CN108400184A - 一种铟单质掺杂的CZTSSe薄膜的制备方法和应用 - Google Patents

一种铟单质掺杂的CZTSSe薄膜的制备方法和应用 Download PDF

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CN108400184A
CN108400184A CN201810184412.3A CN201810184412A CN108400184A CN 108400184 A CN108400184 A CN 108400184A CN 201810184412 A CN201810184412 A CN 201810184412A CN 108400184 A CN108400184 A CN 108400184A
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程树英
余雪
赖云锋
武四新
严琼
周海芳
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Abstract

本发明公开了一种铟单质掺杂的CZTSSe薄膜的制备方法及其在柔性太阳电池中的应用。本发明通过在CZTSSe薄膜中掺杂In以替代部分Sn原子，改善了薄膜体相缺陷，提高了载流子浓度，使由其制备的太阳电池的短路电流密度、开路电压、填充因子、光电转换效率明显提高，因此在太阳电池方面有较好的应用价值。

Description

一种铟单质掺杂的CZTSSe薄膜的制备方法和应用
技术领域
本发明涉及一种铟单质掺杂的CZTSSe薄膜的制备方法及其在柔性太阳电池中的应用，属于薄膜太阳电池技术领域。
背景技术
Cu2ZnSn(SSe)4（CZTSSe）的带隙在1.0-1.5eV范围内连续可调，其理论转换效率可达31%以上。同时，CZTSSe在可见光范围内高达104cm-1的吸收系数，是一种理想的光吸收层材料。但CZTS四元体系相图中的纯相稳定区域非常狭窄，偏离该区域很容易形成二元三元杂相，因此实验上普遍认同贫铜富锌的元素组成（Cu/Zn+Sn>0.8；Zn/Sn>1.2），在改善薄膜P型导电性的同时可以有效控制铜基杂相产生，但是在非化学计量比的条件下杂相的形成是很难避免的。因此，可以预期，在成膜过程中若将金属源、硫源、硒源以单质形式作为吸收层的原料，更容易调节贫铜富锌的化学计量比，减少引入杂质，减少二次、三次相的形成，得到纯相的CZTSSe。
另一方面，CZTSSe薄膜太阳电池的瓶颈是开压损耗过多，电池效率不高。开路电压(Voc)和填充因子(FF)最高仅为423mV和67.3%；而最高转化效率的CZTS及CZTSSe太阳电池的开路电压损失(Voc-deficit)分别为789mV和603mV。显然，该类电池的开路电压损耗以及填充因子损失与理论值相差较大，仍有很大的提升空间，因此，减少开路电压损耗(Voc-deficit)和填充因子损失(FF-deficit)是提高C ZTS体系太阳电池的关键。
为了改善开路电压，优先需要解决的问题有：1)吸收层体相中缺陷的抑制和钝化，2)界面优化。针对CZTSSe吸收层体相中缺陷的抑制和钝化，可以通过在吸收层中引入类原子来改善开压。其中Cu和Sn原子半径相似，容易产生VSn、CuSn等缺陷，而通过在吸收层中用微量的In单质取代部分Sn原子，可以减少有效VSn、CuSn缺陷的产生，形成InSn反位缺陷，提高载流子浓度，从而提高开路电压，改善电池性能。
发明内容
本发明的目的在于提供一种铟单质掺杂的CZTSSe薄膜的制备方法及其在柔性太阳电池中的应用，其通过在前驱体溶液中引入金属单质、硫单质和硒单质，尤其是在吸收层中掺杂适量的单质铟，提高了电池效率；同时，在前驱体溶液中加入稳定剂，提高溶液的稳定性。
为实现上述目的，本发明采用如下技术方案：
一种铟单质掺杂的CZTSSe薄膜的制备方法包括以下步骤：
1）按化学计量比将单质铜、锌、硫、硒按比例加入有机溶剂中，并加入单质锡和铟，加热搅拌至完全溶解后，加入稳定剂继续搅拌至形成稳定的CZTISSe前驱体溶液；
2）将柔性衬底清洗、烘干；
3）将所得CZTISSe前驱体溶液反复旋涂到柔性衬底上，并经200~500℃退火处理后在柔性衬底上形成CZTISSe预制层；
4）在持续通入保护气体的条件下，将步骤3）所得样品置于快速升温炉中进行硒化处理，制得CZTISSe薄膜；
步骤1）中所述有机溶剂是由乙二胺和乙二硫醇按体积比10:1混合而成；所述稳定剂是由乙醇胺、巯基乙酸和乙二醇甲醚按体积比1:1:2混合而成。
