CN113921645A - 单片的变质的多结太阳能电池 - Google Patents

单片的变质的多结太阳能电池 Download PDF

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CN113921645A
CN113921645A CN202110793599.9A CN202110793599A CN113921645A CN 113921645 A CN113921645 A CN 113921645A CN 202110793599 A CN202110793599 A CN 202110793599A CN 113921645 A CN113921645 A CN 113921645A
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M·莫伊泽尔
A·贝格
P·施罗特
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Abstract

一种单片的变质的多结太阳能电池，其包括第一III‑V族子电池和第二III‑V族子电池和第三III‑V族子电池和第四Ge子电池，其中，所述子电池以所说明的顺序彼此上下堆叠，并且所述第一子电池构造最上方的子电池，并且在所述第三子电池与所述第四子电池之间构造有变质缓冲层，并且所有子电池都分别具有n掺杂的发射极层和p掺杂的基极层，并且在所述第二子电池中发射极掺杂小于基极掺杂。

Description

单片的变质的多结太阳能电池
技术领域
本发明涉及一种单片的变质的多结太阳能电池。这种多结太阳能电池优选地在宇宙空间中或在陆地聚光光伏系统(CPV)中使用。在此，具有不同带隙的至少三个或更多的子电池借助隧道二极管彼此上下堆叠。
背景技术
具有由GaInAsP制成的子电池的四结太阳能电池的制造是从Dimroth等人在光伏会议，研究应用，2014年；22：277-282页中的文献《Wafer bonded four-junction GaInP/GaAs/GaInAsP/GaInAs concentrator solar cells with 44.7％efficiency》中已知的。在所提及的文献中，从InP衬底开始，将具有约1.12eV的能带隙的GaInAsP太阳能电池以晶格匹配的方式沉积。
在GaAs衬底上以相反的顺序在第二沉积中制造具有较高带隙的上方的子电池。整个多结太阳能电池的形成通过两个外延半导体晶片的直接半导体键合(Halbleiterbond)进行，伴随着随后去除GaAs衬底和进一步的工艺步骤。然而，制造工艺非常复杂且成本密集。
从EP 2 960 950 A1和EP 3 179 521 A1中已知具有InGaAsP子电池的其它多结太阳能电池。
此外，从US 2018 0226 528 A1、US 2017 0054 048 A1、DE 10 2018 203 509 A1和US 2020 0027 999 A1中以及从van Leest等人的《Recent progress of multi-junction solar cell development for CPV applications at AZUR Space》(第36届EU-PVSEC会议论文集，2019年9月11日，第586至589页，XP055672429)中已知具有变质缓冲层的正置生长的多结电池。
一种基于锗的键合式的多结太阳能电池是由
Figure BDA0003155292590000011
等人的《Development ofGermanium-Based Wafer-Bonded Four-Junction Solar Cells》(IEEE光伏杂志，IEEE，美国，第9卷，第6期，2019年9月11日，第1625至1630页，XP011755777)中已知的，其中，第二子电池包括具有低层厚的无序的、低n掺杂的GaInP层和薄的、p掺杂的AlGaInP层。
