CN105762208B - 一种正向失配四结级联砷化镓太阳电池及其制备方法 - Google Patents
一种正向失配四结级联砷化镓太阳电池及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种正向失配四结级联砷化镓太阳电池，包括顶电池、子电池和底电池，顶电池上为接触层，顶电池和底电池之间依次为第一隧穿结、第二子电池、第二隧穿结、第三子电池、渐变缓冲层、第三隧穿结、缓冲层和成核层，底电池下为衬底。本发明中，顶电池、子电池、子电池和底电池的电流失配小，减小了光电转换过程中的热致损失，提高了电池效率；在子电池和第三隧穿结之间采用一个渐变缓冲层，避免了其它类型四结以上太阳电池采用两个或两个以上渐变缓冲层时较为严重的位错问题；本发明的方法不需要其他技术路线的剥离、金属键合或半导体键合等复杂工艺，电池性能的一致性和均匀性好，生产效率高，易于实现规模生产。
Description
技术领域
本发明属于砷化镓太阳电池结构技术领域，尤其是一种正向失配四结级联砷化镓太阳电池及其制备方法。
背景技术
砷化镓太阳电池的发展是从上世纪50年代开始的，至今经过了从单结到多结叠层结构的几个发展阶段，其发展速度日益加快，效率也不断提高，转化率可达30％以上。目前设计多结级联砷化镓电池的主要思路是采用晶格匹配的设计，即优先考虑多结电池的晶格匹配而将光电流匹配放在次要的位置，德国Azurspace和美国Emcore公司的正向匹配三结级联GaInP/GaAs/Ge太阳电池在AM0光谱下的转换效率都接近30.0％，但此结构电池的光电流密度通常受限于顶电池，底电池上冗余的光电流密度不能被有效的利用，使其不能实现全光谱的吸收利用；同时三结级联砷化镓太阳电池有相当一部分大于对应子电池禁带宽度的能量以热能形式损失，因此要进一步提高多结砷化镓太阳电池的转化效率，必须采用四结或者四结以上级联来提高对太阳光谱的利用且进一步减少热损失。
为了有效的实现太阳电池的对全光谱的吸收利用，日本SHARP、美国NERL和德国Fraunhefor ISE等公司和研究机构采用晶格失配的设计，即优先考虑多结电池的光电流匹配而将晶格匹配放在次要的位置，研究了反向生长和半导体键合等技术。日本SHARP将倒置方法生长的GaInAs/GaAs/GaInP电池的转化效率提高到37.9％(AM1.5G)，法国Soitec和德国Fraunhofer ISE等机构合作，采用Wafer bonding的方法制备的四结砷化镓太阳电池实现了46％(508×)的转换效率，美国Boeing Spectrolab采用键合技术制备的五结砷化镓太阳电池实现了35.8％(AM0)和38.8％(AM1.5G)的转换效率。
晶片键合的四结或者五结砷化镓太阳电池能够保证各个子电池的外延质量，但是仍然存在欧姆损耗和光学损失的问题，同时晶片键合需要GaAs和InP两个衬底，制作成本很高。反向生长的多结级联砷化镓太阳电池能够保证GaInP和GaAs子电池的外延质量，同时通过生长渐变缓冲层减少晶格失配带来的位错，但是渐变缓冲层并不能彻底消除位错对电池性能的影响，对于有两个以上渐变缓冲层的四结以上太阳电池，位错对电池性能的影响会加剧。
这些非标准的器件工艺和标准的GaInP/GaAs/Ge三结砷化镓太阳电池外延工艺较难兼容，影响电池性能的一致性和均匀性，并降低了砷化镓太阳电池的生产效率，增加了电池的制作成本，在可行性方面不容易实现，距离实际应用还有一定的距离。
发明内容
本发明的目的在于克服现有技术的不足，提供一种成本合理、工艺简单、性能优异的一种正向失配四结级联砷化镓太阳电池。
本发明采取的技术方案是：
一种正向失配四结级联砷化镓太阳电池，包括顶电池、子电池和底电池，其特征在于：顶电池上为接触层，顶电池和底电池之间依次为第一隧穿结、第二子电池、第二隧穿结、第三子电池、渐变缓冲层、第三隧穿结、缓冲层和成核层，底电池下为衬底。
而且，所述顶电池为AlGaInP或GaxIn1-xP顶电池，上下两个子电池为AlGaInAs子电池和GaInAs子电池，缓冲层为GaInAs缓冲层，成核层为GaInP成核层，底电池为Ge底电池，衬底为Ge衬底，顶电池和两个子电池三者晶格匹配，底电池与所述顶电池和两个子电池晶格失配。
而且，所述顶电池、子电池、子电池和底电池的禁带宽度优选为1.9eV、1.4eV、1.1eV和0.67eV。
而且，所述第一隧穿结、第二隧穿结和第三隧穿结均包含上层和下层，其中的上层可以是AlGaAs/GaInP，或者是AlGaAs/GaAs；其中的下层(势垒层)可以是Al(Ga)InP，或者是AlGaAs。
