CN104278238A - 一种高质量铜锌锡硫半导体薄膜的制备方法 - Google Patents
一种高质量铜锌锡硫半导体薄膜的制备方法 Download PDFInfo
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- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000004065 semiconductor Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 41
- 238000001704 evaporation Methods 0.000 claims abstract description 19
- 230000008020 evaporation Effects 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000011135 tin Substances 0.000 claims abstract description 15
- 229910052718 tin Inorganic materials 0.000 claims abstract description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 239000010937 tungsten Substances 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 239000011733 molybdenum Substances 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 238000005987 sulfurization reaction Methods 0.000 claims description 3
- 238000007738 vacuum evaporation Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- 238000004073 vulcanization Methods 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 58
- 230000000052 comparative effect Effects 0.000 description 20
- 238000007747 plating Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910007610 Zn—Sn Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910020888 Sn-Cu Inorganic materials 0.000 description 1
- 229910019204 Sn—Cu Inorganic materials 0.000 description 1
- 229910019319 Sn—Cu—Zn Inorganic materials 0.000 description 1
- 229910009076 Sn—Zn—Cu Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
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- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
- C23C14/0623—Sulfides, selenides or tellurides
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract
本发明公开了一种高质量铜锌锡硫半导体薄膜的制备方法。本方法通过真空加热蒸发的方式,将分别放在不同的钨舟或钼舟中的高纯度铜、锌、锡金属依次沉积在加热至20~200℃的衬底上,得到金属薄膜前驱体,然后经过硫化金属薄膜前驱体得到高质量的铜锌锡硫薄膜。本发明通过改变衬底的温度影响前驱体金属层在衬底上的附着以及三元素间的化学结合,提高了硫化效率,实现高质量铜锌锡硫半导体薄膜的制备。本发明设备比较简单、操作容易;制成的薄膜纯度高、质量好;成膜速率快、效率高;解决了现有技术中硫化阶段形成杂质影响薄膜质量以及硫化时间长、硫化温度高的问题。
Description
技术领域
本发明属于光电材料技术领域,具体是一种高质量铜锌锡硫半导体薄膜的制备方法。
背景技术
