CN102312190B - 溅射用于基于碲化镉的光伏器件的rtb薄膜的方法 - Google Patents
溅射用于基于碲化镉的光伏器件的rtb薄膜的方法 Download PDFInfo
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- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000004544 sputter deposition Methods 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 42
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims abstract description 45
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 239000012298 atmosphere Substances 0.000 claims abstract description 26
- 238000000137 annealing Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010409 thin film Substances 0.000 claims abstract description 21
- 239000010408 film Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- KYKLWYKWCAYAJY-UHFFFAOYSA-N oxotin;zinc Chemical compound [Zn].[Sn]=O KYKLWYKWCAYAJY-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 184
- 239000000463 material Substances 0.000 description 18
- 239000011521 glass Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical group Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- -1 sputtering chamber Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 239000005329 float glass Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 238000001228 spectrum Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- MZEWONGNQNXVKA-UHFFFAOYSA-N [Cu].[Cu].[Te] Chemical compound [Cu].[Cu].[Te] MZEWONGNQNXVKA-UHFFFAOYSA-N 0.000 description 1
- 231100000987 absorbed dose Toxicity 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000224 chemical solution deposition Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- WVRIJHGUJNXDRZ-UHFFFAOYSA-N ethane-1,1-diamine Chemical class CC(N)N WVRIJHGUJNXDRZ-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 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
