CN110291647A - 光电箔和光电箔的制造方法 - Google Patents
光电箔和光电箔的制造方法 Download PDFInfo
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- CN110291647A CN110291647A CN201880008575.4A CN201880008575A CN110291647A CN 110291647 A CN110291647 A CN 110291647A CN 201880008575 A CN201880008575 A CN 201880008575A CN 110291647 A CN110291647 A CN 110291647A
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- Prior art keywords
- oxide
- layer
- coating
- oxide skin
- barrier layer
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- 239000011888 foil Substances 0.000 title claims abstract description 84
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 87
- 238000000576 coating method Methods 0.000 claims abstract description 87
- 230000004888 barrier function Effects 0.000 claims abstract description 73
- 239000000463 material Substances 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 43
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 19
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium dioxide Chemical compound O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 14
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 14
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 14
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 14
- 229920000052 poly(p-xylylene) Polymers 0.000 claims abstract description 9
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017105 AlOxNy Inorganic materials 0.000 claims abstract description 7
- 229910004012 SiCx Inorganic materials 0.000 claims abstract description 7
- 229910004205 SiNX Inorganic materials 0.000 claims abstract description 7
- ZWPVWTIRZYDPKW-UHFFFAOYSA-N chromium(VI) oxide peroxide Inorganic materials [O-2].[O-][Cr]([O-])(=O)=O ZWPVWTIRZYDPKW-UHFFFAOYSA-N 0.000 claims abstract description 7
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 7
- NCMAYWHYXSWFGB-UHFFFAOYSA-N [Si].[N+][O-] Chemical class [Si].[N+][O-] NCMAYWHYXSWFGB-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000010410 layer Substances 0.000 claims description 195
