CN102892923A - 导电金属氧化物膜和光伏器件 - Google Patents
导电金属氧化物膜和光伏器件 Download PDFInfo
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- CN102892923A CN102892923A CN2010800498093A CN201080049809A CN102892923A CN 102892923 A CN102892923 A CN 102892923A CN 2010800498093 A CN2010800498093 A CN 2010800498093A CN 201080049809 A CN201080049809 A CN 201080049809A CN 102892923 A CN102892923 A CN 102892923A
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- Prior art keywords
- mix
- oxide
- metal oxide
- conducting metal
- stannic oxide
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 64
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 64
- 239000000758 substrate Substances 0.000 claims abstract description 50
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 98
- 239000000203 mixture Substances 0.000 claims description 58
- 239000011521 glass Substances 0.000 claims description 29
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 23
- 229910052731 fluorine Inorganic materials 0.000 claims description 22
- 239000011737 fluorine Substances 0.000 claims description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 229910001887 tin oxide Inorganic materials 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
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- 239000013081 microcrystal Substances 0.000 claims description 4
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- 239000011701 zinc Substances 0.000 claims description 4
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- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 2
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 claims description 2
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- 238000000034 method Methods 0.000 description 8
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- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 4
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
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- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 2
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- 230000007246 mechanism Effects 0.000 description 2
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- 238000006862 quantum yield reaction Methods 0.000 description 2
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
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- 239000004411 aluminium Substances 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
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- 239000007810 chemical reaction solvent Substances 0.000 description 1
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- 238000007701 flash-distillation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- 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
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- 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
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- 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
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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
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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
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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
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- C03C17/3678—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties specially adapted for use in solar cells
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
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- C—CHEMISTRY; METALLURGY
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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
- C03C2217/00—Coatings on glass
