CN111253080A - 一种单相铜钡锡硫薄膜及其制备方法 - Google Patents
一种单相铜钡锡硫薄膜及其制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XBQLSSQTYJSTFT-UHFFFAOYSA-N [S].[Sn].[Ba].[Cu] Chemical compound [S].[Sn].[Ba].[Cu] XBQLSSQTYJSTFT-UHFFFAOYSA-N 0.000 title description 3
- 239000002243 precursor Substances 0.000 claims abstract description 58
- 239000010949 copper Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 36
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000137 annealing Methods 0.000 claims abstract description 30
- 238000004528 spin coating Methods 0.000 claims abstract description 23
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 159000000009 barium salts Chemical class 0.000 claims abstract description 19
- 150000001879 copper Chemical class 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 15
- 239000010408 film Substances 0.000 claims description 78
- 239000000758 substrate Substances 0.000 claims description 38
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 26
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 26
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical group O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 16
- 238000004073 vulcanization Methods 0.000 claims description 16
- 235000014655 lactic acid Nutrition 0.000 claims description 13
- 239000004310 lactic acid Substances 0.000 claims description 13
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical group [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 8
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 8
- 239000006184 cosolvent Substances 0.000 claims description 8
- 239000003223 protective agent Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 4
- 238000001755 magnetron sputter deposition Methods 0.000 abstract description 13