步骤1）所得CZTISSe前驱体溶液中In+Sn的总浓度为0.15~0.2mol/L，其中，In/（In+Sn）的摩尔百分比为3%~12%。
步骤2）中所述柔性衬底为柔性钼箔或溅射有Mo的柔性聚酰亚胺薄膜；当采用柔性钼箔作为柔性衬底时，将其先在体积比1:8的浓硫酸和甲醇混合溶液中利用常规电化学技术进行清洗，然后放入无水乙醇中超声清洗，再在去离子水中超声清洗，之后在干燥箱中烘干；当采用溅射有Mo的柔性聚酰亚胺薄膜作为柔性衬底时，将其先在无水乙醇中超声清洗，再在去离子水中超声清洗，之后在干燥箱中烘干。
步骤4）中硒化处理的升温速率为6℃/s~10℃/s，硒化时间为8~30min，硒化温度控制在400~600℃之间。
所得CZTISSe薄膜的厚度为1.5~3微米。
本发明方法制得的铟单质掺杂的CZTSSe薄膜可用于制备柔性太阳电池，其制备方法包括以下步骤：
一种铟单质掺杂的CZTSSe薄膜在柔性太阳电池中的应用方法包括以下步骤：
1）在镉盐中加入去离子水，搅拌至其完全溶解，然后加入氨水搅拌均匀，放入所制备的铟单质掺杂的CZTISSe薄膜，并加入硫脲，60~75℃水浴处理8~12min，使薄膜上沉积形成硫化镉缓冲层，然后进行清洗、干燥；
2）采用射频磁控溅射方法在步骤1）所得的硫化镉缓冲层上沉积厚度为50nm的本征氧化锌（i-ZnO）薄膜；其工艺参数为：溅射气体Ar气，本底真空度<1.5×10-5Pa，工作真空度为1Pa，射频溅射功率为80W，溅射时间为25min，衬底温度为室温；
3）采用直流磁控溅射方法在步骤2）所得的i-ZnO薄膜上沉积厚度为200nm的ITO导电层；其工艺参数为：溅射气体Ar气，本底真空度<1.5×10-5Pa，工作真空度为1Pa，射频溅射功率为75W，溅射时间为15min，衬底温度为室温；
4）采用热蒸发的方式在步骤3）所得ITO导电层上制备厚度为500nm的银电极；其工艺参数为：本底真空度<6.0×10-4Pa，衬底温度为室温。
步骤1）中所述镉盐为硫酸盐、氯化盐或醋酸盐。所形成溶液中镉的浓度为0.0014~0.002mol/L，硫的浓度为0.005~0.01mol/L，氨水的质量浓度为25%~28%。所制备的硫化镉缓冲层的厚度为20~100nm，其清洁、干燥的步骤为：依次用自来水、去离子水、无水乙醇洗片，60~80℃烘箱烘干20~30min。
本发明通过将金属单质(Cu、Zn、Sn、In)及硫源、硒源溶解在特定的溶剂中并加热搅拌，再加入稳定剂搅拌得到均匀的金属前驱体溶液，将前驱体溶液利用旋涂方法制备在特定的衬底上，经退火处理后在衬底上形成掺铟的CZTSSe前驱体薄膜，再经硒化处理得到高质量的铟掺杂CZTSSe薄膜，其制备过程简单，对反应条件要求较低，不需要昂贵的大型仪器设备，适于规模化生产。
本发明与现有技术相比具有的优点：
（1）本发明所用金属源和硫源、硒源都是单质，容易控制化学计量比，不引入其他杂质。
（2）本发明通过单质In的掺杂，可以有效减少VSn、CuSn缺陷及ZnSn反位缺陷，提高载流子浓度，改善薄膜的传输特性，提高开路电压，提高器件的光电转换效率。经实验证明，其重复性和稳定性较好，在太阳电池方面有较好的应用价值。
（3）本发明在前驱体溶液的制备中加入稳定剂，能够使溶液长时间保持较为稳定的状态。
（4）本发明所用有机溶剂绿色环保，对制作环境要求低。
附图说明
图1为未掺杂的CZTSSe薄膜（A）及掺杂后的CZTISSe薄膜（B）的SEM图；
图2为实施例1-5中薄膜所制备太阳电池随掺In比例变化的J-V特性曲线；
图3为实施例1-5的薄膜随掺In比例变化的XRD图(A)及XRD局部放大图(B)；
图4为实施例1-5的薄膜随掺In比例变化的Raman图。
具体实施方式
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
实施例1
（1）将单质铜0.0699g、锌0.0494g、锡0.0859g、硫0.0857g、硒0.0234g加入至5.5mL的乙二胺和乙二硫醇混合溶液（10:1，v/v）中，加热搅拌1.5h至完全溶解，加入1mL由乙醇胺、巯基乙酸、乙二醇甲醚（1:1:2，v/v）组成的稳定剂，加热搅拌0.5h，形成棕金色的CZTSSe前驱体溶液；
（2）利用匀胶机将CZTSSe前驱体溶液旋涂到清洁干净的柔性Mo衬底上，然后在热台上350℃退火处理1min；反复操作9次，形成CZTSSe预制层；
（3）在持续通入保护气体N2（流量为80sccm）的条件下，将旋涂完毕的样品置于RTP硒化炉中550℃硒化900s，升温速率为8℃/s，自然降温，即可得到厚度约为2μm的未掺杂的CZTSSe薄膜。
