CN104518044B - 用来制造CdTe薄层太阳能电池的背接触层的方法 - Google Patents

用来制造CdTe薄层太阳能电池的背接触层的方法 Download PDF

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CN104518044B
CN104518044B CN201310446479.7A CN201310446479A CN104518044B CN 104518044 B CN104518044 B CN 104518044B CN 201310446479 A CN201310446479 A CN 201310446479A CN 104518044 B CN104518044 B CN 104518044B
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tellurium
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solar cell
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CN104518044A (zh
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巴斯蒂安·希普欣
贝蒂娜·斯帕特
彭寿
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China Triumph International Engineering Co Ltd
CTF Solar GmbH
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Abstract

本发明涉及一种用来制造CdTe薄层太阳能电池的背接触层的方法。本发明的主题是一种制造基材上置式薄层太阳能电池的背接触层的Sb2Te3层的方法。根据现有技术，Sb2Te3层作为化合物沉积。现在根据本发明提出，Sb2Te3层由碲化镉层的富碲的表面层和沉积在该富碲表面层上的锑，以及锑和碲在表面层上的反应生成。

Description

用来制造CdTe薄层太阳能电池的背接触层的方法
技术领域
本发明的主题是一种用来改进性地实施背接触层，更确切地说是CdTe薄层太阳能电池的背接触层序列的方法。
背景技术
根据现有技术，基材上置（Superstrat-Konfiguration）式CdTe薄层太阳能电池以如下方式制造：把透明的前接触层（TCO；透明导电氧化物）涂覆到基材（优选玻璃）上。在前接触层上沉积硫化镉（CdS）层，并且在硫化镉层上涂覆碲化镉（CdTe）层。再将背接触层或者背接触层序列沉积到CdTe层上。
在此问题是，在CdTe上涂布金属的接触层是不容易实现的，因为这会导致产生整流的肖特基（Schottky）接触。然而所希望的是产生欧姆接触。层序列的任务是，使各个层材料的能级如此地实现调整，即，生成欧姆接触，其中，优选金属层作为最表面的背接触层。
在制造过程中，在涂覆CdTe之后优选借助于CdCl2以及加热进行CdTe的活化。
出自现有技术的方法设置为，碲化镉层接着经受湿法化学腐蚀。此外CdTe太阳能电池被浸入到所谓的NP腐蚀液中。NP腐蚀液是不同的无机酸的水溶液，优选（HNO3（0.5%-5%）/H3PO4（50%-85%）/H2O（15%-45%）（总计100%）。这在室温（18℃到约80℃）的温度范围中进行。腐蚀时间优选为在5s到60s的范围中。NP腐蚀的结果是，产生厚度在1nm到300nm的范围内的富碲层。
溴甲醇备选地用作腐蚀剂。在其中，Br2浓度优选在0.1%-5%的范围中，特别优选地在0.5%-1%。优选地，在腐蚀过程（腐蚀时间3s到30s）中优选维持15℃到50℃的温度，特别优选地维持20℃到35℃的温度，并且十分特别优选地维持21℃到30℃的温度。富碲层所达到的厚度在1nm到30nm的范围中。
此外腐蚀步骤清洁了表面的氧化物，其在制造的过程进程中在与大气接触的情况下在表面上产生。对此，可选地通过还原性的溶液进行额外处理可能是必要的，以便尽可能完全地把氧化物从Te层去除。
接着，在根据现有技术的方法中，经常优选通过溅镀Sb2Te3涂覆Sb2Te3层。接着涂覆背接触层序列的其他覆层，典型地由钼和镍制成的覆层。相应的方法在US7 211 462B1中进行了描述，其中，放弃了腐蚀步骤并且仅仅进行CdCl2表面处理。Sb2Te3层在此通过溅射涂覆。其他公知的涂覆Sb2Te3层的方法设置为蒸发或电沉积。在需要时，还可以设置多个Sb2Te3层。
Sb2Te3层沉积是非常成本高昂的，因为Sb2Te3非常昂贵。
因此提出了以其他备用方式生成Sb2Te3层的任务。
发明内容
根据本发明，所提出的任务通过根据权利要求1的方法解决。优选实施形式在相关从属权利要求中公开。
根据本发明该任务通过如下方式得到解决，即，Sb2Te3层不再由化合物Sb2Te3、而是由它的组成部分制造出来。
研究表明了，在CdTe通过CdCl2活化的进程中在表面上产生氧化物。随后的腐蚀步骤以及其他可选的处理导致表面氧化物的去除以及镉由CdTe层析出。残留下CdTe层的特别富碲的表面层。