- C03C2217/90—Other aspects of coatings
- C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明描述了一种包含基板和邻近所述基板表面的导电金属氧化物膜的制品,其中所述导电金属氧化物膜的电子迁移率(cm2/V-s)等于或大于35。本发明还描述了包含导电金属氧化物膜的光伏器件。
Description
本申请要求2009年10月28日提交的美国临时申请第61/255583号和2010年9月22日提交的美国申请第12/887761号的优先权。
技术领域
本发明的实施方式涉及导电金属氧化物膜、包含所述导电金属氧化物膜的制品,更具体地涉及包含所述导电金属氧化物膜的光伏器件。
背景技术
涂覆有透明和/或导电膜的玻璃可以用于很多的应用,例如用于显示器用途,如作为显示器装置[例如液晶显示器(LCD)]的背板架构,以及用于手机的有机发光二极管(OLED)。涂覆有透明和/或导电膜的玻璃还可以用于太阳能电池应用,例如作为一些种类的光伏电池的电极,以及用于许多其它的快速发展的工业和应用。
透明导电氧化物(TCO)广泛用于LCD显示器面板、低辐射窗(low-Ewindow),最近还用于光伏(PV)电池、电子纸及其它许多工业应用。虽然氧化镉(CdO)是历史上第一种TCO,大约发现于1907年,但今天用得最多的TCO是分别用于各种显示器面板和低辐射窗中的氧化铟锡(ITO)和掺氟氧化锡(FTO)。
TCO在性质上属于宽带半导体(因此具有可见光透射性和导电性);并且多数属于n型半导体,其费米能级ΔE~kT,正好位于导带最小能级下面。后来在1997年实现了第一种实用的p型TCO(即CuAlO2),自此出现了第二代“透明电子器件”领域。但是,近来受到很大关注的薄膜PV技术需要高性能TCO作为透明电极。
就此而言,最近取得的进展之一是在薄膜硅串联PV电池领域,它需要一种专用的具有捕光能力的TCO,以改善微晶硅层对太阳光的吸收,从而提高电池效率。市售的钠钙玻璃上的织构化FTO是PV电池中目前所用的FTO的一个例子。
开发一种可用于TCO应用,例如光伏应用的涂覆有导电金属氧化物膜的玻璃将是有益的。
发明内容
本文所述的导电金属氧化物膜克服了上述导电金属氧化物膜的一个或多个缺点,特别是当所述膜包含氧化锡时。
一个实施方式是一种包含基板和邻近所述基板表面的导电金属氧化物膜的制品,其中所述导电金属氧化物膜的电子迁移率(cm2/V-s)等于或大于35。
另一个实施方式是一种包含基板、邻近所述基板的导电金属氧化物膜和邻近所述导电金属氧化物膜的活性光伏介质的光伏器件,其中所述导电金属氧化物膜的电子迁移率(cm2/V-s)等于或大于35。
在以下的详细描述中列出了本发明的附加特征和优点,其中的部分特征和优点对本领域的技术人员而言由所述内容而容易理解,或按文字描述和其权利要求书以及附图中所述实施本发明而被认识。
应理解,前面的一般性描述和以下的详细描述都只是本发明的示例,用来提供理解要求保护的本发明的性质和特性的总体评述或框架。
所含附图用于进一步理解本发明,附图被结合在本说明书中并构成说明书的一部分。附图呈现了本发明的一个或多个实施方式,并与说明书一起用来解释本发明的原理和操作。
附图说明
可单独通过以下详述或通过以下详述并结合附图理解本发明。
图1A-1C是根据一些实施方式制备的膜的截面扫描电镜(SEM)图像。
图2A-2B是根据一些实施方式制备的膜的截面扫描电镜(SEM)图像。
图2C是示例性膜的截面SEM图像。
图2D是示例性膜的俯视SEM图像。
图3是根据一个实施方式的光伏器件的特征的示意图。
图4是示例性制品的总透射率值和漫透射率值的图线。
图5是两个示例性制品的总透射率值和漫透射率值的图线。
图6是示例性制品的双向光透射(反射)分布函数(BTDF)图。
图7是示例性膜的截面SEM图像。
具体实施方式
下面详细参考本发明的各种实施方式,这些实施方式的例子在附图中示出。
本文所用的术语“体积散射”可以定义为光所通过的材料的折射率非均一性对光路造成的影响。
本文所用的术语“表面散射”可以定义为光伏电池中层间的界面粗糙度对光路造成的影响。
本文所用的术语“基板”可以根据光伏电池的构造用来描述基板或者覆板。例如,若所述基板在装入光伏电池时位于光伏电池的光入射侧,则所述基板是覆板。所述覆板可以为光伏材料提供保护,使其免受冲击和环境劣化,同时允许太阳光谱中合适的波长透过。另外,可以将多个光伏电池组装成光伏模块。
