CN103998388A - 形成具有稳定金属氧化物层的光电器件的方法 - Google Patents
形成具有稳定金属氧化物层的光电器件的方法 Download PDFInfo
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- CN103998388A CN103998388A CN201280061695.3A CN201280061695A CN103998388A CN 103998388 A CN103998388 A CN 103998388A CN 201280061695 A CN201280061695 A CN 201280061695A CN 103998388 A CN103998388 A CN 103998388A
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- metal oxide
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- zinc oxide
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 35
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000005693 optoelectronics Effects 0.000 title 1
- 238000000151 deposition Methods 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 51
- 239000011787 zinc oxide Substances 0.000 claims description 26
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 10
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 10
- 229910000058 selane Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000002940 repellent Effects 0.000 claims description 2
- 239000005871 repellent Substances 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 230000005661 hydrophobic surface Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 39
- 239000000463 material Substances 0.000 description 21
- 229960001296 zinc oxide Drugs 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000011669 selenium Substances 0.000 description 12
- 229910052733 gallium Inorganic materials 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 150000004770 chalcogenides Chemical class 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 229910052738 indium Inorganic materials 0.000 description 7
- 229910052711 selenium Inorganic materials 0.000 description 7
- 150000003346 selenoethers Chemical class 0.000 description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 6
- -1 copper indium gallium sulphur compound Chemical class 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
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- 150000001787 chalcogens Chemical class 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- YNLHHZNOLUDEKQ-UHFFFAOYSA-N copper;selanylidenegallium Chemical class [Cu].[Se]=[Ga] YNLHHZNOLUDEKQ-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
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- 239000011521 glass Substances 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
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- 230000003287 optical effect Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical class C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical class [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- 229910004166 TaN Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
