CN113990975B - 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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CN113990975B
CN113990975B CN202110781830.2A CN202110781830A CN113990975B CN 113990975 B CN113990975 B CN 113990975B CN 202110781830 A CN202110781830 A CN 202110781830A CN 113990975 B CN113990975 B CN 113990975B
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M·莫伊泽尔
D·富尔曼
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Azur Space Solar Power GmbH
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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大于基极层。

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子电池借助隧道二极管彼此上下堆叠。
背景技术
具有由GaInAsP构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子电池。整个多结太阳能电池的形成通过两个外延晶圆的直接半导体键合(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中已知还具有变质缓冲层的正置生长的多结电池。
此外，从OLIVER等人的《Development of Germanium-Based Wafer-Bonded Four-Junction Solar Cells》(IEEE光伏杂志，第9卷，第6期，2019年10月11日，第1625至1630页)、EP 3 179 521 A1、US 2018/240922 A1中，从GERARD BAUHUIS等人的《Deepjunction III-V solar cells with enhanced performance:Deep junction III-Vsolar cells》(PHYSICA STATUS SOLIDI，第213卷，第8期，2016年3月7日，第2216至2222页)中以及从R.H.VAN LEEST等人的《Recent Progress of multi-junction solar celldevelopment 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)、US 2019/378 948 A1、US 6 660 928 B1中已知其他多结电池。
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，本发明的任务包括提供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。
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，随后通过基极层。
在第一、第三和第四子电池中，基极层比发射极层厚多倍。相反，在第二子电池中，发射极层的厚度大于基极层的厚度。
在第二子电池与第三子电池之间构造有半导体镜。可以理解，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。
在一种扩展方案中，在第二子电池与半导体镜之间布置有第二隧道二极管。优选地，半导体镜是n掺杂的。特别地，该掺杂大于1·1017/cm3或大于5·1017/cm3。
在另一实施方式中，隧道二极管构造在半导体镜与第三子电池之间。优选地，半导体镜是p掺杂的。特别地，掺杂大于1·1017/cm3或大于5·1017/cm3。
在一种扩展方案中，半导体镜的掺杂小于5·1019/cm3。
在一种实施方式中，半导体镜具有中心波长在750nm与830nm之间的反射带。优选地，半导体镜的层分别具有大于24％的Al含量。
在目前的多结太阳能电池的情况下，尤其是在多结太阳能电池领域，该方案是令人惊讶的。其原因在于，n掺杂的发射极层中的少数(即空穴)的迁移率比电子的迁移率低大约一个数量级。另一原因在于，在应用期间由于入射的宇宙空间辐射，基极层和发射极层中的少数载流子使用寿命退化(Degradation)。
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。所描述的多结太阳能电池涉及所谓的UMM(upright metamcrphic multijunction，直立变质多结)多结太阳能电池的所谓的正置生长的多结太阳能电池。
一个优点是，所描述的设备以令人惊讶的方式显示出较低的退化。换言之，辐照下的效率的降低较少地降低，即与之前的值相比，EOL(寿命结束)效率增加。
在一种实施方式中，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如下的两个子堆叠构造：所述两个子堆叠沉积在不同衬底上并且随后通过半导体键合接合在一起。特别地，太阳能电池堆叠不具有任何非晶(amorphen)的中间层，如其在键合中可能出现的那样。
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。带隙从第一子电池朝第四子电池下降，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，然后流过第二子电池，然后流过第三子电池，并且最后流过第四子电池。优选地，在两个直接彼此相继的子电池之间分别构造有隧道二极管。
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二极管与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，使各个子电池彼此之间电流匹配是有利的。
