CN112582494B - 具有恰好四个子电池的单片的多结太阳能电池 - Google Patents

具有恰好四个子电池的单片的多结太阳能电池 Download PDF

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CN112582494B
CN112582494B CN202011019140.5A CN202011019140A CN112582494B CN 112582494 B CN112582494 B CN 112582494B CN 202011019140 A CN202011019140 A CN 202011019140A CN 112582494 B CN112582494 B CN 112582494B
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M·莫伊泽尔
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Abstract

具有恰好四个子电池的单片的多结太阳能电池，其中，四个子电池中的每个都具有一个发射极和一个基极，并且最上方的第一子电池具有由具有元素AlInP的化合物制成的层，该层的晶格常数a1在0.572nm至0.577nm之间，并且铟含量处于64％和75％之间，并且Al含量处于18％和32％之间，并且第三子电池具有由至少具有元素GaInAs的化合物制成的层，并且该层的晶格常数处于0.572nm和0.577nm之间，并且该层的铟含量大于17％，第二子电池包括由至少具有元素GaInAsP的化合物制成的层，其中，该层具有22％至33％之间的砷含量和52％至65％之间的铟含量，并且晶格常数a2处于0.572nm和0.577nm之间。

Description

具有恰好四个子电池的单片的多结太阳能电池
技术领域
本发明涉及一种单片的变质的四结太阳能电池。
背景技术
由文献《Wafer bonded four-junction GaInP/GaAs/GaInAsP/GaInAsconcentrator solar cells with 44.7％efficiency》，Dimroth等人，Progr.Photovolt：Res.Appl.2014；22：277-282已知对具有由GaInAsP制成的子电池的四结太阳能电池的制造。在所提及的文献中，从InP衬底出发，GaInAsP太阳能电池以大约1.12eV的能带隙晶格匹配地沉积。
在第二沉积中，在GaAs衬底上以反转的顺序制造具有较高的带隙的上部子电池。整个多结太阳能电池的形成通过两个外延晶片的直接的半导体键合、GaAs衬底的接下来的移除以及其他工艺步骤来进行。然而，制造过程非常复杂且成本密集。
由EP 2 960 950A1和EP 3 179 521A1已知具有GaInAsP子电池的另外的多结太阳能电池。由US 6 660 928B1和WO 2016/015467A1已知具有变质的缓冲层的Ge/InGaAs/InGaAsP/AlGaInP四结太阳能电池。
此外，由Mendorf的博士论文《 Charakterisierung von in GaxIn1-xAsyP1-y-Halbleiterheteroschichten im Raster-Transmissionselektronenmikroskop》已知化合物GaInAsP尤其具有显著的混溶隙
由此可以在GaInAsP中无法实现大范围的晶格常数和带隙——尤其在对关于如下高性能多结太阳能电池的制造的层质量有很高要求的情况下：所述高性能多结太阳能电池在AMO下具有高于32％的效率或者在集中的光下具有高于43％的效率。
虽然可以猜测，在较高的温度下混溶隙在外延上略微减小，但是已知在具有Ge子电池的多结电池中会发生Ge自动掺杂。然而，当在外延沉积中的温度升高时，所述自动掺杂导致显著的生产率问题(Ausbeuteproblem)。
耐辐射性的优化——尤其对于非常高的辐射剂量——是扩展航天太阳能电池的重要目标。除了提高开始效率或者寿命初期(英语beginning-of-life，BOL)的效率之外，目标也在于提高寿命末期(英语end-of-life，EOL)的效率。
此外，制造成本至关重要。目前的工业标准由晶格匹配的三结太阳能电池和变质的GaInP/GaInAs/Ge三结太阳能电池给出。