实施例2
（1）将单质铜0.0699g、铟0.0025g、锌0.0494g、锡0.0833g、硫0.0857g、硒0.0234g加入至5.5mL的乙二胺和乙二硫醇混合溶液（10:1，v/v）中，加热搅拌1.5h至完全溶解，加入1mL由乙醇胺、巯基乙酸、乙二醇甲醚（1:1:2，v/v）组成的稳定剂，加热搅拌0.5h，形成金黄色的CZTISSe前驱体溶液；
（2）利用匀胶机将CZTISSe前驱体溶液旋涂到清洁干净的柔性Mo衬底上，然后在热台上350℃退火处理1min；反复操作9次，形成CZTISSe预制层；
（3）在持续通入保护气体N2（流量为80sccm）的条件下，将旋涂完毕的样品置于RTP硒化炉中550℃硒化900s，升温速率为8℃/s，自然降温，即可得到厚度约为2μm的掺杂3%In的CZTISSe薄膜。
实施例3
（1）将单质铜0.0699g、铟0.0050g、锌0.0494g、锡0.0807g、硫0.0857g、硒0.0234g加入至5.5mL的乙二胺和乙二硫醇混合溶液（10:1，v/v）中，加热搅拌1.5h至完全溶解，加入1mL由乙醇胺、巯基乙酸、乙二醇甲醚（1:1:2，v/v）组成的稳定剂，加热搅拌0.5h，形成金黄色的CZTISSe前驱体溶液；
（2）利用匀胶机将CZTISSe前驱体溶液旋涂到清洁干净的柔性Mo衬底上，然后在热台上350℃退火处理1min；反复操作9次，形成CZTISSe预制层；
（3）在持续通入保护气体N2（流量为80sccm）的条件下，将旋涂完毕的样品置于RTP硒化炉中550℃硒化900s，升温速率为8℃/s，自然降温，即可得到厚度约为2μm的掺杂6%In的CZTISSe薄膜。
实施例4
（1）将单质铜0.0699g、铟0.0075g、锌0.0494g、锡0.0781g、硫0.0857g、硒0.0234g加入至5.5mL的乙二胺和乙二硫醇混合溶液（10:1，v/v）中，加热搅拌1.5h至完全溶解，加入1mL由乙醇胺、巯基乙酸、乙二醇甲醚（1:1:2，v/v）组成的稳定剂，加热搅拌0.5h，形成金黄色的CZTISSe前驱体溶液；
（2）利用匀胶机将CZTISSe前驱体溶液旋涂到清洁干净的柔性Mo衬底上，然后在热台上350℃退火处理1min；反复操作9次，形成CZTISSe预制层；
（3）在持续通入保护气体N2（流量为80sccm）的条件下，将旋涂完毕的样品置于RTP硒化炉中550℃硒化900s，升温速率为8℃/s，自然降温，即可得到厚度约为2μm的掺杂9%In的CZTISSe薄膜。
图1为实施例1中未掺杂的CZTSSe薄膜与本实施例中掺杂9%In的CZTISSe薄膜的SEM对比图。从图中可以看出，与未掺杂的CZTSSe薄膜相比，掺杂9%In的CZTISSe薄膜表面结晶更全面，致密，无空洞，大晶尺寸明显提高。
实施例5
（1）将单质铜0.0699g、铟0.0100g、锌0.0494g、锡0.0756g、硫0.0857g、硒0.0234g加入至5.5mL的乙二胺和乙二硫醇混合溶液（10:1，v/v）中，加热搅拌1.5h至完全溶解，加入1mL由乙醇胺、巯基乙酸、乙二醇甲醚（1:1:2，v/v）组成的稳定剂，加热搅拌0.5h，形成金黄色的CZTISSe前驱体溶液；
（2）利用匀胶机将CZTISSe前驱体溶液旋涂到清洁干净的柔性Mo衬底上，然后在热台上350℃退火处理1min；反复操作9次，形成CZTISSe预制层；
（3）在持续通入保护气体N2（流量为80sccm）的条件下，将旋涂完毕的样品置于RTP硒化炉中550℃硒化900s，升温速率为8℃/s，自然降温，即可得到厚度约为2μm的掺杂12%In的CZTISSe薄膜。
将所得铟单质掺杂的CZTSSe薄膜分别制备成包括柔性衬底、铟掺杂CZTSSe(CZTISSe)吸收层、硫化镉缓冲层、本征氧化锌窗口层、ITO透明导电层及银电极的太阳电池，其依次经历以下步骤：
（1）将所制备的CZTSSe或CZTISSe薄膜在65℃条件下化学浴沉积CdS缓冲层（~30nm）；
（2）射频磁控溅射制备本征氧化锌窗口层(~50nm)；
（3）直流磁控溅射ITO透明导电层(~200nm)；
（4）热蒸发制备金属银电电池效率极(~500nm)。
按照上述步骤制备的太阳电池结构为：Mo/CZTSSe/CdS/i-ZnO/ITO/Ag或Mo/CZTISSe/CdS/i-ZnO/ITO/Ag，其相关性能表征分别见表1及图2-4。
表1 实施例1-5薄膜所制备太阳电池的性能对比
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。