- 238000000151 deposition Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 238000005516 engineering process Methods 0.000 claims description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- 239000002356 single layer Substances 0.000 claims description 20
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 20
- 230000008021 deposition Effects 0.000 claims description 18
- 238000000231 atomic layer deposition Methods 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- -1 polyethylene naphthalenedicarboxylate Polymers 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910005855 NiOx Inorganic materials 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- JAONJTDQXUSBGG-UHFFFAOYSA-N dialuminum;dizinc;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Zn+2].[Zn+2] JAONJTDQXUSBGG-UHFFFAOYSA-N 0.000 claims description 9
- 239000004033 plastic Substances 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 8
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000010894 electron beam technology Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 238000002207 thermal evaporation Methods 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 230000005068 transpiration Effects 0.000 claims description 6
- 229910015711 MoOx Inorganic materials 0.000 claims description 5
- 229910003107 Zn2SnO4 Inorganic materials 0.000 claims description 5
- 229910007694 ZnSnO3 Inorganic materials 0.000 claims description 5
- 230000000903 blocking effect Effects 0.000 claims description 5
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 5
- 238000003851 corona treatment Methods 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- KYKLWYKWCAYAJY-UHFFFAOYSA-N oxotin;zinc Chemical compound [Zn].[Sn]=O KYKLWYKWCAYAJY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 claims description 3
- 239000004793 Polystyrene 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
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- 229910003437 indium oxide Inorganic materials 0.000 claims 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims 2
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims 1