从Bauhuis等人的《Deep junction III-V solar cells with enhanced perfor-10mance》(Phys.Status Solidi A，第213卷，第8期，2016年3月7日，第2216至2222页，XP055743458)中已知一种单个薄膜太阳能电池，其中，该太阳能电池具有薄的、低掺杂的发射极层和厚的、较高掺杂的基极层。
耐辐射性的优化，尤其也对于非常高的辐射剂量，是宇宙航行太阳能电池的发展中的一个重要目标。除了提高初始寿命或寿命开始(beginning-of-life，BOL)效率之外，目标还在于提高寿命结束(end-of-life，EOL)效率。
此外，制造成本至关重要。当前时刻的工业标准是通过晶格匹配的三结太阳能电池和变质的GaInP/GaInAs/Ge三结太阳能电池给定的。
发明内容
在此背景下，本发明的任务包括说明一种扩展现有技术的设备。
该任务通过具有根据本发明的特征的单片的变质的多结太阳能电池解决。本发明的有利构型是优选的实施方式。
在本发明的主题中，提供包括第一III-V族子电池和第二III-V族子电池以及第三III-V族子电池和第四Ge子电池的单片的多结太阳能电池。
子电池以所说明的顺序彼此上下堆叠。
第一子电池构造最上方的子电池。
在第三子电池与第四子电池之间构造有变质缓冲层。
所有子电池都分别具有n掺杂的发射极层和p掺杂的基极层，其中，在第二子电池中，发射极掺杂小于基极掺杂。
应当注意，太阳光总是首先入射通过具有最大带隙的最上方的子电池。换言之，太阳能电池堆叠借助最上方的子电池首先吸收光的短波部分。带隙由第一子电池朝第四子电池降低，其中，第四子电池的带隙为约0.67eV。
因此，在当前情况下，光子首先流过第一子电池，随后流过第二子电池，随后流过第三子电池，最后流过第四子电池。优选地，分别在两个直接彼此相继的子电池之间构造有隧道二极管。
在等效电路图中，多结太阳能电池的各个子电池应理解为p/n二极管以及位于其间的隧道二极管作为串联连接。由此，具有最低电流的子电池起限制作用，换言之，各个子电池彼此之间进行电流匹配是有利的。
还应注意，术语发射极和基极理解为相应子电池中的n掺杂的层或p掺杂的层，换言之，发射极层和基极层。
在一种实施方式中，子电池的最上方的层(在当前情况下，即发射极层)分别构造为n层。由此，光在子电池中总是首先通过发射极层并且随后通过基极层。
优选地，发射极层总是位于基极层上方。特别地，在一种扩展方案中，在发射极层与基极层之间未构造有具有大于500nm的厚度的本征层。
优选地，第一子电池和/或第三子电池分别涉及同质电池(Homozelle)。第四子电池同样涉及同质子电池。在此，术语同质子电池理解为以下子电池：在该子电池中，发射极层具有与基极层相同化学计量的相同元素。
还应注意，在该术语下，元素的化学缩写与完整术语同义使用。
可以理解，特别地，所说明的砷含量是关于V族原子的总含量。相应地，所说明的铟含量是关于III族原子的总含量。这意味着，在化合物Ga1-XInXAsYP1-Y中，铟含量为X值，并且砷含量为Y值，并且由此针对例如25％的砷含量得出0.25的Y值。
一个优点是，所描述的设备以令人惊讶的方式在质子照射下显示出较少的退化(Degradation)。由于第二子电池的发射极比基极掺杂得更低，因此空间电荷区域延伸到发射极中比到基极中要强烈得多。
换言之，辐射下的效率的降低较少地降低，即参量EOL(寿命结束)与迄今为止的值相比有所增加。
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，尤其是包括：在多结太阳能电池的任意两个子电池之间未构造有直接的半导体键合。
由于多结太阳能电池堆叠状地由堆叠构造，因此由此可以理解，多结太阳能电池的堆叠不是由沉积在不同衬底上并且随后通过半导体键合接合在一起的两个子堆叠构造。特别地，太阳能电池堆叠不具有任何非晶的(amorphen)中间层，如其在键合中可能出现的那样。
