CN112259623B - 一种改善铜铟镓硒（cigs）薄膜太阳能电池光吸收层结晶性的方法 - Google Patents
一种改善铜铟镓硒（cigs）薄膜太阳能电池光吸收层结晶性的方法 Download PDFInfo
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Abstract
本发明公开了一种改善铜铟镓硒(CIGS)薄膜太阳能电池光吸收层结晶性的方法，包含：步骤1，使用较高铜含量CIGS四元靶材在以钠钙玻璃为衬底的钼层上溅射沉积CIGS薄膜，形成第一层预制膜；步骤2，使用较低铜含量CIGS四元靶材在第一层预制膜上再次溅射沉积CIGS薄膜，形成第二层预制膜；步骤3，将双层预置膜置于含硒气氛中退火处理。本发明所述方法采用两种不同铜含量的CIGS四元靶材先后溅射，形成下层铜含量多，上层铜含量少的CIGS双层预置膜结构，并且控制CIGS薄膜处于整体贫铜(铜含量小于25at％)状态，然后在含硒气氛中退火，利用预制层铜元素梯度来促进铜元素扩散，改善了CIGS光吸收层薄膜的结晶性。
Description
技术领域
本发明属于薄膜太阳电池技术领域，主要涉及一种改善铜铟镓硒(CIGS)薄膜太阳能电池光吸收层结晶性的方法。
背景技术
能源危机和环境污染是当今全球所面临的两大基本问题。太阳能因其覆盖面积广，取之不尽的优良特性，使之成为解决能源危机的一种重要途径。CIGS薄膜太阳电池因为其材料光学带隙可调、抗辐射能力强、电池性能稳定、弱光性好等优点，使之成为薄膜太阳电池中最有发展前景的光伏材料之一。
近年来，使用铜铟镓硒四元靶材溅射成膜成为一种新的铜铟镓硒光吸收层的制备方法，由于预制膜里已经形成铜铟镓硒四元化合物，使用这种方式有可能不经历复杂的硒化反应既可形成性能良好的吸收层，极大简化电池制备工艺过程，并且使用这种方法也可以获得较高的光电转换效率【S.Rampino,N.Armani,F. Bissoli,M.Bronzoni,D.Calestani,M.Calicchio,N.Delmonte,E.Gilioli, E.Gombia,R.Mosca,L.Nasi,F.Pattini,A.Zappettini and M.Mazzer, 15％efficient Cu(In,Ga)Se2 solar cellsobtained by low-temperature pulsed electron deposition,Applied physicsletters.101(2012)132107-1-4.】，是一种较有发展前景的CIGS薄膜太阳电池制备技术。但是，通过CIGS四元靶制备的吸收层晶粒尺寸一般较小，通常只有0.6-0.8μm，很难达到共蒸法和金属预制膜+硒化法制备的晶粒尺寸。使用四元靶材直接溅射的膜层在溅射态时已经几乎全部是由CIGS相构成，因此膜层中各元素的化学活性受到较大限制，特别是铜元素，从而对退火处理后铜铟镓硒膜层的结晶性带来了不利影响。较差的 CIGS光吸收层结晶性能会影响电池光电转换效率，也造成这种工艺的推广使用受到限制。
发明内容
针对上述问题，本发明的目的在于提供一种改善铜铟镓硒(CIGS)薄膜太阳能电池光吸收层结晶性的方法。所述方法采用两种不同铜含量的CIGS四元靶材先后溅射，形成下层铜含量多，上层铜含量少的CIGS薄膜结构，并且控制CIGS 薄膜处于整体贫铜(铜含量小于25at％)状态，然后在含硒气氛中退火，利用预制层铜元素梯度来促进铜元素扩散，改善CIGS光吸收层的结晶性，从而有助于提高CIGS薄膜太阳电池的光电转换效率。为了达到以上目的，本发明采用的技术方案是：
一种改善铜铟镓硒(CIGS)薄膜太阳能电池光吸收层结晶性的方法，其特征在于，所述方法包含如下步骤：
步骤1，采用磁控溅射法在钠钙玻璃衬底上制备Mo层。
步骤2，使用较高铜含量的CIGS四元靶材，采用磁控溅射法在Mo层上沉积 CIGS薄膜，形成第一层预制膜。
步骤3，使用较低铜含量的CIGS四元靶材，采用磁控溅射法在第一层预制膜上再次沉积CIGS薄膜，形成第二层预制膜。
