CN106531826A - 铜锢稼硒薄膜太阳能电池的制备方法 - Google Patents
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Abstract
本发明公开了铜锢稼硒薄膜太阳能电池的制备方法，属于薄膜太阳能电池领域。本发明解决现有三步真空共蒸法制备CIGS电池存在很难保证大面积条件下多种元素化学计量比的均匀一致性的缺点。方法：一、在衬底温度为350℃条件下，在Se的气氛下先蒸发少量的Ga，随后共蒸In和Ga,得到(In,Ga)2Se3的预制层；二、衬底温度为530℃,共蒸Cu、Se直到薄膜呈富铜状态；三、在维持衬底温度的同时，共蒸In、Ga和Se，获得贫铜CIGS吸收层。本发明用于制备铜锢稼硒薄膜太阳能电池。
Description
技术领域
本发明属于薄膜太阳能电池领域；具体涉及铜锢稼硒薄膜太阳能电池的制备方法。
背景技术
CIGS材料属于Ⅰ-Ⅲ-Ⅵ族四元化合物半导体，具有黄铜矿的晶体结构。衬底一般采用玻璃，也可以采用柔性薄膜衬底。一般采用真空溅射、蒸发或者其它非真空的方法，分别沉积多层薄膜，形成P-N结构而构成光电转换器件。从光入射层开始，各层分别为:金属栅状电极、减反射膜、窗口层(Zn0)、过渡层(CdS)、光吸收层(CIGS)、金属背电极(Mo)、玻璃衬底。经过近30年的研究，CIGS太阳电池发展了很多不同结构。最主要差别在于窗口材料的不同选择。最早是用n型半导体CdS作窗口层，其禁带宽度为2.42eV，一般通过掺入少量的ZnS，成为CdZnS材料，主要目的是增加带隙。但是，铬是重金属元素，对环境有害，而且材料本身带隙偏窄。近年来的研究发现，窗口层改用ZnO效果更好，ZnO带宽可达到3.3eV，CdS的厚度降到只有约50nm，只作为过渡层。为了增加光的入射率，最后在电池表面蒸发一层减反膜(一般采用MgFz)，电池的效率会得到1-2％的提高。
现有三步真空共蒸法步骤如下：
第一步,基底温度较低的情况下(400℃)蒸发In、Ga、Se形成一层In-Ga-Se预置层,其中控制原子比例In/Ga=0.7/0.3,In+Ga/Se=2/3;
第二步,升高基底温度到570℃,蒸发Cu、Se,其目的是为了借助低熔点的Cu2-xSe在高温下具有液相般的特性来促进晶粒生长,得到大尺寸且致密的膜层,这两层复合可转化为稍微富铜的CIGS;
第三步,保持第二步的基底温度,蒸发In、Ga、Se,使多余的Cu2-xSe转化成等化学计量比的CIGS,继续蒸发少量的In、Ga、Se,可得到稍微贫铜的CIGSp型黄铜矿结构,并控制Cu/In+Ga的比例在0.88~0.92这个狭小的范围内。
样品随后在蒸发Se的同时冷却到400℃,关闭Se再冷却到室温。应用该法制备的Mo/CIGS/50nmCdS/50nmZnO/200nmZnO∶Al电池可获得大于19%的转化效率。
虽然现有三步法是比较成熟的蒸发工艺，但对设备要求严格、大面积制备困难、材料利用率偏低。就目前的设备可靠性和制备的工艺水平来看，很难保证大面积条件下多种元素化学计量比的均匀一致性，所以限制了其商业上的大规模应用。
发明内容
本发明解决现有三步真空共蒸法制备CIGS电池存在很难保证大面积条件下多种元素化学计量比的均匀一致性的缺点；而提供了铜锢稼硒薄膜太阳能电池的制备方法。
本发明铜锢稼硒薄膜太阳能电池的制备方法是以苏打玻璃（即碳酸钠玻璃、纳钙玻璃）为衬底；具体步骤如下：
