CN111628031A - 一种基于石墨烯/半导体异质集成的多结太阳能电池 - Google Patents
一种基于石墨烯/半导体异质集成的多结太阳能电池 Download PDFInfo
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Abstract
本发明公开了一种基于石墨烯/半导体异质集成的多结太阳能电池，该太阳能电池利用石墨烯与半导体形成的异质结的发电性能，有效利用石墨烯与半导体中的热电子能量，提升每个单结太阳能电池的开路电压；将多个势垒高度不同的石墨烯基异质结单电池自下而上依次排布，可分别吸收不同光波段的太阳能，大幅提高太阳光的利用率，提高太阳能电池的光电转换效率。此外，与传统PN结太阳能电池相比，本发明的太阳能电池完全无需考虑晶格匹配问题，上层电池可直接键合在下层电池上的隧穿层上，制作工艺简单，转换效率更高，可大规模推广。
Description
技术领域
本发明涉及一种太阳能电池及其制造方法，尤其涉及一种基于石墨烯/半导体异质集成的多结太阳能电池及其制备方法，属于新型太阳能电池技术领域。
背景技术
太阳能的高效利用是人类发展的重要追求，目前常见的太阳能电池都是将太阳光转换为半导体中的空穴与电子，然后通过半导体PN器件的内建电场分离，从而输出电能。但在PN器件中，光激发产生的空穴与电子迅速驰豫到导带底和价带顶，因此不能有效利用高能光子能量，也就是热电子能量。由于半导体中强烈的电子-声子相互作用，热电子的驰豫时间非常短，因此也加大了热电子能量输出的难度。
石墨烯是单原子层碳六环构成的晶体材料，属于半金属，有较好的透光性，且石墨烯与半导体形成的异质器件有很快的载流子输运过程(可以小于50飞秒)，这使得石墨烯中产生的热电子能有效输运到半导体中，且半导体的热电子也能有效输运到石墨烯中，结果使得整个石墨烯/半导体异质器件对于高于半导体能隙的高能光子能量利用效率提升，从而提升太阳能电池的电流密度与转换效率。
但是以前的研究大部分集中在单结石墨烯/半导体异质太阳能电池，由于热电子不可避免的热电子驰豫过程，整体上石墨烯/半导体异质太阳能电池的转换效率还只能到20％左右。以前的研究也有将单结石墨烯/半导体异质太阳能电池与传统PN结进行键合实现高效太阳能电池，但由于传统PN结太阳能电池的效率还不够高且需要晶格匹配要求，多结太阳能电池难以超过5层，且不能充分发挥石墨烯/半导体太阳能电池的优势。因此本发明将不同能隙大小的半导体与石墨烯形成异质结，然后通过隧穿层将以上不同的石墨烯/半导体异质器件连接在一起构成高效太阳能电池，这样既能实现对太阳能光谱的精确匹配，又能实现对热电子的能量更高程度利用，从而获得高转换效率的太阳能电池。
发明内容
本发明的目的在于提供一种基于石墨烯/半导体异质集成的多结太阳能电池及其制备方法。
本发明采用的技术方案如下：
一种基于石墨烯/半导体异质集成的多结太阳能电池，包括设于底部的背面电极、设于顶部的正面电极、以及设于二者之间的N个叠置的石墨烯基异质结单电池，其中N≥2，在相邻的每两个单电池之间均设置有隧穿层；所述的石墨烯基异质结单电池为由下而上设置的石墨烯/半导体层，N个单电池中的半导体层均不相同，每个单电池均采用直接键合的方式设置在前一级单电池上的隧穿层上。上述太阳能电池结构也可完全倒置过来，背面电极为顶，正面电极为底。本发明中的背面电极与所接触的石墨烯之间、正面电极与所接触的半导体层之间应尽可能的形成欧姆接触。
上述技术方案中，进一步的，所述的石墨烯基异质结单电池中的半导体层选自Ge、GaAs、AlGaAs、GaInP、InGaN、GaInAs、GaInAsP、AlGaInP、CdTe、CZTS等。
