CN108603277A - 用于将CdTe-层沉积在基材上的方法 - Google Patents

用于将CdTe-层沉积在基材上的方法 Download PDF

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CN108603277A
CN108603277A CN201780009636.4A CN201780009636A CN108603277A CN 108603277 A CN108603277 A CN 108603277A CN 201780009636 A CN201780009636 A CN 201780009636A CN 108603277 A CN108603277 A CN 108603277A
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CN108603277B (zh
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H.莫格纳
C.梅茨纳
D.希尔施
O.齐维茨基
L.德克
T.维尔纳
B.西普兴
B.施珀特
K.韦拉潘
C.克拉夫特
C.德罗斯特
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Abstract

本发明涉及用于通过物理气相沉积在真空室（1）内将CdTe‑层沉积在基材（2）上的方法，其中将基材（2）在沉积过程之前加热至涂覆温度和然后沿着至少一个容器（3）传送，在该容器中将CdTe（4）转化为蒸气状态，其中通过至少一个入口（5）将气态组分以（相对于真空室中的真空）提高的压力流向基材（2）的待涂覆的表面，从而在将基材（2）沿着至少一个容器（3）传送之前，将所述气态组分吸附在基材（2）的待涂覆的表面上。

Description

用于将CdTe-层沉积在基材上的方法
本发明涉及一种用于将CdTe-层沉积在基材上的方法，利用该方法可以将至少一种另外的化学元素嵌入到沉积的层中。
CdTe-层在半导体工业中越来越重要，尤其是在制造薄膜太阳能电池或照相机的图像接收器中。
对于CdTe-层的沉积，广泛采用所谓的“近空间升华”（缩写CSS）的工艺技术。在该方法中，将CdTe-粒料在容器中加热，使其在容器中升华并且因此转化为蒸气状态。将待涂覆并加热至涂覆温度的基材通常贴近地移动通过容器上方，由此使得CdTe沉积在基材表面上。
例如，在“CdTe Dünnschichtsolarmodule auf dem Weg zur Produktion”，Dieter Bonnet博士，FVS Themen 2000，第116-118页中描述了借助于CSS沉积CdTe-层用于薄膜太阳能电池。
DE 10 2014 202 961 A1公开了一种制造p-掺杂的CdTe-层的方法，其中例如借助于CSS沉积两个CdTe-子层，以及在两个子层之间的包含掺杂元素的牺牲层。掺杂元素从牺牲层扩散到CdTe-子层的邻接区域中。
或者，通过允许反应性气体（例如氧气）进入在升华的CdTe-粒料和待涂覆的基材之间的扩散的CdTe-蒸气的区域中，还可以在CSS-工艺中进行反应性的沉积操作。这里发现的缺点是，CdTe-粒料也在容器中被氧化，这对蒸气产率有不利影响。
用于沉积CdTe-层的另一种已知方法是所谓的“蒸气传输沉积”（缩写VTD）。在VTD沉积方法中，将CdTe在容器中转化为蒸气状态，并且将CdTe-蒸气通过惰性载气的气体流引导到涂覆区中，在该涂覆区中将CdTe-蒸气沉积在基材上。VTD沉积方法通常用于涂覆基材的顶侧，其中涂覆方向从顶部向下。例如，DE 10 2010 051 815 A1公开了一种用于形成至少一个光伏组件的方法，其中可以借助于VTD沉积例如由CdTe制成的吸收剂层。
“Vapor transport deposition of large-area polycrystalline CdTe forradiation image sensor application”，Keedong Yang，Bokyung Cha，Duchang Heo和Sungchae Jeon，Phys. Status Solidi，C 11，No. 7-8，2014，第1341-1344页描述了借助于VTD沉积CdTe-层用于图像接收器的应用。
在借助于VTD沉积CdTe-层的情况下，可以将其他化学元素嵌入到CdTe-层中，例如通过向载气中添加待加入的化学元素的气态组分。然而，当例如将氧气混入到惰性载气时，则会产生如下不利影响，即氧气在CdTe-蒸气传输到涂覆区期间与CdTe-蒸气的颗粒反应产生氧化镉，这降低了沉积层的质量。
因此，本发明的技术问题在于，提供一种在基材上沉积CdTe-层的方法，借助于该方法可以克服现有技术的缺点。更具体地，通过本发明的方法还可以将另外的化学元素嵌入到沉积的层中，而不会（例如由于氧化）导致蒸发材料的化学变化。
通过具有本发明权利要求1的特征的主题解决了所述技术问题。在从属权利要求中，本发明的其他有利实施方案是显而易见的。