- 239000004952 Polyamide Substances 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 claims 1
- 229920002647 polyamide Polymers 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 230000035699 permeability Effects 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001994 activation Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000001429 visible spectrum Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- XVOFZWCCFLVFRR-UHFFFAOYSA-N oxochromium Chemical compound [Cr]=O XVOFZWCCFLVFRR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/081—Oxides of aluminium, magnesium or beryllium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
-
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Abstract
本发明涉及一种光电箔,其特征在于,包括基板(11)和导电层(13),所述导电层(13)包括至少一个氧化物层(131、133)和至少一个金属层(132),其中在所述箔(10)的导电层(13)和基板(11)之间具有阻挡层(12),所述阻挡层(12)包括选自硅氧化物(SiOx)、铝氧化物(Al2O3、AlOxNy)、钛氧化物(TiOx)、硅氮氧化物(SiON)、硅氮化物(Si3N4、SiNx)、有机硅化合物(SiCxHy)、氧化锆(ZrO2)、氧化铪(HfO2)、铬氧化物(CrO、Cr2O3、CrO2、CrO3、CrO5)和聚对二甲苯中的至少一种材料。
Description
本发明涉及光电箔及其制造方法。
在设计方面,光电箔由柔性聚合物箔基底和透明电极组成。它是使用各种技术构造在所述箔上生产的各种光电器件的基础。使用光电箔构造的光电器件包括柔性发射显示器(OLED,QD LCD)、柔性光伏器件、触摸屏传感器、柔性随机存取存储器(RAM)和气体传感器。
光电柔性箔的缺点在于由具有高氧气和水渗透系数的聚合物箔构成的柔性基板的不良密封性,这导致了光电器件的寿命短。特别是在有源层中包含有机材料的器件,例如,OLED(有机发光二极管)对天气条件敏感。来自空气的水分和氧气渗透导致活性材料的降解,其结果是阻止了光电器件的操作。
已知各种技术用于在光电箔的结构中制造保护层,其设计用于延长光电器件的寿命,包括:
-“坝填充”(dam-and fill)封装技术。在此过程中,分布的高粘度流体在器件(例如,OLED)周围形成矩形屏障。所述流体在液滴施加过程中分布,以便填充基板与屏障内的阻挡膜之间的空间。该方法的特点在于简单和稳定性高;
-使用薄的多层箔密封的技术,即“薄膜封装”(TFE)。最常见的TFE技术包括等离子体增强化学气相沉积(PECVD)和原子层沉积(ALD);
-等离子体增强化学气相沉积(PECVD)涉及制备无机-和-无机或有机-和-有机阻挡层,该方法通常使用氮化硅或二氧化硅;该技术的优点在于低温工艺(低于600℃)、非平衡相沉积的可能性,以及所得涂层的相对高纯度;
-原子层沉积技术(ALD),其涉及沉积阻挡膜;这种技术使用例如用于沉积的铝氧化物和氮化物;该方法的优点在于它允许获得以相对良好的密封性为特征的涂层。
此外,已知用于改善FOLED(柔性有机发光二极管)显示器的阻挡特性和一般密封的一些技术涉及使用超薄金属或玻璃箔。这种类型的解决方案的优点是实现具有良好透气性的箔,而它们的缺点是所获得的箔是无光泽的、不透明的并且容易损坏。
此外,专利文献公开了用于构造光电器件的导电材料的结构。
国际专利申请WO2015/179834A1公开了一种导电薄膜的结构,其由含量不低于导电薄膜总原子含量80%的银(Ag)和含量不超过导电膜总原子含量20%的选自Al、Ti、Ni、Cr、Au、Mg、Ta、Ge中的导电金属组成。导电层的制造过程包括在基板上共沉积金、铜和导电金属以形成连续导电膜。然而,WO2015/179834A1没有提供关于制备阻挡层以限制水分或氧气渗透到导电膜中的方法的信息。