在一种扩展方案中，在第二子电池中，发射极层的厚度大于600nm。
自己的研究令人惊讶地表明，与预期相反，在电子照射下，在所提及的成分范围(Kompositionsbereich)内，p-InGaAsP中载流子使用寿命的退化是高的。更令人惊讶的是，在n掺杂的InGaAsP的情况下，发现非常低的退化。
在一种实施方式中，在第二子电池中，基极层具有小于450nm的厚度和/或大于4·1017/cm3的掺杂。替代地，第二子电池中的基极层具有小于200nm的厚度和/或大于8·1017/cm3的掺杂。
在一种扩展方案中，第二子电池SC2的发射极层包括InGaAsP或由InGaAsP组成。
应当注意，在此处的术语下，元素的化学缩写与完整术语同义地使用。
在一种实施方式中，第二子电池的发射极层的砷含量关于V主族元素位于22％与33％之间，且其铟含量关于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。
可以理解，尤其是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，砷含量为Y值，并且由此针对例如25％的砷含量得出Y值为0.25。
研究以令人惊讶的方式表明，GaInAsP在所提及的成分范围中可以借助MOVPE以令人惊讶的良好质量进行沉积。由此克服以下偏见：GaInAsP在所提及的、位于混溶间隙(Mischungslücke)内的成分范围中不能以太阳能电池所需的质量沉积。
这是更令人惊讶的，因为自己的研究表明，借助MOVPE沉积的InGaAsP在其他成分范围中确实具有在文献中发现的混溶间隙或离析(Entmischung)。这意味着，在所提及的成分范围中似乎存在阻止或减轻离析的特殊效应。
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、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量子阱结构(Vielfach-Quantentopf-Struktur)。
在一种实施方式中，第二子电池SC2构造为同质电池(Homozelle)。在此，术语同质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。
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(Heterozelle)。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InGaP或AlInGaP或InAlP或AlInAs，或者由InGaP或由AlInGaP或由InAlP或由AlInAs组成。
在另一扩展方案中，在第二子电池SC2中，在基极层下方，在朝向第三子电池SC3的方向上布置有由AlInAs或AlInGaAs构成的钝化层。
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掺杂的三分之一或五分之一或八分之一。
在一种扩展方案中，第二太阳能电池的发射极层具有第一区域和第二区域，其中，第一区域具有与第二区域不同的掺杂大小，并且第二区域构造成比第一区域更靠近基极。
优选地，第一区域中的掺杂在第一太阳能电池的方向上增加超过3·1017/cm3。
在一种扩展方案中，第二太阳能电池的第二区域具有大于150nm的厚度和小于1·1016/cm3的掺杂。
替代地，第二区域具有大于250nm的厚度和小于5·1015/cm3的掺杂。
在另一实施方式中，在第二子电池中，在第三子电池的方向上的下方区域具有大于150nm的厚度和/或小于1·1016/cm3的掺杂。替代地，在第二子电池中，在第三子电池的方向上的、发射极层的下方区域具有大于250nm的厚度和小于5·1015/cm3的掺杂。
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。
在一种扩展方案中，在第二子电池中，基极层掺杂有碳。替代地，基极层中的碳浓度高于锌浓度。
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，第一子电池具有至少由元素AlInP构成的化合物。关于III主族元素，铟含量位于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，第三子电池具有至少由元素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，在第二子电池的层上方和第一子电池下方布置有如下钝化层：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中，第五子电池构造在第一子电池与第二子电池之间。
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。
优选地，在第五子电池中，发射极层的厚度小于基极层的厚度。
在一种扩展方案中，在第二子电池中，发射极层具有小于1％的锑含量。
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，其具有在处于下方的第二子电池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)支承在p掺杂的基极层上的n掺杂的发射极层。
在第一、第三和第四子电池SC1、SC3、SC4中，发射极层的厚度分别小于相关的基极层的厚度。
在第二子电池SC2中，发射极层的厚度大于基极层的厚度。
图2的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，即不同于基极中的四元化合物，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。
图3的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与第二子电池晶格匹配，而且与第三子电池晶格匹配。

Claims (20)