在本发明的方法中，在真空室内通过物理气相沉积将CdTe-层沉积在基材上。所使用的基材例如可以是玻璃基材；在沉积CdTe-层之前，在其上可以已经沉积了一个或多个由除CdTe之外的其他材料构成的层。或者，也可以使用由金属或塑料构成的基材。在本发明的方法中，将待涂覆CdTe的基材在沉积过程之前加热至涂覆温度，并且然后沿着至少一个容器传送，在该容器中将CdTe转化为蒸气状态，从而将产生的CdTe-蒸气沉积在基材的待涂覆表面上。本发明方法的特征在于，在沉积的CdTe-层中嵌入至少一种另外的化学元素，通过该化学元素例如可以影响CdTe-层的导电性。根据本发明，这是通过以下方式实现的：通过至少一个入口将气态组分以（相对于真空室中的真空）提高的压力流向基材的待涂覆的表面，从而在将基材沿着所述至少一个容器（在该容器中将CdTe转化为蒸气状态）传送之前，将所述气态组分吸附在基材的待涂覆的表面上。然后，将粘附在基材表面上的气态组分在随后的CdTe蒸发的情况下一起并入到产生的层中。
为了实施本发明的方法，可以例如使用包含选自氧、氮、硫、氯、氟、磷、砷、锑、铋、碲的至少一种元素的气态组分。当将CdTe-层沉积为太阳能电池层系统的组成部分时，氧气作为气态组分是特别合适的，因为通过嵌入的氧增强了氯和硫从邻接层进入CdTe-层的所需扩散，这提高了太阳能电池的效率。
在本发明的一个实施方案中，将所述基材多次沿着所述至少一个容器传送，在该容器中将CdTe转化为蒸气状态，其中在所述基材每次进入容器的涂覆区之前，将气态组分吸附在待涂覆的基材表面上。这可以是每次相同的气态组分或者每次不同的气态组分。或者，从基材的移动方向看，在真空室中也可以连续地布置多个容器，在该容器中将CdTe转化为蒸气状态，其中在基材进入容器的涂覆区中之前，通过至少一个入口将气态组分流向待涂覆的基材表面，从而每次将气态组分吸附在待涂覆的基材的表面上。
在另一个实施方案中，在吸附在基材表面上之前和/或之后借助于等离子体活化气态组分，这可以更好地使得气态组分的化学元素并入到CdTe-层中。
优选地，在本发明的方法中借助于CSS工艺沉积CdTe-层。或者，也可以根据本发明借助于VTD沉积CdTe-层。
在本发明的方法中还可以借助于等离子体活化CdTe-蒸气，由此可以影响沉积的CdTe-层的性能。
以下通过具体实施例进一步阐述本发明。图1示出了装置的示意图，借助于该装置可以实施本发明的方法。引导基材2通过真空室1，在基材2的一侧上应当沉积CdTe-层作为太阳能电池层系统的一部分。在此，还应当尽可能均匀地将化学元素氧嵌入到沉积的CdTe-层中。
在该具体实施例中，基材由玻璃组成，在前面的过程中已经在其上沉积了TCO-层和随后的CdS-层。在将基材2引导到真空室1中之前，将其加热到涂覆温度。将基材2加热到涂覆温度和/或保持基材2的涂覆温度也可以替代地在真空室1内例如通过辐射加热器进行。
在真空室1内，沿基材移动的方向布置有三个容器3，基材移动的方向在基材2上方用箭头示出。在容器3内存有CdTe-粒料4，其由于向容器3供热而升华。将基材2在容器3上方以仅几毫米的距离传送，由此将CdTe-层沉积在基材2上。
根据本发明，从基材移动的方向看，在每个容器3之前布置有气体入口5，氧气从该气体入口向着待涂覆的基材表面的方向流动。在该具体实施例中，氧气的流动方向垂直于待涂覆的基材表面。氧气被吸附在待涂覆的基材表面上，通过粘附在基材2上与其一起传送到随后的每个容器3的涂覆区中，并且在此在层沉积的过程中并入到沉积的层中。
如在该具体实施例中所述的，如果将基材2多次传送通过一个或多个容器3的涂覆区，并且之前每次都将气态组分吸附在待涂覆的基材表面上，则本发明的方法可以实现在CdTe-层的层厚度分布上均匀地嵌入至少一种另外的化学元素。
因为基材2在容器3上方以仅几毫米的距离传送，所以一方面侧面的蒸发损失非常小，和另一方面由于基材2和容器边缘之间的间隙小，从而在容器3内在CdTe-粒料4和基材2之间的区域中形成了相对高的蒸气压，这使得仅有非常少的氧气到达CdTe-粒料上。由此，容器3内的CdTe-粒料的氧化程度可忽略地小，并且蒸气产率非常高。
众所周知，在太阳能电池层系统的情况下，在CdTe-层的沉积之后如下用氯化合物活化CdTe-层，即应当使得氯扩散到CdTe-层中。已经令人惊讶地发现，根据本发明的氧嵌入到CdTe-层有利于氯由于随后的氯活化扩散到其中和硫从在CdTe-层下方沉积的CdS-层扩散到其中。在具有根据本发明沉积的CdTe-层的太阳能电池的情况下，与没有根据本发明嵌入的氧的方法相比，因此可以测得更高的效率。
根据本发明沉积的CdTe-层的分析还表明，根据本发明的氧嵌入到CdTe-层不会导致在CdTe-层内形成氧化镉。
值得注意的还在于，使用本发明的方法不仅能够将氧并入到CdTe-层中，而且能够将上面已经提到的其他化学元素并入到CdTe-层中，从而例如掺杂CdTe-层。图1中所示的三个容器3在数目上也仅仅是示例性的。根据技术问题，本发明的方法也可以用多于或少于三个容器3以及相应的气体入口5实施。