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001552 radio frequency sputter deposition Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- KBEVZHAXWGOKCP-UHFFFAOYSA-N zinc oxygen(2-) tin(4+) Chemical compound [O--].[O--].[O--].[Zn++].[Sn+4] KBEVZHAXWGOKCP-UHFFFAOYSA-N 0.000 description 1
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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
- 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
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- H01L31/0392—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03925—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIIBVI compound materials, e.g. CdTe, CdS
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Abstract
本发明名称为“溅射用于基于碲化镉的光伏器件的RTB薄膜的方法”。公开了用于在衬底上沉积电阻透明缓冲薄膜层的方法。所述方法能够包括:在按照体积包括约0.01%到约5%的水蒸气(例如,按照体积约0.05%到约1%的水蒸气)的溅射气氛中,在衬底上冷溅射(例如,在约10℃到约100℃的溅射温度)电阻透明缓冲层。然后能够在约450℃到约700℃的退火温度退火电阻透明缓冲层。在衬底上沉积电阻透明缓冲薄膜层的方法能够用在制造镉薄膜光伏器件的方法中,其中通过在电阻透明缓冲层上形成硫化镉层并且在硫化镉层上形成碲化镉层来制造镉薄膜光伏器件。
Description
技术领域
本文公开的主题一般地涉及电阻透明缓冲薄膜层的沉积方法。更具体的是,本文公开的主题涉及用于在碲化镉薄膜光伏器件中使用的电阻透明缓冲薄膜层的沉积方法。
背景技术
基于碲化镉(CdTe)与硫化镉(CdS)配对作为光反应成分的薄膜光伏(PV)模块(也称为“太阳能电池板”)在工业中正获得广泛接受和关注。CdTe是一种具有尤其适合于将太阳能转换成电能的性能的半导体材料。例如,CdTe具有约1.45eV的能量带隙,这使得它与先前在太阳能电池应有中使用的较低带隙半导体材料(例如,对于硅约1.1eV)相比能够从太阳谱转换更多的能量。此外,与较低带隙材料相比,CdTe在较低或漫射的光条件下转换辐射能量,且因而与其它常规材料相比,在白天期间或多云条件下具有较长的有效转换时间。
当CdTePV模块暴露于光能(例如太阳光)时,n型层和p型层的结通常负责生成电位和电流。特别是,碲化镉(CdTe)层和硫化镉(CdS)层形成p-n异质结,其中CdTe层用作p型层(即正电子接受层(electronacceptinglayer)),并且CdS层充当n型层(即负电子施予层(electrondonatinglayer))。自由载流子对由光能创建且然后由p-n异质结分离以产生电流。
在能量作用于碲化镉层之前,减小窗口玻璃和碲化镉层之间的层(例如,透明导电层,硫化镉层及其之间的任何缓冲层)的厚度能够减小器件对辐射能量(例如,太阳能)的吸收量。因而,能够改进器件的整体转换效率。此外,减小硫化镉层的厚度能够允许更多的较短波长辐射(例如,蓝光)到达碲化镉层,这同样改进器件的整体转换效率。
然而,减小硫化镉层以及玻璃和碲化镉层之间的任何其它层的厚度能够形成可能对器件性能有害的其它问题。例如,相对薄的硫化镉层能导致界面缺陷(例如针孔),这些缺陷在透明导电氧化层和碲化镉层之间创建局部化的结。这些缺陷会降低器件的开路电压(VOC)且减小器件的填充因子(fillfactor)。
因而,存在对于通过窗口玻璃和碲化镉层之间层的减小厚度而具有改进的能量转换效率和/或器件寿命、且同时减小典型地与那些层的减小厚度相关联的副作用的碲化镉光伏器件的需要。