发明内容
在这些背景下，本发明的任务在于提供一种扩展现有技术的设备。
通过具有根据本发明的特征的多结太阳能电池来解决该任务。本发明的有利构型是有利的实施方式。
在该主题中，提供一种具有恰好四个子电池的单片的多结太阳能电池。
该多结太阳能电池具有最上方的第一子电池，所述第一子电池具有在1.85eV与2.07eV之间的范围内的第一带隙Eg1。
在第一子电池下方布置有布置在其下方的第二子电池，该第二子电池具有在1.41eV与1.53eV之间的范围内的第二带隙Eg2。
在第二子电池下方布置有布置在其下方的第三子电池，该第三子电池具有在1.04eV与1.18eV之间的范围内的第三带隙Eg3。
在第三子电池下方布置有最下方的第四子电池，其中，该第四子电池主要包含锗或由锗组成，并且该第四子电池具有在0.65eV与0.68eV之间的带隙。
在第三子电池与第四子电池之间构成有变质的缓冲层，其中，该变质的缓冲层具有至少三个层的序列，并且晶格常数在层的所述序列的情况下朝第三子电池的方向逐层地增大。
四个子电池中的每个都具有一个发射极和一个基极。
最上方的第一子电池具有由至少具有元素AlInP的化合物制成的层。该层的厚度大于100nm，并且该层构造为发射极的一部分和/或基极的一部分和/或位于发射极和基极之间的空间电荷区(Raumladungszone)的一部分。该层的晶格常数a1在0.572nm与0.577nm之间。在III主族的元素方面，该层的铟含量处于64％与75％之间，并且该层的Al含量处于18％与32％之间。
第三子电池具有由至少具有元素GaInAs的化合物制成的层，其中，该层的厚度大于100nm，并且该层构造为发射极的一部分和/或基极的一部分和/或位于发射极和基极之间的空间电荷区的一部分。该层的晶格常数a3处于0.572nm与0.577nm之间，在III主族的元素方面，该层的铟含量大于17％。
第二子电池具有由至少具有元素GaInAsP的化合物制成的层，其中，该层的厚度大于100nm，并且该层构造为发射极的一部分和/或基极的一部分和/或位于发射极与基极之间的空间电荷区的一部分。在Ⅴ主族的元素方面，该层具有22％与33％之间的砷含量，并且在III主族的元素方面具有52％与65％之间的铟含量。晶格常数a2处于0.572nm与0.577nm之间并且与第三子电池的层的晶格常数相差小于0.3％或小于0.2％。
应当注意，太阳光总是首先穿过具有最大带隙的最上方的子电池。换句话说，太阳能电池堆叠首先借助最上方的子电池吸收光的短波部分。在此，光子首先流过第一子电池，然后流过第二子电池、第三子电池和第四子电池。在等效电路图中，多结太阳能电池的各个子电池串联连接——即具有最小电流的子电池进行限制地起作用。
还应注意，术语“发射极”和“基极”应理解为相应的子电池中的p掺杂层或n掺杂层，其中，发射极总是n掺杂的。
还应注意，在本发明中，同义地使用元素的化学缩写与完整术语。
研究已经惊喜地得出，GaInAsP可以在上述组成范围内借助MOVPE以出奇良好的质量沉积。由此克服如下偏见：GaInAsP在处于混溶隙内的上述组成范围内不能以太阳能电池所需的质量进行沉积。也表明，借助安装InGaAsP子电池可以改善耐辐射性并且由此改善所谓的EOL效率。
应当理解，所说明的砷含量尤其与V族原子的总含量有关。相应地，所说明的铟含量与III族原子的总含量有关。也就是说，在化合物Ga1-XInXAsYP1-Y中，铟含量为值X，砷含量为值Y，由此对于例如25％的砷含量得出Y值为0.25。
此外，在一种扩展方案中，在第三子电池与第四子电池之间布置有半导体镜。虽然本领域技术人员还知道布拉格镜的安装增加了多结太阳能电池的总厚度和四结电池的复杂性并且生产率(Ausbeute)趋于降低，但是惊喜地发现多结太阳能电池的耐辐射性增加。耐辐射性的增加(即效率的增加)尤其令人惊喜，因为已知尤其作为InGaAsP子电池的第三子电池已经特别耐辐射。此外，将半导体镜安装在第四子电池上方至少是有问题的，因为半导体镜的安装导致在第四子电池上的光入射减少。
在另一扩展方案中，第一子电池的层的晶格常数与第三子电池的层的晶格常数相差小于0.3％或小于0.2％。