- 239000007787 solid Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 35
- 238000010438 heat treatment Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 14
- 229910052750 molybdenum Inorganic materials 0.000 description 14
- 239000011733 molybdenum Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000005361 soda-lime glass Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 238000005034 decoration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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Abstract
本发明涉及材料制备技术领域，提供了一种单相Cu2BaSnS4薄膜的制备方法。本发明通过将铜盐、锡盐、硫脲和钡盐溶解于乙二醇甲醚中制备前驱溶液，然后再将此前驱溶液旋涂成膜，再采用退火和硫化处理，最终得到单相Cu2BaSnS4薄膜。本发明提供的方法无需使用磁控溅射设备，工艺简单，使用设备易得，而且制备得到的单相Cu2BaSnS4薄膜纯度较高，对于Cu2BaSnS4薄膜大规模廉价制备提供坚实基础。
Description
技术领域
本发明涉及材料制备技术领域，尤其涉及一种单相Cu2BaSnS4薄膜的制备方法。
背景技术
近些年来，Cu2BaSnS4(简称为CBTS，铜钡锡硫)薄膜因为其突出的优点成为近年来大家研究的热点，被广泛应用在多种领域。目前CBTS薄膜已经在太阳光电领域中得到广泛应用。其主要优势在于，CBTS是直接带隙半导体，带隙范围在1.5eV～2.0eV，吸收系数大，使得电池所需厚度薄，有利于降低原料消耗。最重要的优势是CBTS的组成成分都是地球上比较丰富的元素，为未来大规模的发展提供了可能。而且通论理论计算和模拟，发现CBTS无深能级缺陷，为进一步的效率提升提供了坚实的理论基础。除了太阳电池领域，CBTS薄膜也被应用于电解水领域，并取得良好效果。
目前高纯度的CBTS薄膜主要由磁控溅射方法制备。磁控溅射方法制备对于实验器材要求高，制备成本高，不利于CBTS薄膜的大规模发展。
发明内容
本发明提供了一种单相Cu2BaSnS4薄膜的制备方法，本发明提供的制备方法无需磁控溅射，对实验器材要求较低，且制备得到单相Cu2BaSnS4薄膜。
本发明提供了一种单相Cu2BaSnS4薄膜的制备方法，包括以下步骤：
(1)将铜盐、锡盐、钡盐和硫脲溶解于乙二醇甲醚中，得到前驱溶液；
(2)将前驱溶液在基底上旋涂成薄膜，然后进行退火，得到Cu2BaSnS4薄膜前体；
(3)将所述Cu2BaSnS4薄膜前体在保护气氛下进行硫化处理，得到单相Cu2BaSnS4薄膜。
优选的，所述步骤(1)中铜盐为一水合乙酸铜；锡盐为二水合氯化亚锡；钡盐为乙酸钡。
优选的，所述前驱溶液中铜盐、钡盐、锡盐和硫脲的摩尔比为1.5～2:1～1.5:1:4～10；所述前驱溶液中铜盐的浓度为4×10-4～5.5×10-4mol/mL。
优选的，所述步骤(1)制备前驱溶液时，还加入助溶剂乳酸和保护剂乙醇胺，所述助溶剂乳酸的体积和钡盐的摩尔比为1～1.5mL:5.2×10-3mol；所述保护剂乙醇胺在前驱溶液中的体积浓度为1～3％。
优选的，所述步骤(1)中溶解的温度为45～55℃。
优选的，所述步骤(2)中旋涂的速度为2000～6000r/s，旋涂的时间为10～40s。
优选的，所述步骤(2)中退火的温度为265～275℃，退火的时间为4～6min。
优选的，所述步骤(3)中硫化处理的温度570～590℃，硫化处理的时间为35～40min。