发明内容
本发明的方面和优点将部分地在下面的描述中陈述,或者可从描述中显而易见,或者可通过实践本发明而了解。
方法一般被提供以用于在衬底上沉积电阻透明缓冲薄膜层。所述方法能够包括:在按照体积包括约0.01%到约5%的水蒸气(例如,按照体积约0.05%到约1%的水蒸气)的溅射气氛中,在衬底上冷溅射(例如,在约10℃到约100℃的溅射温度)电阻透明缓冲层。然后能够在约450℃到约700℃的退火温度退火电阻透明缓冲层。
在衬底上沉积电阻透明缓冲薄膜层的方法能够用在制造镉薄膜光伏器件的方法中,其中通过在电阻透明缓冲层上形成硫化镉层并且在硫化镉层上形成碲化镉层来制造镉薄膜光伏器件。
参考下面的描述和所附权利要求,本发明的这些和其它特征、方面以及优点将变得更好理解。结合在本说明书中并构成其一部分的附图示出本发明的实施例,以及与描述一起,用来解释本发明的原理。
附图说明
对本领域普通技术人员的、本发明的完整和使能性的公开(包括其最佳模式),在参考附图的说明书中陈述,在附图中:
图1示出根据本发明的一个实施例的示例碲化镉薄膜光伏器件的截面图的概图;
图2示出根据本发明的一个实施例的示例DC溅射室的截面图的概图;以及,
图3示出制造包括碲化镉薄膜光伏器件的光伏模块的示例方法的流程图。
本说明书和附图中重复使用的引用字符旨在表示相同或相似的特征或要素。
具体实施方式
现在将对本发明的实施例进行详细参考,其一个或多个示例在图中示出。每个示例被提供以作为本发明的解释,而不是本发明的限制。事实上,它将对于本领域的技术人员是明白的,并且在不脱离发明的范围和精神的情况下,能在本发明中进行各种修改和变化。例如,作为一个实施例的部分来描述或示出的特征能够与另一个实施例一起使用以产生又一另外的实施例。因而,本发明旨在覆盖在所附权利要求及其等同的范围内的此类修改和变化。
在此公开中,当层被描述为在另一层或衬底“上”或“上方”时,要理解所述层能彼此直接接触,或者具有层之间的另一层或特征。因而,这些术语简单描述层彼此之间的相对位置,而不一定意味着“在……之上”,因为上面或下面的相对位置依赖于器件对观察者的朝向。另外,尽管发明不限于任何具体的膜厚度,但是描述光伏器件任何膜层的术语“薄”一般是指具有小于约10微米(“百万分之一米”或“μm”)的厚度的膜层。
要理解,本文提到的范围和限制包括位于规定限制之内的所有范围(即,子范围)。例如,从约100到约200的范围也包括了从110到150、170到190、153到162、以及145.3到149.6的范围。此外,直到约7的限制也包括了直到约5、直到3、以及直到约4.5的限制,以及包括了在该限制之内的范围,例如从约1到约5,和从约3.2到约6.5。
一般来说,方法公开用于溅射电阻透明缓冲层,尤其是包含在基于碲化镉的薄膜器件中的电阻透明缓冲(RTB)层。电阻透明缓冲层通常在包含水蒸气的溅射气氛中溅射到衬底上。例如,溅射气氛能够包含约0.01%至约5%体积的水蒸气,例如约0.05%至约1%体积的水蒸气。这些溅射方法特别有用于跟随有沉积态(as-deposited)层的退火的“冷溅射”。例如,RTB层能够在含有水蒸气的溅射气氛中、在约10℃至约100℃的溅射温度来溅射,例如约20℃至约50℃(例如,约20℃至25℃的室温)。
将水蒸气添加到溅射室中能够减小能够容易监控的溅射阴极(即靶)的电压。此外,已经发现溅射气氛中的少量水蒸气(例如,约0.01%至约5%体积)能够改进薄膜层在它正在被沉积时到衬底的粘合。最后,在退火前,由于在溅射气氛中存在水蒸气,显示出改进了沉积态RTB层。
在冷溅射后,能够在约450℃至约700℃(例如,约500℃至约650℃)的退火温度退火RTB层。RTB层能够在退火温度对于约5分钟至约5小时来退火,例如对于约15分钟至约1小时。在不希望由任何特定理论来束缚的情况下,认为退火RTB层能够将沉积态分子(例如,锡锌氧化物原子)再结晶为衬底上的更均匀的薄膜层。此外,退火过程能够从沉积态RTB层上差不多去除所有水以便退火的RTB层基本上没有水分子。在本文中使用时,术语“基本上没有”意味着没有多于可忽略的痕量存在以及涵盖完全没有(例如,0摩尔%直到0.0001摩尔%)。
