beaker, adding 3mL of KH560 (gamma-glycidoxypropyltrimethoxysilane), sealing, stirring and ultrasonically dispersing for 30 min; then 0.8g of octadecylamine was added, and stirring and ultrasonic dispersion were continued for 20min, and the mixture formed a hydrolysate of the silane coupling agent.
(c) Placing a certain amount of Tetraethyl orthosilicate (TEOS ) 4mL into a methanol solution 40mL, and stirring and ultrasonically dispersing for 30 min; meanwhile, 10mL of concentrated ammonia water is taken to be put into 80mL of methanol solution, and stirring and ultrasonic dispersion are carried out for 30 min; and mixing the fully and uniformly dispersed TEOS alcohol solution with the diluted and dispersed ammonia water alcohol solution, stirring and ultrasonically dispersing for 50min to prepare the silicon dioxide gel. And then, by adopting a hydrothermal method, adding 20g of the silica gel into 30mL of ethanol solution and 7.5mL of hexamethyldisilazane, reacting for 8h at 100 ℃, and cooling at room temperature to prepare the modified super-hydrophobic silica suspension.
(d) Uniformly and spirally coating the hydrolysate of the silane coupling agent obtained in the step (b) and the silica suspension obtained in the step (c) on the nano SiO in the step (a)2And heating and curing the surface of the coating at 80 ℃ for 15min to obtain the composite coating.
Example 29
A preparation method of a body with a composite coating comprises the following steps:
(a) cleaning the surface of a quartz glass substrate, putting the cleaned quartz glass substrate into a PECVD (plasma enhanced chemical vapor deposition) chamber, and carrying out SiH (hydrogen peroxide)4The gas flow rate was 90sccm, N2The flow rate of O gas is 120sccm, the deposition temperature is 180 ℃, the radio frequency power is 80W, the deposition pressure is 60Pa, the deposition time is 8min, and the nano SiO is prepared2And (4) coating.
(b) Adding 40mL of methanol and 10mL of deionized water into a 100mL beaker, adding 6mL of KH560, sealing, stirring and ultrasonically dispersing for 20 min; then 0.5g of octadecylamine was added, and stirring and ultrasonic dispersion were continued for 20min, and the mixture formed a hydrolysate of the silane coupling agent.
(c) Placing a certain amount of tetraethyl orthosilicate (TEOS) of 7mL into a methanol solution of 40mL, and stirring and ultrasonically dispersing for 30 min; meanwhile, 15mL of concentrated ammonia water is taken to be put into 100mL of methanol solution, and stirring and ultrasonic dispersion are carried out for 30 min; and mixing the fully and uniformly dispersed TEOS alcohol solution with the diluted and dispersed ammonia water alcohol solution, stirring and ultrasonically dispersing for 30min to prepare the silicon dioxide gel. Then, by adopting a hydrothermal method, 10g of the silica gel is added into 35mL of ethanol solution and 3.5mL of hexamethyldisilazane, and the mixture reacts for 10h at 80 ℃, and then the modified super-hydrophobic silica suspension is prepared after cooling at room temperature.
(d) Uniformly and spirally coating the hydrolysate of the silane coupling agent obtained in the step (b) and the silica suspension obtained in the step (c) on the nano SiO in the step (a)2And heating and curing the surface of the coating for 10min at 90 ℃ to obtain the composite coating.
Example 30
A preparation method of a body with a composite coating comprises the following steps:
(a) cleaning the surface of a quartz glass substrate, putting the cleaned quartz glass substrate into a PECVD (plasma enhanced chemical vapor deposition) chamber, and carrying out SiH (hydrogen peroxide)4The gas flow rate is 100sccm, N2The flow rate of O gas is 100sccm, the deposition temperature is 200 ℃, the radio frequency power is 60W, the deposition pressure is 80Pa, the deposition time is 7min, and the nano SiO is prepared2And (4) coating.
(b) Adding 50mL of methanol and 20mL of deionized water into a 100mL beaker, adding 8mL of KH560, sealing, stirring and ultrasonically dispersing for 20 min; then 1.5g of octadecylamine was added, and stirring and ultrasonic dispersion were continued for 20min, and the mixture formed a hydrolysate of the silane coupling agent.
