CN104409566A - 铜锌锡硫薄膜材料的两电极电化学制备方法 - Google Patents
铜锌锡硫薄膜材料的两电极电化学制备方法 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 53
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- 239000000463 material Substances 0.000 title claims abstract description 20
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
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- 239000011733 molybdenum Substances 0.000 claims abstract description 17
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
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- 239000011701 zinc Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
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- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
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- 238000000034 method Methods 0.000 claims description 22
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 15
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 10
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000005864 Sulphur Substances 0.000 claims description 7
- 239000010453 quartz Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 6
- 238000005987 sulfurization reaction Methods 0.000 claims description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 5
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Classifications
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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
-
- 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
- H01L31/036—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
- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
本发明公开了一种采用两电极体系制备铜锌锡硫薄膜材料的方法，包含以下下步骤：（1）柔性钼箔片衬底的清洗，利用丙酮与乙醇去除钼箔片表面残留的油脂，再利用硝酸与盐酸的混合溶液去除钼箔片表面的保护膜；（2）电解液的配置，分别配置铜、锌、锡三种金属的电解液；（3）金属预制层的电化学沉积，采用两电极体系沉积铜锌锡金属预制层；（4）金属预制层的硫化与退火，铜锌锡金属预制层在氮气保护下硫化退火得到铜锌锡硫薄膜。（5）铜锌锡硫薄膜的清洗与干燥，在去离子水中超声清洗后，用氮气吹干。相比于传统的三电极体系，两电极体系在保证不降低铜锌锡硫薄膜品质的条件下具有便于操作与控制、设备简单、成本低廉等优点。
Description