进一步的，所述的N个叠置的单电池自下而上应按照各单电池中半导体层的禁带宽度从小向大排列。
进一步的，所述的石墨烯基异质结单电池中石墨烯的厚度为0.4纳米至10纳米。
进一步的，所述的隧穿层选自均选自ITO、或重掺杂的AlGaAs、GaInP、GaAs、GaInAs、GaInAsP、AlGaInP或CdTe等半导体中的一种或几种。
进一步的，所述的背面电极与所接触的石墨烯之间、所述的正面电极与所接触的半导体层之间均形成欧姆接触，选自金、钯、银、钛、铜、铂、铬、镍、ITO、FTO、AZO的一种或者几种的复合
本发明的多结异质太阳能电池利用石墨烯/半导体异质结单结太阳能电池的性能，有效利用石墨烯与半导体中的热电子能量，从而提高开路电压，同时利用不同半导体的帯隙不同，自下而上依次设置，可极大的扩大电池对太阳能光谱的吸收范围，减少太阳光能的损耗，从而显著提高太阳能电池的光电转换效率。此外，本发明可极大的简化太阳能电池的制备工艺，整个电池中无需考虑晶格匹配问题，各单电池均可直接键合至前一级单电池上的隧穿层上。本发明具有广泛的应用前景，值得推广。
附图说明
图1为基于石墨烯/半导体异质结的多结异质太阳能电池的结构示意图；
图2为石墨烯/Ge-石墨烯/GaAs-石墨烯/GaInP三结异质太阳能电池的结构示意图；
图3为石墨烯/Ge-石墨烯/GaAs-石墨烯/GaInP三结异质太阳能电池的IV曲线；
图4为石墨烯/GaAs-石墨烯/GaInP双结异质太阳能电池的IV曲线；
图5为石墨烯/GaInAs-石墨烯/GaInAsP-石墨烯/GaAs-石墨烯/CdTe四结异质太阳能电池的IV曲线；
图6为石墨烯/GaInAs-石墨烯/GaInAsP-石墨烯/GaAs-石墨烯/AlGaAs-石墨烯/InGaN五结异质太阳能电池的IV曲线；
具体实施方式
下面结合附图和具体实施例对本发明做进一步说明。
参照图1，本发明的基于石墨烯/半导体异质集成的多结异质太阳能电池，自下而上依次有正面电极1、石墨烯/半导体异质层2、第一隧穿层3、石墨烯/半导体异质层4、第二隧穿层5、石墨烯/半导体异质层6，……一直到石墨烯/半导体异质层n以及背面电极n+1。这里n结子电池采用不同禁带宽度的半导体，自上而下实现全光谱的太阳光捕获，减少光能损失从而提高太阳能转换效率。同时，n个石墨烯/半导体异质结子电池之间可以通过键合的方式耦合，无需半导体之间的晶格匹配，减少了子电池之间的隧穿损耗，这为超高效多结太阳能电池的设计提供了一种全新的思路与技术手段。
实施例1：
1)首先制备石墨烯/Ge太阳能子电池：在Ge衬底一面制作电极——Ti/Au电极，然后通过柔性高分子材料如聚甲基丙烯酸甲酯(PMMA)作为支撑层将单层石墨烯湿法转移至Ge的另一侧，然后用丙酮异丙醇去除PMMA，获得石墨烯/Ge异质结太阳能子电池；
2)在石墨烯/Ge太阳能电池上制作重掺杂的GaAs做第一隧穿层；
3)制备石墨烯/GaAs太阳能子电池：用PMMA作为支撑层将单层石墨烯湿法转移至GaAs衬底，然后用丙酮异丙醇去除PMMA，获得石墨烯/GaAs异质结太阳能子电池；
4)将石墨烯/GaAs太阳能子电池键合至第一隧穿层，在石墨烯/GaAs太阳能电池上制作重掺杂的GaAs做第二隧穿层；
5)制备石墨烯/GaInP太阳能子电池：采用湿法转移将石墨烯转移至GaInP上，再将石墨烯/GaInP异质结键合至第二隧穿层上。最后在石墨烯上制备电极Ag，得到基于石墨烯/半导体异质结的三结异质太阳能电池。
