CN108486623A - 一种分步脉冲电沉积后退火制备铜锌锡硫太阳能电池薄膜材料的方法 - Google Patents
一种分步脉冲电沉积后退火制备铜锌锡硫太阳能电池薄膜材料的方法 Download PDFInfo
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- 238000004070 electrodeposition Methods 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 44
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000000137 annealing Methods 0.000 title claims abstract description 33
- 239000010408 film Substances 0.000 claims abstract description 71
- 239000011701 zinc Substances 0.000 claims abstract description 33
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 31
- 239000010409 thin film Substances 0.000 claims abstract description 28
- 238000000151 deposition Methods 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 239000010949 copper Substances 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052718 tin Chemical class 0.000 claims abstract description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- PDYXSJSAMVACOH-UHFFFAOYSA-N [Cu].[Zn].[Sn] Chemical compound [Cu].[Zn].[Sn] PDYXSJSAMVACOH-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000005864 Sulphur Substances 0.000 claims description 10
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
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- 238000004062 sedimentation Methods 0.000 claims description 2
- 229910001432 tin ion Inorganic materials 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 239000011686 zinc sulphate Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 9
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- 238000010521 absorption reaction Methods 0.000 description 7
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- 241000208340 Araliaceae Species 0.000 description 6
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 6
- 235000003140 Panax quinquefolius Nutrition 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 235000008434 ginseng Nutrition 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000002608 ionic liquid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000002083 X-ray spectrum Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- -1 Cu-S Substances 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 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
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DZXKSFDSPBRJPS-UHFFFAOYSA-N tin(2+);sulfide Chemical compound [S-2].[Sn+2] DZXKSFDSPBRJPS-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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- 210000003462 vein Anatomy 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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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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- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/60—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes
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- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
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- H01L31/02—Details
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Abstract
本发明公开了一种分步脉冲电沉积后退火制备铜锌锡硫太阳能电池薄膜材料的方法。先将锌的金属盐溶解于溶剂中，在导电玻璃上以脉冲法电沉积制备锌前驱体薄膜，再将铜和锡的金属盐溶解于溶剂中，在锌前驱体薄膜上沉积铜锡合金薄膜，然后将前驱体薄膜硫化退火，最终生成单相铜锌锡硫薄膜。本发明通过将脉冲电压沉积模式与分步沉积模式的优势结合起来，分步控制脉冲电势和脉冲时间实现对薄膜的成分、晶相、形貌等的可控制备，消除了SnS二元杂质相，改善薄膜形貌、提高电镀速率。相对于一步恒电位沉积技术，薄膜无杂质相且形貌平整致密、退火过程无需加入SnS。与高真空气相法相比，本发明具有成膜质量好、成本低廉、可控性强等优点。
Description
技术领域
本发明属于新能源光电薄膜材料技术领域。涉及一种薄膜太阳能电池吸收层材料的制备方法，具体涉及一种采用分步脉冲电沉积铜锌锡前驱体薄膜后硫化退火制备铜锌锡硫薄膜的方法。
背景技术
随着当今世界能源问题的出现，太阳能电池的开发和利用受到人们的普遍关注。薄膜太阳能电池具有材料消耗少，转换效率高，吸收系数大，光学带隙与太阳光谱较匹配等优点，有望成为现有硅电池的替代者。铜铟镓硒(CIGS)电池已经取得薄膜太阳能电池中的最高转化率21.7％。但地球上铜铟镓硒薄膜所需原材料中的镓铟含量极少，限制了它的广泛推广。新型铜基化合物薄膜太阳能电池铜锌锡硫不仅具有薄膜太阳能电池的众多优点，而且原材料丰富，无毒，是一种具有很大潜力的薄膜太阳能电池吸水层材料。
目前制备铜锌锡硫薄膜的方法主要有：真空蒸发、磁控溅射、溶胶凝胶法和电沉积法。通过真空蒸发法制备的铜锌锡硫薄膜表面存在富铜相，这样的薄膜容易有大颗粒CuS分布整个吸收层表面，制备的电池很容易短路。磁控溅射法制备的薄膜质量好，重复性好，转化效率高。但是制备工艺比较复杂，设备要求高且生产效率比较低，生产成本高，大规模生产难以实施。在直流恒电位模式电沉积制备铜锌锡硫的方法中，由于只有一个参数(沉积电位)可以调节，难以控制薄膜生长过程的化学组分，导致薄膜在后续退火过程中容易产生Sn-S，Cu-S等杂质，薄膜内部缺陷较多，界面复合严重，从而极大地降低铜锌锡硫电池的光电转换效率。纵观目前的文献报道，这些方法都存在着一个比较突出的问题，即如何制备出成分均匀的铜锌锡硫吸收层并实现其化学计量比的精确控制。