溅射沉积通常涉及从作为材料源的靶喷射材料,且将喷射的材料沉积到衬底上以形成膜。DC溅射通常涉及将直流施加到安置在溅射室内衬底(即,阳极)附近的金属靶(即,阴极)以形成直流放电。
除了含有水蒸气外,溅射气氛还能包含在金属靶和衬底之间形成等离子场的惰性气体(例如氩等)和/或反应气体(例如氧气氛、氮气氛等)。溅射气氛的压力对于磁控溅射能够在约1mTorr和约20mTorr之间,并且对于二极管溅射能够更高(例如,从约25mTorr至约100mTorr)。当施加电压使金属原子从靶释放时,金属原子沉积到衬底的表面上。例如,当气氛中含有氧时,从金属靶上释放的金属原子能够在衬底上形成金属氧化物层。
施加到源材料的电流能够根据源材料的大小、溅射室的大小、衬底表面积的量以及其它变量而变化。在一些实施例中,施加的电流能够从约2安培至约20安培。相反地,RF溅射涉及通过在靶(例如,陶瓷源材料)和衬底之间施加交流(AC)或射频(RF)信号而激发电容性放电。溅射室能够具有惰性气氛(例如,氩气氛),其对于磁控溅射可含有或不含具有约1mTorr和约20mTorr之间的压力的反应种类(例如,氧、氮等)。同样,对于二极管溅射,压力能够甚至更高(例如,从约25mTorr至约100mTorr)。
图2示出作为根据本发明的一个实施例的示例DC溅射室60的截面图的概图。DC功率源62配置成控制且供应DC功率到室60。如所示的,DC功率源将电压施加到阴极64以在阴极64和由室壁、暗护罩等形成的阳极(通常接地)之间创建电压电位,使得衬底位于阴极和阳极之间。玻璃衬底12分别经由导线68和69被保持在顶部支撑66和底部支撑67之间。通常,玻璃衬底12安置于溅射室60内以便硫化镉层18形成在面对阴极64的表面上,且通常形成在TCO层14和RTB层16(未示出)上,如下所讨论的。
一旦溅射气氛被点燃,等离子体场70便被创建,并且被保持以响应阴极64与充当阳极的室壁之间的电压电位。电压电位促使等离子体场70内的等离子体离子向阴极64加速,促使原子从阴极64喷向玻璃衬底12上的表面。因此,阴极64能够称为“靶”,并且充当用于面向阴极64的玻璃衬底12的表面上的硫化镉层18的形成的源材料。为了形成硫化镉层,阴极64能够是金属合金靶,例如硫化镉的。另外,在一些实施例中,能够利用多个阴极64。多个阴极64能够对形成包括几种类型的材料的层特别有用(例如,共溅射)。因为溅射气氛含有氧气,等离子场70的氧粒子能够与喷射的靶原子起反应以形成包含氧的硫化镉层18。
虽然仅仅示出单个DC功率源62,但电压电位能够通过使用多个耦合在一起的功率源来实现。此外,示例溅射室60显示为具有垂直的方向,但是能够利用其它任何配置。在从溅射室60退出后,衬底12能够进入邻近的退火炉(未示出)以开始退火过程。
RTB层能够包括例如氧化锌(ZnO)和氧化锡(SnO2)的组合,这能够称为氧化锌锡层(“ZTO”)。在一个特定实施例中,RTB层能够包括比氧化锌多的氧化锡。例如,RTB层能够具有带大约0.25和大约3之间的ZnO/SnO2的化学计量比的成分,例如氧化锡对氧化锌的大约一比二(1∶2)的化学计量比。RTB层16能够通过将DC电流施加到金属源材料(例如,元素锌、元素锡或其混合物)、并且在存在氧化气氛(例如,O2气体)的情况下将金属源材料溅射到TCO层14上,使用DC溅射法而形成。在氧化气氛包括氧气(即,O2)时,该气氛能够大于约95%的氧(按照体积),例如约95%到约99%(按照体积),溅射气氛的剩余部分是水蒸气。
在一个实施例中,除了水蒸气和惰性气体(例如氩)之外,溅射气氛还能包括约1%至25%的氧。在另一实施例中,溅射气氛能够仅包括水蒸气和惰性气体(例如氩)。
在一个特定实施例中,RTB层能够形成为用于基于碲化镉的薄膜光伏器件中。在碲化镉薄膜光伏器件中,RTB层能够通常安置于透明导电氧化(TCO)层和硫化镉层之间,且允许通过减少界面缺陷(即,硫化镉层中的“针孔”)的可能性,而使相对薄的硫化镉层被包括在器件中,界面缺陷在TCO层和碲化镉层之间形成分路(shunt)。因而,在不希望由任何特定理论来约束的情况下,认为RTB层允许了TCO层与碲化镉层之间改进的粘合和/或交互,从而允许相对薄的硫化镉层形成在其上,而没有此类相对薄的硫化镉层直接形成在TCO层上时将否则导致的显著不利影响。此外,RTB层通常比TCO层更具电阻性且在器件处理期间能够保护器件免受TCO层和随后层之间的化学相互作用。例如,在某些实施例中,RTB层具有大于约1000欧姆每平方(ohmpersquare)的片电阻,例如从约10千欧姆每平方到约1000兆欧姆每平方。RTB层16还能够具有宽的光学带隙(例如,大于约2.5eV,例如从约2.7eV到约3.0eV)。