本发明还提供了上述技术方案所述的制备方法制备得到的单相Cu2BaSnS4薄膜。
有益效果：
本发明提供了一种单相Cu2BaSnS4薄膜的制备方法。本发明通过将铜盐、锡盐、硫脲和钡盐先溶解于乙二醇甲醚中制备前驱溶液，将此前驱溶液旋涂成膜，再采用退火和硫化处理，最终得到单相Cu2BaSnS4薄膜。本发明提供的方法无需使用磁控溅射设备，工艺简单，使用设备易得，且制备得到的单相Cu2BaSnS4薄膜无二次相，对于未来Cu2BaSnS4薄膜大规模廉价制备提供坚实基础。
附图说明
图1为本发明实施例1制备得到的单相CBTS薄膜的XRD图。
具体实施方式
本发明提供了一种单相Cu2BaSnS4薄膜的制备方法，包括以下步骤：
(1)将铜盐、锡盐、钡盐和硫脲溶解于乙二醇甲醚中，得到前驱溶液；
(2)将前驱溶液在基底上旋涂成薄膜，然后进行退火，得到Cu2BaSnS4薄膜前体；
(3)将所述Cu2BaSnS4薄膜前体在保护气氛下进行硫化处理，得到单相Cu2BaSnS4薄膜。
本发明将铜盐、锡盐、钡盐和硫脲溶解于乙二醇甲醚中，得到前驱溶液。
在本发明中，所述铜盐优选为一水合乙酸铜，所述锡盐优选为二水合氯化亚锡，所述钡盐优选为乙酸钡。在本发明中，所述前驱体溶液中铜盐、钡盐、锡盐和硫脲的摩尔比优选为1.5～2:1～1.5:1:4～10，更优选为1.925:1.3:1:8；所述前驱溶液中铜盐的浓度优选为4×10-4～5.5×10-4mol/mL，更优选为4.3×10-4mol/mL。本发明优选将原料用量控制在上述范围内，有利于制备得到纯度高的单相Cu2BaSnS4薄膜。在本发明中，所述Cu2BaSnS4薄膜简写为CBTS薄膜。
在本发明中，制备前驱溶液时，优选还加入助溶剂乳酸和保护剂乙醇胺，所述助溶剂乳酸的体积和钡盐的摩尔比优选为1～1.5mL:5.2×10-3mol，更优选为1mL:5.2×10- 3mol；所述保护剂乙醇胺在前驱体溶液中的体积浓度为1～3％。在本发明中，助溶剂乳酸有利于使钡盐溶解，保护剂乙醇胺能够避免旋涂薄膜时产生裂缝。
在本发明中，所述前驱溶液的制备方法优选包括以下步骤：
在加热条件下将铜盐、锡盐和硫脲溶于部分乙二醇甲醚中，得到溶液A；
在加热条件下将钡盐和助溶剂乳酸溶于剩余乙二醇甲醚中，得到溶液B；
将溶液A和溶液B加热混合，得到前驱溶液，随后在常温下加入乙醇胺溶液搅拌混合。
在本发明中，制备溶液A和溶液B的加热温度以及制备前驱溶液的加热温度独立地优选为45～55℃，更优选为50℃。
得到前驱溶液后，本发明将前驱溶液在基底上旋涂成薄膜，然后进行退火，得到Cu2BaSnS4薄膜前体。
在本发明中，所述基底优选由衬底和镀在衬底上的钼层组成，所述衬底优选为玻璃衬底，所述衬底上的钼层优选通过磁控溅射的方法制备。本发明中的基底可以采用市售商品，也可以自制，采用自制的方法时，本发明对磁控溅射的具体实施方式没有特别要求，采用本领域技术人员常规的方法即可。本发明优选在基底的钼层表面旋涂薄膜，有利于制备得到高纯度的Cu2BaSnS4薄膜前体。
在本发明中，所述旋涂的速度优选为2000～6000r/s，更优选为3000～4000r/s，旋涂的时间优选为10～40s，更优选为20～30s。在本发明中，所述退火的温度优选为265～275℃，退火的时间优选为4～6min，更优选为5min。本发明在退火过程中，溶剂蒸发，铜、钡、锡和硫发生反应形成Cu2BaSnS4前驱体。本发明优选将退火温度和退火时间控制在上述范围内，避免溶剂未完全蒸发影响后续步骤，或者溶剂蒸干后，退火产物在空气中被氧化产生杂质。本发明优选采用热盘进行退火，本发明优选重复进行旋涂和退火过程，以得到所需厚度的Cu2BaSnS4薄膜前体。本发明在退火过程中，铜盐、锡盐、钡盐和硫脲发生反应，形成前驱体。
得到Cu2BaSnS4薄膜前体后，本发明将所述Cu2BaSnS4薄膜前体在保护气氛下进行硫化处理，得到Cu2BaSnS4薄膜。
在本发明中，所述保护气氛优选为氮气气氛，所述硫化处理优选在管式炉中进行，所述硫化处理优选在常压下进行；所述硫化处理的温度优选为570～590℃，更优选为570℃、580℃或590℃，所述硫化处理的时间优选为40min。本发明在硫化处理过程中，原料之间进一步反应，生成Cu2BaSnS4相，而且本发明通过硫化处理，制备得到了单相Cu2BaSnS4薄膜。