(c) Putting a certain amount of tetraethyl orthosilicate (TEOS) 9mL into a methanol solution 60mL, and stirring and ultrasonically dispersing for 30 min; meanwhile, 5mL of concentrated ammonia water is taken to be put into 60mL of methanol solution, and stirring and ultrasonic dispersion are carried out for 30 min; and mixing the fully and uniformly dispersed TEOS alcohol solution with the diluted and dispersed ammonia water alcohol solution, stirring and ultrasonically dispersing for 30min to prepare the silicon dioxide gel. And then, adding 15g of the silica gel into 40mL of ethanol solution and 5mL of hexamethyldisilazane by a hydrothermal method, reacting at 60 ℃ for 12h, and cooling at room temperature to prepare the modified super-hydrophobic silica suspension.
(d) Uniformly and spirally coating the hydrolysate of the silane coupling agent obtained in the step (b) and the silica suspension obtained in the step (c) on the nano SiO in the step (a)2And heating and curing the surface of the coating at 80 ℃ for 15min to obtain the composite coating.
Example 31
A preparation method of a body with a composite coating comprises the following steps:
(a) cleaning the surface of a quartz glass substrate, putting the cleaned quartz glass substrate into a PECVD (plasma enhanced chemical vapor deposition) chamber, and carrying out SiH (hydrogen peroxide)4Air flowIs 120sccm, N2The flow rate of O gas is 120sccm, the deposition temperature is 220 ℃, the radio frequency power is 80W, the deposition pressure is 80Pa, the deposition time is 6min, and the nano SiO is prepared2And (4) coating.
(b) Adding 50mL of methanol and 20mL of deionized water into a 100mL beaker, adding 4mL of KH560, sealing, stirring and ultrasonically dispersing for 20 min; then 0.9g of octadecylamine was added, and stirring and ultrasonic dispersion were continued for 20min, and the mixture formed a hydrolysate of the silane coupling agent.
(c) Putting a certain amount of tetraethyl orthosilicate (TEOS) 8mL into a methanol solution 60mL, and stirring and ultrasonically dispersing for 30 min; meanwhile, 7mL of concentrated ammonia water is taken to be put into 60mL of methanol solution, and stirring and ultrasonic dispersion are carried out for 30 min; and mixing the fully and uniformly dispersed TEOS alcohol solution with the diluted and dispersed ammonia water alcohol solution, stirring and ultrasonically dispersing for 30min to prepare the silicon dioxide gel. And then, adding 25g of the silica gel into 40mL of ethanol solution and 8mL of hexamethyldisilazane by a hydrothermal method, reacting for 6h at 100 ℃, and cooling at room temperature to prepare the modified super-hydrophobic silica suspension.
(d) Uniformly and spirally coating the hydrolysate of the silane coupling agent obtained in the step (b) and the silica suspension obtained in the step (c) on the nano SiO in the step (a)2And heating and curing the surface of the coating at 60 ℃ for 20min to obtain the composite coating.
Example 32
Different from the embodiment 1, the preparation method of the composite coating body is that the gamma-aminopropyl triethoxysilane in the embodiment is mixed with acetic acid to react for 70min, and a hydrolysate of the silane coupling agent is obtained. The rest is the same as in example 1.
Comparative example 1
A preparation method of a body with a composite coating comprises the following steps:
(a) depositing a nano silicon dioxide layer on the surface of the mica sheet by adopting a low-temperature chemical vapor deposition method; the gas source is a gas source with the volume ratio of 1: SiH of 64And N2O; the thickness of the nano silicon dioxide layer is 1.5 mu m, and the particle size of the silicon dioxide is 30 nm; the deposition temperature is 330 ℃, the radio frequency power is 15W, the deposition pressure is 200Pa, and the deposition time is 15min；
(b) Mixing silicon dioxide and trimethyl methoxy silane for reaction to obtain a silicon dioxide suspension;
(c) and spraying the silicon dioxide suspension on the surface of the nano silicon dioxide layer, and curing to obtain the composite coating, wherein the curing temperature is 220 ℃ and the curing time is 65 min.
Unlike example 1, this comparative example did not contain the steps of preparing a hydrolysate of a silane coupling agent and spraying it on the surface of the nano silica layer.