在某些实施例中,RTB层16具有约0.075μm和约1μm的厚度,例如约0.1μm到约0.5μm。在特定实施例中,RTB层16具有约0.08μm和约0.2μm的厚度,例如约0.1μm到0.15μm。
当前提供的在包括水蒸气的溅射气氛中溅射RTB层的方法能用于利用RTB层的任何膜堆叠的形成中。例如,在利用碲化镉层的任何碲化镉器件的形成期间能够使用RTB层,例如在Murphy等人的名称为“Ultra-highCurrentDensityCadmiumTelluridePhotovoltaicModules”的美国公布No.2009/0194165中公开的碲化镉薄膜光伏器件中。
图1示出能够依据本文描述的方法来形成的示例碲化镉薄膜光伏器件10。图1的示例器件10包括用作衬底的玻璃12的顶部片。在此实施例中,玻璃12能够称为“上衬底(superstrate)”,因为它是其上形成后续层的衬底,即使它在碲化镉薄膜光伏器件10在使用中时向上面对辐射源(例如,太阳)。玻璃12的顶部片能够是高透射玻璃(例如,高透射硼硅酸盐玻璃)、低铁浮法玻璃、或其它高透明材料。玻璃通常足够厚以为后续膜层提供支撑(例如,从约0.5mm至约10mm厚),并且基本平整以为形成后续膜层提供良好表面。在一个实施例中,玻璃12能够是含有小于约0.015%重量的铁(Fe)的低铁浮法玻璃,并且在关注谱(例如,从约300nm至约900nm的波长)中具有约0.9或更大的透射率。在另一个实施例中,可利用硼硅酸盐玻璃以便更好地承受高温处理。
透明导电氧化(TCO)层14显示在图1的示例器件10的玻璃12上。TCO层14允许光以极小的吸收穿过,同时还允许器件10产生的电流侧向行进到不透明的金属导体(未示出)。例如,TCO层14能够具有小于约30欧姆每平方的片电阻,例如从约4欧姆每平方到约20欧姆每平方(例如,从约8欧姆每平方至约15欧姆每平方)。在某些实施例中,TCO层14能够具有在约0.1μm和约1μm之间的厚度,例如从约0.1μm到约0.5μm,例如从约0.25μm到约0.35μm。
电阻透明缓冲层16(RTB层)示出为在示例碲化镉薄膜光伏器件10的TCO层14上,且已在上面更详细地描述。
硫化镉层18示出为在图1的示例器件10的RTB层16上。硫化镉层18是通常包括硫化镉(CdS)的n型层,但也可包括其它材料,例如硫化锌、硫化锌镉等和其混合物,以及掺杂剂和其它杂质。硫化镉层18能够具有宽带隙(例如,从约2.25eV至约2.5eV,例如约2.4eV)以便允许大多数辐射能量(例如,太阳辐射)穿过。因此,硫化镉层18被认为是器件10上的透明层。
硫化镉层18能够通过溅射、化学气相沉积、化学浴沉积、以及其它合适的沉积方法来形成。在一个特定实施例中,硫化镉层18能够通过溅射(例如,直流(DC)溅射或射频(RF)溅射)而形成在电阻透明层16上。
由于存在电阻透明层16,硫化镉层18能够具有小于约0.1μm的厚度,例如在约10nm至约100nm之间,例如从约50nm至约80nm,其中电阻透明层16与硫化镉层18之间存在的针孔极少。此外,具有小于约0.1μm的厚度的硫化镉层18减小了硫化镉层18对辐射能量的任何吸收,有效地增加了到达在下面的碲化镉层22的辐射能量的量。
碲化镉层20示出为在图1的示例碲化镉薄膜光伏器件10中的硫化镉层18上。碲化镉层20是通常包含碲化镉(CdTe)但也可包含其它材料的p型层。作为器件10的p型层,碲化镉层20是与硫化镉层18(即n型层)相互作用的光伏层,以通过因其高吸收系数而吸收穿入器件10的辐射能量的大部分且创建电子-空穴对来从辐射能量的吸收产生电流。例如,碲化镉层20通常能从碲化镉而形成,且能具有为吸收辐射能量而调整的带隙(例如,从约1.4eV至约1.5eV,例如约1.45eV)以在吸收辐射能量时创建具有最高电位(电压)的最大数量的电子-空穴对。电子可以从p型侧(即,碲化镉层20)跨结而行进到n型侧(即,硫化镉层18),并且相反地,空穴可以从n型侧传递到p型侧。因而,形成在硫化镉层18和碲化镉层20之间的p-n结形成二极管,其中电荷不均衡导致跨越p-n结的电场的创建。常规电流仅允许在一个方向中流动并且将光诱发的电子-空穴对分离。