参照图2，本发明的基于石墨烯/半导体异质结的三结异质太阳能电池，自下而上依次有正电极1、石墨烯/Ge层2、第一隧穿层3、石墨烯/GaAs层4、第二隧穿层5、石墨烯/GaInP层6和背电极7。GaInP的帯隙宽度为1.88eV，而GaAs的帯隙宽度为1.424eV，Ge的帯隙宽度为0.661eV，三者自下而上以石墨烯/Ge、石墨烯/GaAs、石墨烯/GaInP序列排布，帯隙宽度依次增大，可对不同频率的太阳能分别吸收，从而显著提高太阳能电池的光电转换效率。基于石墨烯/半导体异质结的三结电池效率可达37.7％，其IV曲线如图3所示。
实施例2：
1)首先制备石墨烯/GaAs太阳能电池：在GaAs一面制作电极——Ag电极，然后通过柔性高分子材料如聚甲基丙烯酸甲酯(PMMA)作为支撑层将单层石墨烯湿法转移至GaAs的另一侧，然后用丙酮异丙醇去除PMMA，获得石墨烯/GaAs太阳能子电池；
2)在石墨烯/GaAs太阳能电池上制作重掺杂的GaAs第一隧穿层；
3)制备石墨烯/GaInP太阳能电池：用PMMA作为支撑层将单层石墨烯湿法转移至GaInP表面，然后用丙酮异丙醇去除PMMA，获得石墨烯/GaInP太阳能子电池；
4)将石墨烯/GaInP太阳能子电池键合至第一隧穿层，最后在石墨烯上制备电极Cu，得到基于石墨烯/半导体异质结的双结异质太阳能电池。基于石墨烯/半导体异质结的双结电池效率可达34.9％，IV曲线如图4所示。
实施例3：
1)首先制备石墨烯/GaInAs太阳能电池：在GaInAs衬底一面制作电极——Au电极，然后通过柔性高分子材料如聚甲基丙烯酸甲酯(PMMA)作为支撑层将单层石墨烯湿法转移至GaInAs的另一侧，然后用丙酮异丙醇去除PMMA，获得石墨烯/GaInAs太阳能子电池；
2)在石墨烯/GaInAs太阳能电池上制作重掺杂的AlGaAs第一隧穿层；
3)制备石墨烯/GaInAsP太阳能电池：用PMMA作为支撑层将单层石墨烯湿法转移至GaInAsP，然后用丙酮异丙醇去除PMMA，获得石墨烯/GaInAsP太阳能子电池；
4)将石墨烯/GaInAsP太阳能电池键合至第一隧穿层，在石墨烯/GaInAsP太阳能电池上制作重掺杂的AlGaAs做第二隧穿层；
5)制备石墨烯/GaAs太阳能电池：用PMMA作为支撑层将单层石墨烯湿法转移至GaAs太阳能电池，然后用丙酮异丙醇去除PMMA，获得石墨烯/GaAs太阳能子电池；
6)将石墨烯/GaAs太阳能电池键合至第二隧穿层，在石墨烯/GaAs太阳能电池上制作重掺杂的AlGaAs做第三隧穿层；
7)制备石墨烯/CdTe太阳能电池：用PMMA作为支撑层将单层石墨烯湿法转移至CdTe表面，然后用丙酮异丙醇去除PMMA，获得石墨烯/CdTe太阳能子电池；
8)将石墨烯/CdTe太阳能子电池键合至第三隧穿层，最后在石墨烯上制备电极Au，得到基于石墨烯/半导体异质结的四结异质太阳能电池。基于石墨烯/半导体异质结的四结电池效率可达41.5％，IV曲线如图5所示。
实施例4：
1)首先制备石墨烯/GaInAs太阳能电池：在GaInAs衬底一面制作电极——Au电极，然后通过柔性高分子材料如聚甲基丙烯酸甲酯(PMMA)作为支撑层将单层石墨烯湿法转移至GaInAs的另一侧，然后用丙酮异丙醇去除PMMA，获得石墨烯/GaInAs太阳能子电池；
2)在石墨烯/GaInAs太阳能电池上制作重掺杂的AlGaAs第一隧穿层；
3)制备石墨烯/GaInAsP太阳能电池：用PMMA作为支撑层将单层石墨烯湿法转移至GaInAsP，然后用丙酮异丙醇去除PMMA，获得石墨烯/GaInAsP太阳能子电池；