本文所用的术语“邻近”可以定义为紧邻。邻近的结构可以互相发生物理接触,也可以不发生物理接触。邻近的结构可以包括设置在它们之间的其它的层和/或结构。
本文所用的术语“平面的”可以定义为具有形貌基本上平坦的表面。
尽管在实施方式中描述了示例性的数值范围,但是各个范围可以包括由各个范围的端点组成的范围内的任意小数位的数值。
一个实施方式是一种包含基板和邻近所述基板表面的导电金属氧化物膜的制品,其中所述导电金属氧化物膜的电子迁移率(cm2/V-s)等于或大于35。在一个实施方式中,导电金属氧化物膜的电子迁移率(cm2/V-s)等于或大于40,例如等于或大于45,例如等于或大于50,例如等于或大于55。在另一个实施方式中,所述导电金属氧化物膜的电子迁移率(cm2/V-s)在35-60的范围内。
在一个实施方式中,所述导电金属氧化物膜的载流子浓度(1/cm3)等于或大于9.00x1020。
在一个实施方式中,所述导电金属氧化物膜的中值孔隙率等于或大于5%,例如为5-20%。孔隙可描述为膜中细粒边界周围的空隙。
在一个实施方式中,所述导电金属氧化物膜包含掺氯氧化锡、掺氟氯氧化锡、掺氟氧化锡、掺镉氧化锡、掺钛氧化锡、掺铟氧化锡、掺铝氧化锡、掺铌氧化锡、掺钽氧化锡、掺钒氧化锡、掺磷氧化锡、掺锌氧化锡、掺镁氧化锡、掺锰氧化锡、掺铜氧化锡、掺钴氧化锡、掺镍氧化锡、掺铝氧化锌、氧化锌或其组合。
在一个实施方式中,导电金属氧化物膜的厚度等于或小于3μm,例如等于或小于2μm,例如等于或小于1μm,例如等于或小于500nm,例如等于或小于100nm,例如等于或小于50nm。在另一个实施方式中,所述膜的厚度在10-1000nm的范围内,例如10-500nm。
在一些实施方式中,所述导电金属氧化物膜是透明的。在一些实施方式中,所述导电膜的雾度值等于或小于55%,例如等于或小于50%,例如等于或小于40%。导电膜的雾度值为大于0至55%,并保持高透射率值。所述导电金属氧化物膜在可见光范围内的透射率值等于或大于75%。
根据一些实施方式,光伏器件、显示器件或有机发光二极管可包含所述制品。
根据一个实施方式,所述基板包含玻璃层。在另一个实施方式中,所述基板是玻璃基板。
本文所述的导电金属氧化物膜可通过例如以下过程制备:提供包含金属氧化物前体和溶剂的溶液,制备该溶液的气溶胶小滴,将该气溶胶小滴施加到热玻璃基板上,将所述金属氧化物前体转化为金属氧化物,在玻璃基板上形成金属氧化物膜。在一些实施方式中,金属氧化物前体是金属卤化物。所述溶液可包含水,或者在一些情况中,所述溶液是水。
当溶剂包含水的时候,可以进行水解反应。在这些反应中,所述金属卤化物与水反应,转化为相应的氧化物。当溶剂仅包含醇的时候,可以在存在氧气的情况下进行闪蒸反应(flash reaction),使得醇蒸发和/或燃烧。在氧化反应中,金属卤化物(例如氯化锡)与氧气反应,形成相应的氧化物。在一个实施方式中,氧化物烧结形成导电金属氧化物膜。
当金属氧化物前体是锡前体时,在一个实施方式中,该锡前体选自氯化锡(SnCl2)、四氯化锡(SnCl4)及其组合。所述锡前体的含量可以占溶液的5-20重量%,例如等于或大于溶液的13重量%。
所述溶液还可包含掺杂剂前体。所述掺杂剂前体可以选自例如HF、NH4F、SbCl3以及它们的组合。
气溶胶小滴可通过雾化溶液制备。在雾化器中,可将气体例如氩气、氦气、氮气、一氧化碳、氮气中的氢气和/或氧气通入溶液。除上述气体之外,或者代替上述气体,可将环境空气通入雾化器。在一些实施方式中,雾化液的速率可以为2-7L/min,例如为3L/min。在一个实施方式中,所述气溶胶小滴的中值滴径(median droplet size)等于或小于1μm,例如,滴径为10-999nm,例如为50-450nm。
气溶胶小滴可从适合接收雾化器中的气溶胶小滴并位于玻璃基板附近的一个或多个喷雾器喷射。
根据待涂覆的玻璃基板的形状以及待涂覆的玻璃基板的面积,所述气溶胶喷雾器可以具有任意的形状。对气溶胶小滴进行喷雾的操作可以包括相对于玻璃基板沿着一个或多个方向平移所述喷雾器,例如,在三维笛卡尔坐标系中,沿着X方向、Y方向、Z方向或其组合平移。
可通过使气溶胶小滴流入炉子来施涂气溶胶小滴。可将玻璃基板设置在炉子中,以便接收气溶胶小滴流,使得小滴沉积在玻璃基板上。
在一个实施方式中,所述基板包含选自玻璃、陶瓷、玻璃陶瓷、聚合物、塑料、金属(例如不锈钢和铝)或其组合的材料。在一个实施方式中,所述基板是平面状、圆形、管形、纤维或其组合。