开发太阳能这一可再生清洁能源成为缓解日益严重的环境污染和能源短缺问题的重要战略决策之一。因此,太阳能利用技术是人类可持续发展策略的关键。太阳能光伏发电最核心的器件是太阳能电池。目前太阳能电池发展迅速,种类繁多。最早开发的单晶硅太阳能电池生产成本高,于是人们开始研究在廉价衬底上沉积多晶硅薄膜制备多晶硅太阳能电池。之后,美国贝尔实验室制成第一个非晶硅太阳能电池,研究人员不断的优化该类太阳能电池使其首先实现了商品化。还有其他材料的太阳能电池被研制出来作为单晶硅电池的替代品,其中主要有硫化镉、碲化镉、铜铟硒、III-V族化合物等多元化合物薄膜太阳能电池。但是因为镉会污染环境,III-V族化合物及铟和硒元素来源稀少,这类太阳能电池的发展受到限制。近年来,铜锌锡硫(CZTS)薄膜的研究工作发展起来,因其材料环保、价格低廉、来源广泛及最佳的禁带宽度(1.5eV)、高吸收系数(高于104cm-1)而倍受青睐。
太阳能电池的制备中不仅需要开发廉价、无毒的吸收层材料以降低成本,还很注重用高效率的方法制备高质量的吸收层材料来提高电池的转换效率。制备CZTS薄膜的方法主要包括真空加热蒸发法、电子束蒸发法、磁控溅射法、喷雾热解法、电沉积法、溶胶凝胶法、分子束外延法等。真空加热蒸发法的设备比较简单、操作容易,制成的薄膜纯度高、质量好,厚度可准确控制,成膜速率快、效率高,且薄膜的生长机理比较单纯,被广泛应用。用硫化锌、锡和铜共蒸发制得的金属前驱体制备CZTS薄膜,由于金属蒸发顺序的不可调控,限制了优化CZTS薄膜的结晶质量和结构特性的工作。顺序蒸镀铜、锌、锡金属的叠层金属前驱体被硫化形成CZTS的同时常伴随产生CuxS1-x、ZnS、SnS或SnS2等杂质相,会降低CZTS薄膜的质量,而且需要很高的硫化温度和很长的硫化时间。
发明内容
本发明的目的是提供一种高效率制备高质量的铜锌锡硫半导体薄膜的方法,以解决现有技术中硫化阶段形成杂质影响薄膜质量以及硫化时间长、硫化温度高的问题。
本发明为实现其目的所采用的技术方案是:
一种高质量铜锌锡硫半导体薄膜的制备方法,包括以下步骤:
(1)将金属铜、锌和锡分别放在不同的钨舟或钼舟中,加热衬底,通过真空加热蒸发将金属沉积到衬底上,得到金属薄膜前驱体;
(2)将金属薄膜前驱体与硫粉置于真空或者保护气体下,升温至硫化温度进行硫化,得到高质量的铜锌锡硫半导体薄膜。
进一步地,在步骤(1)中加热衬底至20~200℃。
进一步地,在步骤(1)中加热衬底至50~100℃。
进一步地,在步骤(1)中加热衬底至50℃。
进一步地,在步骤(1)中通过转动衬底载台,确保衬底在蒸发源正上方位置,从而实现不同的金属蒸发顺序。
进一步地,在步骤(1)中真空加热蒸发的真空度高于10-4Pa。
进一步地,在步骤(2)中所述保护气体是氮气或氩气。
进一步地,步骤(2)的硫化温度为200~400℃,硫化时间为0.5~2h。
进一步地,铜、锌和锡的摩尔比是3~5:2~4:2~3。
进一步地,所述的衬底为玻璃、硅片或不锈钢片。
进一步地,在步骤(1)之前依次用丙酮、酒精、去离子水浸泡、超声清洗衬底,然后烘箱烘干备用。
本发明的有益效果是:本发明用真空加热蒸发法分两步制备铜锌锡硫半导体薄膜,该方法通过加热衬底至20~200℃,可使顺序蒸镀到衬底上的铜、锌、锡形成合金结构,减少硫化阶段杂质相的形成,有效提高铜锌锡硫相的生成,优化薄膜结构,从而提高所制备的铜锌锡硫半导体薄膜的质量;同时还可以缩短硫化时间、降低硫化温度,从而提高薄膜制备的速度,降低生产成本;本发明制备的半导体薄膜廉价环保、生长机理比较单纯,使用该薄膜制备太阳能电池可以降低太阳能电池的成本,质量更高的薄膜也提高了太阳能转化效率。综上所述,本发明的设备简单、操作容易;成膜速率快、效率高;制成的铜锌锡硫半导体薄膜纯度高、质量好。
附图说明
图1为实施例1和对比例1、对比例2所制备的铜锌锡硫半导体薄膜的XRD图;
图2为实施例1和对比例1、对比例2所制备的铜锌锡硫半导体薄膜的Raman图;
图3为实施例1和对比例1、对比例2所制备的铜锌锡硫半导体薄膜的吸收系数平方与能量之间的关系图。
具体实施方式
下面将结合具体实施方式对本发明中的技术方案进行清楚、完整地描述。
(1)清洗衬底
依次用丙酮、酒精、去离子水浸泡、超声清洗衬底,然后烘箱烘干备用。
(2)制备金属薄膜前驱体
将99.99%及以上高纯度的粉体或颗粒或片状或丝状的铜、锌、锡金属分别放在三个钨舟或钼舟中,置于真空镀膜机的真空腔。加热玻璃衬底到设定的温度,待真空腔的真空度高于10-4Pa,可通过调控电流源调节蒸发温度使蒸发源完全蒸发,通过转动衬底载台,确保衬底在蒸发源正上方位置,实现不同的金属蒸发顺序,金属层沉积在衬底上,得到金属薄膜前驱体。
(3)制备高质量铜锌锡硫半导体薄膜
将制备的合金结构的金属前薄膜驱体和硫粉放在管式炉中,置于氮气或氩气保护气体下或将管式炉抽成真空,防止在空气中暴露被氧化,加热到硫化温度,保温一段时间,待硫化反应结束后,自然冷却至室温,取出样品,得到高质量铜锌锡硫半导体薄膜。
实施例1
将摩尔比为2:1:1的铜、锌和锡分别放在三个钨舟中,置于真空镀膜机的真空腔,取清洗过的玻璃衬底加热到50℃,按照Cu-Zn-Sn的顺序蒸发完全,得到金属薄膜前驱体。将此金属薄膜前驱体和足量高纯的硫粉置于管式炉中,在氮气保护下加热,先以5℃/min的速率升温至400℃,再保温1h,最后得到厚度约为1.5μm的铜锌锡硫半导体薄膜。
实施例2