此外还应注意，借助变质缓冲层，第四电池与第三电池之间的晶格常数差异得到补偿。在此，变质缓冲层由至少三个III-V族层组成。
在一种扩展方案中，在第二子电池的层上方和在第一子电池的下方布置有如下的钝化层：该钝化层由至少具有元素GaInP或至少具有元素AlInP的化合物构成。换言之，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，第一子电池的晶格常数与第三子电池的晶格常数相差小于0.3％或小于0.2％。换言之，第三子电池与第二子电池和第一子电池彼此晶格匹配。
在另一扩展方案中，在第二子电池的层下方和在变质缓冲层上方布置有如下的钝化层：该钝化层由至少具有元素GaInP或至少具有元素AlInP的化合物构成。
在一种实施方式中，第二子电池和/或其他子电池不具有多重量子阱结构。
在一种扩展方案中，第二子电池的发射极层和基极层分别包括InGaAsP或由InGaAsP组成。
在一种实施方式中，第二子电池构造为异质电池。优选地，第二子电池的发射极层包括InGa(As)P或由InGa(As)P组成。基极层包括InGaAsP或由InGaAsP组成。优选地，发射极层的砷含量比基极层的砷含量少至少5％，或者在一种替代的实施方式中，发射极层不含砷地构造。
优选地，发射极层由InGaP组成，并且基极层由InGaAsP组成，或者发射极层包括InGaP，并且基极层包括InGaAsP，其中，与基极层不同，发射极层分别不含砷。
令人惊讶地，关于在质子照射下电压的降低，有利地，空间电荷区域延展到更加耐辐射
Figure BDA0003155292590000041
的材料——在这种情况下是GaInP发射极层。这是通过发射极层的掺杂小于基极层的掺杂来实现的。
在一种扩展方案中，在第二子电池中，发射极层的铟含量位于53％与75％之间。
在另一扩展方案中，在第二子电池中，发射极层的厚度小于基极层的厚度。在一种替代的实施方式中，发射极层的厚度与基极层的厚度相同大小或基本相同大小，发射极层的厚度或大于基极层的厚度。
在一种实施方式中，在第二子电池中，发射极掺杂至多是基极层掺杂的三分之一或五分之一或八分之一。
尤其是在发射极层的方向上的区域中，基极层具有小于5·1017/cm3的掺杂剂浓度。
在另一扩展方案中，在第二子电池中，基极层至少部分地具有掺杂剂梯度。优选地，掺杂剂浓度从发射极层的附近的区域的小于5·1017/cm3的值在第三子电池的方向上增加到大于1·1018/cm3的值。
优选地，发射极掺杂的大小小于2·17/cm3或小于7·16/cm3，然而分别大于1·1016/cm3。
在一种扩展方案中，第二子电池的基极层至少部分地具有掺杂剂Zn或C或Mg。优选地，发射极层至少部分地具有掺杂剂Si或Te或Se或Ge。
在一种实施方式中，在第二子电池中，基极层的厚度大于100nm，其中，基极层的砷含量关于V主族元素位于22％与33％之间，且基极层的铟含量关于III主族元素位于52％与65％之间。在一种扩展方案中，基极层的晶格常数位于0.572nm与0.577nm之间。
在一种扩展方案中，第一子电池具有比第二子电池更大的带隙。第二子电池具有比第三子电池更大的带隙。第三子电池具有比第四子电池更大的带隙。
优选地，第一子电池具有在1.85eV与2.07eV之间的范围中的带隙，第二子电池具有在1.41eV与1.53eV之间的范围中的带隙，第三子电池具有在1.04eV与1.18eV之间的范围中的带隙。
在一种实施方式中，第一子电池具有由至少元素AlInP构成的化合物。铟含量关于III主族元素位于64％与75％之间，并且Al含量位于18％与32％之间。
在一种扩展方案中，第三子电池具有由至少元素InGaAs构成的化合物。铟含量关于III主族元素大于17％。
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。通过安装半导体镜，与没有半导体镜的基极层的厚度相比，基极层的厚度在50％与90％之间的范围内降低。
