CN110176517B - 结构优化的银掺杂铜锌锡硫薄膜太阳电池及其制备方法 - Google Patents

结构优化的银掺杂铜锌锡硫薄膜太阳电池及其制备方法 Download PDF

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CN110176517B
CN110176517B CN201910323143.9A CN201910323143A CN110176517B CN 110176517 B CN110176517 B CN 110176517B CN 201910323143 A CN201910323143 A CN 201910323143A CN 110176517 B CN110176517 B CN 110176517B
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郝瑞亭
顾康
郭杰
刘欣星
孙帅辉
魏国帅
刘斌
王璐
马晓乐
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Yunnan Normal University
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Abstract

本发明公开了一种结构优化的银掺杂铜锌锡硫薄膜太阳电池及其制备方法，属于太阳电池领域。所述太阳电池包括依次连接的玻璃衬底、背电极、吸收层、缓冲层、透明导电窗口层和上电极，所述吸收层的预制层结构为Cu/Sn/Ag/ZnS。本发明所述吸收层的预制层采用Cu/Sn/Ag/ZnS结构，Ag沉积在Sn上层抑制了Sn元素的损失，减少了晶界间的孔洞，同时，Ag替代Cu有效的减少了CuZn反结构缺陷，提高了光生载流子的收集效率，此外，银掺杂对增大铜锌锡硫薄膜的晶粒尺寸、改善与Mo背电极的附着性等都有益处。

Description

结构优化的银掺杂铜锌锡硫薄膜太阳电池及其制备方法
技术领域
本发明涉及太阳电池领域，具体涉及一种结构优化的银掺杂铜锌锡硫薄膜太阳电池及其制备方法。
背景技术
具有锌黄锡矿结构的四元半导体化合物铜锌锡硫（Cu2ZnSnS4,简称CZTS）薄膜因其较高的吸收系数（大于10 4 cm -1 ）、组成元素地壳储量丰富、接近太阳电池的最佳吸收带隙（1.5eV）而在近年来成为研究热点。
目前，制备CZTS薄膜的方法有很多，比如溶胶凝胶法、旋涂法、原子层沉积法、磁控溅射法、电化学法等，其中磁控溅射法因可实现大面积、均匀沉积而被广泛采用。磁控溅射法一般分为两种沉积方式：共溅射法和分步溅射法。相比于共溅射法，分步溅射法成分、结构均匀性相对较好，化学计量比和薄膜厚度更容易控制，而且在大面积连续生产、降低成本方面有很大优势。
采用分步溅射法制备银（Ag）掺杂CZTS预制层，选用合适的Ag叠层位置极其重要。目前，溅射法制备的Ag掺杂CZTS一般将Ag沉积在底层与钼（Mo）背电极接触，然后依次沉积Zn-Sn-Cu预制层。最后退火形成Ag掺杂CZTS。由于Ag在底层位置，受Ag元素扩散速率影响，一般很难保证Ag能在纵向中均匀分布。因此，如何制备出致密性、附着好、结构性好的Ag掺杂CZTS是本领域技术人员亟待解决的技术问题。
发明内容
鉴于现有技术存在的上述缺陷，本发明的目的是提供一种相对优化的银掺杂铜锌锡硫薄膜太阳电池，解决了Ag掺杂CZTS致密性差、附着性差的问题。