碲化镉层20能够通过任意已知过程来形成,例如气相传输沉积,化学气相沉积(CVD)、喷雾热解、电镀沉积、溅射、近空间升华(CSS)等。在一个特定实施例中,通过溅射沉积硫化镉层18且通过近空间升华沉积碲化镉层20。在特定实施例中,碲化镉层20能够具有约0.1μm和约10μm之间的厚度,例如从约1μm到约5μm。在一个特定实施例中,碲化镉层20能够具有约2μm和约4μm之间的厚度,例如约3μm。
能够对碲化镉层20的暴露表面施加一系列后形成处理。这些处理能够调整碲化镉层20的功能性且将其表面准备用于到背接触层22的后续粘合。例如能够在升高的温度(例如,从约350℃至约500℃,例如从约375℃至424℃)将碲化镉层20退火足够的时间(例如,从约1至约10分钟)以创建碲化镉的品质p型层(qualityp-typelayer)。在不希望由理论束缚的情况下,认为退火碲化镉层20(和器件10)将通常轻p型掺杂的或甚至n型掺杂的碲化镉层20转换成具有相对低电阻率的更强p型碲化镉层20。另外,在退火期间碲化镉层20能再结晶并经历颗粒生长。
为了用氯化物离子来掺杂碲化镉层20,能在存在氯化镉时执行退火碲化镉层20。例如,碲化镉层20能用包含氯化镉的水溶液来洗涤(wash),并然后在升高的温度退火。
在一个具体实施例中,在存在氯化镉时退火碲化镉层20之后,能洗涤表面以去除形成在表面上的任何氧化镉。该表面的制备能通过从表面去除氧化物(例如,CdO、CdTeO3、CdTe2O5等)而留下碲化镉层20上的富Te(Te-rich)表面。例如,能够用适合的溶剂(例如,也称为1,2二氨基乙烷(1,2diaminoethane)或“DAE”的乙二胺)来洗涤表面,以从表面去除任何氧化镉。
此外,铜能添加到碲化镉层20。伴随合适的蚀刻,铜添加到碲化镉层20能在碲化镉层20上形成铜-碲化物表面,以便获得碲化镉层20(即,p型层)和背接触层之间的低电阻电接触。特别是,铜的添加能在碲化镉层20和背接触层22之间创建碲化亚铜(Cu2Te)的表面层。因而,碲化镉层20的富Te表面能通过碲化镉层20和背接触层22之间的较低电阻率,来增强由器件创建的电流的收集。
铜能通过任何过程施加到碲化镉层20的暴露表面。例如,铜能在具有合适溶剂的溶液(例如甲醇、水等、或其组合物)中被洗涤或喷射在碲化镉层20的表面上,然后退火。在特定实施例中,可以氯化铜、碘化铜、或醋酸铜的形式在溶液中供给铜。退火温度足以允许铜离子扩散到碲化镉层20中,例如从约125℃到约300℃(例如,从约150℃到约200℃),对于约5分钟到约30分钟,例如从约10到约25分钟。
碲化镉层20上示出了背接触层22。背接触层22一般用作背电接触,相对于用作前电接触的、相对的TCO层14。背接触层22能形成在碲化镉层20上,且在一个实施例中直接与其接触。背接触层22合适地由一个或多个高传导材料(例如,元素的镍、铬、铜、锡、铝、金、银、锝或其合金或混合物)制成。另外,背接触层22能够是单个层或能够是多个层。在一个特定实施例中,背接触层22能包括石墨,例如由金属(例如,上面描述的金属)的一个或多个层跟随的p层上沉积的碳层。如果由一个或多个金属制成或包含一个或多个金属,则背接触层22适于通过例如溅射或金属蒸发的技术来施加。如果它由石墨和聚合物混和物(blend)制成,或由碳胶制成,则通过用于散布混和物或胶的任何适合方法(例如,丝网印刷、喷射或通过“刮”刀(“doctor”blade))向半导体器件施加该混和物或胶。在施加石墨混和物或碳胶后,能加热器件,以将该混和物或胶转换成传导的背接触层。如果使用碳层,则其厚度能从约0.1μm到约10μm,例如从约1μm到约5μm。如果背接触的金属层用于背接触层22或作为背接触层22的部分,则其厚度能从约0.1μm到约1.5μm。
图1的示例性碲化镉薄膜光伏器件10中还示出封装玻璃24。