将摩尔比为5:3:2的铜、锌和锡分别放在三个钨舟中,置于真空镀膜机的真空腔,取清洗过的硅片衬底加热到20℃,按照Sn-Zn-Cu的顺序蒸发完全,得到金属薄膜前驱体。将此金属薄膜前驱体和足量高纯的硫粉置于管式炉中,在氩气保护下加热,先以5℃/min的速率升温至200℃,再保温2h,最后得到厚度约为1.6μm的铜锌锡硫半导体薄膜。
实施例3
将摩尔比为3:2:2的铜、锌和锡分别放在三个钼舟中,置于真空镀膜机的真空腔,取清洗过的不锈钢片衬底加热到200℃,按照Zn-Sn-Cu的顺序蒸发完全,得到金属薄膜前驱体。将此金属薄膜前驱体和足量高纯的硫粉置于管式炉中,将管式炉抽成真空,加热,先以5℃/min的速率升温至300℃,再保温0.5h,最后得到厚度约为1.4μm的铜锌锡硫半导体薄膜。
实施例4
将摩尔比为5:4:3的铜、锌和锡分别放在三个钼舟中,置于真空镀膜机的真空腔,取清洗过的硅片衬底加热到100℃,按照Sn-Cu-Zn的顺序蒸发完全,得到金属薄膜前驱体。将此金属薄膜前驱体和足量高纯的硫粉置于管式炉中,在氩气保护下加热,先以5℃/min的速率升温至400℃,再保温1h,最后得到厚度约为1.2μm的铜锌锡硫半导体薄膜。
对比例1
将摩尔比为2:1:1的铜、锌和锡分别放在三个钨舟中,置于真空镀膜机的真空腔,取清洗过的玻璃衬底,不加热,按照Cu-Zn-Sn的顺序蒸发完全,得到金属薄膜前驱体。将此前驱体置于真空管式炉中,在300℃的温度下退火1h,再将所得到的薄膜和足量高纯的硫粉置于真空管式炉中加热,先以5℃/min的速率升温至400℃,再保温1h,最后得到厚度约为1.5μm的铜锌锡硫半导体薄膜。
对比例2
将摩尔比为2:1:1的铜、锌和锡分别放在三个钨舟中,置于真空镀膜机的真空腔,取清洗过的玻璃衬底,不加热,按照Cu-Zn-Sn的顺序蒸发完全,得到金属薄膜前驱体。将此前驱体和足量高纯的硫粉置于真空管式炉中加热,先以5℃/min的速率升温至500℃,再保温1.5h,最后得到厚度约为1.5μm的铜锌锡硫半导体薄膜。
图1为实施例1和对比例1、对比例2所制备的铜锌锡硫半导体薄膜的XRD图,曲线从上往下依次是实施例1、对比例1、对比例2所制备的铜锌锡硫半导体薄膜的XRD谱。从图中看到,Tsub=50℃的曲线明显比其他两条曲线衍射峰强且半高宽窄。峰强说明加热衬底制备的铜锌锡硫薄膜的结晶度比没有加热衬底、对前驱体先退火再硫化或直接硫化所制备的样品有很大提高。半高宽窄表明实施例1所制备的铜锌锡硫半导体薄膜结晶质量更好。
图2为实施例1和对比例1、对比例2所制备的铜锌锡硫半导体薄膜的Raman图,曲线从上往下依次是实施例1、对比例1、对比例2所制备的铜锌锡硫半导体薄膜的Raman谱。如图所示,和曲线Tsub=50℃比较,曲线Tsul=500℃的峰成包状且峰位偏移,曲线Tpre=300℃峰强度相对弱些。说明实施例1所制备的铜锌锡硫半导体薄膜晶度高质量好,与XRD图结论一致,证明了制备样品过程中加热衬底的优越性。
图3中从左到右分别为对比例2、对比例1及实施例1所制备的铜锌锡硫半导体薄膜的吸收系数平方与能量之间的关系图。三者显示出非常相近的禁带宽度,都接近于理想的光学带隙(1.50eV)。说明实施例1、对比例1和对比例2都成功制得纯度高的铜锌锡硫半导体薄膜。然而比较其实验条件可发现加热衬底或对前驱体进行退火可以有效降低硫化温度和减少硫化时间。
以上所述,仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,任何属于本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求的保护范围为准。
Claims (9)
1.一种高质量铜锌锡硫半导体薄膜的制备方法,其特征在于,包括以下步骤:
(1)将金属铜、锌和锡分别放在不同的钨舟或钼舟中,加热衬底,通过真空加热蒸发将金属沉积到衬底上,得到金属薄膜前驱体;
(2)将金属薄膜前驱体与硫粉置于真空或者保护气体下,升温至硫化温度进行硫化,得到高质量的铜锌锡硫半导体薄膜。
2.根据权利要求1所述的一种高质量铜锌锡硫半导体薄膜的制备方法,其特征在于,在步骤(1)中加热衬底至20~200℃。
3.根据权利要求1所述的一种高质量铜锌锡硫半导体薄膜的制备方法,其特征在于,在步骤(1)中加热衬底至50~100℃。
4.根据权利要求1所述的一种高质量铜锌锡硫半导体薄膜的制备方法,其特征在于,在步骤(1)中加热衬底至50℃。
5.根据权利要求1所述的一种高质量铜锌锡硫半导体薄膜的制备方法,其特征在于,在步骤(1)中通过转动衬底载台,确保衬底在蒸发源正上方位置,从而实现不同的金属蒸发顺序。
6.根据权利要求1所述的一种高质量铜锌锡硫半导体薄膜的制备方法,其特征在于,在步骤(2)中所述保护气体是氮气或氩气。
7.根据权利要求1所述的一种高质量铜锌锡硫半导体薄膜的制备方法,其特征在于,步骤(2)的硫化温度为200~400℃,硫化时间为0.5~2h。
8.根据权利要求1所述的一种高质量铜锌锡硫半导体薄膜的制备方法,其特征在于,铜、锌和锡的摩尔比是3~5:2~4:2~3。
9.根据权利要求1所述的一种高质量铜锌锡硫半导体薄膜的制备方法,其特征在于,所述的衬底为玻璃、硅片或不锈钢片。
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