Claims (7)

1.一种铟单质掺杂的CZTSSe薄膜的制备方法，其特征在于，包括以下步骤：
1）按化学计量比将单质铜、锌、硫、硒加入有机溶剂中，并加入单质锡和铟，加热搅拌至完全溶解后，加入稳定剂继续搅拌至形成稳定的CZTISSe前驱体溶液；
2）将柔性衬底清洗、烘干；
3）将所得CZTISSe前驱体溶液反复旋涂到柔性衬底上，并经200~500℃退火处理后在柔性衬底上形成CZTISSe预制层；
4）在持续通入保护气体的条件下，将步骤3）所得样品置于快速升温炉中进行硒化处理，制得CZTISSe薄膜。
2.根据权利要求1所述的制备方法，其特征在于，步骤1）中所述有机溶剂是由乙二胺和乙二硫醇按体积比10:1混合而成；
所述稳定剂是由乙醇胺、巯基乙酸和乙二醇甲醚按体积比1:1:2混合而成。
3.根据权利要求1所述的制备方法，其特征在于，步骤1）所得CZTISSe前驱体溶液中In+Sn的总浓度为0.15~0.2mol/L，其中，In/（In+Sn）的摩尔百分比为3%~12%。
4.根据权利要求1所述的制备方法，其特征在于，步骤2）中所述柔性衬底为柔性钼箔或溅射有Mo的柔性聚酰亚胺薄膜；
所述清洗、烘干的具体操作为：当采用柔性钼箔作为柔性衬底时，将其先在体积比1:8的浓硫酸和甲醇混合溶液中利用电化学技术进行清洗，然后放入无水乙醇中超声清洗，再在去离子水中超声清洗，之后在干燥箱中烘干；
当采用溅射有Mo的柔性聚酰亚胺薄膜作为柔性衬底时，将其先在无水乙醇中超声清洗，再在去离子水中超声清洗，之后在干燥箱中烘干。
5.根据权利要求1所述的制备方法，其特征在于，步骤4）中硒化处理的升温速率为6℃/s~10℃/s，硒化时间为8~30min，硒化温度控制在400~600℃之间。
6.根据权利要求1所述的制备方法，其特征在于，所得CZTISSe薄膜的厚度为1.5~3微米。
7.一种如权利要求1所述方法制得的铟单质掺杂的CZTSSe薄膜在制备柔性太阳电池中的应用。
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