CN103606574B - 采用BiOCuS作为吸收层的薄膜太阳能电池及其制备方法 - Google Patents

采用BiOCuS作为吸收层的薄膜太阳能电池及其制备方法 Download PDF

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CN103606574B
CN103606574B CN201310594516.9A CN201310594516A CN103606574B CN 103606574 B CN103606574 B CN 103606574B CN 201310594516 A CN201310594516 A CN 201310594516A CN 103606574 B CN103606574 B CN 103606574B
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黄富强
陈海杰
谢宜桉
王耀明
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Shandong Zhongke Taiyang Photoelectric Technology Co.,Ltd.
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Abstract

本发明涉及采用BiOCuS作为吸收层的薄膜太阳能电池及其制备方法，所述薄膜太阳能电池的吸收层为BiOCuS薄膜。本发明利用更为廉价BiOCuS取代传统的昂贵的Cu(In,Ga)(S,Se)2，BiOCuS的禁带宽度为0.93电子伏特，导电性与CuInS2相比拟，而且还可通过掺杂及固溶等方法在较大范围内调节其带隙，因此，本发明的薄膜太阳能电池成本低廉、转换效率高，具有较大应用前景。

Description

采用BiOCuS作为吸收层的薄膜太阳能电池及其制备方法
技术领域
本方法涉及一种采用BiOCuS作为吸收层的薄膜太阳能电池及其制备方法，利用更为廉价BiOCuS取代传统的昂贵的Cu(In,Ga)(S,Se)2，成本低廉，转换效率高，具有较大应用前景，属于太阳能光伏材料领域。
背景技术
太阳能电池可以直接将可见光能转化为电能，相比于传统的单晶硅和多晶硅太阳能电池，薄膜太阳能电池利用原料少，成本更加低廉。Cu(In,Ga)(S,Se)2基薄膜太阳能电池，具有禁带宽度可调、吸收系数高、转换效率高、抗辐射能力高、稳定性强等优点，有望成为新一代太阳能电池的主流。其典型结构为衬底、Mo电极层、吸收层、CdS、ZnO、Al-ZnO、顶电极等。
然而，由于需要使用地球上稀缺的元素In及Ga，因此寻找可以替代Cu(In,Ga)(S,Se)2的新型吸收层材料成为一个研究热点。BiOCuS粉末的禁带宽度为0.93电子伏特（参见图1），导电性与CuInS2相比拟，可通过掺杂及固溶等方法在较大范围内调节其带隙。因此，可能也是很好的吸收层材料。
发明内容
本发明目的在于提供一种采用BiOCuS替代Cu(In,Ga)(S,Se)2作为吸收层材料的薄膜太阳能电池及其制备方法，从而进一步降低太阳能电池的制备成本。
在此，本发明提供一种薄膜太阳能电池，所述薄膜太阳能电池的吸收层为BiOCuS薄膜。
本发明利用更为廉价BiOCuS取代传统的昂贵的Cu(In,Ga)(S,Se)2，BiOCuS的禁带宽度为0.93电子伏特，导电性与CuInS2相比拟，而且还可通过掺杂及固溶等方法在较大范围内调节其带隙，因此，本发明的薄膜太阳能电池成本低廉、转换效率高，具有较大应用前景。
较佳地，利用Newport生产的模拟光源表征所述薄膜太阳能电池的电池性能，具有光电转化响应，电池效率可达0.8%以上。
较佳地，所述BiOCuS薄膜的厚度为500nm～2μm。
较佳地，所述薄膜太阳能电池的衬底可以为玻璃、石英、硅片等常见衬底，也可以为SrTiO3、LaAlO3、金属、塑料等其他衬底。较佳地，所述薄膜太阳能电池的导电层可以为Mo导电层。
较佳地，所述薄膜太阳能电池的半导体层的材料可以为CdS、ZnS、ZnIn2Se4、和/或In2Se3。
另一方面，本发明还提供一种制备上述薄膜太阳能电池的方法，包括：
（1）通过磁控溅射、脉冲激光沉积、化学浴、旋涂、化学气相沉积、和/或电化学沉积在沉积有导电层的衬底上形成BiOCuS薄膜作为吸收层；以及
（2）沉积n型化合物薄膜形成n型半导体层并组装成薄膜太阳能电池。
本发明的方法，工艺简单易控，适合规模生产，用于形成BiOCuS薄膜的BiOCuS原料可以通过传统的固相反应法（例如高能球磨法）来制备，也可以通过溶液法制备，还可以为先制备成薄膜后再通过反应合成等方法来制备。
附图说明
图1为BiOCuS光吸收曲线。
具体实施方式
以下结合附图和下述实施方式进一步说明本发明，应理解，附图及下述实施方式仅用于说明本发明，而非限制本发明。
本发明提供一种采用BiOCuS作为吸收层的薄膜太阳能电池，该薄膜太阳能电池可以采用现有技术中的薄膜太阳能电池的结构，例如依次包括衬底、导电层、p型吸收层、n型半导体层、窗口层、透明电极层和顶电极，其中p型吸收层即为BiOCuS薄膜。
衬底的材料不限，可以采用公知的各种衬底，例如可以为玻璃、石英、硅片等常见衬底，也可以为SrTiO3、LaAlO3、金属、塑料等其他衬底。
导电层沉积于衬底上。导电层可以是但不限于钼，也包括其它适用金属材料，例如铝、钛、铜、不锈钢等。沉积方法可以采用现有技术，例如可以是真空镀膜方法，例如物理气相沉积或化学气相沉积。