技术领域
本发明涉及铜锌锡硫薄膜的电化学制备方法，属于光电材料新能源技术领域。
背景技术
随着各国加大对新型铜锌锡硫薄膜太阳电池材料的制备研究的投入，铜锌锡硫薄膜太阳电池的制备工艺及电池性能也得到了很大的发展，其中高质量铜锌锡硫薄膜材料的制备成为整个铜锌锡硫薄膜太阳电池研制的核心。目前，铜锌锡硫薄膜的制备方法包含真空法和非真空法，真空法所需设备复杂昂贵，制备成本较高，目前以真空法为基础研制的铜锌锡硫太阳电池最高光电转换效率已达到8.4%。
非真空法具有低成本、材料利用率高和易于大规模化生产等优点而受到广泛重视，目前以非真空法为基础研制的铜锌锡硫薄膜电池效率已高达11.1%。在所有非真空法中，电化学法的研究较多，目前普遍采用电化学工作站及三电极体系沉积铜锌锡硫薄膜的铜锌锡金属预制层，然后在硫的气氛下硫化并退火，最终制得铜锌锡硫薄膜。虽然在铜锌锡预制层的制备过程中采用电化学工作站及三电极体系可以实现对工艺过程的精确控制，但涉及到的设备复杂昂贵、工艺过程较为繁琐。并且要求较高的理论依据。使得电化学沉积技术在制备CZTS薄膜方面的应用受到限制。
鉴于采用三电级法制备铜锌锡预制层的复杂性，本领域的研究人员希望通过简化工艺难度、降低设备成本、提高工艺重复性来制备出优质的铜锌锡硫薄膜，进一步提高电化学沉积技术在制备铜锌锡硫薄膜方面的实用性。
发明内容
本发明的目的在于提供一种较为简便的以电化学法为基础的铜锌锡硫薄膜制备方法，从而简化铜锌锡硫薄膜的制备工艺、降低铜锌锡硫薄膜的制备成本。
本发明所涉及的一种电化学法制备铜锌锡硫薄膜的方法按以下步骤实施：
（1）轧制箔片或镀钼玻璃基片先后在丙酮、乙醇、去离子水、硝酸盐酸混合液、去离子水中超声浸泡，去除表面油脂及保护膜；
（2）按摩尔浓度（mol/l）计，硫酸铜、柠檬酸钠的浓度分别为0.02～0.06、0.4，硫酸亚锡、柠檬酸钠的浓度分别为0.04～0.06、0.4。分别配置铜、锡的电解液，最后加入适量酒石酸将铜、锡电解液的pH值调至4～5。以200～250ml的乙二醇或异丙醇作为溶剂，适量无水氯化锌为溶质，配置0.2～0.4mol/l的无水氯化锌电解液；
（3）调节极化电流先后沉积铜、锡、锌层，得到铜锌锡金属预置层；
（4）在570~590℃、通入氮气的石英硫化炉中硫化退火40~50分钟后得到铜锌锡硫薄膜；
（5）将铜锌锡硫薄膜放入去离子水中超声振荡，去除表面可能残留的杂质粒子和二次相，冲洗并吹干，得到最终的铜锌锡硫薄膜。
本发明一种采用两电极系统制备铜锌锡硫薄膜材料的方法，在步骤（1）中，裁剪得到的钼箔片长4cm、宽2cm。衬底的预处理要满足先去除钼箔片表面的油脂，再去除钼箔片表面的氧化膜。
本发明一种采用两电极系统制备铜锌锡硫薄膜材料的方法，在步骤（1）中，除去钼箔片表面保护膜的硝酸盐酸混合液中使用的浓硝酸和浓盐酸按体积比，硝酸：盐酸=1:3~4.5。
本发明一种采用两电极系统制备铜锌锡硫薄膜材料的方法，在步骤（2）中，
配置锌电解液时为了避免氢离子，需要使用有机物作为溶剂，推荐使用乙二醇或异丙醇。
本发明一种采用两电极系统制备铜锌锡硫薄膜材料的方法，在步骤（3）中，三种金属的沉积顺序为铜→锡→锌，沉积电流分别保持在13~14mA，9~10mA，14~15mA。对应的沉积时间分别为160~140秒、210~200秒、960~900秒。
本发明一种采用两电极系统制备铜锌锡硫薄膜材料的方法，在步骤（4）中，铜锌锡金属预制层与硫粉共舟放置，且硫粉指向铜锌锡金属预制层的方向与氮气流向一致，在取出铜锌锡硫薄膜前，薄膜需在硫化炉低温区冷却至100℃左右，防止氧化。
本发明一种采用两电极系统制备铜锌锡硫薄膜材料的方法，在步骤（5）中，制备好的铜锌锡硫薄膜在去离子水中超声浸泡。
附图说明
图1为本发明制备的铜锌锡硫薄膜的XRD图
图2为本发明制备的铜锌锡硫薄膜的Raman图
图3为本发明制备的铜锌锡硫薄膜的SEM图
图4为本发明制备的铜锌锡硫薄膜的EDS图。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
操作步骤如下：
（1）裁剪好长4cm，宽2cm的钼箔片；
（2）首先将裁剪好的钼箔片依次在丙酮、酒精中超声浸泡，去除钼箔片表面油脂，取出后用去离子水冲洗。然后将钼片放入硝酸盐酸混合液中（按体积比，硝酸：盐酸=1：3.5）超声浸泡，去除其表面氧化膜；