其它组件(未示出)能包括在示例性器件10中,例如汇流条、外部接线、激光蚀刻剂(laseretch)等。例如,当器件10形成光伏模块的光伏电池时,多个光伏电池能例如通过电接线连接而串联连接,以便获得期望的电压。串联连接的电池的每端能附连到诸如导线或汇流条的适合导体,以将光伏生成的电流引导到用于连接到使用生成的电的器件或其它***的便利位置。获得此类串联连接的便利方式是激光刻划器件,以将该器件分成由互连连接的一系列电池。在一个特定实施例中,例如,能使用激光来刻划半导体器件的沉积的层,以将器件分成多个串联连接的电池。
图3示出根据本发明的一个实施例的制造光伏器件的示例方法30的流程图。根据示例方法30,在32,TCO层形成在玻璃衬底上。在34,在含有水蒸气的溅射气氛中将电阻透明缓冲层溅射到TCO层上,以及在35进行退火。在36将硫化镉层形成在电阻透明缓冲层上。在38将碲化镉层形成在硫化镉层上。在40,碲化镉层能够在存在氯化镉的情况下退火,且在42被洗涤以移除形成在表面上的氧化物。在44,能够用铜来掺杂碲化镉层。在46,能够在碲化镉层上施加背接触层,且在48能将封装玻璃施加在背接触层上。
本领域普通技术人员应当认识到其它处理和/或处置能包括在方法30中。例如,该方法还可包括激光刻划,以在器件中形成电隔离的(isolated)的光伏电池。然后,这些电隔离的光伏电池能串联连接,以形成光伏模块。而且,电导线能连接到光伏模块的正极端子和负极端子,以提供利用由光伏模块产生的电流的引线(leadwire)。
此书面描述使用示例来公开包括最佳模式的本发明,以及还使本领域技术人员能实践本发明,包括制作和使用任何器件或***及执行任何结合的方法。本发明可取得专利的范围由权利要求来定义,并且可包括本领域技术人员想到的其它示例。如果此类其它示例包括与权利要求字面语言无不同的结构要素,或者如果它们包括与权利要求字面语言无实质不同的等同结构要素,则它们旨在在权利要求的范围之内。
10光伏器件
12衬底
14透明导电氧化层
16电阻透明缓冲层
18硫化镉层
20碲化镉层
22背接触层22
24封装玻璃
30方法
32343536384042444648步骤
60溅射室
62功率源
64阴极
66顶部支撑
67底部支撑
68导线
69导线
70等离子场
Claims (11)
1.一种制造镉薄膜光伏器件的方法,所述方法包括:
将电阻透明缓冲薄膜层(16)沉积在衬底(12)上;
在所述电阻透明缓冲层上形成硫化镉层;以及
在所述硫化镉层上形成碲化镉层;
其中,用于在衬底(12)上沉积电阻透明缓冲薄膜层(16)的方法包括:
在按照体积包括0.01%到5%的水蒸气的溅射气氛中,在10℃到100℃的溅射温度将电阻透明缓冲层(16)溅射在衬底(12)上;以及
在450℃到700℃的退火温度退火所述电阻透明缓冲层(16);
其中从包括锌、锡或其混合物的靶来溅射所述电阻透明缓冲层。
2.如权利要求1所述的方法,其中所述溅射气氛按照体积包括0.05%到1%的水蒸气。
3.如权利要求1所述的方法,其中所述衬底上形成的所述电阻透明缓冲层包括氧化锌锡。
4.如权利要求1至3中任意一项所述的方法,其中所述溅射气氛还包括氧。
5.如权利要求4所述的方法,其中所述溅射气氛包括1%到25%的氧。
6.如权利要求1所述的方法,其中所述电阻透明缓冲层(16)上或内沉积的任何水分子在退火期间从所述电阻透明缓冲层(16)蒸发出去。
7.如权利要求1所述的方法,其中所述电阻透明缓冲层对于5分钟到5小时进行退火。
8.如权利要求1所述的方法,其中所述电阻透明缓冲层对于15分钟到1小时进行退火。
9.如权利要求1所述的方法,其中所述电阻透明缓冲层(16)溅射到衬底(12)上的导电透明氧化层(14)上。
10.如权利要求1所述的方法,还包括:
在溅射所述电阻透明缓冲层(16)之前、在所述衬底(12)上形成导电透明氧化层(14)。
11.如权利要求10所述的方法,其中所述电阻透明缓冲层(16)具有0.075μm和1μm的厚度。
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US9000549B2 (en) | 2012-11-14 | 2015-04-07 | First Solar, Inc. | Spatially distributed CdS in thin film photovoltaic devices and their methods of manufacture |
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