因此,希望提供一种柔性光电箔结构,其具有改进的对气体和水蒸气颗粒的阻挡性能,这将允许制造具有延长寿命而不会降低整个箔材料透明度的光电器件。还希望提供光电箔,其可用于引入阻挡溶液的无源器件和包括柔性透明电极的有源光电器件。
本发明涉及一种光电箔,其特征在于,所述光电箔包括基板和导电层,所述导电层包括至少一个氧化物层和至少一个金属层,其中,在所述箔的导电层和基板之间具有阻挡层,所述阻挡层包括选自氧化硅(SiOx)、铝氧化物(Al2O3、AlOxNy)、钛氧化物(TiOx)、氮氧化硅(SiON)、硅氮化物(Si3N4、SiNx)、有机硅化合物(SiCxHy)、氧化锆(ZrO2)、氧化铪(HfO2)、铬氧化物(CrO、Cr2O3、CrO2、CrO3、CrO5)和聚对二甲苯中的至少一种材料。
优选地,所述阻挡层是单层结构。
优选地,所述阻挡层是由至少两个子层组成的多层结构,所述至少两个子层在阻挡层内一层叠加在另一层上并且由不同材料制成。
优选地,所述基板由选自聚对苯二甲酸乙二醇酯(PET)、聚乙烯萘(PEN)、聚乙烯(PE)、聚丙烯(PP)、聚醚砜(PES)、聚酰亚胺(PI)、聚苯乙烯(PS)、乙烯/四氟乙烯(ETFE)和聚对二甲苯中的至少一种塑料制成。
优选地,将无机纳米复合材料混合到所述基板上。
优选地,所述氧化物层由选自ZnO、AZO(氧化铝锌)、SnO2、IZO(氧化铟锌)、FTO(氟氧化锡)、ZTO(氧化锡锌)、ITO(氧化锡铟)、GZO(氧化锌镓)、GIO(氧化铟镓)、In2O3、Sb:SnO2、IO:H(氢氧化铟)、CdO、Zn2SnO4、ZnSnO3、Zn2In2O5、NiOx、NiOx:Li、TiOx、ZnS、ZnSe、Te2O3、MoOx、V2O5和WO3中的至少一种氧化物制成。
优选地,所述氧化物层是单层结构。
优选地,所述氧化物层是由至少两个子层组成的多层结构,所述至少两个子层在阻挡层内一层叠加在另一层上且由不同材料制成。
优选地,所述箔包括一个氧化物层。
优选地,所述箔包括至少两个氧化物层。
优选地,所述金属层由选自Al、Ti、Ni、Cr、Au、Mg、Ta、Ge、Ag、Cu、Zr、Pt和W中的至少一种材料制成。
优选地,所述箔在相邻的氧化物层之间具有金属层。
优选地,在所述导电层内,所述箔具有n个氧化物层、和在相邻氧化物层之间交替设置的n-1个金属层。
本发明还涉及一种制造光电箔的方法,其特征在于,清洁和活化所述基板的选定表面,在该选定表面上沉积阻挡层,以便在所述清洁和活化的基板上形成阻挡层,所述阻挡层包括选自硅氧化物(SiOx)、铝氧化物(Al2O3、AlOxNy)、钛氧化物(TiOx)、氮氧化硅(SiON)、硅氮化物(Si3N4、SiNx)、有机硅化合物(SiCxHy)、氧化锆(ZrO2)、氧化铪(HfO2)、氧化铬(CrO、Cr2O3、CrO2、CrO3、CrO5)和聚对二甲苯中的至少一种材料,然后在阻挡层上沉积包括至少一个氧化物层和至少一个金属层的导电层。
优选地,通过在基板上沉积一层材料以形成具有单层结构的阻挡层来形成所述阻挡层。
优选地,通过在基板上沉积不同材料的至少两个子层以形成具有多层结构的阻挡层来形成阻挡层。
优选地,形成导电层使得在阻挡层上独立地、一层叠加在另一层上地形成至少一个氧化物层,该氧化物层由氧化物材料制成,所述氧化物材料包括选自ZnO、AZO(氧化铝锌)、SnO2、IZO(氧化铟锌)、FTO(氟氧化锡)、ZTO(氧化锡锌)、ITO(氧化锡铟)、GZO(氧化锌镓)、GIO(氧化铟镓)、In2O3、Sb:SnO2、IO:H(氢氧化铟)、CdO、Zn2SnO4、ZnSnO3、Zn2In2O5、NiOx、NiOx:Li、TiOx、ZnS、ZnSe、Te2O3、MoOx、V2O5和WO3中的至少一种氧化物;和至少一个如下材料的金属层,所述材料包括选自Al、Ti、Ni、Cr、Au、Mg、Ta、Ge、Ag、Cu、Zr、Pt和W中的至少一种金属。
优选地,形成导电层,使得在阻挡层上独立地、一层叠加在另一层上地形成氧化物层和金属层交替设置的n个氧化物层和n-1个金属层,其中n是自然数。
优选地,形成导电层,使得在阻挡层上分别形成第一氧化物层,然后在第一氧化物层上形成金属层,然后在金属层上形成第二氧化物层。
优选地,通过沉积一层氧化物材料以形成具有单层结构的氧化物层来形成至少一个氧化物层。
优选地,通过沉积不同材料的至少两个氧化物子层以形成具有多层结构的氧化物层来形成至少一个氧化物层。
优选地,使用选自等离子体处理、电晕放电处理、二氧化碳处理、紫外线辐射和臭氧处理中的至少一种技术,以及采用选自丙酮、异丙醇、水、丙酮与水的混合物以及异丙醇和水的混合物中的溶剂的清洗处理,对所述基板进行清洁和活化。
优选地,使用选自原子层沉积(ALD)、磁控溅射、电子束溅射技术和热蒸发技术中的至少一种技术将阻挡层沉积到基板上。
优选地,使用选自原子层沉积(ALD)、磁控溅射、电子束溅射技术和热蒸发技术中的至少一种技术将导电层沉积到所述基板上。
