CN108321216A - 一种可调光学带隙的氧锌镁材料、制备方法及太阳能电池 - Google Patents

一种可调光学带隙的氧锌镁材料、制备方法及太阳能电池 Download PDF

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Publication number
CN108321216A
CN108321216A CN201810090928.1A CN201810090928A CN108321216A CN 108321216 A CN108321216 A CN 108321216A CN 201810090928 A CN201810090928 A CN 201810090928A CN 108321216 A CN108321216 A CN 108321216A
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China
Prior art keywords
band gap
elements
zinc
layer
optical band
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CN201810090928.1A
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郭逦达
王磊
陈涛
李新连
杨立红
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Beijing Apollo Ding Rong Solar Technology Co Ltd
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Beijing Apollo Ding Rong Solar Technology Co Ltd
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Priority to CN201810090928.1A priority Critical patent/CN108321216A/zh
Priority to US16/094,958 priority patent/US20210234053A1/en
Priority to PCT/CN2018/090297 priority patent/WO2019148731A1/zh
Priority to EP18731952.0A priority patent/EP3547373A1/en
Publication of CN108321216A publication Critical patent/CN108321216A/zh
Pending legal-status Critical Current

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Abstract

本发明涉及一种可调光学带隙的氧锌镁材料、制备方法及太阳能电池，氧锌镁材料为光学带隙渐变的复合材料，包括两层或两层以上的复合薄膜层；每层复合薄膜层均由Zn元素与Mg元素按设定的原子比制备而成。本技术方案通过调节Zn/Mg的原子比，制备多层组份不同的复合薄膜，而非单一组份的单层薄膜；多层组份不同的复合薄膜，可实现最终制成薄膜光学带隙的连续调控；并且可以形成光学带隙渐变结构，具备此结构的电池将具有较高的开路电压、较好的填充因子和转换效率。