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)，所述第一III-V族子电池(SC1)包括第一发射极层和第一基极层，
-第二III-V族子电池(SC2)，所述第二III-V族子电池(SC2)包括第二发射极层和第二基极层，其中，所述第二发射极层包括InGaP，并且所述第二基极层包括InGaAsP，
-第三III-V族子电池(SC3)，所述第三III-V族子电池(SC3)包括第三发射极层和第三基极层，
-第四Ge子电池(SC4)，所述第四Ge子电池(SC4)包括第四发射极层和第四基极层，其中，所述第一III-V族子电池(SC1)、所述第二III-V族子电池(SC2)、所述第三III-V族子电池(SC3)和所述第四Ge子电池(SC4)以所说明的顺序彼此上下堆叠，并且所述第一III-V族子电池(SC1)构造最上方的子电池，
-在所述第三III-V族子电池(SC3)与所述第四Ge子电池(SC4)之间构造有变质缓冲层(MP1)，
-其中，所述第一发射极层、所述第二发射极层、所述第三发射极层和所述第四发射极层是n掺杂的，并且所述第一基极层、所述第二基极层、所述第三基极层和所述第四基极层是p掺杂的，
-其中，所述第一发射极层的厚度小于所述第一基极层的厚度，所述第三发射极层的厚度小于所述第三基极层的厚度，所述第四发射极层的厚度小于所述第四基极层的厚度，
其特征在于，
所述第二发射极层的厚度大于所述第二基极层的厚度，
-在所述第二III-V族子电池(SC2)与所述第三III-V族子电池(SC3)之间构造有第一半导体镜。
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III-V族子电池(SC2)与半导体镜之间布置有隧道二极管(TD2)。
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，半导体镜是n掺杂的并且所述掺杂大于5·1017/cm3。
4.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，所述第二发射极层具有大于600nm的厚度。
5.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，所述第二基极层的厚度小于450nm和/或所述第二基极层的掺杂大于4·1017/cm3。
6.根据权利要求4所述的单片的变质的多结太阳能电池，其特征在于，所述第二发射极层的砷含量关于V主族元素位于22％与33％之间，并且所述第二发射极层的铟含量关于III主族元素位于52％与65％之间，并且所述第二基极层的晶格常数位于0.572nm与0.577nm之间。
7.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，所述第二III-V族子电池(SC2)构造为异质电池。
8.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，所述第一III-V族子电池(SC1)具有在1.85eV与2.07eV之间的范围中的带隙，并且所述第二III-V族子电池(SC2)具有在1.41eV与1.53eV之间的范围中的带隙，并且所述第三III-V族子电池(SC3)具有在1.04eV与1.18eV之间的范围中的带隙。
9.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，所述第一III-V族子电池(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。
10.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，在所述第三III-V族子电池(SC3)与所述第四Ge子电池(SC4)之间布置有第二半导体镜。
11.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，所述第二发射极层至少部分地具有掺杂剂梯度，并且所述掺杂剂浓度在所述第一III-V族子电池(SC1)的方向上增加到超过3·1017/cm3。
12.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，所述第二发射极层具有第一区域和第二区域，其中，与所述第二区域相比，所述第一区域具有不同的掺杂大小，并且与所述第一区域相比，所述第二区域构造成更靠近所述第二基极层。
13.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，在所述第一III-V族子电池(SC1)与所述第二III-V族子电池(SC2)之间构造有第五子电池(SC5)。
14.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，所述第二基极层掺杂有碳，和/或在第二太阳能电池的所述第二基极层中碳浓度高于锌浓度。
15.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，所述第二发射极层的掺杂至多是所述第二基极层的掺杂的三分之一。
16.根据权利要求10所述的单片的变质的多结太阳能电池，其特征在于，所述第二半导体镜的铝含量大于24％。
17.根据权利要求12所述的单片的变质的多结太阳能电池，其特征在于，所述第一半导体镜的铝含量大于24％。
18.根据权利要求12所述的单片的变质的多结太阳能电池，其特征在于，在所述第一III-V族子电池(SC1)、所述第二III-V族子电池(SC2)、所述第三III-V族子电池(SC3)和所述第四Ge子电池(SC4)之间未构造有半导体键合。
19.根据权利要求12所述的单片的变质的多结太阳能电池，其特征在于，所述第一区域中的掺杂大小大于所述第二区域中的掺杂大小。
20.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，所述第二发射极层由InGaP组成，并且所述第二基极层由InGaAsP组成。
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