在一种实施方式中，第二子电池中基极层的厚度和第三子电池中基极层的厚度分别大于0.4μm或大于0.8μm。
在另一实施方式中，在第三子电池中，发射极层的掺杂大于、小于或等于基极层的掺杂。优选地，第一子电池中以及第四子电池中发射极层的掺杂大于基极层的掺杂。
在一种扩展方案中，在第一子电池和第四子电池中，发射极层的厚度小于基极层的厚度。优选地，第一子电池和第二子电池中发射极层的掺杂剂浓度大于5·1017/cm3。
在一种实施方式中，在第二子电池的层上方和在第一子电池下方布置有如下的钝化层：该钝化层由至少具有元素GaInP或至少具有元素AlInAs或至少具有元素AlInP的化合物构成。
在一种实施方式中，在第二子电池的层下方和在变质缓冲层上方布置有如下的钝化层：该钝化层由至少具有元素GaInP或至少具有元素AlInP的化合物构成。
在一种实施方式中，设置正好四个子电池或正好五个子电池，其中，在具有五个子电池的多结太阳能电池的情况下，在第一子电池与第二子电池之间构造有第五子电池。
可以理解，第五子电池具有比第二子电池更大的带隙和比第一子电池更小的带隙。第五子电池与第二子电池晶格匹配。
在一种扩展方案中，第五子电池具有大于、小于或等于基极层的掺杂的发射极层的掺杂。
优选地，在第五子电池中，发射极层的厚度大于或等于或小于基极层的厚度。
附图说明
下面参照附图更详细地阐述本发明。在此，相同种类的部件标有相同的附图标记。所示出的实施方式是高度示意性的，即间距以及横向和垂直延伸不是按比例的，并且除非另有说明，否则彼此之间也不具有可推导的几何关系。在此示出：
图1示出单片的变质的多结太阳能电池的第一实施方式的视图；
图2示出单片的变质的多结太阳能电池的第二实施方式的视图；
图3示出单片的变质的多结太阳能电池的第三实施方式的视图。
具体实施方式
图1的示图示出单片的变质的多结太阳能电池的第一实施方式，其具有在处在下方的第二子电池SC2上的、上方的第一子电池SC1。在照射时，光L首先照射到第一子电池SC1的上侧上。
在第一子电池SC1与第二子电池SC2之间构造有上方的隧道二极管TD1。
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与第三子电池SC3之间构造有第二隧道二极管TD2。
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与第四子电池SC4之间构造有第三隧道二极管TD3。
在第四子电池SC4与第三隧道二极管TD3之间布置有变质缓冲层MP。
子电池SC1、SC2、SC3和SC4中的每个都具有材料锁合地(stoffschlüssig)置于p掺杂的基极层上的n掺杂的发射极层。
第二子电池SC2具有由InGa(As)P构成的发射极和由InGaAsP构成的基极。在此，发射极中砷的比例小于基极中砷的比例或恰好为零。第二子电池SC2的发射极中的掺杂也小于基极中的掺杂。
图2的示图示出四结太阳能电池的第二实施方式。下面仅阐述与第一实施方式的不同之处。
第二子电池SC2具有由InGaP构成的发射极和由InGaAsP构成的基极，即与基极中的四元化合物相反，发射极具有三元化合物。由此，第二子电池SC2构造为所谓的异质电池(Heterozelle)。
图3的示图示出四结太阳能电池的第三实施方式。下面仅阐述与以上实施方式的不同之处。
在第一子电池SC1与第二子电池SC2之间布置有第五子电池SC5。在第五子电池SC5与第二子电池SC2之间布置有第四隧道二极管TD4。第五子电池SC5与第二子电池以及第三子电池晶格匹配。

Claims (15)

1.一种单片的变质的多结太阳能电池，所述单片的变质的多结太阳能电池包括：
-第一III-V族子电池(SC1)，
-第二III-V族子电池(SC2)，
-第三III-V族子电池(SC3)，
-第四Ge子电池(SC4)，所述子电池(SC1，SC2，SC3，SC4)以所说明的顺序彼此上下堆叠，并且所述第一子电池(SC1)构造最上方的子电池，
