CN105332026B - 电化学沉积法制备Cu2FeSnS4薄膜 - Google Patents
电化学沉积法制备Cu2FeSnS4薄膜 Download PDFInfo
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- KYRUBSWVBPYWEF-UHFFFAOYSA-N copper;iron;sulfane;tin Chemical group S.S.S.S.[Fe].[Cu].[Cu].[Sn] KYRUBSWVBPYWEF-UHFFFAOYSA-N 0.000 claims abstract description 15
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- C—CHEMISTRY; METALLURGY
- 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
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01L31/0248—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
- H01L31/0256—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 the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
本发明公开了一种光伏电池用黄锡矿结构铜铁锡硫(Cu2FeSnS4)薄膜的电化学沉积制备方法，即三元共沉积制备金属预制层并通过后续硫化退火形成Cu2FeSnS4薄膜，主要通过以下过程来实现：首先，按摩尔比CuCl2·2H2O∶FeCl2·4H2O∶SnCl2·2H2O＝2∶20∶1的原则依次称取试剂，同时配以一定量的柠檬酸三钠、酒石酸、D‑山梨醇、抗坏血酸，将烧杯内溶液搅拌均匀，调节PH直至沉淀完全溶解，完成电解液的配置；然后采用恒电位沉积的方式电化学沉积得到铜铁锡金属预制层；最后，用高纯氩气作保护气体，用硫粉作为硫源，对铜铁锡金属预制层进行硫化退火，得到Cu2FeSnS4薄膜。该黄锡矿结构Cu2FeSnS4薄膜材料的电化学沉积制备方法反应时间短，温度低，操作简便，成本低廉，绿色无污染，适合Cu2FeSnS4薄膜材料的大规模产业化生产。
Description
技术领域
本发明属于太阳光伏电池用原材料制备方法领域，涉及一种黄锡矿结构Cu2FeSnS4薄膜材料及其电化学沉积制备方法，该黄锡矿结构 Cu2FeSnS4薄膜材料是Cu2FeSnS4薄膜太阳能电池的重要组成部分。
背景技术
近年来，随着能源紧缺问题和环境污染问题的不断凸显，国家加大对清洁能源的扶持力度，很大程度上推动了新兴能源的快速发展，其中，光伏技术的发展十分突出，特别是薄膜太阳能电池的制造技术吸引了很多学者来进行相关的研究。对于薄膜太阳能电池，电池材料的种类很多，而且电池的结构也很多样。目前，已经实现商业化的薄膜太阳能电池材料主要有非晶硅(a-Si)、碲化镉(CdTe)、铜铟硒(CIS) 这三类，它们的厚度只有几微米。但是，这些电池材料由于一些缺陷而使自身的发展收到限制。其中，非晶硅太阳能电池不稳定，存在光致衰退现象，故而光电转换效率一直很低；碲化镉和铜铟镓硒的光电转换效率虽然较高，但是材料中的主要组成元素不仅储量稀少，而且是有毒物质，不利于这类薄膜太阳能电池的进一步发展。
正是当前避免太阳能电池的发展出现瓶颈，所以科学家们将目光转向了低成本、高转换效率的新型薄膜光伏电池的开发。在新一代的薄膜太阳能电池中，I-II-IV-VI族四元化合物铜铁锡硫(Cu2FeSnS4) 为直接带隙半导体，其禁带宽度的范围大约是1.2-1.5eV，和太阳辐射能较好地匹配，而且具有光吸收系数高(＞104cm-1)、原料在地壳中储量丰富、价格便宜、无毒等众多优点，是很有潜力的第三代光伏电池，有望取代碲化镉(CdTe)、铜铟镓硒(CIGS)等薄膜光伏电池，使得太阳能发电的成本有一个较大幅度的下降，从而推动光伏技术在人们生活中的应用，使得可再生能源能真正起到调整整个世界能源结构的作用。