实现本发明目的的技术方案是：本发明所述的结构优化的银掺杂铜锌锡硫薄膜太阳电池，包括依次连接的玻璃衬底（1）、背电极（2）、吸收层（3）、缓冲层（4）、透明导电窗口层（5）和上电极（6），所述背电极为双层Mo薄膜，包括高阻层Mo薄膜和低阻层Mo薄膜，其总厚度为1μm；所述吸收层为银掺杂铜锌锡硫，厚度为1000nm~1500nm，其中，吸收层的预制层结构为Cu/Sn/Ag/ZnS，厚度为570nm；背电极（2）与吸收层（3）的叠加顺序为Mo/Cu/Sn/Ag/ZnS；所述缓冲层为CdS薄膜，厚度为50~60nm；所述透明导电窗口层为依次沉积的60~80nm的i-ZnO薄膜和500~600nm的ZnO:Al薄膜；所述上电极为蒸发镀银电极。
上述结构优化的银掺杂铜锌锡硫薄膜太阳电池的制备方法，包括以下步骤：
（1）玻璃衬底清洗：将钠钙玻璃衬底依次用去污粉、洗衣粉清洗，然后放入酒精、丙酮中各超声30分钟，使用Ⅰ号液（溶液体积比为氨水：过氧化氢：水=1:2:5）、Ⅱ号液（溶液体积比为盐酸：过氧化氢：水=1:2:8）加热煮沸10分钟，最后待样品冷却后用去离子水冲洗并用N2吹干；
（2）在洁净的钠钙玻璃衬底上采用直流法溅射双层Mo薄膜作为背电极；
（3）在背电极上，采用射频法分步溅射，依次溅射Cu、Sn、Ag和ZnS靶制备Cu/Sn/Ag/ZnS预制层；
（4）将步骤（3）所得预制层进行合金、硫化制备吸收层；
（5）在吸收层上，采用化学水浴法沉积CdS薄膜作为缓冲层；
（6） 在缓冲层上，采用射频溅射法溅射一层i-ZnO薄膜和一层ZnO:Al薄膜作为透明导电窗口层；
（7）在透明导电窗口层上，采用电子束蒸发法制备银电极作为上电极。
进一步的，步骤 (2) 中，所述的双层Mo薄膜包括高阻层Mo薄膜和低阻层Mo薄膜，首先在洁净的钠钙玻璃衬底上溅射高阻层Mo薄膜，溅射功率为200W，工作气压为1.2Pa，溅射时间为15min；接着溅射低阻层Mo薄膜，溅射功率为200W，工作气压为0.3Pa，溅射时间为50min。
进一步的，步骤 (3) 中， Cu靶的溅射功率为100W，溅射气压为0.3Pa，溅射厚度为100nm；Sn靶的溅射功率为50W，溅射气压为0.3Pa，溅射厚度为196nm；Ag靶的溅射功率为100W，溅射气压为0.3Pa，溅射厚度为20nm；ZnS靶的溅射功率为50W，溅射气压为0.3Pa，溅射厚度为254nm，Cu/Sn/Ag/ZnS预制层的厚度为570nm。
更进一步的，在沉积背电极和预制层前，抽真空至5×10-4Pa，溅射时通入Ar作为工作气体。
进一步的，步骤（4）中，合金温度为260℃，保温时间为20min；硫化温度为560℃，保温时间为45min。
进一步的，步骤 （5） 中，采用化学水浴法沉积CdS薄膜的过程如下：取10mL 浓度为0.01mol/L乙酸镉、12mL 浓度为1mol/L的硫脲、8mL 浓度为1mol/L乙酸铵和15mL浓度为25~28%氨水，加入450mL的去离子水中加热至80℃~85℃保持12min；后取出样品，在干燥箱干燥。
进一步的，步骤（6）中， i-ZnO薄膜的溅射功率为60~80W，溅射气压为0.3~0.5Pa；ZnO:Al薄膜的溅射功率为60~80W，溅射气压为0.3~0.5Pa。
与现有技术相比，本发明具有以下优点：（1）本发明通过对银掺杂叠层顺序进行结构优化，抑制了Sn元素在退火过程中的损失、减少了表面的孔洞，并且具有较好的结晶性与致密性。（2）本发明使银掺杂铜锌锡硫与硫化镉更紧密结合，降低了载流子的界面复合，从而减小了暗电流。
附图说明