在一个实施方式中,所述玻璃基板选自以下的形式:玻璃片、载玻片、织构化的玻璃基板、玻璃球、玻璃立方体、玻璃管、蜂窝体、玻璃纤维以及它们的组合。在另一个实施方式中,玻璃基板是平面的,可用作薄膜光伏器件中的覆板或基板。
根据一个实施方式,所述方法包括在300-530℃的温度下,将所述气溶胶小滴施涂于玻璃基板。在一些应用中,温度范围的上限取决于玻璃基板的软化点。导电膜通常在低于玻璃基板的软化点的温度下施加。根据一个实施方式,所述导电膜在环境压力下形成。
可以在气溶胶小滴传输和/或沉积到基板上的过程中,使气溶胶小滴中的溶剂蒸发。在一些实施方式中,溶剂的蒸发可以在已经将气溶胶小滴沉积到基板上之后发生。可以通过所述的方法实现一些反应机理,例如,使气溶胶小滴中的金属卤化物与溶剂之间发生均相反应,使溶剂和/或气体与形成的或正在形成的氧化物发生非均相反应,以及/或者氧化物核与基材表面结合并结晶。
通过控制气溶胶传输温度,可以控制气溶胶小滴中溶剂的蒸发,由此可以控制气溶胶小滴的平均尺寸,使得沉积更高效和/或更均匀。通过控制传输温度可以提高溶剂与金属卤化物之间的反应,以及小滴内固体核的形成。
通过对玻璃基材进行加热,可以为氧化物的形成提供足够的活化能。与此同时,剩余的溶剂从加热的玻璃基板蒸发。加热还可以为沉积的小颗粒提供能量,使其结晶并形成较大的晶体。
可通过将氧化物和/或掺杂剂的前体溶解在溶剂中制备溶液。例如,为制备基于SnO2的透明导电氧化物(TCO)膜,可用SnCl4和SnCl2作为Sn前体。HF、NH4F、SbCl3等可以用作F和Sb掺杂剂前体。这些前体所用的溶剂可以是水。当用水作为溶剂,用SnCl2或SnCl4作为制备SnO2的前体的时候,用水使SnCl2或SnCl4水解,此反应在溶液中、小滴中以及沉积的表面上发生。产生的HCl促进了水对Sn的完全氧化。可以在沉积过程中将掺杂剂(例如F和Sb)加入SnO2晶格内。Sn上残留的Cl也残留在晶格内,形成Cl掺杂。
在气溶胶小滴沉积过程中,发生以下水解反应:
Cl也掺杂在SnO2晶格中。如果溶液中同时存在其它的掺杂剂,例如HF、NH4F或SbCl3,则还可以将掺杂元素F或Sb结合在SnO2晶格中。此种掺杂有助于形成稳定的导电金属氧化物膜。
导电膜形成之后,可对其进行热处理。热处理可以在空气中进行,热处理温度可以低于250℃,例如为150-250℃,例如为200℃。可以在惰性气氛中进行热处理,例如可以在允许采用更高的热处理温度(例如高于250℃,例如400℃)的氮气中进行热处理。
所述导电膜的导电性可以通过后热处理进一步提高。这种热处理可以从细粒边缘和颗粒表面除去吸附物质,释放被俘获的自由电子。如果在空气中进行所述后处理,则该后处理的温度应当低于SnO2的氧化温度。
另一个实施方式是光伏器件,图3示出了其特征300。所述光伏器件包含基板10、邻近所述基板的导电金属氧化物膜12和邻近所述导电金属氧化物膜的活性光伏介质16,其中所述导电金属氧化物膜的电子迁移率(cm2/V-s)等于或大于35。在一个实施方式中,导电金属氧化物膜的电子迁移率(cm2/V-s)等于或大于40,例如等于或大于45,例如等于或大于50,例如等于或大于55。在另一个实施方式中,所述导电金属氧化物膜的电子迁移率(cm2/V-s)在35-60的范围内。
根据一个实施方式,活性光伏介质与导电金属氧化物膜发生物理接触。
在另一个实施方式中,所述光伏器件还包含反电极18,该反电极位于活性光伏介质的表面上并与导电金属氧化物膜相背。在一个实施方式中,反电极与活性光伏介质发生物理接触。
所述活性光伏介质可以包含多个层,例如无定形硅层和微晶硅层。
在一个实施方式中,所述活性光伏介质包含碲化镉、二硒化铜铟镓、无定形硅、晶体硅、微晶硅或者它们的组合。
在一个实施方式中,所述基板是玻璃。
在另一个实施方式中,所述基板是平面的。在一个实施方式中,所述基板是平面玻璃片。
在一个实施方式中,所述导电金属氧化物膜的载流子浓度(1/cm3)等于或大于9.00x1020。
在一个实施方式中,所述导电金属氧化物膜的中值孔隙率等于或大于5%,例如为5-20%。孔隙可描述为膜中细粒边界周围的空隙。图7是示例性膜的SEM图像。膜46是同时掺杂了F和Cl的氧化锡。在一个实施方式中,如图7所示,膜的孔隙率可以变化,在基板膜界面44处的相对孔隙率较高,在膜中间42更紧密,孔隙率相对较低,而在膜表面40上的相对孔隙率较高。