以下将参考附图以示例的方式描述本发明的实施例,其中:
图1示意性地示出了根据本发明的一个实施例的光电箔的结构的横截面;
图2示出了光电箔制造工艺的流程图,和
图3示意性地示出了根据本发明另一实施例的光电箔的结构的横截面。
根据本发明的光电箔具有不小于50%的透明度,并且其特征在于低水蒸汽渗透性,因为光电箔10的水蒸气透过率(WVTR)每天在10-3和10-6g/m2之间。由于光电性质和高透明度,箔可用于制造各种器件,包括但不限于来自成像光电子学和光伏光电子学领域的器件。例如,该箔可用于制造光伏系统中的柔性OLED或QD LCD显示器,包括但不限于可放置在窗玻璃、计算机屏幕、移动电话、服装零件和其他日常用品上的超薄透明光伏电池。由于改善的阻隔性能和改善的寿命,所述箔还可用于汽车或建筑业。
图1示意性地示出了光电箔的横截面,示出了分层箔结构。
光电箔具有基板11,基板11具有阻挡层12,在阻挡层12上沉积包括至少一个氧化物层131和至少一个金属层132的导电层13。
光电箔10的基板11可以由各种透明基板材料制成,所述透明基板材料选自塑料和/或具有无机材料的纳米复合材料的塑料。例如,用于基板11的塑料可以以选自聚对苯二甲酸乙二醇酯(PET)、聚乙烯萘(PEN)、聚乙烯(PE)、聚丙烯(PP)、聚醚砜(PES)、聚酰亚胺(PI)、聚苯乙烯(PS)、乙烯/四氟乙烯(ETFE)和蒸发到表面上的来自聚对二甲苯组的聚合物(统称为聚对二甲苯)中的至少一类塑料的形式提供。
箔10的阻挡层12具有阻挡功能并且防止湿气和氧气从基板11渗透到导电层13中,从而确保显著减少构成箔10的光电元件的导电层、以及可以沉积在光电箔10上的器件的有源层的劣化过程。
阻挡层12由选自硅氧化物(SiOx)、铝氧化物(Al2O3、AlOxNy)、钛氧化物(TiOx)、氮氧化硅(SiON)、硅氮化物(Si3N4、SiNx)、有机硅化合物(SiCxHy)、氧化锆(ZrO2)、氧化铪(HfO2)、铬氧化物(CrO、Cr2O3、CrO2、CrO3、CrO5)和聚对二甲苯中的至少一种材料组成。更优选地,阻挡层可以由选自硅氧化物(SiOx)、铝氧化物(Al2O3、AlOxNy)、钛氧化物(TiOx)、氮氧化硅(SiON)、硅氮化物(Si3N4、SiNx)、有机硅化合物(SiCxHy)、氧化锆(ZrO2)、氧化铪(HfO2)、铬氧化物(CrO、Cr2O3、CrO2、CrO3、CrO5)和聚对二甲苯中的至少两种不同材料组成。
在一个实施例中,阻挡层可以采用例如仅由一种材料(例如,Al2O3)组成的单层形式。在另一个实施例中,阻挡层可以采用包含至少两种不同材料的单层形式,并且可以由例如掺杂有TiO2的Al2O3制成。在又一个实施例中,阻挡层12可以由至少两种不同的材料组成,并且它可以采取多层的形式,该多层包括在阻挡层12内彼此叠加的至少两个子层,其中每个子层可以由不同的材料制成。例如,阻挡层可以具有两个子层,其中一个子层由Al2O3制成,另一个子层由TiO2制成。阻挡层12内的每个子层可以具有相同或不同的厚度,优选地在5nm和500nm之间的范围内,而不管另一个子层的厚度。
优选地,阻挡层12可以包括两个子层,每个子层由选自上面列出的材料组中的不同材料制成。阻挡层12的总厚度优选地在5nm和1000nm之间的范围内。
导电层13是具有导电性能的箔的光电活性层。导电层13包括相互叠加的至少一个氧化物层131、133和至少一个金属层132。
此外,如图1所示,导电层可包括由金属层132隔开的至少两个氧化物层131和133、或多于两个氧化物层以形成夹层结构。导电层13中的所有层131、132、133基本上平行地一层叠加在另一层上。
在导电层13的每个实施例中,例如,包括一个或包括多于一个,例如两个氧化物层131、133,氧化物层131、133由选自ZnO、AZO(氧化铝锌)、SnO2、IZO(氧化铟锌)、FTO(氟氧化锡)、ZTO(氧化锡锌)、ITO(氧化锡铟)、GZO(氧化锌镓)、GIO(氧化铟镓)、In2O3、Sb:SnO2、IO:H(氢氧化铟)、CdO、Zn2SnO4、ZnSnO3、Zn2In2O5、NiOx、NiOx:Li、TiOx、ZnS、ZnSe、Te2O3、MoOx、V2O5和WO3中的至少一种氧化物制成。在光电箔10的导电层13的每个实施例中,氧化物层131、133的厚度优选地在15nm和150nm之间的范围内。
在一个实施例中,氧化物层131、133可以采用单层的形式,并且由一种类型的氧化物组成,氧化物来自上面列出的氧化物,例如ZnO。在另一个实施例中,氧化物层可以采用单层的形式并且由多种材料组成,例如单层形式的氧化物层131、133可以由掺杂有Al的ZnO制成。在又一个实施例中,氧化物层131、133可以由至少两种不同的氧化物组成,并且可以采用多层的形式,该多层包括在一个氧化物层131、133内的至少两个子层,其中每个子层由包含至少一种氧化物的不同氧化物材料制成。例如,氧化物层131、133可以由在一个氧化物层131、133内一层叠加在另一层上的两个子层组成,其中一个子层由ZnO制成,另一个子层由掺杂有Al的AZO或IZTO制成。