Comparative example 2
A preparation method of a body with a composite coating comprises the following steps:
(a) spraying a super-hydrophobic coating on the surface of the mica sheet by a blending method;
(b) mixing 3.5ml of ethyl orthosilicate, 10ml of methanol and 7.5ml of water, performing ultrasonic dispersion for 20min, adding 3.5ml of 1mol/L hydrochloric acid solution, stirring for 20min, dropwise adding ammonia water to adjust the pH value of the solution to be between 8 and 9, and performing ultrasonic treatment to obtain silicon dioxide sol;
(c) mixing 10g of silica sol, 50ml of methanol and 5ml of trimethyl methoxy silane, reacting for 8 hours at 100 ℃, taking out, and drying to obtain super-hydrophobic silica powder;
(d) adding a certain amount of super-hydrophobic silicon dioxide into PDMS, uniformly blending, diluting with methanol as a solvent, sequentially and directly spraying onto the surface of PE plate, and curing to obtain the composite coating, wherein the curing temperature is 80 ℃ and the curing time is 45 min.
Comparative example 3
A preparation method of a body with a composite coating comprises the following steps:
(a) spin-coating the surface of the glass slide by adopting a spin-coating method to form a super-hydrophobic modified nano silicon dioxide solution;
(b) mixing 3.5ml of ethyl orthosilicate, 10ml of methanol and 7.5ml of water, performing ultrasonic dispersion for 20min, adding 3.5ml of 1mol/L hydrochloric acid solution, stirring for 20min, dropwise adding ammonia water to adjust the pH value of the solution to be between 8 and 9, and performing ultrasonic treatment to obtain silicon dioxide sol;
(c) mixing 10g of silica sol, 50ml of methanol and 7.5ml of hexamethyldisilazane, and reacting at 80 ℃ for 6 hours to obtain a modified silica super-hydrophobic solution;
(d) and uniformly spin-coating the modified silicon dioxide super-hydrophobic solution on a glass substrate by using a spin coater, and curing to obtain the composite coating, wherein the curing temperature is 100 ℃, and the curing time is 30 min.
Performance testing
The coatings obtained in each of the above examples and comparative examples were subjected to a rub resistance test (a back and forth abrasion test was performed on a 1200cw sandpaper surface using a 100g weight placed on the sample, wherein the sample front surface was in contact with the sandpaper, the single side abrasion distance was 10cm, and the back and forth was recorded once as one cycle); and packaging the solar cells by using the composite coating bodies, wherein the solar cells are used outdoors for 60 days under the same conditions, and the photoelectric conversion efficiency of each solar cell is tested after 60 days. The test results are shown in Table 1.
TABLE 1
As can be seen from table 1, the surface water contact angle of each example after 140 times of abrasion was higher than that of each comparative example, and the photoelectric conversion efficiency of the solar cell corresponding to each example after 60 days of use was higher than that of each comparative example. Therefore, the preparation method is scientific and reasonable in process, and the obtained composite coating body with the composite coating has excellent wear resistance and long-term contamination resistance, and is favorable for ensuring that the solar cell still has high photoelectric conversion efficiency after long-term outdoor use.
Further analysis shows that the overall performance of examples 2-4 is better than that of example 1, with examples 3-4 being better, indicating that SiH is preferred4And N2The volume ratio of O can further improve the comprehensive performance of the composite coating; the overall performance of examples 5-6 is superior to that of example 4, illustrating the preferred thickness of the nanosilica layer to achieveAnd the particle size of the silicon dioxide can further improve the comprehensive performance of the composite coating body; the overall performance of example 7 is superior to that of example 4, indicating that the preferred use of plasma enhanced chemical vapor deposition can further improve the overall performance of the composite coated body; the combination of properties of examples 8-10 is superior to example 7, where the best of example 10 illustrates that the preferred deposition temperature can further enhance the combination of properties of the composite coated body; the overall performance of examples 11-13 is superior to that of example 10, where the best of example 13 illustrates that the preferred rf power can further enhance the overall performance of the composite coated body; the combination of properties of examples 14-16 is superior to example 13, where the best of example 16 illustrates that the preferred deposition pressure can further enhance the combination of properties of the composite coated body; the combination of properties of examples 17-19 is superior to example 16, with the best of example 19 illustrating that the preferred deposition time can further improve the combination of properties of the composite coated body; the combination of properties of examples 20-22 is superior to example 19, where the best of example 22 illustrates that the preferred mixing reaction time further enhances the combination of properties of the composite coated body; example 23 has an overall performance superior to example 22, illustrating that the preferred mode of step (b) can further improve the overall performance of the composite coated body; example 24 has an overall performance superior to example 23, illustrating that the preferred mode of step (c) can further improve the overall performance of the composite coated body; the combination of properties of examples 25-27 is superior to example 24, where the best of example 27 illustrates that the preferred curing temperature and curing time further enhance the combination of properties of the composite coated body. The overall performance of example 1 is superior to example 32, indicating that hydrolyzing the silane coupling agent, preferably under alkaline conditions, can further improve the overall performance of the composite coated body.