在一种实施方式中，在四个子电池之间未构造有半导体键合。应当注意，借助所述术语“半导体键合(Halbleiterbond)”尤其包括以下情况：在太阳能电池堆叠的任意两个子电池之间也未构造有直接的半导体键合。即太阳能电池堆叠不是由如下两个子堆叠制成：所述两个子堆叠已经被分别沉积在不同的衬底上并接着通过半导体键合接合在一起。太阳能电池堆叠尤其不具有如在键合中可能出现的无定形的中间层。
在一种扩展方案中，第二子电池中层的厚度和第三子电池中层的厚度分别大于0.4μm或大于0.8μm。
在一种实施方式中，在第二子电池中，层的砷含量处于23％与33％之间，并且层的铟含量处于52％与63％之间。
在另一实施方式中，第二子电池中的层的砷含量处于24％与33％之间，并且层的铟含量处于52％与61％之间。
在一种扩展方案中，第二子电池的层至少部分地p掺杂以掺杂剂Zn或C或Mg，或者至少部分地n掺杂以掺杂剂Si或Te或Se。
在另一扩展方案中，第二子电池的层不仅构成n掺杂的发射极，而且构成p掺杂的基极。
在一种实施方式中，掺杂剂浓度至少在第二子电池的层的一部分上朝第三子电池的方向增大超过1×1017/cm3。
在另一实施方式中，第二子电池的层的至少一部分构成第二子电池的发射极的至少一部分，并且掺杂剂浓度在此小于5×1017/cm3。
在一种扩展方案中，第二子电池构造为所谓的均质子电池(Homo-Teilzelle)，或者所有子电池构造为均质子电池——即相应的子电池的发射极层和基极层在具有优选相同的化学计量的化合物中具有相同数量的元素。
在另一扩展方案中，子电池的最上层(在此即发射极层)构造为n层。优选地，发射极层总是在基极层上方。在一种扩展方案中，在发射极层与基极层之间尤其未构造有本征层。
在一种扩展方案中，在第二子电池的层上方并且在第一子电池下方布置有由至少具有元素GaInP的化合物制成的钝化层。换句话说，钝化层构造在第一子电池与第二子电池之间。
在另一扩展方案中，在第二子电池的层下方并且在变质的缓冲层上方布置有由至少具有元素GaInP的化合物制成的钝化层。
在一种实施方式中，第二子电池和/或其他子电池不具有多结量子阱(Quantentopf)结构。
附图说明
以下参照附图进一步阐述本发明。在此，以相同的名称标记相同类型的部分。所示的实施方式是极其示意性的——即距离以及横向和竖直延伸不成比例并且彼此之间不具有可推导的几何关系，除非另有说明。附图示出：
图1示出四结太阳能电池的第一实施方式的层结构；
图2示出四结太阳能电池的第二实施方式的层结构；
图3示出四结太阳能电池的第三实施方式的层结构；
图4示出四结太阳能电池的第四实施方式的层结构；
图5示出四结太阳能电池的第五实施方式的层结构。
具体实施方式
图1的图示示出四结太阳能电池的第一实施方式，该四结太阳能电池在位于下方的第二子电池SC2上具有最上方的第一子电池SC1。
在第一子电池SC1和第二子电池SC2之间构造有上部的隧道二极管OTD。
在第二子电池SC2下方布置有第三子电池SC3。在第二子电池SC2和第三子电池SC3之间构造有中部的隧道二极管MTD。
在第三子电池SC3下方布置有第四子电池SC4。在第三子电池SC3和第四子电池SC4之间构造有中部的隧道二极管MTD。
在第三子电池SC3和中部的隧道二极管MTD之间布置有变质的缓冲层MP。
图2的图示示出四结太阳能电池的第二实施方式。以下仅阐述与第一实施方式的区别。
在第三子电池SC3和第四子电池SC4之间构造有下部的隧道二极管UTD，其中，变质的缓冲层MP现在布置在下部的隧道二极管UTD与第四子电池之间。
图3的图示示出四结太阳能电池的第三实施方式。以下仅阐述与第二实施方式的区别。
在下部的隧道二极管UTD与变质的缓冲层MP之间布置有半导体镜HS。换句话说，在第三子电池SC3下方，首先构造有下部的隧道二极管UTD，然后构造有半导体镜HS，然后构造有变质的缓冲层MP，然后再构造有最下方的第四子电池SC4。
图4的图示示出四结太阳能电池的第四实施方式。以下仅阐述与第三实施方式的区别。
在第三子电池SC3下方，首先构造有半导体镜HS，然后构造有变质的缓冲层MP，然后构造有下部的隧道二极管UTD，然后再构造有最下方的第四子电池SC4，其中，所提及的层按所提及的顺序布置。
图5的图示示出四结太阳能电池的第五实施方式。以下仅阐述与第四实施方式的区别。
在第三子电池SC3下方，首先构造有半导体镜HS，然后构造有下部的隧道二极管UTD，然后构造有变质的缓冲层MP，然后再构造有最下方的第四子电池SC4，其中，所提及的层按所提及的顺序布置。