本发明还提供了上述技术方案所述制备方法制备得到的单相Cu2BaSnS4薄膜。本发明制备得到的单相Cu2BaSnS4薄膜的纯度较高，由XRD表征数据可知，本发明提供的Cu2BaSnS4薄膜中只有Cu2BaSnS4相，没有明显的二次相。
下面将结合本发明中的实施例，对本发明中的技术方案进行清楚、完整地描述。
实施例1
取10mL乙二醇甲醚作为溶剂，7.7×10-3mol一水合乙酸铜，4.0×10-3mol二水合氯化亚锡，0.032mol硫脲作为溶质，在50℃经过水浴加热1h得到溶液A；
取5mL乙二醇甲醚作为溶剂，5.2×10-3mol乙酸钡作为溶质，加入1mL乳酸助溶，在70℃经过水浴加热30min得到无色透明溶液B；
将溶液A与溶液B混合，在40℃经过水浴加热15min后，得到前驱溶液,然后再加入0.3mL乙醇胺，在常温下搅拌均匀；
采用匀胶机在基底上在3000r转速下旋转20s旋涂一层薄膜，其中基底结构为：底层为纳钙玻璃衬底，在钠钙玻璃衬底上磁控溅射有钼层；在基底的钼层表面旋涂薄膜，然后采用热盘在270℃退火5min，多次重复旋涂和退火过程，得到CBTS薄膜前体；
将CBTS薄膜前体(包括基底)放入管式炉，在氮气气氛下，将反应气压调节至大气压强，进行硫化反应，硫化反应温度为580℃，反应时长为40min，最终得到高纯度单相CBTS薄膜。
实施例2
取10mL乙二醇甲醚作为溶剂，7.7×10-3mol一水合乙酸铜，4.0×10-3mol二水合氯化亚锡，0.032mol硫脲作为溶质，在50℃经过水浴加热1h得到溶液A；
取5mL乙二醇甲醚作为溶剂，5.2×10-3mol乙酸钡作为溶质，加入1mL乳酸助溶，在70℃经过水浴加热30min得到无色透明溶液B；
将溶液A与溶液B混合，在40℃经过水浴加热15min后，得到前驱溶液，然后再加入0.1mL乙醇胺搅拌均匀；
采用匀胶机在基底上在3000r转速下旋转20s旋涂一层薄膜，其中基底结构为：底层为纳钙玻璃衬体，在钠钙玻璃衬底上磁控溅射有钼层；在基底的钼层表面旋涂薄膜，然后采用热盘在265℃退火5min，多次重复旋涂和退火过程，得到CBTS薄膜前体；
将CBTS薄膜前体(包括基底)放入管式炉，在氮气气氛下，将反应气压调节至大气压强，进行硫化反应，硫化反应温度为570℃，反应时长为40min，最终得到高纯度单相CBTS薄膜。
实施例3
取10mL乙二醇甲醚作为溶剂，7.7×10-3mol一水合乙酸铜，4.0×10-3mol二水合氯化亚锡，0.032mol硫脲作为溶质，在50℃经过水浴加热1h得到溶液A；
取5mL乙二醇甲醚作为溶剂，5.2×10-3mol乙酸钡作为溶质，加入1mL乳酸助溶，在70℃经过水浴加热30min得到无色透明溶液B；
将溶液A与溶液B混合，在40℃经过水浴加热15min后，得到前驱溶液，然后再加入0.2mL乙醇胺搅拌均匀即可；
采用匀胶机在基底上以3000r转速下旋转20s旋涂一层薄膜，其中基底结构为：底层为纳钙玻璃衬体，在钠钙玻璃衬底上磁控溅射有钼层；在基底的钼层表面旋涂薄膜，然后采用热盘在275℃退火5min，多次重复旋涂和退火过程，得到CBTS薄膜前体；
将CBTS薄膜前体(包括基底)放入管式炉，在氮气气氛下，将反应气压调节至大气压强，进行硫化反应，硫化反应温度为590℃，反应时长为40min，最终得到高纯度单相CBTS薄膜。
实施例4
取10mL乙二醇甲醚作为溶剂，7.7×10-3mol一水合乙酸铜，4.0×10-3mol二水合氯化亚锡，0.032mol硫脲作为溶质，在50℃经过水浴加热1h得到溶液A；
取5mL乙二醇甲醚作为溶剂，5.2×10-3mol乙酸钡作为溶质，加入1mL乳酸助溶，在70℃经过水浴加热30min得到无色透明溶液B；
将溶液A与溶液B混合，在40℃经过水浴加热15min后，得到前驱溶液，然后再加入0.25mL乙醇胺搅拌均匀；
采用匀胶机在基底上在3000r转速下旋转20s旋涂一层薄膜，其中基底结构为：底层为纳钙玻璃衬体，在钠钙玻璃衬底上磁控溅射有钼层；在基底的钼层表面旋涂薄膜，然后采用热盘在270℃退火6min，多次重复旋涂和退火过程，得到CBTS薄膜前体；