4)将石墨烯/GaInAsP太阳能电池键合至第一隧穿层，在石墨烯/GaInAsP太阳能电池上制作重掺杂的AlGaAs做第二隧穿层；
5)制备石墨烯/GaAs太阳能电池：用PMMA作为支撑层将单层石墨烯湿法转移至GaAs太阳能电池，然后用丙酮异丙醇去除PMMA，获得石墨烯/GaAs太阳能子电池；
6)将石墨烯/GaAs太阳能电池键合至第二隧穿层，在石墨烯/GaAs太阳能电池上制作重掺杂的AlGaAs做第三隧穿层；
7)制备石墨烯/AlGaAs太阳能电池：用PMMA作为支撑层将单层石墨烯湿法转移至AlGaAs太阳能电池，然后用丙酮异丙醇去除PMMA，获得石墨烯/AlGaAs太阳能子电池；
8)将石墨烯/AlGaAs太阳能电池键合至第三隧穿层，在石墨烯/AlGaAs太阳能电池上制作重掺杂的AlGaAs做第四隧穿层；
9)制备石墨烯/InGaN太阳能电池：用PMMA作为支撑层将单层石墨烯湿法转移至InGaN表面，然后用丙酮异丙醇去除PMMA，获得石墨烯/InGaN太阳能子电池；
10)将石墨烯/InGaN太阳能子电池键合至第四隧穿层，最后在石墨烯上制备电极Au，得到基于石墨烯/半导体异质结的五结异质太阳能电池。基于石墨烯/半导体异质结的五结电池效率可达45.6％，IV曲线如图6所示。
本发明的基于石墨烯/半导体异质结的多结异质太阳能电池利用用石墨烯/半导体异质结费米能级可调的特点，结合异质结热电子的高效收集与利用，提升单结太阳能电池的性能。同时利用不同半导体的帯隙不同，自下而上依次设置，可极大的扩大电池对太阳能光谱的吸收范围，减少太阳光能的损耗，从而显著提高太阳能电池的光电转换效率。此外，本发明的太阳能电池中子电池间不需要晶格匹配，上层子电池可直接键合至下层子电池的隧穿层上。工艺简单，便于推广。
Claims (6)
1.一种基于石墨烯/半导体异质集成的多结太阳能电池，其特征在于，包括设于底部的背面电极、设于顶部的正面电极、以及设于二者之间的N个叠置的石墨烯基异质结单电池，其中N≥2，在相邻的每两个单电池之间均设置有隧穿层；所述的石墨烯基异质结单电池为由下而上设置的石墨烯/半导体层，N个单电池中的半导体层均不相同，每个单电池均采用直接键合的方式设置在前一级单电池上的隧穿层上；上述太阳能电池可倒置。
2.根据权利要求1所述的基于石墨烯/半导体异质集成的多结太阳能电池，所述的石墨烯基异质结单电池中的半导体层选自Ge、GaAs、AlGaAs、GaInP、InGaN、GaInAs、GaInAsP、AlGaInP、CdTe、CZTS。
3.根据权利要求1所述的基于石墨烯/半导体异质集成的多结太阳能电池，其特征在于，所述的N个叠置的单电池自下而上应按照各单电池中半导体层的禁带宽度从小向大排列。
4.根据权利要求1所述的基于石墨烯/半导体异质集成的多结太阳能电池，其特征在于，所述的石墨烯基异质结单电池中石墨烯的厚度为0.4纳米至10纳米。
5.根据权利要求1所述的基于石墨烯/半导体异质集成的多结太阳能电池，其特征在于，所述的隧穿层选自均选自ITO、或重掺杂的AlGaAs、GaInP、GaAs、GaInAs、GaInAsP、AlGaInP或CdTe等半导体中的一种或几种。
6.根据权利要求1所述的基于石墨烯/半导体异质集成的多结太阳能电池，其特征在于，所述的背面电极与所接触的石墨烯之间、所述的正面电极与所接触的半导体层之间均形成欧姆接触，选自金、钯、银、钛、铜、铂、铬、镍、ITO、FTO、AZO的一种或者几种的复合。
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