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- CYRGZAAAWQRSMF-UHFFFAOYSA-N aluminium selenide Chemical compound [Al+3].[Al+3].[Se-2].[Se-2].[Se-2] CYRGZAAAWQRSMF-UHFFFAOYSA-N 0.000 description 1
- COOGPNLGKIHLSK-UHFFFAOYSA-N aluminium sulfide Chemical compound [Al+3].[Al+3].[S-2].[S-2].[S-2] COOGPNLGKIHLSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000000224 chemical solution deposition Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
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- 239000002305 electric material Substances 0.000 description 1
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- 238000007641 inkjet printing Methods 0.000 description 1
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- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
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- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- 150000003958 selenols Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
- C03C17/2453—Coating containing SnO2
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C2217/20—Materials for coating a single layer on glass
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- C03C2217/216—ZnO
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- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
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- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
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- C03C2217/24—Doped oxides
- C03C2217/243—Doped oxides with S, Se, Te
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- C03C2217/00—Coatings on glass
- C03C2217/90—Other aspects of coatings
- C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
- C03C2217/944—Layers comprising zinc oxide
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- C03C2217/00—Coatings on glass
- C03C2217/90—Other aspects of coatings
- C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
- C03C2217/948—Layers comprising indium tin oxide [ITO]
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- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
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- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
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Abstract
本发明是一种方法，所述方法包括沉积金属氧化物层作为生产光电有源器件的一部分，并将所述金属氧化物层暴露于反应剂以形成相对疏水性表面。本发明还包括如此制造的器件，优选光伏器件，其与没有进行所述处理的器件相比，显示出改进的稳定性。
Description
技术领域
本发明涉及处理作为光电有源器件例如光伏器件或有机发光二极管的一部分的金属氧化物层的方法。本发明还涉及利用这种方法形成的器件。
背景技术