而且，
所述第一隧穿结包括n型掺杂的GaInP层和p型掺杂的AlGaAs层；所述GaInP层的掺杂浓度优选为1×1019～1×1020cm-3、厚度0.01～0.02μm；所述AlGaAs层的掺杂浓度优选为1×1019～1×1020cm-3、厚度0.01～0.02μm；
所述第二隧穿结包括n型掺杂的GaAs层和p型掺杂的AlGaAs层；所述GaAs层的掺杂浓度优选为1×1019～1×1020cm-3、厚度0.01～0.02μm；所述AlGaAs层的掺杂浓度优选为1×1019～1×1020cm-3、厚度0.01～0.02μm；
所述第三隧穿结包括n型掺杂的GaAs层和p型掺杂的AlGaAs层；所述GaAs层的掺杂浓度优选为1×1019～1×1020cm-3、厚度0.01～0.02μm；所述AlGaAs层的掺杂浓度优选为1×1019～1×1020cm-3、厚度0.01～0.02μm。
而且，所述渐变缓冲层采用In组分线性渐进和/或步进的方法将Ge底电池和GaInAs子电池串联，包括GaxIn1-xAs，其中Ga的组分由1.00变化至0.77，带隙小于1.1eV。
而且，所述顶电池、子电池均包括窗口层、发射区、基区和背场层。
而且，所述太阳电池使用MOCVD法或者MBE法依次生长制得成品。
而且，所述MOCVD法，Ge层的N型掺杂原子为As或P，其余层N型掺杂原子为Si、Se、S或Te，P型掺杂原子为Zn、Mg或C。
而且，所述MBE法中，Ge层的N型掺杂原子为As或P，其余层N型掺杂原子为Si、Se、S、Sn或Te，P型掺杂原子为Be、Mg或C。
本发明的优点和积极效果是：
本发明中，AlGaInP或GaInP顶电池、AlGaInAs子电池、GaInAs子电池和Ge底电池的禁带宽度分别为1.9eV，1.4eV，1.1eV，0.67eV，各个电池的电流失配小，减小了光电转换过程中的热致损失，提高了电池效率；在GaInAs子电池和第三隧穿结之间采用一个渐变缓冲层，避免了其它类型四结以上太阳电池采用两个或两个以上渐变缓冲层时较为严重的位错问题；最下方的衬底为Ge衬底，降低了成本；采用本发明的方法生产太阳电池时，技术路线大概4小时，不需要其他技术路线的剥离、金属键合或半导体键合等复杂工艺，电池性能的一致性和均匀性好，生产效率高，易于实现规模生产。
附图说明
图1为本发明太阳电池的结构示意图；
图2为本发明渐变缓冲层的显微镜图像；
图3为采用第二层渐变缓冲层的显微镜图像。
具体实施方式
下面结合实施例，对本发明进一步说明，下述实施例是说明性的，不是限定性的，不能以下述实施例来限定本发明的保护范围。
一种正向失配四结级联砷化镓太阳电池，如图1所示，包括顶电池、子电池和底电池，本发明的创新在于：顶电池上为接触层，顶电池和底电池之间依次为第一隧穿结、子电池、第二隧穿结、子电池、渐变缓冲层、第三隧穿结、缓冲层和成核层，底电池下为衬底。
本实施例中，所述顶电池为AlGaInP或GaInP顶电池，上下两个子电池为AlGaInAs子电池和GaInAs子电池，缓冲层为GaInAs缓冲层，成核层为GaInP成核层，底电池为Ge底电池，衬底为Ge衬底，顶电池和两个子电池三者晶格匹配，底电池与所述顶电池和两个子电池晶格失配。
所述顶电池(AlGaInP或GaInP)、子电池(AlGaInAs)、子电池(GaInAs)和Ge底电池的禁带宽度分别为1.9eV、1.4eV、1.1eV和0.67eV。所述第一隧穿结、第二隧穿结和第三隧穿结包含依次设置的AlGaAs层(或GaInP、GaAs层)和Al(Ga)InP(或AlGaAs)势垒层。
上述各个隧穿结具体结构是：
所述第一隧穿结包括n型掺杂的GaInP层和p型掺杂的AlGaAs层；所述GaInP层的掺杂浓度为1×1020cm-3、厚度0.01～0.02μm；所述AlGaAs层的掺杂浓度为1×1020cm-3、厚度0.01～0.02μm；
所述第二隧穿结包括n型掺杂的GaAs层和p型掺杂的AlGaAs层；所述GaAs层的掺杂浓度为1×1020cm-3、厚度0.01～0.02μm；所述AlGaAs层的掺杂浓度为1×1020cm-3、厚度0.01～0.02μm；
所述第三隧穿结包括n型掺杂的GaAs层和p型掺杂的AlGaAs层；所述GaAs层的掺杂浓度为1×1020cm-3、厚度0.01～0.02μm；所述AlGaAs层的掺杂浓度为1×1020cm-3、厚度0.01～0.02μm。