Fig. 1 is a schematic structural view of a composite coated body obtained in example 28, and it can be seen that the composite coated body includes a substrate 1 and a composite coating layer 2 formed on a surface of the substrate, and the composite coating layer 2 includes: the nano silicon dioxide layer 201, the super-hydrophobic silicon dioxide layer 202 and the intermediate connecting layer 203 formed by condensation of the hydrolysate of the silane coupling agent, the nano silicon dioxide layer 201 and the super-hydrophobic silicon dioxide layer 202.
Fig. 2 is a light transmittance UV spectrum of the blank glass, the intermediate connection layer and the composite coated body with tape obtained in example 28, from which it can be seen that the transmittance of the composite coated body with tape in the visible and ultraviolet wavelength ranges is not much different from that of the blank glass and the intermediate connection layer, indicating that the composite coated body with tape has good transmittance. In FIG. 1, the intermediate connecting layer means a solid layered substance obtained by curing the hydrolyzate of the silane coupling agent obtained by the method of step (b) of example 28.
FIG. 3 is a graph comparing the photoelectric conversion efficiency of the solar cell with composite coating body encapsulation obtained in example 28 with that of a blank glass encapsulated solar cell in outdoor use for 60 days, and it can be seen that the photoelectric conversion efficiency of the solar cell with composite coating body encapsulation is slightly lower than that of the blank glass encapsulated solar cell within 35 days of use, but the photoelectric conversion efficiency is not significantly reduced; however, after 35 days of use, the photoelectric conversion efficiency of the solar cell is obviously higher than that of the solar cell packaged by the blank glass, the photoelectric conversion efficiency of the solar cell is not obviously reduced after 60 days of use, and the photoelectric conversion efficiency of the solar cell packaged by the blank glass is obviously reduced after 60 days of use. In fig. 3, the super-hydrophobic glass refers to the solar cell with composite coating body encapsulation obtained in example 28, and the blank glass refers to a blank glass encapsulated solar cell.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (10)
1. A coated composite body, comprising: the composite coating comprises a substrate and a composite coating formed on the surface of the substrate, wherein the composite coating comprises:
the nano silicon dioxide layer is formed on the surface of the base material by adopting a chemical vapor deposition method;
the super-hydrophobic silicon dioxide layer is arranged opposite to the nano silicon dioxide layer;
the nano silicon dioxide layer is connected with the super-hydrophobic silicon dioxide layer through a silicon-oxygen bond; wherein, the nano silicon dioxide layer and the super-hydrophobic silicon dioxide layer respectively contain hydroxyl and are condensed with a hydrolysate of a silane coupling agent to form a silicon-oxygen bond.
2. The composite coated body of claim 1, wherein the substrate comprises glass, silicon, mica, or polymer sheets;
preferably, the glass comprises quartz glass, high borosilicate glass or soda lime glass, preferably quartz glass;
preferably, the polymeric sheet comprises a polyethylene sheet, a polyvinyl chloride sheet, a polypropylene sheet, a polycarbonate sheet, a polymethylmethacrylate sheet or a polyphenylsulfone sheet;
preferably, the thickness of the nano silicon dioxide layer is 200-800 nm; an intermediate connecting layer is formed between the nano silicon dioxide layer and the super-hydrophobic silicon dioxide layer, and the thickness of the intermediate connecting layer is 0.5-1 mu m; the thickness of the super-hydrophobic silicon dioxide layer is 200-600 nm;
preferably, the particle size of the silicon dioxide in the nano silicon dioxide layer is 10-20 nm;
preferably, the silane coupling agent includes at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (2, 3-glycidoxypropyl) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, or gamma-aminopropylmethyldiethoxysilane.
3. The method of manufacturing a body with a composite coating according to claim 1 or 2, comprising the steps of:
(a) providing a base material, and depositing a nano silicon dioxide layer on the surface of the base material by adopting a chemical vapor deposition method;
(b) providing a hydrolysate of a silane coupling agent;
(c) providing a super-hydrophobic silica suspension;
(d) and sequentially coating the hydrolysate of the silane coupling agent and the super-hydrophobic silica suspension on the surface of the nano silica layer, and curing to obtain the composite coating body.
