CN107611013A - 一种ZnS太阳能电池薄膜材料的制备方法 - Google Patents
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Abstract
本发明公开了一种ZnS太阳能电池薄膜材料的制备方法，该工艺利用锌离子溶液及硒粉溶液作为薄膜前驱体，在粘度调节剂的作用下将薄膜母液涂布在衬底上，然后进行真空硫化作用，退火稳固得到ZnS薄膜材料。制备而成的ZnS太阳能电池薄膜材料，其制作工艺简单、薄膜材料电导率高、电容量大，具有较好的应用前景。
Description
技术领域
本发明涉及薄膜材料这一技术领域，特别涉及到一种ZnS太阳能电池薄膜材料的制备方法。
背景技术
利用太阳能的最佳方式是光伏转换，就是利用“光伏效应”，使太阳光射到半导体材料上产生电流直接发电。以硅材料的应用开发形成的产业链条称之为光伏产业，包括高纯多晶硅原材料生产、太阳能电池生产、太阳能电池组件生产、相关生产设备的制造等。太阳能光伏发电在不远的将来会占据世界能源消费的重要席位，不但要替代部分常规能源，而且将成为世界能源供应的主体。预计到2030年，可再生能源在总能源结构中将占到30％以上，而太阳能光伏发电在世界总电力供应中所占比例也将达到10％以上；到2040年，可再生能源将占总能耗的50％以上，太阳能光伏发电将占总电力的20％以上；到21世纪末，可再生能源在能源结构中将占到80％以上，太阳能发电将占到60％以上。这些数字足以显示出太阳能光伏产业的发展前景及其在能源领域重要的战略地位。
从2005年开始，全球在硅材料紧缺、价格飙升的情况下，光伏产业仍以每年44％的增幅持续高速发展。2006年全球实际产量已接近2.6GW(千兆瓦)，产能超过3GW，2007年产能突破5GW。据统计，2007年全球光伏发电量比例还不到0.01％，即使到2010年这一比例也不超过0.1％，光伏产业正处于蓬勃发展的初期阶段，世界市场远远没有达到饱和。
太阳能电池材料，以硅为例，非晶硅、多晶硅以及单晶硅的光电转换效应分别为17％，24％和29％。显然，单晶硅的转换效率是最高的，因而是最理想的材料。然而，现在的单晶硅电池都是单晶硅棒切片制造的，单晶硅棒的生产成本很高，而且切下来的部分只有表面的一小薄层(约为硅片厚度的1/50)参与光电转换过程，这造成了单晶硅电池的成本居高不下。从2005年开始，全球硅材料紧缺、价格飙升，价格问题显得更加突出。传统的化合物薄膜太阳能电池，一般采用化学浴法制备的CdS薄膜作为缓冲层材料，并且已经获得了较高的电池转换效率。后来人们逐渐意识到CdS是一种对环境和人体有害的材料，要研究制备无污染的太阳能电池就该寻找新的材料作为替代。在以后的研究中人们慢慢发现ZnS是替代CdS的良好的材料。本发明采用电沉积法连续沉积ZnS缓冲层材料，可简化现有射频溅射法和化学气相沉积法的制备工艺并保证薄膜的大面积均匀性，这对大面积太阳能电池的制作乃至实现低成本大规模商业化生产都有着重要的意义和广泛的发展前景。
发明内容
为解决上述技术问题，本发明提供一种ZnS太阳能电池薄膜材料的制备方法，该工艺利用锌离子溶液及硒粉溶液作为薄膜前驱体，在粘度调节剂的作用下将薄膜母液涂布在衬底上，然后进行真空硫化作用，退火稳固得到ZnS薄膜材料。制备而成的ZnS太阳能电池薄膜材料，其制作工艺简单、薄膜材料电导率高、电容量大，具有较好的应用前景。
本发明的目的可以通过以下技术方案实现：
一种ZnS太阳能电池薄膜材料的制备方法，包括以下步骤：