-在所述第三子电池(SC3)与所述第四子电池(SC4)之间构造有变质缓冲层(MP1)，
-所有子电池(SC1，SC2，SC3，SC4)都分别具有n掺杂的发射极层和p掺杂的基极层，其特征在于，
-在四个子电池之间未构造有半导体键合，
-所述第二子电池(SC2)的发射极层的厚度小于所述基极层的厚度，
-在所述第二子电池(SC2)中，发射极掺杂小于基极掺杂，
所述第二子电池(SC2)构造为异质电池。
2.根据权利要求1所述的单片的变质的多结太阳能电池，其特征在于，在所述第二子电池(SC2)中，所述发射极掺杂至多是所述基极掺杂的三分之一。
3.根据权利要求1或2所述的单片的变质的多结太阳能电池，其特征在于，在所述第二子电池(SC2)中，所述基极层包括InGaAsP或由InGaAsP组成。
4.根据权利要求3所述的单片的变质的多结太阳能电池，其特征在于，在所述第二子电池(SC2)中，所述基极层的厚度大于100nm，其中，所述基极层的砷含量关于V主族元素位于22％与33％之间，且所述基极层的铟含量关于III主族元素位于52％与65％之间，并且所述基极层的晶格常数位于0.572nm与0.577nm之间。
5.根据以上权利要求中任一项所述的单片的变质的多结太阳能电池，其特征在于，所述第一子电池(SC1)直到包括所述第三子电池(SC3)在内彼此晶格匹配。
6.根据以上权利要求中任一项所述的单片的变质的多结太阳能电池，其特征在于，所述第一子电池(SC1)具有在1.85eV与2.07eV之间的范围中的带隙，并且所述第二子电池(SC2)具有在1.41eV与1.53eV之间的范围中的带隙，并且所述第三子电池(SC3)具有在1.04eV与1.18eV之间的范围中的带隙。
7.根据以上权利要求中任一项所述的单片的变质的多结太阳能电池，其特征在于，所述第一子电池(SC1)具有由至少元素AlInP构成的化合物，并且铟含量关于III主族元素位于64％与75％之间，并且Al含量位于18％与32％之间。
8.根据以上权利要求中任一项所述的单片的变质的多结太阳能电池，其特征在于，所述第三子电池(SC3)具有由至少元素InGaAs构成的化合物，并且铟含量关于III主族元素大于17％。
9.根据以上权利要求中任一项所述的单片的变质的多结太阳能电池，其特征在于，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。
10.根据以上权利要求中任一项所述的单片的变质的多结太阳能电池，其特征在于，在所述第二子电池(SC2)中所述基极层的厚度以及在所述第三子电池(SC3)中所述基极层的厚度分别大于0.4μm或大于0.8μm。
11.根据以上权利要求中任一项所述的单片的变质的多结太阳能电池，其特征在于，在所述第二子电池(SC2)中，所述基极层至少部分地具有掺杂剂梯度，并且掺杂剂浓度在所述第三子电池(SC3)的方向上增加至大于1·1018/cm3。
12.根据以上权利要求中任一项所述的单片的变质的多结太阳能电池，其特征在于，在所述第二子电池(SC2)中，所述基极层在所述发射极层的方向上的区域中具有小于5·1017/cm3的掺杂剂浓度。
13.根据以上权利要求中任一项所述的单片的变质的多结太阳能电池，其特征在于，设置正好四个子电池或正好五个子电池，其中，在所述第一子电池(SC1)与所述第二子电池(SC2)之间构造有第五子电池(SC5)。
14.根据以上权利要求中任一项所述的单片的变质的多结太阳能电池，其特征在于，所述第二子电池SC2的发射极层具有小于2·1017/cm3且大于1·1016/cm3的掺杂。
15.根据以上权利要求中任一项所述的单片的变质的多结太阳能电池，其特征在于，在所述第二子电池(SC2)中，所述发射极层包括InGa(As)P或由InGa(As)P组成，并且所述基极层包括InGaAsP或由InGaAsP组成，其中，所述发射极层的砷含量比所述基极层的砷含量小至少5％或所述发射极层不含砷。
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