对于制造Cu2FeSnS4薄膜太阳能电池，首先也是关键的一步是合成高质量的Cu2FeSnS4薄膜，然而到目前为止，Cu2FeSnS4薄膜制备方面的报道还很少。因此，提出一种可以大量制备，成本低廉，环境友好的Cu2FeSnS4薄膜的制备方法，对于本领域具有重要意义。同时，电化学沉积制备方法具有常温常压下进行、设备简单廉价、镀层形貌好、附着牢固、电解液利用率高、易于柔性衬底大规模生产制备等优点，广泛应用到薄膜材料的制备之中。
发明内容
本发明所要解决的技术问题是提出一种新的黄锡矿结构 Cu2FeSnS4薄膜的电化学沉积制备方法，该黄锡矿结构Cu2FeSnS4薄膜材料的电化学沉积制备方法绿色无污染，反应时间短，所需温度低，操作简便，成本低廉，适合Cu2FeSnS4薄膜材料的大规模产业化生产。
为了解决上述技术问题，发明是通过以下技术方案实现的。
一种黄锡矿结构Cu2FeSnS4薄膜的电化学沉积制备方法，先通过三元共沉积制备金属预制层，然后硫化退火形成Cu2FeSnS4薄膜。
包括如下步骤：
(1)按摩尔比CuCl2·2H2O∶FeCl2·4H2O∶SnCl2·2H2O＝2∶20∶1 的原则称量依次溶解于超纯水烧杯，同时配以一定量的柠檬酸三钠、酒石酸、D-山梨醇、抗坏血酸，将烧杯内溶液搅拌均匀，调节PH直至沉淀完全溶解；
(2)采用含工作电极、对电极和参比电极的三电极电化学体系，以Mo玻璃衬底作为工作电极、石墨作为对电极、甘汞电极作为参比电极，采用恒电位沉积的方式，沉积得到铜铁锡金属预制层；
(3)然后用硫粉作为硫源，在高纯氩气的保护下硫化退火得到 Cu2FeSnS4薄膜。
步骤(1)中，当CuCl2·2H2O、FeCl2·4H2O、SnCl2·2H2O的摩尔比为2∶20∶1时，加入的添加剂柠檬酸三钠、酒石酸、D-山梨醇、抗坏血酸的摩尔比为10∶5∶1∶0.6。
步骤(2)中，进行-1.0～1.1伏特恒电位电化学沉积，时间为2000s。
步骤(2)中，对制得的铜铁锡金属预制层依次使用无水乙醇和超纯水洗涤5-7次，然后置于干燥箱中在40-80℃下干燥2-10小时。
步骤(3)中，在合硫高纯氩气氛下，铜铁锡金属预制层于550℃下硫化退火60min。
本发明的黄锡矿结构Cu2FeSnS4薄膜材料是由上述方法制备而成的。
本发明使用电化学沉积法，两步合成了黄锡矿结构的Cu2FeSnS4薄膜，与现有技术相比，本发明具有如下的有益效果：
(1)原料均是普通的金属盐类，成本较低，且产物的质量较好；
(2)与其他制备方法相比，电化学沉积制备方法具有常温常压下进行、设备简单廉价、镀层形貌好、附着牢固、电解液利用率高、易于柔性衬底大规模生产制备等优点；
(3)整个过程绿色无污染，反应时间短，所需温度低，操作简便，成本低廉，适合大规模产业化生产。
附图说明
图1为实施例1合成的Cu2FeSnS4样品的XRD能谱图。
图2为实施例1合成的Cu2FeSnS4样品的SEM图。
图3为实施例1为确定沉积电位而得到的循环伏安CV曲线。
图4为实施例2为确定沉积电位而得到的循环伏安CV曲线。
具体实施方式
下面给出本发明的较佳实施例，使能更好地理解本发明的过程。
实施例1
1)Mo玻璃衬底清洗，流程具体如下：(i)首先使用洗洁精和洗手液分别用手清洗衬底，去除手上和衬底上的油脂；(ii)然后将衬底置于无水乙醇中超声清洗10min，去除Mo玻璃上的油污以及清洗剂等；(iii)接着将衬底放入超纯水中超声清洗10min，用以清洗残留的乙醇；(iv)将衬底烘干待用；