（1）将锌硝酸盐或氯化盐溶于醇类，再将高纯硒粉按0.08M的浓度溶于胺类，将上述的两份溶液按照体积比5:2混溶在一起，并添加粘度调节剂，室温充分搅拌5-10小时，形成稳定的前驱体溶液，通过添加或减少醇类或胺类的用量，将前驱体溶液中Zn离子的浓度控制在0.8-1M；
（2）将步骤（1）前驱体溶液加入涂布混匀仪，将薄膜母液在衬底上形成薄膜前体;
（3）将上述步骤（2）的薄膜前体置于真空环境中喷洒硫化物进行硫化作用；
（4）将步骤（3）的硫化薄膜进行退火，即得成品。
优选地，所述步骤（1）中的醇类选自季戊四醇、二丙烯醛缩季戊四醇、2,5-双(1,1-二甲基丙基)-1,4-苯二醇摩尔质量比为5:7:1的混合物。
优选地，所述步骤（1）中的胺类选自对甲苯磺酰胺、甲基丙烯酰胺、2-氨基苯酚-4-磺酰苯胺中的一种或几种。
优选地，所述步骤（1）中的粘度调节剂选自聚乙烯蜡、沙索蜡、尿素中的一种或几种。
优选地，所述步骤（3）中的硫化物选自硫化锌、硫化镉、二硫化碳中的一种或几种。
优选地，所述步骤（3）中的硫化条件为1200-1500℃，喷洒的速率为15cm2/sec。
优选地，所述步骤（4）中的退火条件为300-500℃，氮气保护，退火时间为15-20min。
本发明与现有技术相比，其有益效果为：
（1）本发明的一种ZnS太阳能电池薄膜材料的制备方法利用锌离子溶液及硒粉溶液作为薄膜前驱体，在粘度调节剂的作用下将薄膜母液涂布在衬底上，然后进行真空硫化作用，退火稳固得到ZnS薄膜材料。制备而成的ZnS太阳能电池薄膜材料，其制作工艺简单、薄膜材料电导率高、电容量大，具有较好的应用前景。
（2）本发明的ZnS太阳能电池薄膜材料原料易得、工艺简单，适于大规模工业化运用，实用性强。
具体实施方式
下面结合具体实施例对发明的技术方案进行详细说明。
实施例1
（1）将锌硝酸盐或氯化盐溶于醇类，其中醇类为季戊四醇、二丙烯醛缩季戊四醇、2,5-双(1,1-二甲基丙基)-1,4-苯二醇摩尔质量比为5:7:1的混合物，再将高纯硒粉按0.08M的浓度溶于对甲苯磺酰胺，将上述的两份溶液按照体积比5:2混溶在一起，并添加聚乙烯蜡5份，室温充分搅拌5小时，形成稳定的前驱体溶液，通过添加或减少醇类或胺类的用量，将前驱体溶液中Zn离子的浓度控制在0.8M；
（2）将步骤（1）前驱体溶液加入涂布混匀仪，将薄膜母液在衬底上形成薄膜前体;
（3）将上述步骤（2）的薄膜前体置于真空环境中喷洒硫化锌进行硫化作用，硫化条件为1200℃，喷洒的速率为15cm2/sec；
（4）将步骤（3）的硫化薄膜进行退火，退火条件为300℃，氮气保护，退火时间为15min，即得成品。
制得的ZnS太阳能电池薄膜材料的性能测试结果如表1所示。
实施例2
（1）将锌硝酸盐或氯化盐溶于醇类，其中醇类为季戊四醇、二丙烯醛缩季戊四醇、2,5-双(1,1-二甲基丙基)-1,4-苯二醇摩尔质量比为5:7:1的混合物，再将高纯硒粉按0.08M的浓度溶于甲基丙烯酰胺7份，将上述的两份溶液按照体积比5:2混溶在一起，并添加沙索蜡，室温充分搅拌10小时，形成稳定的前驱体溶液，通过添加或减少醇类或胺类的用量，将前驱体溶液中Zn离子的浓度控制在1M；
（2）将步骤（1）前驱体溶液加入涂布混匀仪，将薄膜母液在衬底上形成薄膜前体;
（3）将上述步骤（2）的薄膜前体置于真空环境中喷洒硫化镉进行硫化作用，硫化条件为1500℃，喷洒的速率为15cm2/sec；
（4）将步骤（3）的硫化薄膜进行退火，退火条件为500℃，氮气保护，退火时间为20min，即得成品。