这种已经富集了碲的表面层，具有优选1nm到300nm，特别优选10nm到150nm的厚度。现在开始制造Sb2Te3层，其方式是向这种表面层导入锑，从而可以逐渐产生所追求的Sb2Te3层。
锑的导入通过根据现有技术的方法进行。因此，例如溅射以及蒸发为特别适合的设置方式。同样适合的是电化学或湿法化学沉积。此外，到根据US5 124 278方法被视为是适合的，在该方法中，锑的导入通过特殊的CVD（化学气相沉积；Chemical VapourDeposition）方法，也就是说MOCVD（金属有机化学气相沉积；metallo-organic chemicalvapour deposition）或OMVPE（有机金属气相外延；organometallic vapour phaseepitaxy）进行。在此原材料是金属有机锑化合物。三甲基锑在富Te表面上的热分解也是可行的。在把锑涂覆到富Te表面层上时，特别是在干法的情况下，锑层形成。在此取决于所选择的方法，温度处理步骤对于随后形成的Sb2Te3层可能是必要的。在真空中的随后的温度处理步骤，优选在50℃-300℃的温度范围中持续1min-30min，特别优选的在130℃-170℃的温度范围中持续8min-10min。经验表明了，最优值为约150℃持续约10min。然而，这可以取决于所使用的用来涂覆锑的方法以及其他过程参数而有所不同。
优选使用以下方法：
·溅射：基材温度20℃-300℃，所达到的层厚度10nm-150nm
·蒸发：基材温度20℃-300℃，所达到的层厚度10nm-150nm
·湿法化学：基材温度20℃-100℃，所达到的层厚度10nm-150nm
·MOCVD或OMVPE，原料为根据US5 124 278的金属有机锑化合物
·在520℃到550℃的情况下，在富Te层上热分解三甲基锑，所达到的层厚度10nm-150nm
优选地，单个的层厚度在以下范围中：Te20nm-150nm，Sb10nm-150nm，特别优选地：Te40nm-100nm，Sb20nm-60nm，以及十分特别优选地：Te55nm-60nm，Sb40nm-45nm。
在制造Sb2Te3层之后，背接触层序列的其他层相应于现有技术被涂覆。优选地，在此可以溅镀钼和Ni:V层。
因此，根据本发明的方法，由两种元素Sb和Te制造Sb2Te3层作为背接触层栈的基底层，而不必提供作为化合物的昂贵的Sb2Te3。
附图说明
图1至图5的图，示意性地示出了根据本发明过程步骤的流程。
图1示出了准备好的、带有基材1的太阳能电池，在基材上已经涂覆了透明的前接触21以及CdS层3，并且在CdS层上方已经涂覆了CdTe层4；
在图2中示意性地示出了借助于NP腐蚀液6的腐蚀过程；
如在图3中示意性地所示出的那样，在腐蚀过程后残留富Te层41，Cd由该富Te层中被大部分地析取走。
图4示意性地示出，在富Te层41之上布置有Sb层。
如在图5中示意性地所示出的那样，富Te层41与Sb层7在温度作用下反应成Sb2Te3层5。
图6示意性地示出了，在背接触部22涂覆到Sb2Te3层5之后制成的太阳能电池的层序列。在此，背接触层22可以形成为层序列。
具体实施方式
以下依据实施例阐述根据本发明的过程，而本发明的过程不局限于这个示例。
在玻璃基材1上涂覆前接触层21、CdS层3和CdTe4层之后（图1），根据现有技术，通过CdCl2在400℃的情况下活化CdTe表面层。随后通过NP腐蚀溶液6：（HNO3（1%）/H3PO4（77%）/H2O（22%），在温度为20℃的情况下进行NP腐蚀步骤（图2）。逐渐产生具有150nm的层厚度的富Te层41（图3）。在这种层中在化学计量上非常少地含有镉。
随后在150℃的基材温度的情况下，45nm的Sb层7被溅镀到富碲层41上（图4）。
随后，整个层序列在150℃的情况在真空中再次加热12min的时间段，以便导致Sb2Te3化合物的形成。所生成的Sb2Te3的层厚度为90nm（图5）。
随后，进行背接触层22的沉积，该背接触层由钼层和带有钒添加物的镍层构成。钼层（150nm）借助于溅射沉积到Sb2Te3层上。最后，还在钼层上沉积带有钒添加物的镍层（溅射，150nm）。
附图标记列表
1 基材（玻璃）
21 前接触（透明的、TCO）
22 背接触（金属）
3 CdS层
4 CdTe层
41 腐蚀后的富Te层
5 Sb2Te3层
6 NP腐蚀液
7 溅镀的Sb层

Claims (3)

1.一种制造基材上置式CdTe薄层太阳能电池的背接触层的Sb2Te3层的方法，所述方法包括如下步骤：
-生成碲化镉层的富碲表面层；
-将锑层通过溅射、蒸发、湿法化学沉积或者化学气相沉积方法涂覆到所述富碲表面层上；以及
-通过所涂覆的锑和富碲表面层中的碲在所述富碲表面层上的反应生成所述Sb2Te3层，其中通过加热所述基材来支持所述Sb2Te3层的形成，基材的加热在150℃-300℃的情况下进行1min-30min。
2.根据权利要求1所述的方法，其特征在于，所述富碲的表面层通过NP腐蚀步骤或者溴/甲醇腐蚀步骤生成。
3.根据权利要求2所述的方法，其特征在于，通过在腐蚀步骤中加热基材来支持所述富碲的表面层的生成。
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