步骤4，将CIGS双层预置膜置于含硒气氛中退火处理。
上述的一种改善铜铟镓硒(CIGS)薄膜太阳能电池光吸收层结晶性的方法，其特征在于，所述CIGS四元靶材由铜、铟、镓、硒四种元素构成，所述较高铜含量为CIGS靶材中铜元素原子百分比含量为25～30at％，所述较低铜含量为CIGS 靶材中铜元素原子百分比含量为15～25at％。
上述的一种改善铜铟镓硒(CIGS)薄膜太阳能电池光吸收层结晶性的方法，其特征在于，所述CIGS双层预制膜总厚度为200～2000nm，整体铜含量小于 25at％，处于贫铜状态。
上述的一种改善铜铟镓硒(CIGS)薄膜太阳能电池光吸收层结晶性的方法，其特征在于，所述含硒气氛为在退火时通入Ar气与H2Se气体或者固态硒蒸气的混合气体。
上述的一种改善铜铟镓硒(CIGS)薄膜太阳能电池光吸收层结晶性的方法，其特征在于，所述退火处理温度为520～600℃，保温时间为15～120min。
本发明的有益结果是：本发明采用不同铜含量的两种CIGS四元靶材进行依次溅射，形成下层铜含量多，上层铜含量少的具有一定铜含量梯度的双层预制膜，由于下层铜含量>25％，处于富铜状态，从而在退火过程中促进了晶粒长大，进而改善了Mo/CIGS界面性能；由于吸收层薄膜整体贫铜，从而减少了富铜相的形成及其对电池效率的损害，达到改善CIGS光吸收层薄膜结晶性能，进而提升CIGS 电池效率的目的。
附图说明
图1为本发明所述采用CIGS四元靶溅射沉积的双层预制膜结构示意图。
其中，1-玻璃衬底，2-Mo层，3-较高铜含量的第一层预制膜，4-较低铜含量的第二层预制膜。
图2为本发明实施例1中退火后CIGS光吸收层薄膜截面形貌图。
具体实施方式
以下结合实施例和附图对本发明的技术方案作进一步地说明。
实施例1
(1)将钠钙玻璃衬底清洗干净之后采用磁控溅射法制备一层0.8μm厚的 Mo膜；
(2)使用铜含量为28at％的CIGS四元靶材，采用磁控溅射法在Mo层上沉积第一层预制膜，厚度为600nm；
(3)，使用铜含量为20at％的CIGS四元靶材，采用磁控溅射法在第一层预制膜上沉积第二次预置膜，厚度为600nm，从而形成如图1所示的双层预制膜结构，预制膜总厚度为1200nm，整体铜含量为24at％，处于贫铜状态。
(4)将上述CIGS双层预制膜放入退火炉中，抽真空后通入Ar+H2Se混合气体，然后升温至550℃进行退火处理，保温时间为10min。退火后的CIGS光吸收层薄膜截面形貌如图2所示。
以上所述是本发明的优选实例，并非因此局限了本发明的权利范围。凡是有不脱离本发明范围和实质性修改、替换和改进，应属于本发明专利的权利范围之内。
Claims (3)
1.一种改善铜铟镓硒CIGS薄膜太阳能电池光吸收层结晶性的方法，其特征在于，所述方法包含如下步骤：
步骤1，采用磁控溅射法在钠钙玻璃衬底上制备Mo层；
步骤2，使用较高铜含量的CIGS四元靶材，采用磁控溅射法在Mo层上沉积CIGS薄膜，形成第一层预制膜；
步骤3，使用较低铜含量的CIGS四元靶材，采用磁控溅射法在第一层预制膜上再次沉积CIGS薄膜，形成第二层预制膜；
步骤4，将CIGS双层预制膜置于含硒气氛中退火处理；
所述CIGS四元靶材由铜、铟、镓、硒四种元素构成，所述较高铜含量为CIGS靶材中铜元素原子百分比含量为25～30at％，所述较低铜含量为CIGS靶材中铜元素原子百分比含量为15～25at％；
所述CIGS双层预制膜总厚度为200～2000nm，整体铜含量小于25at％，处于贫铜状态。
2.根据权利要求1所述的一种改善铜铟镓硒CIGS薄膜太阳能电池光吸收层结晶性的方法，其特征在于，所述含硒气氛为在退火时通入Ar气与H2Se气体或者固态硒蒸气的混合气体。
3.根据权利要求1所述的一种改善铜铟镓硒CIGS薄膜太阳能电池光吸收层结晶性的方法，其特征在于，所述退火处理温度为520～600℃，保温时间为15～120min。
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