制得的ZnS太阳能电池薄膜材料的性能测试结果如表1所示。
对比例1
（1）将锌硝酸盐或氯化盐溶于醇类，其中醇类为季戊四醇、二丙烯醛缩季戊四醇、2,5-双(1,1-二甲基丙基)-1,4-苯二醇摩尔质量比为5:7:1的混合物，再将高纯硒粉按0.08M的浓度溶于2-氨基苯酚-4-磺酰苯胺7份，将上述的两份溶液按照体积比5:2混溶在一起，并添加尿素，室温充分搅拌10小时，形成稳定的前驱体溶液，通过添加或减少醇类或胺类的用量，将前驱体溶液中Zn离子的浓度控制在1M；
（2）将步骤（1）前驱体溶液加入涂布混匀仪，将薄膜母液在衬底上形成薄膜前体;
（3）将步骤（2）的薄膜前体直接进行退火，退火条件为500℃，氮气保护，退火时间为20min，即得成品。
制得的ZnS太阳能电池薄膜材料的性能测试结果如表1所示。
将实施例1-2和对比例的制得的ZnS太阳能电池薄膜材料及市售常见同类薄膜材料分别进行电容量、介电常数和击穿强度这几项性能测试。
表1
本发明的一种ZnS太阳能电池薄膜材料的制备方法利用锌离子溶液及硒粉溶液作为薄膜前驱体，在粘度调节剂的作用下将薄膜母液涂布在衬底上，然后进行真空硫化作用，退火稳固得到ZnS薄膜材料。制备而成的ZnS太阳能电池薄膜材料，其制作工艺简单、薄膜材料电导率高、电容量大，具有较好的应用前景。本发明的ZnS太阳能电池薄膜材料原料易得、工艺简单，适于大规模工业化运用，实用性强。
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。
Claims (7)
1.一种ZnS太阳能电池薄膜材料的制备方法，其特征在于，包括以下步骤：
（1）将锌硝酸盐或氯化盐溶于醇类，再将高纯硒粉按0.08M的浓度溶于胺类，将上述的两份溶液按照体积比5:2混溶在一起，并添加粘度调节剂，室温充分搅拌5-10小时，形成稳定的前驱体溶液，通过添加或减少醇类或胺类的用量，将前驱体溶液中Zn离子的浓度控制在0.8-1M；
（2）将步骤（1）前驱体溶液加入涂布混匀仪，将薄膜母液在衬底上形成薄膜前体;
（3）将上述步骤（2）的薄膜前体置于真空环境中喷洒硫化物进行硫化作用；
（4）将步骤（3）的硫化薄膜进行退火，即得成品。
2.根据权利要求1所述的ZnS太阳能电池薄膜材料的制备方法，其特征在于，所述步骤（1）中的醇类选自季戊四醇、二丙烯醛缩季戊四醇、2,5-双(1,1-二甲基丙基)-1,4-苯二醇摩尔质量比为5:7:1的混合物。
3.根据权利要求1所述的ZnS太阳能电池薄膜材料的制备方法，其特征在于，所述步骤（1）中的胺类选自对甲苯磺酰胺、甲基丙烯酰胺、2-氨基苯酚-4-磺酰苯胺中的一种或几种。
4.根据权利要求1所述的ZnS太阳能电池薄膜材料的制备方法，其特征在于，所述步骤（1）中的粘度调节剂选自聚乙烯蜡、沙索蜡、尿素中的一种或几种。
5.根据权利要求1所述的ZnS太阳能电池薄膜材料的制备方法，其特征在于，所述步骤（3）中的硫化物选自硫化锌、硫化镉、二硫化碳中的一种或几种。
6.根据权利要求1所述的ZnS太阳能电池薄膜材料的制备方法，其特征在于，所述步骤（3）中的硫化条件为1200-1500℃，喷洒的速率为15cm2/sec。
7.根据权利要求1所述的ZnS太阳能电池薄膜材料的制备方法，其特征在于，所述步骤（4）中的退火条件为300-500℃，氮气保护，退火时间为15-20min。
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