然后，在导电层上制备BiOCuS薄膜。制备方法可以采用真空制膜法、和/或非真空制膜法，例如磁控溅射、脉冲激光沉积、化学浴、旋涂、化学气相沉积、电化学沉积等各种薄膜制备方法。在一个示例中，采用磁控溅射法制备BiOCuS薄膜，具体地是，将Bi2O3、Cu、S按照BiOCuS的化学计量比称量并真空封装于石英管中，缓慢升温至500℃后经10小时降温至室温，随后冷却后取出、研磨、封管，重复前述步骤一遍得到BiOCuS粉末。利用热压炉500℃和60MPa压力下制备直径为30cm的靶材。利用磁控溅射在沉积了导电层的衬底沉积BiOCuS薄膜。BiOCuS薄膜的厚度可以根据需要选择，例如可以为500nm～2μm，优选为～1μm。
随后制备n型半导体层、窗口层、透明电极层和顶电极等，组装完成对应的薄膜太阳能电池。上述各层的材料可以采用公知的适用材料，例如，n型半导体层可以为CdS、ZnS、ZnIn2Se4、和/或In2Se3；窗口层可以ZnO；透明电极层可以为Al-ZnO。制备方法可以参见现有技术，例如中国专利CN102201495A、CN101764168A、CN102856424A等。
本发明中，组装完成薄膜太阳能电池后，还可以利用Newport生产的模拟光源表征其性能。经测试，本发明的薄膜太阳能电池的电池效率为0.8%以上。
下面进一步例举实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的温度、压力、时间等工艺参数也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。
实施例1
将Bi2O3、Cu、S按照BiOCuS的化学计量比称量并真空封装于石英管中，缓慢升温至500℃后经10h降温至室温，随后冷却后取出、研磨、封管，重复前述步骤一遍得到BiOCuS粉末。利用热压炉500℃和60MPa压力下制备直径为30cm的靶材。利用磁控溅射在沉积了Mo导电层的衬底沉积BiOCuS薄膜，完成后续工艺组装成太阳能电池。利用Newport生产的模拟光源表征电池性能，具有2.4%的电池效率。
实施例2
将Bi2O3、Cu、S按照BiOCuS的化学计量比称量并真空封装于石英管中，缓慢升温至500℃后经10h降温至室温，随后冷却后取出、研磨、封管，重复前述步骤一遍得到BiOCuS粉末。利用等离子体增强热压炉500℃和100MPa压力下制备直径为20cm的靶材。利用磁控溅射在沉积了Mo导电层的衬底沉积BiOCuS薄膜，完成后续工艺组装成太阳能电池。利用Newport生产的模拟光源表征电池性能，具有1.8%的电池效率。
实施例3
将Bi2O3、Cu、S按照BiOCuS的化学计量比称量并真空封装于石英管中，缓慢升温至500℃后经10h降温至室温，随后冷却后取出、研磨、封管，重复前述步骤一遍得到BiOCuS粉末。利用等离子体增强热压炉400℃和120MPa压力下制备直径为15cm的靶材。利用脉冲激光沉积在沉积了Mo导电层的衬底上沉积BiOCuS薄膜，完成后续工艺组装成太阳能电池。利用Newport生产的模拟光源表征电池性能，具有3.8%的电池效率。
实施例4
将Bi2O3、Cu、S按照BiOCuS的化学计量比称量并封装于Ar保护的钢罐中，高能球磨24h，取出得到相关粉末。利用等离子体增强热压炉500℃和150MPa压力下制备直径为40cm的靶材。利用磁控溅射在沉积了Mo导电层的衬底沉积BiOCuS薄膜，完成后续工艺组装成太阳能电池。利用Newport生产的模拟光源表征电池性能，具有1.5%的电池效率。
实施例5
将Bi2O3、Cu、S按照BiOCuS的化学计量比称量并封装于Ar保护的钢罐中，高能球磨24h，取出得到相关粉末。加入适量酒精，超声分散得到相应溶液，利用旋涂法在沉积了Mo导电层的衬底上制备BiOCuS层，完成后500℃下退火1h，冷却后取出并陆续沉积CdS、ZnO、Al-ZnO、顶电极等工艺组装出最终电池。利用Newport生产的模拟光源表征电池性能，具有3.2%的电池效率。
实施例6
将Bi2O3、Cu、S按照BiOCuS的化学计量比称量并封装于Ar保护的钢罐中，高能球磨24h，取出得到相关粉末。加入适量酒精，超声分散得到相应溶液，利用提拉法在沉积了Mo导电层的衬底上沉积对应薄膜，完成后500℃下退火30min，冷却后取出并陆续沉积CdS、ZnO、Al-ZnO、顶电极等工艺组装出最终电池。利用Newport生产的模拟光源表征电池性能，具有2.8%的电池效率。
实施例7
将Bi(NO)3、Cu(ac)2、硫脲按照BiOCuS的化学计量比称量并溶解于蒸馏水中配成相应溶液。利用电化学沉积法在沉积了Mo导电层的衬底上制备BiOCuS层，取出后完成沉积CdS、ZnO、Al-ZnO、顶电极等工艺组装出最终电池。利用Newport生产的模拟光源表征电池性能，具有1.3%的电池效率。
实施例8
将Bi(NO)3、Cu(ac)2、硫脲按照BiOCuS的化学计量比称量并溶解于蒸馏水中配成相应溶液。利用提拉法在沉积了Mo导电层的衬底上沉积相应薄膜，取出后至于空气中500℃下退火30min，随后沉积CdS、ZnO、Al-ZnO、顶电极等工艺组装出最终电池。利用Newport生产的模拟光源表征电池性能，具有0.8%的电池效率。
产业应用性：本发明利用BiOCuS作为薄膜太阳能电池的吸收层，原料成本低，制备的太阳能电池转化效率高，在太阳电池领域有较大的应用前景。