本发明通过设计合适的分步沉积体系，将脉冲电压沉积模式与分步沉积模式的优势结合起来，不仅可以利用脉冲电压来控制通断比，减少双电层外层与本体溶液的浓度差，降低溶液的浓差极化，控制薄膜晶粒的形核和生长，改善薄膜的微观形貌，增强薄膜与基底的结合力；而且通过调节各步中脉冲的沉积时间，有效的调控薄膜的化学计量比，可以得到特定的元素组成，使薄膜平整均匀致密，从而可以制备出成分均匀的铜锌锡硫吸收层并实现其化学计量比的精确控制。此外通过分步沉积模式消除一步电沉积中金属锌与铜及锡的沉积电势差太大导致金属锌难以沉积和薄膜成分不均匀的缺陷。
发明内容
本发明的目的在于提供一种分步脉冲电沉积法制备铜锌锡合金预制薄膜后退火制备高质量的铜锌锡硫太阳能电池吸收层薄膜的方法。先以锌的金属盐为原料，按一定摩尔比溶解于一定溶剂(包含去离子水，乙醇，离子液体)中作为电化学沉积的电解质溶液。在三电极系统下，脉冲电沉积锌；再以铜和锡的金属盐为原料、按一定摩尔比溶解于一定溶剂(包含去离子水，乙醇，离子液体)中作为电化学沉积的电解质溶液，脉冲电沉积铜锡合金；最后将前驱体薄膜在真空环境下硫化退火，得到铜锌锡硫薄膜材料。本发明工艺简单，成本低，形貌与成分可控性强。
本发明实现上述目的的技术方案为：
一种分步脉冲电沉积后退火制备铜锌锡硫太阳能电池薄膜材料的方法，包括以下步骤：
(1)将锌的金属盐溶解在溶剂中，加热搅拌使其充分溶解，得到电沉积锌的电解质溶液；
(2)以基底材料为工作电极，铂电极为对电极，饱和甘汞电极为参比电极，采用脉冲电沉积法在步骤(1)所得电解质溶液中进行脉冲电沉积锌，得到锌预制膜；
(3)将铜的金属盐溶解在溶剂中，搅拌使其充分溶解，然后再加入锡的金属盐搅拌使其充分溶解，得到电沉积铜锡合金薄膜的电沉积溶液；
(4)以步骤(2)所得锌预制膜为工作电极，铂电极为对电极，饱和甘汞电极为参比电极，采用脉冲电沉积法在步骤(3)所得电沉积溶液中进行脉冲电沉积铜锡合金，得到铜锌锡前驱体薄膜；
(5)将步骤(4)所得铜锌锡前驱体薄膜置于含有硫粉的真空中硫化退火，最后得到铜锌锡硫太阳能电池薄膜材料。
进一步地，步骤(1)中，电解质溶液中的锌离子浓度为0.01～0.1mol/L。
进一步地，所述锌的金属盐为ZnCl2、ZnSO4或Zn(NO3)2中的任意一种。
进一步地，步骤(3)中，电沉积溶液中铜离子浓度为0.001～0.05mol/L，锡离子浓度为0.005～0.1mol/L。
进一步地，所述铜的金属盐为CuCl2、CuSO4或Cu(NO3)2中的任意一种，锡盐为SnCl4。
进一步地，步骤(1)和步骤(3)的溶剂为去离子水、乙醇溶液或离子溶液。
进一步地，步骤(3)中，基底材料在使用前先用丙酮、乙醇、异丙醇、氨水中的任意两种超声清洗10～30分钟，再用去离子水超声波清洗10～30分钟，最后用氮气吹干备用。
进一步地，步骤(2)中，脉冲电沉积中高电位电势范围为-1.2V～-1.7V，高电位的脉冲宽度范围为2s～30s，低电位电势范围为-0.2V～+0.2V，低电位的脉冲宽度范围为1s～30s，循环次数为20～240次。
进一步地，步骤(4)中，脉冲电沉积中高电位电势范围为-0.6V～-1.2V，高电位的脉冲宽度范围为2s～30s，低电位电势范围为-0.2V～+0.2V，低电位的脉冲宽度范围为1s～60s，循环次数为20～240次。
进一步地，步骤(5)硫化退火过程中，需先将制备的铜锌锡前驱体薄膜和硫粉放入封闭的容器中，抽真空后通入惰性保护气体，再将退火炉升温至300～350℃并恒温30～60分钟，然后将退火炉升温至500～550℃并恒温30～60分钟，退火完成后将容器取出在空气中冷却至室温。
本发明所参与反应的试剂均为分析纯、市售。
为研究所制备材料的结构、形貌、成分以及光电性能，对所制备的样品进行了X射线衍射分析(XRD)、扫描电子显微镜分析(SEM)、能量色散X射线光谱分析(EDS)、拉曼测试分析、和紫外-可见光(Uv-Vis)吸收光谱分析。
本发明的有益效果在于：
本发明通过分步脉冲电沉积能够非常很好地消除杂相，所得材料为较好的纯相，且形貌致密，克服了现有技术元素比例难以控制，有较多二元杂相的技术问题，相对于一步恒电位沉积技术，薄膜无杂质相且形貌平整致密、退火过程无需加入SnS；而与高真空气相法相比，本发明具有成膜质量好、成本低廉、可控性强等优点。因此，本发明具有成膜质量好、无杂质、工艺简单、低成本、退火过程中无需加SnS等优点。脉冲反应有效减小了双电层外层与溶液本体之间的浓度差，分步沉积避免了铜锡与锌沉积电压差大的问题，改善了薄膜的成分以及形貌等微观特征，实现了铜锌锡硫薄膜的可控制备，能够实现大面积高质量薄膜制备。