第一步，衬底温度为350°C时,在Se的气氛下先蒸发少量的Ga；随后共蒸In和Ga,得到(In,Ga)2Se3的预制层；
第二步,衬底温度为530°C,共蒸Cu、Se直到薄膜呈富铜状态；
第三步,补充In、 Ga和Se吸收层，以获得贫铜CIGS吸收层。
本发明以苏打玻璃为衬底。在苏打玻璃衬底上，采用直流磁控溉射制备双层Mo背电极。
与现有方法相比，本发明的有益技术效果:
(1）沉积得到的CIGS薄膜，具有更加平整的表面，薄膜的内部非常致密均匀。从而减少了CIGS层的粗糙度，这就可以改善CIGS层与缓冲层的接触界面，在减少漏电流的情况下，提高了内建电场，同时也消除了载流子的复合中心。
（2）可以获得较好的Ga的背梯度,从而更适合在超薄电池中应用。
（3）降低对设备的要求，提高材料的利用率，实现大面积制备。
（4）保证大面积条件下多种元素化学计量比的均匀一致性，实现其商业上的大规模应用。
具体实施方式
具体实施方式一：本发明铜锢稼硒薄膜太阳能电池的制备方法是以苏打玻璃（即碳酸钠玻璃、纳钙玻璃）为衬底，采用直流磁控溉射在所述衬底上形成双层Mo背电极层，即在2Pa高气压下沉积厚度约为0.2 μm的Mo薄膜，再在电极层上形成CIGS吸收层；CIGS吸收层的具体步骤如下：
第一步，衬底温度为350°C时,在Se的气氛下先蒸发少量的Ga；随后共蒸In和Ga,得到(In,Ga)2Se3的预制层；
第二步,衬底温度为530°C,共蒸Cu、Se直到薄膜呈富铜状态；
第三步,补充In、 Ga和Se吸收层，以获得贫铜CIGS吸收层。
第一步中控制原子比为In:Ga=0.7:0.3，(,In+Ga): Se=2:3。
第三步获得的贫铜CIGS吸收层中Cu: (,In+Ga) 原子比为（0.88~0.92）:1。
第一步和第三步中In的蒸发量为3 Å∕S，第一步中 Ga的蒸发量为1.6Å∕S，第三步中 Ga的蒸发量为1.5Å∕S。
本实施方式中的电池器件的面积可达到8cml平方厘米，吸收面积可达36平方厘米。
Claims (7)
1.铜锢稼硒薄膜太阳能电池的制备方法，其特征在于铜锢稼硒薄膜太阳能电池的制备方法是按下述步骤进行的：
第一步、在衬底温度为350℃条件下，在Se的气氛下先蒸发少量的Ga，随后共蒸In和Ga,得到(In,Ga)2Se3的预制层；
第二步、衬底温度为530℃,共蒸Cu、Se直到薄膜呈富铜状态；
第三步、在维持衬底温度的同时，共蒸In、 Ga和Se，获得贫铜CIGS吸收层。
2.根据权利要求1所述铜锢稼硒薄膜太阳能电池的制备方法，其特征在于以苏打玻璃为衬底。
3.根据权利要求1所述铜锢稼硒薄膜太阳能电池的制备方法，其特征在于在苏打玻璃衬底上，采用直流磁控溉射制备双层Mo背电极。
4.根据权利要求1所述铜锢稼硒薄膜太阳能电池的制备方法，其特征在于先在2Pa高气压下沉积厚度约为0.2 μm的Mo薄膜。
5.根据权利要求1所述铜锢稼硒薄膜太阳能电池的制备方法，其特征在于其中第一步中控制原子比为In:Ga=0.7:0.3，(,In+Ga): Se=2:3。
6.根据权利要求1所述铜锢稼硒薄膜太阳能电池的制备方法，其特征在于第三步获得的贫铜CIGS吸收层中Cu: (,In+Ga) 原子比为（0.88~0.92）:1。
7.根据权利要求1所述铜锢稼硒薄膜太阳能电池的制备方法，其特征在于第一步和第三步中In的蒸发量为3 Å∕S，第一步中 Ga的蒸发量为1.6Å∕S，第三步中 Ga的蒸发量为1.5Å∕S。
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