Description

一种可调光学带隙的氧锌镁材料、制备方法及太阳能电池
技术领域
本发明属于光学技术领域，特别是指一种可调光学带隙的氧锌镁材料、制备方法及太阳能电池。
背景技术
在传统的铜铟镓硒(CIGS)薄膜太阳能电池中，设置有缓冲层，缓冲层的主要作用是与吸收层形成pn结，用以作为薄膜太阳能电池的工作区，可以将光能转换成电能。
为了能与吸收层形成良好的pn结，缓冲层与吸收层间必须具有良好的能带匹配，以获得最大的开路电压。现有技术中，使用CdS作为缓冲层，但是Cd是有毒元素，对环境会产生危害，而且，CdS的禁带宽度在2.4-2.5eV，会吸收太阳光谱中350-550nm的高能光子，导致光电流的损失，因此，现无Cd缓冲层材料成为CIGS电池研究的一大热点，现主要集中在Zn(O,S)、(Zn,Mg)O及(Zn,Sn)Oy方面。
现已经有技术采用原子层沉积法(ALD)制备(Zn,Mg)O薄膜作为缓冲层。ALD的优点是可在纳米级别精确控制薄膜厚度；可保证大面积成膜均匀性；实现低温下薄膜生长；适用于各种形状的衬底。(Zn,Mg)O薄膜具有较大的禁带宽度，以使可见光透过缓冲层并到达吸收层，增加太阳能电池量子效率。
如图1所示，为现有技术(Zn,Mg)O光学带隙材料表，通过控制Mg：Zn比值，操控(Zn,Mg)O的光学带隙，但其只制备出单一光学带隙的材料，并没有制备出带隙渐变的(Zn,Mg)O材料；并且图1中的光学带隙无法连续调节，在其他实验条件不变的情况下，只能每个比例对应一种带隙。
发明内容
本发明的目的是提供一种可调光学带隙的氧锌镁材料、制备方法及太阳能电池，以解决现有技术采用原子层沉积法制备(Zn,Mg)O缓冲层，当制备某个Zn/Mg原子比的单层薄膜材料时，该比值只能是整数，因而所制备材料的光学带隙也是根据比例一一对应，无法实现对带隙的连续调控。
本发明是通过以下技术方案实现的：
一种可调光学带隙的氧锌镁材料，所述氧锌镁材料为光学带隙渐变的复合材料，包括两层或两层以上的复合薄膜层；每层所述复合薄膜层均由Zn元素与Mg元素按设定的原子比制备而成；
且，任一层所述复合薄膜层中的Zn元素与Mg元素的原子比均与其它所述复合薄膜层中的Zn元素与Mg元素的原子比不同。
所述Zn元素与Mg元素设定的原子比范围为1：1至20：1。
沿着光子入射方向，自最上层的所述复合薄膜层向最下层的所述复合薄膜层延伸时，所述Zn元素与所述Mg元素的原子比逐渐增加，带隙逐渐减小。
所述Zn元素来源于含锌化合物。
所述含锌化合物为二乙基锌。
所述Mg元素来源于含镁化合物。
所述含镁化合物为二茂镁。
一种可调光学带隙的氧锌镁材料制备方法，用于制备上述任一项的可调光学带隙的氧锌镁材料，包括以下步骤：
1)将基底清洗干净；
2)使用三种前驱体源制备ZnMgO，二乙基锌为Zn元素来源，二茂镁为Mg元素来源，水为O元素来源；
3)将所述基底放置于样品托盘中，并放置于原子层沉积设备中；设定沉积温度，及按氧锌镁材料所包括的复合薄膜层中Zn元素与Mg元素设定的原子比为复合薄膜层的生长程序，进行沉积反应；
4)取出沉积有复合薄膜层的基底。
所述沉积温度为100℃至250℃。
一种太阳能电池，使用上述中任一项的可调光学带隙的氧锌镁材料作为缓冲层材料。
本发明的有益效果是：
本技术方案通过调节Zn/Mg的原子比，制备多层成分不同的复合薄膜，而非单一组份的单层薄膜；多层成分不同的复合薄膜，可实现最终制成薄膜光学带隙的连续调控；并且可以形成光学带隙渐变结构，具备此结构的电池将具有较高的开路电压(Voc)、较好的填充因子(FF)和转换效率。
附图说明
图1为本发明氧锌镁材料沿光子射入方向性能变化表；
图2为本发明另一实施例氧锌镁材料沿光子射入方向性能变化表；
图3为本发明氧锌镁材料截面示意图。
附图标记说明
1第一层复合薄膜层，2第二层复合薄膜层，3第三层复合薄膜层，4第四层复合薄膜层，5第五层复合薄膜层，6第六层复合薄膜层。
具体实施方式
以下通过实施例来详细说明本发明的技术方案，以下的实施例仅是示例性的，仅能用来解释和说明本发明的技术方案，而不能解释为是对本发明技术方案的限制。
本发明是指用于铜铟镓硒薄膜太阳能电池中的缓冲层材料，本申请的缓冲材料为氧锌镁材料，在本申请中的氧锌镁材料为光学带隙渐变的复合材料。
本申请的氧锌镁材料包括两层或两层以上的复合薄膜层，如图3所示为包括有六层复合薄膜层的氧锌镁材料，分别为第一层复合薄膜层1、第二层复合薄膜层2、第三层复合薄膜层3、第四层复合薄膜层4、第五层复合薄膜层5及第六层复合薄膜层6；并且在本申请的其它实施例中，复合薄膜层的层数根据实际需要确定。在本申请的多层复合薄膜层中，任何一层的复合薄膜层均按Zn元素与Mg元素按设定的原子比制备而成，即任何一层的复合薄膜层的组成均相同，不同的各组成的含量比例不同。
在本申请的技术方案中，Zn元素的来源为含锌化合物，优选为二乙基锌；Mg元素的来源为含镁化合物，优选为二茂镁。
在本申请的技术方案中，氧锌镁材料不论包括有多少层的复合薄膜层，每一层复合薄膜层中的Zn元素与Mg元素的原子比均不相同。
在本申请中，Zn元素与Mg元素设定的原子比范围为1：1至20：1，在本申请的这一范围之外的原子比并不是不能用于制备缓冲层材料，而是本申请的原子比范围属于最佳范围，超出此范围的氧锌镁材料所制备的缓冲层均不具有最佳效果。
在本申请的实施例中，如图1和图2所示，自最上层的复合薄膜层向最下层的复合薄膜层延伸时，Zn元素与Mg元素的原子比逐渐增大。当本申请的氧锌镁材料用于铜铟镓硒薄膜太阳能电池中时，最上层至最下层是沿光子的入射方向区分。
如图1和图2所示，沿着光子的入射方向，各复合薄膜层的光学带隙Eg是递减的,有利于吸收整个波长范围(E>Eg(CIGS))的光子能量,并且,折射率是递增的,可有效地减少光子反射,提高吸收效率。
本申请还提供一种调光学带隙的氧锌镁材料制备方法，用于制备上述任一项的可调光学带隙的氧锌镁材料，包括以下步骤：
1)将基底清洗干净，此处的基底清洗为现有技术，在此不进行详细的说明。
2)使用三种前驱体源制备ZnMgO，二乙基锌为Zn元素来源，二茂镁为Mg元素来源，水为O元素来源。
3)将洗静后的基底放置于样品托盘中，并放置于原子层沉积设备中。设定沉积温度，在本申请中，沉积温度一般设定在100℃至250℃范围内。
按氧锌镁材料所包括的复合薄膜层中Zn元素与Mg元素设定的原子比为复合薄膜层的生长程序，进行沉积反应；具体步骤为，手动启动原子层沉积设备，在此以氧锌镁材料包括三层复合薄膜层为例，参见图1所示，首先原子层沉积，设备向样品托盘上的基底喷射二乙基锌与水的蒸汽四次，在基底上反应沉积得到第一层锌原子(在厚度方向代指四个锌原子)，然后向第一层锌原子上喷射由二茂镁与水的蒸汽一次(在厚度方向代指一个镁原子)，以完成第一层的复合薄膜层的沉积，第一层的复合薄膜层的Zn元素与Mg元素的原子比为4：1。
然后再向第一层的复合薄膜层上喷射二乙基锌与水的蒸汽六次，以沉积第二层锌原子，同样，再喷射二茂镁与水的蒸汽一次以沉积第二层的镁原子，以完成第二层的复合薄膜层的沉积，第二层的复合薄膜层的Zn元素与Mg元素的原子比为6：1。
再向第二层的复合薄膜层上喷射二乙基锌与水的蒸汽九次，以沉积第三层锌原子，同样，再喷射二茂镁与水的蒸汽一次以沉积第三层的镁原子，以完成第三层的复合薄膜层的沉积，第三层的复合薄膜层的Zn元素与Mg元素的原子比为9：1。
4)取出沉积有复合薄膜层的基底。
在本申请的其它实施例中，如图3所示，依次沉积第四层的复合薄膜层。
在本申请的技术方案中，各复合薄膜层中的Zn元素与Mg元素的原子比在1：1至20：1之间的任何值。
沉积完成，取出沉积有复合薄膜层的基底后，通过扫描电子显微镜(SEM)表征其形貌，通过EDS测其中Zn/Mg原子比，通过分光光度计测试样品透过率并由此计算样品的光学带隙。
本申请的可调光学带隙的氧锌镁材料用于太阳能电池的缓冲层材料。
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变形，本发明的范围由所附权利要求极其等同限定。