在一些实施方式中,所述导电金属氧化物膜是透明的。在一些实施方式中,所述导电膜的雾度值等于或小于55%,例如等于或小于50%,例如等于或小于40%。导电膜的雾度值为大于0至55%,并保持高透射率值。所述导电金属氧化物膜在可见光范围内的透射率值等于或大于75%。
在一个实施方式中,活性光伏介质与导电金属氧化物膜发生物理接触。
根据一个实施方式,所述器件还包含反电极,所述反电极与所述活性光伏介质发生物理接触,位于活性光伏介质的表面上并与导电金属氧化物膜相背。
根据一个实施方式,所述导电金属氧化物膜包含掺氯氧化锡、掺氟氯氧化锡、掺氟氧化锡、掺镉氧化锡、掺钛氧化锡、掺铟氧化锡、掺铝氧化锡、掺铌氧化锡、掺钽氧化锡、掺钒氧化锡、掺磷氧化锡、掺锌氧化锡、掺镁氧化锡、掺锰氧化锡、掺铜氧化锡、掺钴氧化锡、掺镍氧化锡、掺铝氧化锌、氧化锌或其组合。
实施例
制备两种浓度的SnCl4,一种是0.27M,另一种是0.6M。为掺氟,加入氢氟酸(HF),使F/Sn原子比为60∶40。用TSI六喷嘴雾化器产生气溶胶,其中两个喷嘴打开。氮气(N2)用来产生气溶胶并作为载气。用来产生气溶胶和用作载气时,N2压力均设定为30psi。所产生的气溶胶小滴的直径为0.4-4μm。在350-600℃范围内的不同温度下沉积FTO膜15分钟。图1A-1C显示了用0.27M溶液制备的膜20的截面SEM图像。沉积温度分别为360℃、380℃和530℃。图2A-2B显示了用0.6M溶液制备的膜20的截面SEM图像。沉积温度分别为380℃和530℃。图2C显示了示例性膜20的截面SEM图像。图2D是示例性膜20的俯视SEM图像。这两幅图显示了根据一个实施方式在FTO膜上沉积的无定形硅膜。
对于图1A-1C所示的用0.27M SnCl4溶液进行的沉积,膜20的表面粗糙度与组成膜的粒度一致。(沉积温度越低,粒度越小。)膜厚度随涂覆温度增大,从在360℃涂覆时的200nm增大到在380℃涂覆时的250nm。前体浓度越高,得到的粒度越大。
图4是示例性制品的总透射率值(用线22表示)和漫透射率值(用线24表示)的图线。此实施例中的导电膜是掺氟氧化锡。
图5是两个示例性制品的总透射率值和漫透射率值的图线。线26和32分别显示了示例性制品的总透射率值和漫透射率值。线28和30分别显示了示例性制品的总透射率值和漫透射率值。
图6是示例性制品的双向光透射(反射)分布函数(BTDF)图。
膜的导电性用薄层电阻度量。在更高的涂覆温度下,观察到膜电阻增大。
用示例性制品,例如通过前述纳米化学液体沉积(NCLD)方法制备的掺氟氧化锡(FTO),制备光伏电池样品。样品尺寸为1英寸x1英寸。测量了表1所示的性质。相比于一些通常可得的ITO膜,NCLD-FTO表现出潜在的优势,它在高载流子浓度下具有高电子迁移率。用所述导电金属氧化物膜制备了无定形硅PV电池,它产生7.2%的量子效率(QE)。此外,FTO的电阻率约为1.7x10-4Ω.cm,接近于常规可得的掺铟氧化锡(ITO)膜。在可见光范围内的透射率为80%-85%。
表1
导电金属氧化物膜可用于光伏器件,其部分原因是所述膜具有透明性和/或导电性。在光伏应用中,较佳的是,膜不仅导电,而且在某些波长窗口内透明,在此窗口内,光子能量高于光伏器件中活性吸光剂(活性光伏材料)的带隙。
在透明导电氧化物中,电学性质和光学性质均可用德鲁德(Drude)模型描述,该模型利用自由电子和束缚电子的运动解释了金属的热学性质以及电学和光学性质。以下公式分别描述了导电金属氧化物的导电率和等离子体频率:
其中σ是导电率,ωp是等离子体频率,m*是电子的有效质量,μ是自由电子的光学迁移率,e是电子电荷,τ是电子弛豫时间,N是自由电子的密度。
对于具有宽透明窗口的高导电、高透明导电氧化物来说,材料应具有更少的自由电子、更重的有效电子质量和更高的自由载流子迁移率。
对通过NCLD方法制备的导电掺氟SnO2膜、掺氯SnO2膜进行了光学光谱测量、椭圆光度法测量和反射IR光谱测量,数据表明掺氯SnO2膜中的有效电子质量约为0.34me,比掺氟SnO2膜中的有效电子质量(约0.28me)重。当这两种膜具有同等水平的自由电子载流子密度时,相比于掺氟SnO2膜的等离子体频率,此结果将使掺氯SnO2膜的等离子体频率更加移向红外区。这导致掺氯SnO2膜的透明窗口比掺氟SnO2膜的透明窗口更宽。