附图不意在按比例绘制。在附图中，在各个图中示出的每个相同或近似相同的组成部分可以用相同的标号表示。为了清晰起见，在每个图中，并非每个组成部分均被标记。现在，将通过例子并参考附图来描述本发明的各个方面的实施例，其中：
图1为本发明所述的银掺杂铜锌锡硫薄膜太阳电池的结构示意图。
图2为本发明银掺杂铜锌锡硫薄膜预制层结构设计示意图。
图3为本发明实施例1制备的银掺杂铜锌锡硫薄膜的X射线衍射谱。
图4为本发明实施例1制备的银掺杂铜锌锡硫薄膜的拉曼光谱。
图5为本发明实施例1制备的银掺杂铜锌锡硫薄膜的扫描电子显微镜表面图。
图6为本发明实施例1制备的银掺杂铜锌锡硫薄膜的扫描电子显微镜截面图。
图7为本发明实施例2制备的银掺杂铜锌锡硫薄膜的X射线衍射谱。
图8为本发明实施例2制备的银掺杂铜锌锡硫薄膜的拉曼光谱。
图9为本发明实施例2制备的银掺杂铜锌锡硫薄膜的扫描电子显微镜表面图。
图10为本发明实施例2制备的银掺杂铜锌锡硫薄膜的扫描电子显微镜截面图。
具体实施方式
为了使本发明的沉积顺序等内容更容易被清楚理解，下面根据具体实施例并结合附图，对本发明作进一步详细的说明。
银掺杂铜锌锡硫吸收层的制备工艺包含两个步骤：第一步采用磁控溅射法溅射各个金属元素，形成堆栈，俗称：预制层。第二步将预制层放在硫蒸气中高温发生化学反应，形成一种新的物质，银掺杂铜锌锡硫。本文的主旨就是采用优化的金属堆栈结构，便于各个元素之间的均匀融合，从而形成高质量的银掺杂铜锌锡硫。
结合图1、图2，本发明所述的银掺杂锌锡硫薄膜太阳电池由下而上包括依次连接的玻璃衬底1、背电极2、吸收层3、缓冲层4、透明导电窗口层5和上电极6。所述背电极为Mo薄膜，厚度为1μm；所述吸收层3为银掺杂铜锌锡硫，其厚度为1000~1500nm，吸收层3的预制层的叠层顺序为Cu/Sn/Ag/ZnS，其中，Cu与背电极2即Mo薄膜连接；缓冲层4为CdS薄膜，厚度为50~60nm；透明导电窗口层5为依次沉积的60~80nm的i-ZnO薄膜和500~600nm的ZnO:Al薄膜；上电极6为蒸发镀银电极。
本发明原理在于：所述的吸收层3的预制层的叠层结构为Cu/Sn/Ag/ZnS，其中，Cu与背电极2的低阻层Mo薄膜连接。Sn元素在退火过程中容易形成蒸气压较大的SnS从而逸出表面。Ag层主要以两种方式抑制SnS损失：1）硫化升温过程中形成致密的Ag2S覆盖在SnS上层，作为一层阻挡层抑制SnS的挥发；2）；
Figure DEST_PATH_IMAGE001
；
在化学平衡反应方程式中，作为反应物促进向生成物方向移动。另外，Ag作为Cu的替代物，与Zn的原子半径有较大差距，因此对减少CuZn反结构缺陷，增加光生载流子的分离特别有利。
实施例1
（1）衬底清洗：将钠钙玻璃依次用去污粉、洗衣粉清洗，然后放入酒精、丙酮中各超声30分钟。之后用去离子水冲洗3~4遍，使用Ⅰ号液（氨水：过氧化氢：水=1:2:5）、Ⅱ号液（盐酸：过氧化氢：水=1:2:8）加热煮沸10分钟。最后待样品冷却后用去离子水冲洗并用氮气吹干；
（2）将清洗好的样品放入磁控溅射腔室内，抽真空至5×10-4pa。再通入气体流量5.5 sccm的高纯氩气作为工作气体。调整基片台转速为8.0rpm。采用直流法溅射高、低阻层的双层Mo薄膜作为背电极，首先溅射高阻层Mo薄膜，溅射功率为200W，工作气压为1.2Pa，溅射时间为15min；接着溅射低阻层Mo薄膜，溅射功率为200W，工作气压为0.3Pa，溅射时间为50min。