光伏器件用吸收入射光并产生电输出的材料制成。这样的光电活性材料的例子包括IB-IIIB族硫属元素化物、结晶和/或非晶硅、碲化镉类、砷化镓类等等。这些器件中的一些可以制成为在光电活性材料之上具有金属氧化物层。所述金属氧化物充当导体或半导体并根据它们对光的透过性而进行选择。金属氧化物还用于有机发光二极管作为顶部电极。经常使用氧化锌类,特别是在基于IB-IIIB族硫属元素化物的光伏电池中。
US2007/0295390教导了金属氧化物例如氧化锌可用作保护层。
发明内容
令人惊讶地，与US2007/0295390的教导相反，本发明人发现氧化锌可能易受与水分的反应影响，这可降低器件的长期稳定性。这种反应可以由于存在即使是弱酸而被加速。
因此，发明人进一步发现，所述金属氧化物层与某些材料的反应可降低所述金属氧化物层易受水的影响，并使得光电有源器件随着时间更加稳定。
因此，根据第一种实施方式，本发明是一种方法，所述方法包括沉积金属氧化物层作为生产光电有源器件的一部分，并将所述金属氧化物层暴露于反应剂以形成相对疏水性表面。
根据第二种实施方式，本发明是具有至少一个背面电极、一个光电活性层、和在所述光电活性层之上的金属氧化物的光电活性器件，其中所述金属氧化物层的顶部部分包含所述金属氧化物与增加所述金属氧化物层对水分的抗性同时对所述层的光学或电性质基本无影响的化合物的反应产物。
附图说明
图1是本发明有用的光伏电池的一种实施方式的示意图。
具体实施方式
本发明的光电有源器件可以是任何这样的器件，例如有机发光二极管，或更优选光伏器件。所述器件的特征为背面(远离光发射或光接收)电极、至少一个光电活性层、和在所述光电活性层之上的金属氧化物。所述金属氧化物可以充当正面电极或可以是与附加的正面电极组合使用的中间层。
所述金属氧化物层优选是掺杂或未掺杂氧化锌或者掺杂或未掺杂氧化锡(例如氧化铟锡)，但是更优选氧化锌层例如氧化锌、掺杂氧化锌(例如铝掺杂氧化锌、镓掺杂氧化锌或铟掺杂氧化锌)。
当所述器件是有机发光二极管时，所述活性层可以是当向材料施加电流时发射光的任何小分子或聚合材料。优选地，所述器件是上述类别的光伏电池。所述光伏电池包括背面电极、吸收体和至少一种金属氧化物层，优选氧化锌基层。IB-IIIB族硫属元素化物是优选的吸收体。这些成分在下文中应该统称为光电活性的硫属元素基(PACB)成分。
图1显示了可以通过本发明的方法制造的光伏制品10的一种实施方式。这种制品10包含结合载体22、背面电接触24和硫属元素化物吸收体20的衬底。所述制品10还包括掺有本发明的n-型硫属元素化物成分的缓冲区28、任选的正面电接触窗口区26、透明导电区30、集电栅40、和帮助保护制品10并与环境条件分隔的任选的阻挡区34。这些组分的每一个在图1中显示为包括单层，但是它们中的任何可以根据需要独立地由多个亚层形成。也可以提供当前已知或在今后发展中常规用于光伏电池的附加层(没有显示)。在本文中偶尔使用时，所述电池的顶部12被认为是接收入射光16的面。在吸收体上形成基于硫化镉的层的方法还可以用于串联电池结构，其中两个电池在彼此的顶部叠加，每个都具有吸收不同波长辐射的吸收体。
载体22可以是刚性或柔性的衬底。载体22可以由范围广泛的材料形成。这些包括玻璃、石英、其他陶瓷材料、聚合物、金属、金属合金、金属间组合物、纸、纺织或非纺织物、这些的组合等等。不锈钢是优选的。优选柔性衬底能够最大化利用所述薄膜吸收体和其他层的柔性。
背面电接触24提供将制品10与外部电路电耦合的便利方式。接触24可以由范围广泛的导电材料形成，所述材料包括Cu、Mo、Ag、Al、Cr、Ni、Ti、Ta、Nb、W的一种或多种，这些的组合，等等。掺有Mo的导电组合物是优选的。所述背面电接触24还可以有助于吸收体20与载体22的隔离，以最小化载体成分迁移到吸收体20中。例如，背面电接触24可有助于阻断不锈钢载体22的Fe和Ni成分迁移到吸收体20中。例如，如果Se用于形成吸收体20的话，背面电接触24还可通过防御Se来保护载体22。
吸收体20优选掺有至少一种p-型1b-IIIb族硫属元素化物，例如包括铜、铟和/或镓的至少一种的硒化物、硫化物和硒化物-硫化物。在许多实施方式中，这些材料以多晶形式存在。有利地，这些材料表现出优异的光吸收截面，这允许吸收体20非常薄和柔性。在说明性的实施方式中，典型的吸收体区20可以具有在约300nm至约3000nm，优选约1000nm至约2000nm范围内的厚度。
这样的p-型硫属元素化物吸收体的代表性例子是包括铜、铟、铝和/或镓的至少一种的硒化物、硫化物、碲化物和/或这些的组合。更通常存在Cu、In、Ga和Al中的至少两种或甚至至少三种。硫化物和/或硒化物是优选的。一些实施方式包括铜和铟的硫化物或硒化物。另外的实施方式包括铜、铟和镓的硒化物或硫化物。铝可以用作附加的或替代的金属，通常替代一部分或全部的镓。具体的例子包括但是不限于铜铟硒化物类、铜铟镓硒化物类、铜镓硒化物类、铜铟硫化物类、铜铟镓硫化物类、铜镓硒化物类、铜铟硫化硒化物类、铜镓硫化硒化物类、铜铟铝硫化物、铜铟铝硒化物、铜铟铝硫化硒化物、铜铟铝镓硫化物、铜铟铝镓硒化物、铜铟铝镓硫化硒化物、和铜铟镓硫化硒化物类。所述吸收体材料还可以掺杂其他材料，例如Na、Li等，以增强性能。此外，许多硫属元素材料可以掺有至少一些氧作为少量杂质而对电子性质没有显著的有害效应。一种优选类别的CIGS材料可以由下式表示：
CuaInbGacAldSewSxTeyNaz (A)
其中，如果“a”定义为1，那么：
“(b+c+d)/a”＝1.0至2.5，优选1.0至1.65
“b”是0至2，优选0.8至1.3
“c”是0至0.5，优选0.05至0.35
“d”是0至0.5，优选0.05至0.35，优选d＝0
"(w+x+y)"是2至3，优选2至2.8
"w"是0或更大，优选至少1和更优选至少2至3
"x"是0至3，优选0至0.5
"y"是0至3，优选0至0.5
“z”是0至0.5，优选0.005至0.02
吸收体20可以利用各种各样的一种或多种技术例如蒸发、溅射、电沉积、喷涂和烧结，通过任何合适的方法形成。一种优选的方法是组成元素从一种或多种合适的源(例如溅射靶)共同蒸发，其中各个组成元素同时、顺序或这些的组合在热表面上共同热蒸发，以形成吸收体20。沉积之后，沉积的材料可以进行一种或多种进一步的处理以最后确定吸收体性质。