附图说明
图1为实施例1制备的铜锌锡硫薄膜的X射线衍射分析(XRD)。
图2为实施例1制备的铜锌锡硫薄膜的扫描电镜图分析(SEM)。
图3为实施例1制备的铜锌锡硫薄膜的能量色散X射线光谱分析(EDS)。
图4为实施例1制备的铜锌锡硫薄膜的紫外-可见光吸收光谱图分析(Uv-Vis)。
具体实施方式
为了更好的理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。
实施例1
一种分步脉冲电沉积后退火制备铜锌锡硫太阳能电池薄膜材料的方法，制备步骤如下：
(1)将0.04mol/L的氯化锌溶解在去离子水中，搅拌使其充分溶解；
(2)将基底材料Mo玻璃用丙酮、乙醇、分子水分别超声清洗10分钟、氮气吹干待用；
(3)以步骤(2)处理过的Mo玻璃为工作电极，铂电极为对电极，饱和甘汞电极为参比电极，在步骤(1)获得的电沉积溶液中进行脉冲电沉积锌，脉冲阴极电压为-1.5V，时间为2s，阳极电压为-0.2V，时间为1s，循环240次，得到锌预制膜；
(4)将0.01mol/L的氯化铜溶解在去离子水中，然后再加入0.02mol/L的氯化锡，搅拌使其充分溶解；
(5)以步骤(3)获得的锌预制膜为工作电极，铂电极为对电极，饱和甘汞电极为参比电极，在步骤(4)获得的电沉积溶液中进行脉冲电沉积铜锡合金薄膜，脉冲阴极电压为-1.2V，时间为2s，阳极电压为-0.2V，时间为1s，循环150次，得到铜锌锡前驱体薄膜；
(6)将铜锌锡前驱体薄膜置于含有0.0025g硫粉、体积为20cm-3封闭容器中，抽真空后通入氮气，将退火炉用90分钟从室温升温至300℃，恒温30分钟，再用90分钟从300℃升温至500℃，恒温30℃，最后自然冷却到室温，得到铜锌锡硫薄膜材料。
本实施例所制备的铜锌锡硫薄膜的XRD图谱见图1，扫描电镜图见图2，能量色散X射线光谱图见图3，紫外-可见光吸收光谱图见图4。
图1给出了实施例1制备样品的XRD图谱和特征衍射峰的局部放大图。样品各特征衍射峰的位置对应铜锌锡硫标准卡片图谱(JCPDS# 26-0575)的(111)、(200)、(220)、和(311)晶面方向，除了基底Mo的衍射峰外，XRD图谱中没有其它的衍射杂峰，说明本发明提出分步脉冲电沉积后硫化退火制备出的是纯相的铜锌锡硫。
图2的低倍扫描电镜图可以看出生成的薄膜由颗粒密排而成，表面平整，致密度高，晶粒大小均匀，完全覆盖基底，薄膜与基底的附着性较好。
图3的能谱图表明生成的产物只有铜，锌，锡和硫元素，组成的化学计量比为铜：锌：锡：硫＝0.99：0.57：0.31：2.13。
图4为实施例1制备样品的紫外-可见吸收光谱图，波谱波长范围从400nm至800nm。从图中可以发现一个明显的吸收带边。在800nm附近出现的吸收对应铜锌锡硫的吸收带边，根据禁带公式：(αhv)2～hv拟合得出，本实施例中制备的铜锌锡硫薄膜材料的禁带宽度为1.5eV，所制备的薄膜具有高效率薄膜太阳能电池的特征。其它实施例所制备的样品有类似的表征结果。
实施例2
脉冲分步电沉积制备太阳能吸收层材料铜锌锡硫薄膜的方法，制备步骤如下：
(1)将0.01mol/L的氯化锌溶解在乙醇溶液中，搅拌使其充分溶解；
(2)将Mo玻璃用丙酮、乙醇、分子水分别超声清洗10分钟、氮气吹干待用；
(3)以步骤(2)处理过的Mo玻璃为工作电极，铂电极为对电极，饱和甘汞电极为参比电极，在步骤(1)获得的电沉积溶液中进行脉冲电沉积锌，脉冲阴极电压为-1.7v，时间为10s，阳极电压为-0.2v，时间为5s，循环60次，得到锌预制膜；
(4)将0.03mol/L的氯化铜溶解在乙醇溶液中，然后再加入0.05mol/L的氯化锡，搅拌使其充分溶解；
(5)以步骤(3)获得的锌预制膜为工作电极，铂电极为对电极，饱和甘汞电极为参比电极，在步骤(4)获得的电沉积溶液中进行脉冲电沉积铜锡合金薄膜，脉冲阴极电压为-1.0v，时间为20s，阳极电压为-0.2v，时间为10s，循环40次，得到铜锌锡前驱体薄膜；
(6)将铜锌锡前驱体薄膜置于含有0.0025g硫粉、体积为20cm-3封闭容器中，抽真空后通入氮气，将退火炉用60分钟从室温升温至300℃，恒温30分钟，再用60分钟从300℃升温至500℃，恒温30℃，最后自然冷却到室温，得到铜锌锡硫薄膜材料。
实施例3
脉冲分步电沉积制备太阳能吸收层材料铜锌锡硫薄膜的方法，制备步骤如下：
(1)将氯化胆碱与乙二醇按照摩尔比1：2混合置于70℃真空干燥箱中12h至形成无色透明的离子液体；
(2)将0.08mol/L的氯化锌溶解在步骤(1)所得离子液体中，搅拌使其充分溶解；