（3）在背电极上，采用射频溅射法，按照Cu/Sn/Ag/ZnS的先后顺序溅射靶材。Cu、Sn、Ag、ZnS靶的溅射功率依次为：100W、50W、100W、50W。溅射厚度分别为：20nm、100nm、196nm、254nm。开始溅射前，预溅射3min。最终得到总厚度约570nm的预制层；CZTS预制层在硫化退火中的生长过程一般经历以下两个阶段：Cu6Sn5+S→Cu2SnS3；Cu2SnS3+ZnS→Cu2ZnSnS4。因此，一般情况下铜与锡沉积在相邻位置。ZnS薄膜的致密性比铜小，将ZnS放在顶层有利于硫化过程中S元素的扩散。
（4）先将所制得的预制层放入20cm长的石墨舟中，然后将石墨舟放入管式炉中通入N2作为保护气体，升温速率调为15℃/min,升温至260℃后保温20min。待样品自然冷却至室温(约2h），取出石墨舟放入硫粉0.05g，再放入管式炉充入N2作为保护气体，升温速率12℃/min，升温至580℃后保温45min。预制层在加热硫化过程中往往伴随着体积膨胀。因此，待硫化后自然冷却至室温即可制得厚度为1000nm~1500nm的银掺杂铜锌锡硫吸收层薄膜。
（5）在采用水浴法沉积CdS缓冲层，沉积厚度为50~60nm。取10mL 浓度为0.01mol/L乙酸镉、12mL 浓度为1mol/L的硫脲、8mL 浓度为1mol/L乙酸铵和15mL度为25~28%氨水加入450mL的去离子水中加热至80℃~85℃保持12min；后取出样品，在干燥箱干燥。
（6） 采用射频溅射法溅射一层60~80nm的i-ZnO薄膜和一层500~600nm的ZnO:Al薄膜，其中，i-ZnO薄膜的溅射功率为60~80W，溅射气压为0.3~0.5Pa；ZnO:Al薄膜的溅射功率为60~80W，溅射气压为0.3~0.5Pa。
（7）采用电子束蒸发法制备银电极。将待制备样品置于真空吸附平台上，使待制样品保持平整状态，选择相应掩膜板悬架于待制样品上方，调整掩膜板位置，铺平银浆，开始印刷。印刷完成后取下掩膜板，将制备好的样品置于固化装置当中，使其在相应工艺温度下完全固化。
图3为实施例1制备的银掺杂铜锌锡硫薄膜的X射线衍射谱图，从图中可以看出所制备的银掺杂铜锌锡硫与铜锌锡硫的标准衍射峰吻合，并在（112）、（220）、（312）择优生长，说明20nm的银掺杂对CZTS的基本衍射峰位并未造成太大影响。图中衍射峰较高，半高宽较窄，说明结晶性很好，晶粒尺寸大。图4为实施例1制备的银掺杂铜锌锡硫薄膜拉曼谱图。该图显示位于251cm-1，287cm-1、338cm-1和371cm-1波数处出现了特征散射峰，经过比对，这些峰均为CZTS薄膜的Raman特征峰，无其他二次相峰。从图3和图4中均未发现银和银的硫化物峰位，说明了银原子很好的掺入铜锌锡硫的晶格中。图5和图6分别为实施例1制备的银掺杂铜锌锡硫薄膜的场发射扫描电镜表面图和截面图。图5表面图和图6截面图显示实施例1制备的银掺杂铜锌锡硫薄膜表面比较平整，无孔洞，结晶性比较好，结构比较完整。晶粒尺寸在0.8μm~1.8μm。这对载流子的传输比较有利。
实施例2
观察提高硫化温度后是否符合预期。
实施例2与实施例1的区别在于，实施例1硫化温度为560℃，实施例2硫化温度为580℃。温度过高一般会加速铜锌锡硫的分解并使元素损失加局，从图9、图10可以看见少量的孔洞，说明元素损失并不明显，从一定程度上说明Ag的掺入对减少Sn元素损失具有显著成效。
综上所述，图3和图7别为实施例1和实施例2所制备的银掺杂铜锌锡硫的X射线衍射谱。两个图都与铜锌锡硫的标准衍射峰吻合，衍射峰的强度较高，表明样品结晶性较好。证明了Ag沉积在Sn的上层，从一定程度上抑制了Sn元素在退火过程中形成饱和蒸汽压较大的SnS从而逸出表面，保持了各元素较好的化学计量比。图4和图8分别为实施例1和实施例2所制备的银掺杂铜锌锡硫的拉曼谱。三个图显示位于251cm-1，287cm-1、338cm-1和371cm-1波数处出现了特征散射峰，与铜锌锡硫拉曼峰基本吻合。