根据现在已知或今后发展的常规实践，可以在衬底上使用任选的层(未显示)，以帮助提高背面电接触24与载体22之间和/或背面电接触24与吸收体区20之间的附着。另外，还可以在载体22的背面上提供一个或多个阻挡层(未显示)，以帮助器件10与周围环境隔离和/或电隔离器件10。
缓冲区28优选是沉积在吸收体20上的基于硫化镉的材料。所述缓冲区可以通过任何已知的方法包括化学浴沉积或溅射形成。
任选的窗口区26可以是单层或由多个亚层形成，其可有助于防止分流。窗口区26还可以在随后沉积TC区30期间保护缓冲区28。所述窗口区26可以由范围广泛的材料形成，并经常由电阻性透明氧化物(TCO)形成，所述氧化物例如Zn、In、Cd、Sn的氧化物、这些的组合等等。示例性的窗口材料是本征ZnO。典型的窗口区26可以具有在约1nm至约200nm，优选约10nm至约150nm，更优选约80至约120nm范围内的厚度。
TCO区30可以是单层或由多个亚层形成，与缓冲区28电耦合以提供制品10的顶部导电电极。在许多适当的实施方式中，TCO区30具有至少10nm，优选至少50nm并更优选至少100nm，并且小于1500nm，优选小于500nm的厚度。正如所示，TCO区30与窗口区26直接接触，但是因各种原因，例如为了促进附着、提高电性能等等，可以任选插入一个或多个中间层。
在形成透明导电区30中，可以使用种类广泛的透明导电氧化物；很薄的导电透明金属膜；或这些的组合。透明导电氧化物是优选的。这样的TCO的例子包括氟掺杂氧化锡、氧化锡、氧化铟、氧化铟锡(ITO)、铝掺杂氧化锌(AZO)、氧化锌、这些的组合等等。在一种说明性实施方式中，TCO区30具有双层结构，其中邻近缓冲区的第一亚层掺有氧化锌并且第二亚层掺有ITO和/或AZO。TCO层通过溅射或其它合适的沉积技术方便地形成。
金属氧化物层的处理可以在所述任选的窗口层和所述透明导体任一或二者中发生，但是所述表面处理优选在顶部或暴露表面上进行。
所述金属氧化物层的顶部部分在本发明中通过暴露于增加金属氧化物对与水分反应的抗性的化合物进行处理。优选处理过的金属氧化物层是氧化锌或铝掺杂氧化锌。所述表面处理暴露于反应性气体或其他材料，它们在所述表面处反应并从而抑制所述金属氧化物与水分反应，同时基本上保持总体金属氧化物层的电和光学性质。优选的反应性气体是硫化氢或硒化氢，但是也可使用其他材料例如硫或硒的挥发性有机化合物。例如挥发性的硫醇(R-SH)或硒醇(seleols)(R-she)、硫醚(R-S-R)或硒醚(R-Se-R)，其中R表示有机官能团。为了避免任何残余碳污染，优选使用反应性气体例如H2S或H2Se。对H2S和H2Se而言，所述表面处理优选通过将所述TCO在0.01毫巴至1巴、优选0.05毫巴至0.2毫巴的气体压力和在0℃至250℃、优选25℃至150℃范围内的温度下暴露于反应性气体达足以影响顶层转化的时限，所述时限为从1秒至30分钟，优选10秒至60秒。
根据优选的实施方式，通过角分辨x-射线光电子光谱法(XPS)测量，所述反应性化合物是硫化氢或硒化氢并且所生成的金属氧化物显示在5nm深度处金属与氧的摩尔比小于0.8，优选不大于0.7，但是大于0.2，表明在表面处可利用的反应的氧的量降低。此外，优选在5nm处硫或硒与金属的比率(取决于使用的气体)是至少0.1，更优选至少0.3，并且最优选至少0.5，表明所述反应性气体的表面反应。
或者，通过二次离子-质谱法(SIMS)>>利用1keV铯溅射束指示所述表面处理的反应深度，发现主要在优选顶部20nm，更优选顶部10nm，并且最优选5nm，由所述膜中反应性物质(例如Se或S)的剩余信号指示。在大于这些范围的深度处，主体膜优选基本上不被所述表面处理改变，虽然仍然可以观察到小于1％的很小的残留反应性物质信号。
任选的集电栅结构40可以沉积在TCO区30之上，以降低该层的薄层电阻。所述栅结构40优选掺有Ag、Al、Cu、Cr、Ni、Ti、Ta、TiN、TaN的一种或多种，及其组合。优选所述栅由Ag制成。任选的Ni膜(未显示)可以用于增强栅结构与TCO区30的附着。这种结构可用多种多样的方式形成，包括由线网或类似的导线结构制成，通过丝网印刷、喷墨印刷、电镀、光刻和利用任何适当的沉积技术透过适当的掩模喷镀金属来形成。
可以通过向光伏制品10的顶部直接低温施加适当的阻挡保护层34，来使得基于硫属元素化物的光伏电池更不易受水分相关降解的影响。所述阻挡保护层可以是单层或多个亚层。如所示，所述阻挡层没有覆盖所述电栅结构，但是除所显示的阻挡层外或代替所显示的阻挡层，可以使用覆盖这样的栅的阻挡层。
实施例
实施例1
通过射频溅射沉积本征ZnO和2wt％Al掺杂ZnO膜的叠层样品。具体而言，首先利用100W、～0.25％O2(余量为Ar)在～0.003毫巴的压力下沉积150nm的i-ZnO膜。然后以100W、100％Ar在～0.003毫巴的压力下沉积～230nm厚的Al掺杂ZnO膜。所述膜在～150℃的衬底温度下沉积在硼硅玻璃上。
在这些膜没有暴露于环境条件下时，所述膜然后在0.1毫巴的压力和两种不同的衬底温度：～25℃和～140℃下与H2S或H2Se反应。X-射线光电子光谱法(XPS)用于确定反应程度。结果显示在表1中。
表1.通过X-射线光电子光谱法获得的与H2S或H2Se反应的窗口层叠层的原子比(硫属元素(即Se或S)比锌)
所述数据显示，反应在近表面区内发生，因为当取样深度降低时，硫或硒与锌的比率增加。此外，对H2Se的反应程度更高，因为Se/Zn比率接近理论最大值1。反应过的膜的吸光度与未反应的对照样品比较，显示所述叠层的光学性质不受与硫化氢和硒化氢反应的影响。
将所述反应过的和对照膜放入保持在85℃和85％相对湿度(RH)的环境室中，在不同的时间间隔下测量所述膜的霍尔(Hall)电阻率。在每个时间间隔，获得三个重复测量结果。表2显示，所述反应确实提供了一些有益的保护效应，因为所述膜的电阻率增加在反应过的膜上显著较少。
表2.暴露于85℃/85％RH环境下的窗口层膜在t＝0小时和t＝48小时时的平均霍尔电阻率
实施例2
氧化铟锡涂布在玻璃衬底上。所述涂层然后用硫化氢在0.1毫巴和140℃下处理39分钟。所述膜利用角分辨XPS以出射角为90、30和15度进行分析，分别相当于分析深度10、5和3nm。结果显示，每个深度下金属与氧摩尔比是约0.7，同时硫与金属比率刚低于0.1。