根据预期用途和所需参数,光电箔可以包括至少两个氧化物层131、133,其中一个氧化物层采用单层的形式,另一个氧化物层采用多层形式,该多层包括由不同氧化物材料制成的至少两个子层。此外,在包括一个或多个氧化物层的导电层13的每个实施例中,金属层132由选自Al、Ti、Ni、Cr、Au、Mg、Ta、Ge、Ag、Cu、Zr、Pt和W中的至少一种金属制成。对于光电箔10的导电层13的每个实施例,金属层132的厚度优选地在2nm和20nm之间的范围内。
根据光电箔的目标效用参数,箔10可以仅具有一个氧化物层131、133,其是多层或单层,并且在导电层13内仅具有一个金属层132。此外,在另一个实施例中,如图1中示意性地所示,导电层13可以包括两个氧化物层131、133,每个氧化物层可以是多层或单层,以及分隔两个氧化物层的一个金属层132。在另一个实施例中,导电层13可以具有三个氧化物层和两个金属层,其在导电层内交替地一层叠加在另一层上,使得每个金属层将两个相邻的氧化物层分隔。在又一个实施例中,导电层可以具有n个氧化物层131、133,每个氧化物层可以是多层或单层,以及一层叠加在另一层上的n-1个金属层,使得每个金属层132分隔两个相邻的氧化物层132、133以形成夹层结构,其中n是选自自然数组中的任何数。例如,n可以是2、3、4、5、6或7。例如,n可以高达33,或者n可以高于33。
图2示意性地示出了光电箔的制造方法。
制备基板材料11以在步骤21中制造光电箔。制备过程包括彻底清洁和活化所选择的基板表面。使用选自等离子体处理;电晕放电处理;二氧化碳处理;用如丙酮、异丙醇、水或丙酮和水的混合物或异丙醇和水的混合物的溶剂清洁以及紫外线(UV)辐射和臭氧处理中的至少一种技术来实施步骤21的清洁和活化过程。
然后,在步骤22中,将阻挡层12沉积在基板11的清洁和活化的表面上。
根据阻挡层12的结构,步骤22可包括一个或多个步骤。例如,为了形成具有单层结构并由至少一类材料(例如,Al2O3或掺杂有TiO2的Al2O3)制成的阻挡层,在步骤22中,可以在一个步骤中沉积阻挡层。然而,为了形成具有包括由不同材料制成的至少两个子层的多层结构的阻挡层,沉积步骤22可以包括若干子步骤,每个子步骤包括将一个子层沉积到阻挡层12上。例如,为了形成包括两个子层的阻挡层,实施步骤22中的沉积,使得在第一步骤中沉积一种材料的子层,然后沉积选自上面列出的用于阻挡层12的材料组中的另一种材料的子层。沉积具有多层和单层结构的阻挡层12的工艺可以使用选自原子层沉积(ALD)技术、磁控溅射技术、电子束溅射技术和热蒸发技术中的至少一种已知的沉积技术来实施。
然后,在步骤23中,将导电层13沉积在具有多层或单层结构的阻挡层上,其中导电层13的每个子层,即至少一个氧化物层131、133和至少一种金属层132分别沉积在阻挡层12上,以获得导电层13的适当功能和例如夹层结构的结构。导电层的每个子层131、132、133可以使用本领域已知的选自原子层沉积(ALD)技术、磁控溅射、电子束溅射技术和热蒸发技术中的各种沉积方法沉积。
例如,在步骤23中沉积具有如图1所示结构的导电层13,其包括两个氧化物层131、133和在氧化物层之间的金属层132,使得在第一步骤中,将第一氧化物层131直接沉积在阻挡层12的表面上,然后将金属层132沉积在第一氧化物层上,然后将第二氧化物层133沉积在金属层132上。每个子层131、132、133可以使用相同或不同的沉积技术沉积。
此外,根据氧化物层131、133的目标结构,每个氧化物层131、133可以采用单层或多层的形式,氧化物层131、133可以在步骤23中以单个步骤或几个步骤沉积,每个步骤可以使用一种技术以及不同的沉积技术来实施。例如,对于具有由包含一种氧化物的氧化物材料(例如,Al2O3)或包含两种氧化物的氧化物材料(例如,掺杂有TiO2的Al2O3)制成的单层结构的氧化物层131、133,氧化物层131、133可以在单个步骤23中沉积。现在,为了形成具有由至少两个彼此叠加的子层组成的多层结构的氧化物层131、133,氧化物层可以在步骤23中以几个步骤沉积,每个步骤包括在氧化物层131、133内沉积一个子层。
根据分别用作氧化物层和金属层131、132、133的材料的材料,所获得的光电箔结合了阻挡性能和有效的导电层13,其优选地可以具有电极的结构。在箔10的每个实施例中,导电层13与具有阻挡特性的柔性基板11、12集成在一起。
光电箔的阻挡层具有每天10-3至10-6g/m2范围内的水蒸气渗透率(WVTR),并具有包括高疏水性和抗紫外线辐射性的稳定的阻隔性能,这改善了根据本发明的箔的导电层的寿命。