Claims (10)

1.一种可调光学带隙的氧锌镁材料，其特征在于，所述氧锌镁材料为光学带隙渐变的复合材料，包括两层或两层以上的复合薄膜层；每层所述复合薄膜层均由Zn元素与Mg元素按设定的原子比制备而成；
且，任一层所述复合薄膜层中的Zn元素与Mg元素的原子比均与其它所述复合薄膜层中的Zn元素与Mg元素的原子比不同。
2.根据权利要求1所述的可调光学带隙的氧锌镁材料，其特征在于，所述Zn元素与Mg元素设定的原子比范围为1：1至20：1。
3.根据权利要求1所述的可调光学带隙的氧锌镁材料，其特征在于，沿着光子入射方向，自最上层的所述复合薄膜层向最下层的所述复合薄膜层延伸时，所述Zn元素与所述Mg元素的原子比逐渐增加，带隙逐渐减小。
4.根据权利要求1所述的可调光学带隙的氧锌镁材料，其特征在于，所述Zn元素来源于含锌化合物。
5.根据权利要求4所述的可调光学带隙的氧锌镁材料，其特征在于，所述含锌化合物为二乙基锌。
6.根据权利要求1所述的可调光学带隙的氧锌镁材料，其特征在于，所述Mg元素来源于含镁化合物。
7.根据权利要求6所述的可调光学带隙的氧锌镁材料，其特征在于，所述含镁化合物为二茂镁。
8.一种可调光学带隙的氧锌镁材料制备方法，其特征在于，用于制备上述权利要求1至7中任一项的可调光学带隙的氧锌镁材料，包括以下步骤：
1)将基底清洗干净；
2)使用三种前驱体源制备ZnMgO，二乙基锌为Zn元素来源，二茂镁为Mg元素来源，水为O元素来源；
3)将所述基底放置于样品托盘中，并放置于原子层沉积设备中；设定沉积温度，及按氧锌镁材料所包括的复合薄膜层中Zn元素与Mg元素设定的原子比为复合薄膜层的生长程序，进行沉积反应；
4)取出沉积有复合薄膜层的基底。
9.根据权利要求8所述的可调光学带隙的氧锌镁材料制备方法，其特征在于，所述沉积温度为100℃至250℃。
10.一种太阳能电池，其特征在于，使用上述权利要求1至7中任一项的可调光学带隙的氧锌镁材料作为缓冲层材料。
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CN104025309A (zh) * 2011-11-11 2014-09-03 Lg伊诺特有限公司 太阳能电池及其制造方法
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CN110459630A (zh) * 2019-06-18 2019-11-15 北京铂阳顶荣光伏科技有限公司 薄膜太阳能电池及其制备方法

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