实施例3
利用硒化氢而不是硫化氢重复实施例2。结果显示，金属与氧比率在3和5nm处为约0.6以及在10nm处为3.7，表明在顶部水平反应更多，同时硒与金属比率在10nm处为约0.3以及在3和5nm处为约0.4。
实施例4
重复实施例2，但是在氧化锌而不是氧化铟锡涂层上。结果显示，金属与氧摩尔比在每个深度处为约0.5至0.7，同时硫与金属比率为0.4至0.7。这与未处理的氧化锌膜的金属与氧比率约0.8至0.9相比较。
实施例5
重复实施例3，但是在氧化锌而不是氧化铟锡涂层上。结果显示，金属与氧比率为约0.4至0.6，同时硒与金属比率为约0.3至约0.4。
Claims (8)
1.一种方法，所述方法包括沉积金属氧化物作为生产光电有源器件的一部分，并将所述金属氧化物暴露于与氧化物反应的反应剂以形成相对疏水性表面。
2.权利要求1的方法，其中所述光电有源器件是光伏器件。
3.权利要求1或2的方法，其中所述金属氧化物是氧化锌或氧化铟锡。
4.权利要求3的方法，其中所述金属氧化物是氧化锌或铝掺杂氧化锌。
5.前述权利要求任一项的方法，其中所述反应剂是硫化氢或硒化氢。
6.光电有源器件，其通过权利要求1-5任一项的方法制造。
7.光伏器件，其具有吸收体层和至少一个包含金属氧化物的附加层，其中所述金属氧化物层的表面包含所述金属氧化物与增加所述层对水分的抗性同时对所述层的光学或电性质基本无影响的化合物的反应产物。
8.权利要求7的器件，其中所述表面改性的深度小于20nm。
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| KR102009308B1 (ko) * | 2018-02-28 | 2019-08-09 | 한국에너지기술연구원 | 산화갈륨 패시베이션층이 삽입된 고효율 양면 투광형 cigs계 태양전지와 그 제조방법 및 이를 적용한 건물일체형태양광발전모듈과 탠덤태양전지 |
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- 2012-12-07 BR BR112014014471A patent/BR112014014471A2/pt not_active IP Right Cessation
- 2012-12-07 IN IN4559CHN2014 patent/IN2014CN04559A/en unknown
- 2012-12-07 KR KR1020147019432A patent/KR20140114366A/ko not_active Application Discontinuation
- 2012-12-07 US US14/359,936 patent/US20140290738A1/en not_active Abandoned
- 2012-12-07 MX MX2014007159A patent/MX2014007159A/es not_active Application Discontinuation
- 2012-12-07 CN CN201280061695.3A patent/CN103998388B/zh not_active Expired - Fee Related
- 2012-12-07 WO PCT/US2012/068354 patent/WO2013090131A2/en active Application Filing
- 2012-12-07 JP JP2014547308A patent/JP6181665B2/ja not_active Expired - Fee Related
- 2012-12-07 EP EP12812438.5A patent/EP2791072B1/en not_active Not-in-force
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| US20070295390A1 (en) * | 2006-05-05 | 2007-12-27 | Nanosolar, Inc. | Individually encapsulated solar cells and solar cell strings having a substantially inorganic protective layer |
| CN101636362A (zh) * | 2007-01-15 | 2010-01-27 | 法国圣戈班玻璃厂 | 覆有机械强度改善的层的玻璃基材 |
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Also Published As
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|---|---|
| WO2013090131A2 (en) | 2013-06-20 |
| EP2791072A2 (en) | 2014-10-22 |
| WO2013090131A3 (en) | 2013-09-26 |
| CN103998388B (zh) | 2017-06-13 |
| EP2791072B1 (en) | 2016-05-11 |
| US20140290738A1 (en) | 2014-10-02 |
| KR20140114366A (ko) | 2014-09-26 |
| IN2014CN04559A (zh) | 2015-09-18 |
| JP6181665B2 (ja) | 2017-08-16 |
| BR112014014471A2 (pt) | 2017-06-13 |
| MX2014007159A (es) | 2014-08-29 |
| JP2015507353A (ja) | 2015-03-05 |
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