此外,光电箔是柔性的并且具有相对高的透明度,而箔的导电层具有良好的导电性并且是现有技术中已知的单个较厚的导电ITO(氧化铟锡)层的替代物,该导电ITO相对脆性、导电性有限且价格昂贵。
实施例1
图1中示意性地示出了根据本发明的一个实施例的光电箔的横截面。光电箔包括基板11,在该实施例中基板11由塑料制成,即聚对苯二甲酸乙二醇酯(PET)。使用氧等离子体处理清洁并活化基板11的顶表面。然后,在反应磁控溅射工艺中在由此制备的基板11的顶表面上沉积由AlOx制成的厚度为300nm的单层阻挡层12(为非晶层)。接下来,在反应磁控溅射工艺中,在阻挡层12上沉积导电层13,其包括由ITO制成的厚度为20nm的第一氧化物层131,由Ag制成的厚度为9nm的金属层132和由ITO制成的厚度为20nm的第二氧化物层133。对如此获得的光电箔进行测试,包括通过四点探针测量表面电阻,通过钙测试测量WVTR渗透率(测量条件RH=40%,T=25℃)和使用UV-Vis分光光度计在可见光谱中测量光透射率。所进行的试验得到导电层13的表面电阻为12Ω/□,WVTR渗透率为10-3g/m2/天,可见光谱中的透光率为70~78%。
使用三层电极结构(导电层13),其中两个氧化物层131、133通过薄金属层132分隔,为导电层13提供高柔性(由于金属层12的存在),其结果是,确保整个光电箔伴有高导电性,如上述试验中所证明的那样。
实施例2
图3中示意性地示出了根据本发明另一实施例的光电箔的横截面。光电箔包括基板11,在该实施例中基板11由塑料制成,即聚对苯二甲酸乙二醇酯(PET)。使用氧等离子体处理清洁并活化基板11的顶表面。然后,在反应磁控溅射工艺中在如此制备的基板11的顶表面上沉积以厚度为100nm的AlOx层121和厚度为150nm的TiOx层122(构成非晶层)形式的阻挡层12。接下来,在反应磁控溅射工艺中,在阻挡层12上沉积导电层13,其包含由ITO制成的厚度为20nm的第一氧化物层131,由Ag制成的厚度为9nm的金属层132和由ITO制成的厚度为20nm的第二氧化物层133。对如此获得的光电箔进行测试,包括通过四点探针测量表面电阻,通过钙测试测量WVTR渗透率(测量条件RH=40%,T=25℃)和使用UV-Vis分光光度计在可见光谱中测量透射光。所进行的试验得到导电层13的表面电阻为12Ω/□,WVTR渗透率小于5×10-4g/m2/天,可见光谱中的透光率为67~80%。
Claims (24)
1.一种光电箔,其特征在于,所述光电箔包括基板(11)和导电层(13),所述导电层(13)包括至少一个氧化物层(131、133)和至少一个金属层(132),其中,在所述箔(10)的所述导电层(13)和所述基板(11)之间具有阻挡层(12),所述阻挡层(12)包括选自由硅氧化物(SiOx)、铝氧化物(Al2O3、AlOxNy)、钛氧化物(TiOx)、硅氮氧化物SiON、硅氮化物(Si3N4、SiNx)、有机硅化合物(SiCxHy)、氧化锆(ZrO2)、氧化铪(HfO2)、铬氧化物(CrO、Cr2O3、CrO2、CrO3、CrO5)和聚对二甲苯所组成的组中的至少一种材料。
2.根据权利要求1所述的光电箔,其特征在于,所述阻挡层(12)是单层结构。
3.根据权利要求1所述的光电箔,其特征在于,所述阻挡层(12)是由至少两个子层组成的多层结构,所述至少两个子层在所述阻挡层(12)内一层叠加在另一层上且具有不同的材料。
4.根据权利要求1至3中任一项所述的光电箔,其特征在于,所述基板(11)由选自聚对苯二甲酸乙二醇酯(PET)、聚乙烯萘(PEN)、聚乙烯(PE)、聚丙烯(PP)、聚醚砜(PES)、聚酰亚胺(PI)、聚苯乙烯(PS)、乙烯/四氟乙烯(ETFE)和聚对二甲苯所组成的组中的至少一种塑料制成。
5.根据权利要求4所述的光电箔,其特征在于,所述基板(11)掺杂有无机纳米复合材料。
6.根据权利要求1至5中任一项所述的光电箔,其特征在于,所述氧化物层(131、133)由选自ZnO、AZO(氧化铝锌)、SnO2、IZO(氧化铟锌)、FTO(氟氧化锡)、ZTO(氧化锡锌)、ITO(氧化锡铟)、GZO(氧化锌镓)、GIO(氧化铟镓)、In2O3、Sb:SnO2、IO:H(氢掺杂的氧化铟)、CdO、Zn2SnO4、ZnSnO3、Zn2In2O5、NiOx、NiOx:Li、TiOx、ZnS、ZnSe、Te2O3、MoOx、V2O5和WO3中的至少一种氧化物制成。
7.根据权利要求6所述的光电箔,其特征在于,所述氧化物层(131、133)是单层结构。
8.根据权利要求6所述的光电箔,其特征在于,所述氧化物层(131、133)是由至少两个子层组成的多层结构,所述至少两个子层在氧化物层(131、133)内一层叠加在另一层上且具有不同的材料。
9.根据权利要求7或8所述的光电箔,其特征在于,所述光电箔包括一个氧化物层(131或133)。