Claims (6)

1.一种薄膜太阳能电池，其特征在于，所述薄膜太阳能电池包括衬底、导电层、吸收层、半导体层、窗口层、透明电极层和顶电极，以及其中的吸收层为BiOCuS薄膜。
2.根据权利要求1所述的薄膜太阳能电池，其特征在于，利用模拟光源表征所述薄膜太阳能电池的电池性能，具有光电转化响应，电池效率达0.8%以上。
3.根据权利要求1或2所述的薄膜太阳能电池，其特征在于，所述BiOCuS薄膜的厚度为500nm～2μm。
4.根据权利要求1或2所述的薄膜太阳能电池，其特征在于，所述薄膜太阳能电池的衬底为玻璃、石英、硅片、SrTiO3、LaAlO3、金属或塑料，导电层为Mo导电层。
5.根据权利要求1或2所述的薄膜太阳能电池，其特征在于，所述薄膜太阳能电池的半导体层的材料为CdS、ZnS、ZnIn2Se4、或In2Se3。
6.一种制备权利要求1至5中任一项所述的薄膜太阳能电池的方法，其特征在于，包括：
（1）通过磁控溅射、脉冲激光沉积、化学浴、旋涂、化学气相沉积、或电化学沉积在沉积有导电层的衬底上形成BiOCuS薄膜作为吸收层；以及
（2）沉积n型化合物薄膜形成n型半导体层并组装成薄膜太阳能电池。
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"BiOCuS:A new superconducting compound with oxypnictide-related structure ";A.Ubaldini;《Physica C》;20100112;第470卷;356-357 *
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