图5和图9分别为实施例1和实施例2所制备的银掺杂铜锌锡硫的表面图。图6和图10分别为实施例1和实施例2所制备的银掺杂铜锌锡硫的截面图。图5和图6中可以看出实施例1制备的样品表面比较平整、均匀，晶粒尺寸在0.8~1.8μm，且无孔洞。图9和图10可以看出实施例2制备的样品结晶性较好，但是表面、截面存在少量孔洞。可能是温度较高所致。图2~图10这八个图说明我们制备出表面均匀、致密，附着性较好的银掺杂铜锌锡硫薄膜太阳电池。
从上述实施例和本发明所描述的方案可知，本发明解决了银掺杂铜锌锡硫致密性差、结构松散的问题。对银掺杂铜锌锡硫的表面形貌、与Mo背电极的附着性有明显的提升。

Claims (10)

1.一种银掺杂铜锌锡硫薄膜太阳电池，包括依次连接的玻璃衬底(1)、背电极(2)、吸收层 (3)、缓冲层(4)、透明导电窗口层(5)和上电极(6)；其特征在于，所述吸收层(3)的预制层结构为Cu/Sn/Ag/ZnS。
2.根据权利要求1所述的太阳电池，其特征在于，背电极（2）为双层Mo薄膜，包括高阻层Mo薄膜和低阻层Mo薄膜，其总厚度为1μm。
3.根据权利要求1所述的太阳电池，其特征在于，吸收层（3）为银掺杂铜锌锡硫，厚度为1000nm~1500nm。
4.根据权利要求1所述的太阳电池，其特征在于，吸收层(3)的预制层结构为Cu/Sn/Ag/ZnS，预制层结构中的Cu与背电极(2)连接，预制层厚度为570nm。
5.根据权利要求1所述的太阳电池，其特征在于，缓冲层(4)为CdS薄膜，厚度为50~60nm。
6.根据权利要求1所述的太阳电池，其特征在于，透明导电窗口层(5)包括一层60~80nm的i-ZnO薄膜和一层500~600nm的ZnO:Al薄膜，其中，i-ZnO薄膜与缓冲层(4)连接。
7.根据权利要求1所述的太阳电池，其特征在于，上电极(6)为银电极。
8.一种如权利要求1-7任一所述的银掺杂铜锌锡硫薄膜太阳电池的制备方法，其特征在于，包括如下制作步骤：
（1）在洁净的钠钙玻璃衬底上采用直流法溅射双层Mo薄膜作为背电极；
（2）在背电极上，采用射频法分步溅射，依次溅射Cu、Sn、Ag和ZnS靶制备Cu/Sn/Ag/ZnS预制层；
（3）将步骤（3）所得预制层进行合金、硫化制备吸收层；
（4）在吸收层上，采用化学水浴法沉积CdS薄膜作为缓冲层；
（5） 在缓冲层上，采用射频溅射法溅射一层i-ZnO薄膜和一层ZnO:Al薄膜作为透明导电窗口层；
（6）在透明导电窗口层上，采用电子束蒸发法制备银电极作为上电极。
9. 如权利要求8所述的方法，其特征在于，步骤 (1) 中，双层Mo薄膜包括高阻层Mo薄膜和低阻层Mo薄膜，首先在洁净的钠钙玻璃衬底上溅射高阻层Mo薄膜，溅射功率为200W，工作气压为1.2Pa，溅射时间为15min；接着溅射低阻层Mo薄膜，溅射功率为200W，工作气压为0.3Pa，溅射时间为50min。
10. 如权利要求8所述的方法，其特征在于，步骤 (2) 中， Cu靶的溅射功率为100W，溅射气压为0.3Pa，溅射厚度为100nm；Sn靶的溅射功率为50W，溅射气压为0.3Pa，溅射厚度为196nm；Ag靶的溅射功率为100W，溅射气压为0.3Pa，溅射厚度为20nm；ZnS靶的溅射功率为50W，溅射气压为0.3Pa，溅射厚度为254nm。
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