（3）采用分析纯级的硫酸铜、硫酸亚锡、柠檬酸钠、酒石酸作为溶质，分别配置500ml的铜电解液与500ml的锡电解液。按摩尔浓度（mol/l）计，其中铜电解液中硫酸铜、柠檬酸钠的浓度分别为0.06、0.4，锡电解液中硫酸亚锡、柠檬酸钠的浓度分别为0.06、0.4，加入适量酒石酸将配置好的铜电解液与锡电解液的pH值调至5；
（4）取200ml的分析纯级乙二醇作为溶剂，加入适量分析纯级无水氯化锌并超声直至氯化锌完全溶解，配置成0.4mol/l的氯化锌溶液作为锌电解液；
（5）将第（2）步中得到的钼箔片作为阴极，用石墨片作为阳极。将三种金属按铜→锡→锌的顺序分别沉积，对应的沉积电流和时间分为14mA、9mA、15mA；140秒、210秒、900秒。制得铜锌锡金属预制层；
（6）将第（5）步得到的铜锌锡预制层与2g硫粉放入石英舟内，再将石英舟推入温度已达580℃的硫化炉内硫化退火40分钟，待铜锌锡硫薄膜逐渐冷却至100℃时从硫化炉中取出；
（7）将铜锌锡硫薄膜浸泡在去离子水中超声30秒钟后取出并吹干，得到最终的铜锌锡硫薄膜。
实施例2
（1）同实施例1中步骤（1）；
（2）同实施例1中步骤（2）；
（3）采用分析纯级的硫酸铜、硫酸亚锡、柠檬酸钠、酒石酸作为溶质，分别配置500ml的铜电解液与500ml的锡电解液。摩尔浓度（mol/l）计，其中铜电解液中硫酸铜、柠檬酸钠的浓度分别为0.04、0.4，锡电解液中硫酸亚锡、柠檬酸钠的浓度分别为0.04、0.4，加入适量酒石酸将配置好的铜电解液与锡电解液的pH值调至5；
（4）取200ml的分析纯级乙二醇作为溶剂，加入适量分析纯级无水氯化锌并超声直至氯化锌完全溶解，配置成0.3mol/L的氯化锌溶液作为锌电解液；
（5）将第（2）步中得到的钼片作为阴极，用石墨片作为阳极。将三种金属按铜→锡→锌的顺序沉积，对应的沉积电流和时间分为13.5mA，10mA，14mA。对应的沉积时间分别为150秒、200秒、920秒。制得铜锌锡金属预制层；
（6）将第（5）步得到的铜锌锡预制层与2g硫粉放入石英舟内，再将石英舟放入温度达到590℃的硫化炉内硫化退火50分钟，使铜锌锡硫薄膜冷却至100℃时从硫化炉中取出；
（7）同实施例1中步骤（7）。
Claims (8)
1.一种采用两电极体系制备铜锌锡硫薄膜材料的方法，其特征在于，制备步骤如下：
（1）钼箔片衬底的清洗：将钼箔片衬底放入有机溶剂中超声浸泡，去除其表面残留的油脂；
将洗净后的钼箔片放入硝酸与盐酸的混合溶液中超声浸泡除去包裹在钼箔片表面的氧化膜，最后用去离子水冲洗并吹干；
（2）配制金属预制层的电解液：首先配制铜与锡的电解液；
其次采用无水氯化锌与有机溶剂制备锌电解液；
（3）沉积金属预制层，采用两电极体系及恒电流源在钼箔片衬底上先后沉积铜、锡、锌层；
（4）在氮气保护与硫气氛下硫化并退火制得CZTS薄膜；
（5）清洗制备好的铜锌锡硫薄膜并吹干。
2.如权利要求1所述的铜锌锡硫薄膜材料的制备方法，其特征在于，所述步骤（1）中，硝酸与盐酸的混合溶液中硝酸与盐酸的体积比为1:3～4.5。
3.如权利要求1所述的铜锌锡硫薄膜材料的制备方法，其特征在于，所述步骤（2）中，以摩尔浓度（mol/l）计，铜电解液中硫酸铜、柠檬酸钠的浓度分别为0.02～0.06、0.4，锡电解液中硫酸亚锡、柠檬酸钠的浓度分别为0.04～0.06、0.4。
4.如权利要求1所述的铜锌锡硫薄膜材料的制备方法，其特征在于，所述步骤（2）中，锌电解液中以乙二醇或异丙醇作为溶剂，将无水氯化锌溶于乙二醇或异丙醇，将无水氯化锌的浓度控制在0.2～0.4mol/l。
5.如权利要求1所述的铜锌锡硫薄膜材料的制备方法，其特征在于，所述步骤（2）中，在制备锌电解液时，采用超声振荡加速无水氯化锌在乙二醇或异丙醇中的溶解。
6.如权利要求1所述的铜锌锡硫薄膜材料的制备方法，其特征在于，所述步骤（3）中，沉积铜时，极化电流保持在13～14mA；沉积锡时，极化电流保持在9～10mA；沉积锌时，极化电流保持在14～15mA。
7.如权利要求1所述的铜锌锡硫薄膜材料的制备方法，其特征在于，所述步骤（4）中，铜锌锡预制层与硫粉共同放入敞开的石英舟中，将石英舟推入温度为570～590℃并通入氮气保护的石英硫化炉中硫化并退火40～50分钟，然后将石英舟送至硫化炉低温区，待铜锌锡硫薄膜温度降至100℃左右时，从硫化炉中取出。
8.如权利要求1所述的铜锌锡硫薄膜材料的制备方法，其特征在于，所述步骤（5）中，将制备好的铜锌锡硫薄膜放入去离子水中，并在超声振荡下浸泡30秒，再用去离子水冲洗，最后用氮气吹干。
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