(3)将Mo玻璃用丙酮、乙醇、分子水分别超声清洗10分钟、氮气吹干待用；
(4)以步骤(3)处理过的Mo玻璃为工作电极，铂电极为对电极，饱和甘汞电极为参比电极，在步骤(2)获得的电沉积溶液中进行脉冲电沉积锌，脉冲阴极电压为-1.6v，时间为15s，阳极电压为-0.2v，时间为5s，循环45次，得到锌预制膜；
(5)将0.02mol/L的氯化铜溶解在步骤(1)所得离子液体中，然后再加入0.05mol/L的氯化锡，搅拌使其充分溶解；
(6)以步骤(4)获得的锌预制膜为工作电极，铂电极为对电极，饱和甘汞电极为参比电极，在步骤(5)获得的电沉积溶液中进行脉冲电沉积铜锡合金薄膜，脉冲阴极电压为-0.8v，时间为20s，阳极电压为-0.2v，时间为10s，循环50次，得到铜锌锡前驱体薄膜；
(7)将铜锌锡前驱体薄膜置于含有0.0025g硫粉、体积为20cm-3封闭容器中，抽真空后通入氮气，将退火炉用30分钟从室温升温至300℃，恒温30分钟，再用30分钟从300℃升温至500℃，恒温30℃，最后自然冷却到室温，得到铜锌锡硫薄膜材料。
最后，在此应说明的是：在不脱离本发明的精神和原理基础上，本领域技术人员所做的任何等效替换均应属于本发明的保护范围。
Claims (10)
1.一种分步脉冲电沉积后退火制备铜锌锡硫薄膜太阳能电池薄膜材料的方法，其特征在于，包括如下步骤：
(1)将锌的金属盐溶解在溶剂中，加热搅拌使其充分溶解，得到电沉积锌的电解质溶液；
(2)以基底材料为工作电极，铂电极为对电极，饱和甘汞电极为参比电极，采用脉冲电沉积法在步骤(1)所得电解质溶液中进行脉冲电沉积锌，得到锌预制膜；
(3)将铜的金属盐溶解在溶剂中，搅拌使其充分溶解，然后再加入锡的金属盐搅拌使其充分溶解，得到电沉积铜锡合金薄膜的电沉积溶液；
(4)以步骤(2)所得锌预制膜为工作电极，铂电极为对电极，饱和甘汞电极为参比电极，采用脉冲电沉积法在步骤(3)所得电沉积溶液中进行脉冲电沉积铜锡合金，得到铜锌锡前驱体薄膜；
(5)将步骤(4)所得铜锌锡前驱体薄膜置于含有硫粉的真空中硫化退火，最后得到铜锌锡硫太阳能电池薄膜材料。
2.根据权利要求1所述的分步脉冲电沉积后退火制备铜锌锡硫薄膜太阳能电池薄膜材料的方法，其特征在于：步骤(1)中，电解质溶液中的锌离子浓度为0.01～0.1mol/L。
3.根据权利要求1所述的分步脉冲电沉积后退火制备铜锌锡硫薄膜太阳能电池薄膜材料的方法，其特征在于：所述锌的金属盐为ZnCl2、ZnSO4或Zn(NO3)2中的任意一种。
4.根据权利要求1所述的分步脉冲电沉积后退火制备铜锌锡硫薄膜太阳能电池薄膜材料的方法，其特征在于：步骤(3)中，电沉积溶液中铜离子浓度为0.001～0.05mol/L，锡离子浓度为0.005～0.1mol/L。
5.根据权利要求4所述的分步脉冲电沉积后退火制备铜锌锡硫薄膜太阳能电池薄膜材料的方法，其特征在于：所述铜的金属盐为CuCl2、CuSO4或Cu(NO3)2中的任意一种，锡盐为SnCl4。
6.根据权利要求1所述的分步脉冲电沉积后退火制备铜锌锡硫薄膜太阳能电池薄膜材料的方法，其特征在于：步骤(1)和步骤(3)的溶剂为去离子水、乙醇溶液或离子溶液。
7.根据权利要求1所述的分步脉冲电沉积后退火制备铜锌锡硫薄膜太阳能电池薄膜材料的方法，其特征在于：步骤(3)中，基底材料在使用前先用丙酮、乙醇、异丙醇、氨水中的任意两种超声清洗10～30分钟，再用去离子水超声波清洗10～30分钟，最后用氮气吹干备用。
8.根据权利要求1所述的分步脉冲电沉积后退火制备铜锌锡硫薄膜太阳能电池薄膜材料的方法，其特征在于：步骤(2)中，脉冲电沉积中高电位电势范围为-1.2V～-1.7V，高电位的脉冲宽度范围为2s～30s，低电位电势范围为-0.2V～+0.2V，低电位的脉冲宽度范围为1s～30s，循环次数为20～240次。
9.根据权利要求1所述的分步脉冲电沉积后退火制备铜锌锡硫薄膜太阳能电池薄膜材料的方法，其特征在于：步骤(4)中，脉冲电沉积中高电位电势范围为-0.6V～-1.2V，高电位的脉冲宽度范围为2s～30s，低电位电势范围为-0.2V～+0.2V，低电位的脉冲宽度范围为1s～60s，循环次数为20～240次。
10.根据权利要求1所述的分步脉冲电沉积后退火制备铜锌锡硫太阳能电池薄膜材料的方法，其特征在于：步骤(5)硫化退火过程中，需先将制备的铜锌锡前驱体薄膜和硫粉放入封闭的容器中，抽真空后通入惰性保护气体，再将退火炉升温至300～350℃并恒温30～60分钟，再将退火炉升温至500～550℃并恒温30～60分钟，退火完成后将容器取出在空气中冷却至室温。
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