表2显示了通过本文所述的NCLD方法制备的示例性掺氯SnO2膜、掺氟SnO2膜以及氟氯共掺SnO2膜的有效电子质量、自由电子密度以及光学迁移率。
表2
人们往往希望尽可能获得最高的导电率。导电率可通过以下方程式定义:
=qn
其中q是单个电子上的电荷,μ是迁移率,n是载流子浓度。导电率可通过增大迁移率或者增大载流子浓度来增大。但是,增大载流子浓度并非总是容易的事。此外,增大载流子浓度会降低材料的透射率(特别是在近IR区),这对薄膜太阳能电池可能是重要问题,因为它的透射率越大越有利,同时,它的导电率也是越大越有利,因为这保证了透明导电氧化物不会具有大的串联电阻,否则会降低太阳能电池的光电转化效率。因此,使迁移率尽可能大是有利的。
表3显示了示例性膜样品1-10的迁移率。示例性膜是掺氟氧化锡膜。
表3
用典型的霍尔测量系统获得了迁移率和载流子密度测量结果。磁场强度是0.2T,采用范德堡几何法(van der Pauw geometry)。测量在室温下进行。假定霍尔散射因子取单位值。霍尔散射因子通常在1与2之间变化,取决于材料中的散射机理。报告霍尔迁移率时,通常假设霍尔散射因子是单位值。
对本领域的技术人员而言显而易见的是,可以在不偏离本发明的精神或范围的情况下对本发明进行各种修改和变动。因此,本发明应涵盖对本发明的修改和变动,只要这些修改和变动在所附权利要求及其等同方案的范围之内。
Claims (20)
1.一种制品,所述制品包含基板和邻近所述基板表面的导电金属氧化物膜,其中所述导电金属氧化物膜的电子迁移率(cm2/V-s)等于或大于35。
2.如权利要求1所述的制品,其特征在于,所述导电金属氧化物膜的载流子浓度(1/cm3)等于或大于9.00x1020。
3.如权利要求1所述的制品,其特征在于,所述导电金属氧化物膜的中值孔隙率等于或大于5%。
4.如权利要求1所述的制品,其特征在于,所述导电金属氧化物膜在可见光范围内的透射率等于或大于75%。
5.如权利要求1所述的制品,其特征在于,所述导电金属氧化物膜的平均厚度等于或小于3μm。
6.如权利要求1所述的制品,其特征在于,所述导电金属氧化物膜包含掺氯氧化锡、掺氟氯氧化锡、掺氟氧化锡、掺镉氧化锡、掺钛氧化锡、掺铟氧化锡、掺铝氧化锡、掺铌氧化锡、掺钽氧化锡、掺钒氧化锡、掺磷氧化锡、掺锌氧化锡、掺镁氧化锡、掺锰氧化锡、掺铜氧化锡、掺钴氧化锡、掺镍氧化锡或其组合。
7.如权利要求1所述的制品,其特征在于,所述基板包含选自玻璃、陶瓷、玻璃陶瓷、聚合物、塑料、金属或其组合的材料。
8.如权利要求1所述的制品,其特征在于,所述基板是平面状、圆形、管形、纤维或其组合。
9.一种包含权利要求1所述的制品的光伏器件、显示器件或有机发光二极管。
10.一种光伏器件,所述光伏器件包含:
基板;
邻近所述基板表面的导电金属氧化物膜,其中所述导电金属氧化物膜的电子迁移率(cm2/V-s)等于或大于35;以及
邻近所述导电金属氧化物膜的活性光伏介质。
11.如权利要求10所述的器件,其特征在于,所述基板是玻璃。
12.如权利要求10所述的器件,其特征在于,所述基板是平面的。
13.如权利要求10所述的器件,其特征在于,所述导电金属氧化物膜的载流子浓度(1/cm3)等于或大于9.00x1020。
14.如权利要求10所述的器件,其特征在于,所述导电金属氧化物膜在可见光范围内的透射率等于或大于75%。
15.如权利要求10所述的器件,其特征在于,所述导电金属氧化物膜的中值孔隙率等于或大于5%。
16.如权利要求10所述的器件,其特征在于,所述活性光伏介质与所述导电金属氧化物膜发生物理接触。
17.如权利要求10所述的器件,所述器件还包含反电极,所述反电极与所述活性光伏介质发生物理接触,位于所述活性光伏介质的表面上并与所述导电金属氧化物膜相背。
18.如权利要求10所述的器件,其特征在于,所述活性光伏介质包含多个层。
19.如权利要求10所述的器件,其特征在于,所述活性光伏介质包含碲化镉、二硒化铜铟镓、无定形硅、晶体硅、微晶硅或其组合。
20.如权利要求10所述的器件,其特征在于,所述导电金属氧化物膜包含掺氯氧化锡、掺氟氯氧化锡、掺氟氧化锡、掺镉氧化锡、掺钛氧化锡、掺铟氧化锡、掺铝氧化锡、掺铌氧化锡、掺钽氧化锡、掺钒氧化锡、掺磷氧化锡、掺锌氧化锡、掺镁氧化锡、掺锰氧化锡、掺铜氧化锡、掺钴氧化锡、掺镍氧化锡或其组合。
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