Claims (11)

1.一种单片的多结太阳能电池，所述多结太阳能电池具有恰好四个子电池，所述多结太阳能电池包括：
最上方的第一子电池(SC1)，所述第一子电池具有在1.85eV与2.07eV之间的范围内的第一带隙Eg1；
第二子电池(SC2)，所述第二子电池布置在所述第一子电池下方并且具有在1.41eV与1.53eV之间的范围内的第二带隙Eg2；
第三子电池(SC3)，所述第三子电池布置在所述第二子电池下方并且具有在1.04eV与1.18eV之间的范围内的第三带隙Eg3；
最下方的第四子电池(SC4)，其中，所述第四子电池(SC4)由锗组成并且具有在0.65eV与0.68eV之间的带隙；
变质的缓冲层(MP1)，所述变质的缓冲层构造在所述第三子电池(SC3)与所述第四子电池(SC4)之间，其中，所述变质的缓冲层(MP1)具有至少三个层的序列，并且晶格常数在所述层的序列的情况下朝所述第三子电池(SC3)的方向逐层地增大；
四个子电池(SC1，SC2，SC3，SC4)中的每个子电池都具有一个发射极和一个基极；
所述最上方的第一子电池(SC1)具有由至少具有元素Al和In和P的化合物构成的层，并且所述层的厚度大于100nm，并且所述层构造为所述发射极的一部分和/或所述基极的一部分和/或位于所述发射极与所述基极之间的空间电荷区的一部分，并且层(S1)的晶格常数a1在0.572nm与0.577nm之间，在III主族的元素方面，所述层(S1)的铟含量处于64％与75％之间，并且所述层(S1)的Al含量处于18％与32％之间；
所述第三子电池(SC3)具有由如下化合物构成的层：所述化合物至少具有元素Ga和In和As，并且所述层的厚度大于100nm，并且所述层构造为所述发射极的一部分和/或所述基极的一部分和/或位于所述发射极与所述基极之间的空间电荷区的一部分，并且层(S3)的晶格常数a3处于0.572nm与0.577nm之间，并且在III主族的元素方面，所述层的铟含量大于17％；
所述第二子电池(SC2)具有由如下化合物构成的层：所述化合物至少具有元素Ga和In和As和P，并且所述层的厚度大于100nm，并且所述层构造为所述发射极的一部分和/或所述基极的一部分和/或位于所述发射极与所述基极之间的空间电荷区的一部分，其中，在Ⅴ主族的元素方面，所述层具有22％与33％之间的砷含量并且在III主族的元素方面具有52％与65％之间的铟含量；
晶格常数a2处于0.572nm与0.577nm之间，并且所述晶格常数a2与所述第三子电池(SC3)的层的晶格常数相差小于0.3％或小于0.2％；
在所述第三子电池(SC3)与所述第四子电池(SC4)之间布置有半导体镜(HS)；
所述第二子电池(SC2)的层的至少一部分构成所述第二子电池(SC2)的发射极的至少一部分，并且具有小于5×1017/cm3的掺杂剂浓度。
2.根据权利要求1所述的多结太阳能电池，其特征在于，所述第一子电池(SC1)的层的晶格常数与所述第三子电池(SC3)的层的晶格常数相差小于0.3％或小于0.2％。
3.根据权利要求1或2所述的多结太阳能电池，其特征在于，在所述四个子电池(SC1，SC2，SC3，SC4)之间分别未构造有半导体键合。
4.根据权利要求1或2所述的多结太阳能电池，其特征在于，在所述第二子电池(SC2)中所述层的厚度和在所述第三子电池(SC3)中所述层的厚度分别大于0.4μm或大于0.8μm。
5.根据权利要求1或2所述的多结太阳能电池，其特征在于，在所述第二子电池(SC2)中，所述层的砷含量处于24％与33％之间，并且所述层的铟含量处于52％与61％之间。
6.根据权利要求1或2所述的多结太阳能电池，其特征在于，所述第二子电池(SC2)的层至少部分地p掺杂以掺杂剂Zn或C或Mg，或者至少部分地n掺杂以掺杂剂Si或Te或Se。
7.根据权利要求1或2所述的多结太阳能电池，其特征在于，所述第二子电池(SC2)的层不仅构成n掺杂的发射极，而且构成p掺杂的基极。
8.根据权利要求1或2所述的多结太阳能电池(MS)，其特征在于，所述掺杂剂浓度至少在所述第二子电池(SC2)的层的一部分上朝所述第三子电池(SC3)的方向增大超过1×1017/cm3。
9.根据权利要求1或2所述的多结太阳能电池，其特征在于，在所述第二子电池(SC2)的层上方并且在所述第一子电池(SC1)下方布置有由至少具有元素GaInP的化合物构成的钝化层。
10.根据权利要求1或2所述的多结太阳能电池，其特征在于，在所述第二子电池(SC2)的层下方并且在所述变质的缓冲层(MP)上方布置有由至少具有元素GaInP的化合物构成的钝化层。
11.根据权利要求1或2所述的多结太阳能电池，其特征在于，所述第二子电池(SC2)不具有多结量子阱结构。
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