2)按照摩尔比称取4mmol CuCl2·2H2O，40mmol FeCl2·4H2O， 2mmol SnCl2·2H2O，每次称量的药品依次溶解于加入超纯水的烧杯中，同时配以20mmol柠檬酸三钠、10mmol酒石酸、2mmol D-山梨醇、1.2mmol抗坏血酸，将烧杯内溶液搅拌均匀，调节PH直至沉淀完全溶解；
3)对电解液体系循环伏安扫描，确定生长电位，进行-1.1V (vs.SCE)的电位沉积，其中SCE即为饱和甘汞电极，沉积时间为 2000s，得到铜铁锡金属预制层；
4)对金属预制层进行硫化退火，所用硫源为硫粉，需要Ar气作为保护，在550℃下硫化退火60min，退火后即可得所要合成的光伏薄膜。
实施例2
1)Mo玻璃衬底清洗，流程具体如下：(i)首先使用洗洁精和洗手液分别用手清洗衬底，去除手上和衬底上的油脂；(ii)然后将衬底置于无水乙醇中超声清洗10min，去除Mo玻璃上的油污以及清洗剂等；(iii)接着将衬底放入超纯水中超声清洗10min，用以清洗残留的乙醇；(iv)将衬底烘干待用；
2)按照摩尔比称取1mmol CuCl2·2H2O，10mmol FeCl2·4H2O， 0.5mmol SnCl2·2H2O，每次称量的药品依次溶解于加入超纯水的烧杯中，同时配以5mmol柠檬酸三钠、2.5mmol酒石酸、0.5mmol D-山梨醇、0.3mmol抗坏血酸，将烧杯内溶液搅拌均匀，调节PH直至沉淀完全溶解；
3)对电解液体系循环伏安扫描，确定生长电位，进行-1.0V (vs.SCE)的电位沉积，其中SCE即为饱和甘汞电极，沉积时间为 2000s，得到铜铁锡金属预制层；
4)对金属预制层进行硫化退火，所用硫源为硫粉，需要Ar气作为保护，在550℃下硫化退火60min，退火后即可得所要合成的光伏薄膜。
对于实施例1，所合成的Cu2FeSnS4薄膜样品XRD图谱进行分析处理之后如图1所示。从图中可以看出，除了最强的那个峰是衬底 Mo玻璃的衍射峰之外，发现了黄锡矿结构Cu2FeSnS4晶体的特征衍射峰(112)，(004)，(204)，(116)。同时，杂峰也比较小，可以判定生成了黄锡矿结构的Cu2FeSnS4光伏薄膜材料。
所合成的Cu2FeSnS4光伏薄膜的微观形貌如图2所示。图2中左边是放大了10万倍的微观形貌图，右边是放大了5万倍的微观形貌。从图中可以看出，Cu2FeSnS4薄膜样品的晶粒尺寸比较大，呈现出块状岛状生长，分布相对均匀。
Claims (4)
1.一种黄锡矿结构Cu2FeSnS4薄膜的电化学沉积制备方法，其特征在于，三元共沉积制备金属预制层，再通过硫化退火形成Cu2FeSnS4薄膜：
按摩尔比CuCl2·2H2O∶FeCl2·4H2O∶SnCl2·2H2O＝2∶20∶1的原则称量，搅拌并溶解于超纯水，同时配以一定量的柠檬酸三钠、酒石酸、D-山梨醇、抗坏血酸，调节pH 直至沉淀完全溶解；采用含工作电极、对电极和参比电极的三电极电化学体系，以Mo作为工作电极、石墨作为对电极、甘汞电极作为参比电极，采用恒电位沉积的方式，沉积得到铜铁锡金属预制层；然后用硫粉作为硫源，在高纯氩气的保护下硫化退火得到Cu2FeSnS4薄膜。
2.根据权利要求1所述的黄锡矿结构Cu2FeSnS4薄膜的电化学沉积制备方法，其特征在于，当CuCl2·2H2O、FeCl2·4H2O、SnCl2·2H2O的摩尔比为2∶20∶1时，加入的添加剂柠檬酸三钠、酒石酸、D-山梨醇、抗坏血酸的摩尔比为10∶5∶1∶0.6。
3.根据权利要求1所述的黄锡矿结构Cu2FeSnS4薄膜的电化学沉积制备方法，其特征在于，-1.0～1.1伏特恒电位电化学沉积，时间为2000s，对制得的铜铁锡金属预制层依次使用无水乙醇和超纯水洗涤5-7次，然后置于干燥箱中在40-80℃下干燥2-10小时。
4.根据权利要求1所述的黄锡矿结构Cu2FeSnS4薄膜的电化学沉积制备方法，其特征在于，在含硫高纯氩气气氛下，铜铁锡金属预制层于550℃下硫化退火60min。
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