4. The method of claim 3, wherein the chemical vapor deposition process comprises plasma enhanced chemical vapor deposition, ultra high vacuum chemical vapor deposition, or low temperature chemical vapor deposition, preferably plasma enhanced chemical vapor deposition.
5. The method of claim 3, wherein the source of the chemical vapor deposition reaction gas comprises SiH4Si and N2O；
Preferably, SiH4And N2The volume ratio of O is 1: 0.1 to 5, preferably 1: 0.1 to 2;
preferably, the deposition conditions of the chemical vapor deposition method include at least one of the following conditions:
the deposition temperature is 30-300 ℃, preferably 150-250 ℃, and more preferably 150-180 ℃;
the radio frequency power is 20-200W, preferably 60-80W, and further preferably 65-75W;
the deposition pressure is 10-150Pa, preferably 80-100Pa, and more preferably 85-95 Pa;
the deposition time is 1-10min, preferably 5-10min, and more preferably 6-9 min.
6. The method of claim 3, wherein step (b) comprises: under the alkaline condition, the silane coupling agent is subjected to hydrolysis reaction in an aqueous solution of alcohol to obtain a hydrolysate of the silane coupling agent;
preferably, step (b) comprises: firstly, uniformly mixing a silane coupling agent with an aqueous solution of alcohol, and then uniformly mixing the silane coupling agent with an alkaline substance to obtain a hydrolysate of the silane coupling agent;
preferably, the time of the hydrolysis reaction is 10-60min, preferably 20-40 min;
preferably, the alcohol comprises a C1-C4 alcohol;
preferably, the C1-C4 alcohol comprises at least one of methanol, ethanol, isopropanol, n-butanol, propylene glycol, or glycerol;
preferably, the mass ratio of alcohol to water in the aqueous alcohol solution is 1: 0.01 to 5, preferably 1: 0.05 to 1;
preferably, the alkaline substance includes an organic alkaline substance and/or an inorganic alkaline substance;
preferably, the organic basic substance includes an organic amine;
preferably, the organic amine comprises an aliphatic amine;
preferably, the fatty amine comprises at least one of decylamine, dodecylamine, hexadecylamine, or octadecylamine;
preferably, the inorganic alkaline substance comprises ammonia and/or sodium carbonate.
7. The method of preparing a composite coated body according to claim 3, wherein step (c) comprises: carrying out surface grafting reaction on the silica gel obtained by the sol-gel method and a low surface energy modifier to obtain a super-hydrophobic silica suspension;
preferably, a silicon source, a catalyst and a solvent are mixed, and silica gel is obtained after sol-gel reaction;
preferably, the silicon source comprises a silicate;
preferably, the silicate comprises at least one of methyl orthosilicate, tetraethyl orthosilicate, tetrapropyl silicate, or butyl orthosilicate;
preferably, the solvent comprises an aqueous solution of an alcohol;
preferably, the catalyst comprises ammonia, hydrochloric acid, acetic acid or carbon dioxide;
preferably, the low surface energy modifying agent comprises at least one of hexamethyldisilazane, trimethylmethoxysilane, or triethylethoxysilane.
8. The method of preparing the composite coated body according to any one of claims 3 to 7, wherein the coating comprises blade coating, spray coating or spin coating;
preferably, the curing temperature is 20-200 ℃, preferably 50-100 ℃; and/or the curing time is 1-60min, preferably 10-30 min.
9. Use of the composite coated body according to claim 1 or 2 or the composite coated body obtained by the method for producing a composite coated body according to any one of claims 3 to 8 for producing a solar cell.
10. A solar cell comprising the composite coated body according to claim 1 or 2 or the composite coated body obtained by the method for producing a composite coated body according to any one of claims 3 to 8.
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| WO2022141705A1 (en) * | 2021-01-04 | 2022-07-07 | 深圳市华星光电半导体显示技术有限公司 | Display panel, array substrate and preparation method therefor |
| US20220399288A1 (en) * | 2021-01-04 | 2022-12-15 | Shenzhen China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Display panel, array substrate, and manufacturing method thereof |
| US11869901B2 (en) | 2021-01-04 | 2024-01-09 | Shenzhen China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Display panel, array substrate, and manufacturing method thereof |
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