将CBTS薄膜前体(包括基底)放入管式炉，在氮气气氛下，将反应气压调节至大气压强，进行硫化反应，硫化反应温度为580℃，反应时长为40min，最终得到高纯度单相CBTS薄膜。
实施例5
取10mL乙二醇甲醚作为溶剂，7.7×10-3mol一水合乙酸铜，4.0×10-3mol二水合氯化亚锡，0.032mol硫脲作为溶质，在50℃经过水浴加热1h得到溶液A；
取5mL乙二醇甲醚作为溶剂，5.2×10-3mol乙酸钡作为溶质，加入1mL乳酸助溶，在70℃经过水浴加热30min得到无色透明溶液B；
将溶液A与溶液B混合，在40℃经过水浴加热15min后，得到前驱溶液，然后再加入0.25mL乙醇胺搅拌均匀；
采用匀胶机在基底上在3000r转速下旋转20s旋涂一层薄膜，其中基底结构为：底层为纳钙玻璃衬体，在钠钙玻璃衬底上磁控溅射有钼层；在基底的钼层表面旋涂薄膜，然后采用热盘在270℃退火4min，多次重复旋涂和退火过程，得到CBTS薄膜前体；
将CBTS薄膜前体(包括基底)放入管式炉，在氮气气氛下，将反应气压调节至大气压强，进行硫化反应，硫化反应温度为590℃，反应时长为40min，最终得到高纯度单相CBTS薄膜。
对实施例1制备得到的高纯度CBTS薄膜进行XRD测试，结果如图1所示，图1中最上边的曲线为实施例1制备得到的高纯度CBTS薄膜的XRD曲线，图1中中间的曲线为CBTS标准品的PDF卡片，图1中最下边的曲线为钼衬底的PDF卡片。由图1可知，本发明得到的单相CBTS薄膜纯度较高，没有明显二次相产生。对实施例2～5制备得到的高纯度单相CBTS薄膜进行XRD测试，结果与图1相同，在此不再赘述。由此可知，本发明所述方法制备得到的单相CBTS薄膜纯度较高。
本发明提供了一种高纯度CBTS薄膜的制备方法。本发明通过将铜盐、锡盐、硫脲和钡盐先溶解于乙二醇甲醚中制备前驱溶液，将此前驱溶液旋涂成膜，再采用退火和硫化处理，最终得到单相CBTS薄膜。本发明提供的方法无需使用磁控溅射方法，工艺简单，使用设备易得，且制备得到的单相CBTS薄膜纯度较高，无二次相。对于未来CBTS材料大规模廉价制备及其在其他领域的应用提供坚实基础。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (9)
1.一种单相Cu2BaSnS4薄膜的制备方法，包括以下步骤：
(1)将铜盐、锡盐、钡盐和硫脲溶解于乙二醇甲醚中，得到前驱溶液；
(2)将前驱溶液在基底上旋涂成薄膜，然后进行退火，得到Cu2BaSnS4薄膜前体；
(3)将所述Cu2BaSnS4薄膜前体在保护气氛下进行硫化处理，得到单相Cu2BaSnS4薄膜。
2.根据权利要求1所述的制备方法，其特征在于，所述步骤(1)中铜盐为一水合乙酸铜；锡盐为二水合氯化亚锡；钡盐为乙酸钡。
3.根据权利要求1或2所述的制备方法，其特征在于，所述前驱溶液中铜盐、钡盐、锡盐和硫脲的摩尔比为1.5～2:1～1.5:1:4～10；所述前驱溶液中铜盐的浓度为4×10-4～5.5×10-4mol/mL。
4.根据权利要求1所述的制备方法，其特征在于，所述步骤(1)制备前驱溶液时，还加入助溶剂乳酸和保护剂乙醇胺，所述助溶剂乳酸的体积和钡盐的摩尔比为1～1.5mL:5.2×10-3mol；所述保护剂乙醇胺在前驱溶液中的体积浓度为1～3％。
5.根据权利要求1所述的制备方法，其特征在于，所述步骤(1)中溶解的温度为45～55℃。
6.根据权利要求1所述的制备方法，其特征在于，所述步骤(2)中旋涂的速度为2000～6000r/s，旋涂的时间为10～40s。
7.根据权利要求1所述的制备方法，其特征在于，所述步骤(2)中退火的温度为265～275℃，退火的时间为4～6min。
8.根据权利要求1所述的制备方法，其特征在于，所述步骤(3)中硫化处理的温度570～590℃，硫化处理的时间为35～40min。
9.权利要求1～8任一项所述的制备方法制备得到的单相Cu2BaSnS4薄膜。
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