10.根据权利要求7或8中任一项所述的光电箔,其特征在于,所述光电箔包括至少两个氧化物层(131、133)。
11.根据权利要求1至10中任一项所述的光电箔,其特征在于,所述金属层(132)由选自Al、Ti、Ni、Cr、Au、Mg、Ta、Ge、Ag、Cu、Zr、Pt和W所组成的组中的至少一种材料制成。
12.根据权利要求10或11所述的光电箔,其特征在于,所述光电箔在相邻的氧化物层(131、133)之间具有金属层(132)。
13.根据权利要求1至12中任一项所述的光电箔,其特征在于,在所述导电层(13)内,所述光电箔具有n个氧化物层(131、133)和在相邻氧化物层(131、133)之间交替设置的n-1个金属层(132)。
14.一种光电箔的制造方法,其特征在于:
-清洁和活化所述基板的选定表面,在所述选定表面上沉积阻挡层,以便在所述清洁和活化的基板(11)上形成阻挡层(12),所述阻挡层(12)包括选自硅氧化物(SiOx)、铝氧化物(Al2O3、AlOxNy)、钛氧化物(TiOx)、硅氮氧化物SiON、硅氮化物(Si3N4、SiNx)、有机硅化合物(SiCxHy)、氧化锆(ZrO2)、氧化铪(HfO2)、铬氧化物(CrO、Cr2O3、CrO2、CrO3、CrO5)和聚对二甲苯所组成的组中的至少一种材料,
-然后在所述阻挡层(12)上沉积包括至少一个氧化物层(131、133)和至少一个金属层(132)的导电层(13)。
15.根据权利要求14所述的方法,其特征在于,通过在所述基板(11)上沉积一层材料以形成具有单层结构的阻挡层(12)来形成所述阻挡层(12)。
16.根据权利要求14或15所述的方法,其特征在于,通过在所述基板(11)上沉积不同材料的至少两个子层以形成具有多层结构的阻挡层(12)来形成所述阻挡层(12)。
17.根据权利要求14至16中任一项所述的方法,其特征在于,形成所述导电层(13),使得在所述阻挡层(12)上独立地、一层叠加在另一层上地形成至少一个氧化物层(131、133),所述氧化物层(131、133)由氧化物材料制成,所述氧化物材料包括选自ZnO、AZO(氧化铝锌)、SnO2、IZO(氧化铟锌)、FTO(氟氧化锡)、ZTO(氧化锡锌)、ITO(氧化锡铟)、GZO(氧化锌镓)、GIO(氧化铟镓)、In2O3、Sb:SnO2、IO:H(氢掺杂的氧化铟)、CdO、Zn2SnO4、ZnSnO3、Zn2In2O5、NiOx、NiOx:Li、TiOx、ZnS、ZnSe、Te2O3、MoOx、V2O5和WO3中的至少一种氧化物;和至少一个如下材料的金属层(132),所述材料包括选自Al、Ti、Ni、Cr、Au、Mg、Ta、Ge、Ag、Cu、Zr、Pt和W中的至少一种金属。
18.根据权利要求14至16中任一项所述的方法,其特征在于,形成所述导电层(13),使得在所述阻挡层(12)上独立地、一层叠加在另一层上形成氧化物层(131、133)和金属层(132)交替设置的n个氧化物层(131、133)和n-1个金属层(132),其中n是自然数。
19.根据权利要求17或18所述的方法,其特征在于,形成导电层(13),使得在阻挡层(12)上单独地形成第一氧化物层(131),然后在第一氧化物层(131)上形成金属层(132),然后在所述金属层(132)上形成第二氧化物层(133)。
20.根据权利要求14至19中任一项所述的方法,其特征在于,通过沉积一层氧化物材料以形成具有单层结构的氧化物层(131、133)来形成至少一个氧化物层(131、133)。
21.根据权利要求14至19中任一项所述的方法,其特征在于,通过沉积不同材料的至少两个氧化物子层以形成具有多层结构的氧化物层(12)来形成至少一个氧化物层(131、133)。
22.根据权利要求14至21中任一项所述的方法,其特征在于,使用选自由等离子体处理、电晕放电处理、二氧化碳处理、紫外线辐射和臭氧处理所组成的组中的至少一种技术,以及采用选自由丙酮、异丙醇、水、丙酮与水的混合物以及异丙醇和水的混合物所组成的组中的溶剂的清洗,清洁和活化所述基板(11)。
23.根据权利要求14至22中任一项所述的方法,其特征在于,使用选自由原子层沉积(ALD)、磁控溅射、电子束溅射技术和热蒸发技术所组成的组中的至少一种技术将所述阻挡层(12)沉积到所述基板(11)上。
24.根据权利要求14至23中任一项所述的方法,其特征在于,使用选自由原子层沉积(ALD)、磁控溅射、电子束溅射技术和热蒸发技术所组成的组中的至少一种技术将所述导电层(13)沉积到所述基板上。
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PL420300A1 (pl) | 2018-07-30 |
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