所述渐变缓冲层采用In组分线性渐进和/或步进的方法将Ge底电池和GaInAs子电池串联，包括GaxIn1-xAs，其中Ga的组分(X)由1.00变化至0.77，带隙小于1.1eV。所述AlGaInP(或GaInP)顶电池、AlGaInAs子电池和GaInAs子电池均包括窗口层、发射区、基区和背场层。
上述正向失配四结级联砷化镓太阳电池可以使用MOCVD法或者MBE法依次生长制得成品。
MOCVD法，Ge层的N型掺杂原子为As或P，其余层N型掺杂原子为Si、Se、S或Te，P型掺杂原子为Zn、Mg或C。
MBE法中，Ge层的N型掺杂原子为As或P，其余层N型掺杂原子为Si、Se、S、Sn或Te，P型掺杂原子为Be、Mg或C。
以MOCVD法(Metal Organic Chemical Vapor Deposition，金属有机化合物化学气相沉淀)为例，在p形Ge衬底上依次外延生长Ge底电池、GaInP成核层、GaInAs缓冲层、第三隧穿结、GaxIn1-xAs渐变缓冲层、GaInAs子电池、第二隧穿结、AlGaInAs子电池、第一隧穿结和AlGaInP或GaInP顶电池、以及n型重掺杂的GaAs接触层。
本发明中，顶电池(AlGaInP或GaInP)、子电池(AlGaInAs)、子电池(GaInAs)和Ge底电池的禁带宽度分别为1.9eV、1.4eV、1.1eV和0.67eV，各个电池的电流失配小，减小了光电转换过程中的热致损失，提高了电池效率。
在GaInAs子电池和第三隧穿结之间采用一个渐变缓冲层，避免了其它类型四结以上太阳电池采用两个或两个以上渐变缓冲层时较为严重的位错问题；具体比较见图2、3，采用图2所示的一层渐变缓冲层后，其表面的显微镜图像显示位错较少，而图3的采用两层渐变缓冲层后，表面形貌变差，具有较多的穿透性位错。
正向晶格失配四结砷化镓太阳电池在完成外延生长后不需要其他技术路线的剥离、金属键合或半导体键合等复杂工艺，技术路线大概4个小时，其它反向生长的的技术路线至少6个小时，还需要衬底剥离，键合等额外的时间。本发明电池性能的一致性和均匀性好，生产效率高，易于实现规模生产。
Claims (1)
1.一种正向失配四结级联砷化镓太阳电池，包括顶电池、子电池和底电池，其特征在于：顶电池上为接触层，顶电池和底电池之间依次为第一隧穿结、第二子电池、第二隧穿结、第三子电池、渐变缓冲层、第三隧穿结、缓冲层和成核层，底电池下为衬底；
所述顶电池为AlGaInP或GaxIn1-xP顶电池，上下两个子电池为AlGaInAs子电池和GaInAs子电池，缓冲层为GaInAs缓冲层，成核层为GaInP成核层，底电池为Ge底电池，衬底为Ge衬底，顶电池和两个子电池三者晶格匹配，底电池与所述顶电池和两个子电池晶格失配；
所述顶电池、子电池、子电池和底电池的禁带宽度为1.9eV、1.4eV、1.1eV和0.67eV；
所述第一隧穿结、第二隧穿结和第三隧穿结均包含上层和下层，其中的上层可以是AlGaAs/GaInP，或者是AlGaAs/GaAs；其中的下层(势垒层)可以是Al(Ga)InP，或者是AlGaAs；
所述第一隧穿结包括n型掺杂的GaInP层和p型掺杂的AlGaAs层；所述GaInP层的掺杂浓度为1×1019～1×1020cm-3、厚度0.01～0.02μm；所述AlGaAs层的掺杂浓度为1×1019～1×1020cm-3、厚度0.01～0.02μm；
所述第二隧穿结包括n型掺杂的GaAs层和p型掺杂的AlGaAs层；所述GaAs层的掺杂浓度为1×1019～1×1020cm-3、厚度0.01～0.02μm；所述AlGaAs层的掺杂浓度为1×1019～1×1020cm-3、厚度0.01～0.02μm；
所述第三隧穿结包括n型掺杂的GaAs层和p型掺杂的AlGaAs层；所述GaAs层的掺杂浓度为1×1019～1×1020cm-3、厚度0.01～0.02μm；所述AlGaAs层的掺杂浓度为1×1019～1×1020cm-3、厚度0.01～0.02μm；
所述渐变缓冲层采用In组分线性渐进和/或步进的方法将Ge底电池和GaInAs子电池串联，包括GaxIn1-xAs，其中Ga的组分由1.00变化至0.77，带隙小于1.1eV；
所述顶电池、子电池均包括窗口层、发射区、基区和背场层；
所述太阳电池使用MOCVD法或者MBE法依次生长制得成品；
所述MOCVD法，Ge层的N型掺杂原子为As或P，其余层N型掺杂原子为Si、Se、S或Te，P型掺杂原子为Zn、Mg或C；
所述MBE法中，Ge层的N型掺杂原子为As或P，其余层N型掺杂原子为Si、Se、S、Sn或Te，P型掺杂原子为Be、Mg或C。
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