Claims (8)

1.用于通过物理气相沉积在真空室（1）内将CdTe-层沉积在基材（2）上的方法，其中将基材（2）在沉积过程之前加热至涂覆温度和然后沿着至少一个容器（3）传送，在该容器中将CdTe（4）转化为蒸气状态，其特征在于，通过至少一个入口（5）将气态组分以相对于真空室中的真空提高的压力流向基材（2）的待涂覆的表面，从而在将基材（2）沿着至少一个容器（3）传送之前，将所述气态组分吸附在基材（2）的待涂覆的表面上。
2.根据权利要求1所述的方法，其特征在于，使用包含选自氧、氮、硫、氯、氟、磷、砷、锑、铋、碲的至少一种元素的气态组分。
3.根据权利要求1或2所述的方法，其特征在于，在基材（2）的移动方向上连续布置多个容器（3），其中在这些容器中使CdTe（4）升华，并且在每个容器（3）之前，通过至少一个入口（5）将气态组分以相对于真空室中的真空提高的压力流向基材（2）的待涂覆的表面。
4.根据权利要求1或2所述的方法，其特征在于，将所述基材多次沿着所述至少一个容器传送。
5.根据前述权利要求中任一项所述的方法，其特征在于，借助于等离子体活化所述气态组分。
6.根据权利要求1至5中任一项所述的方法，其特征在于，借助于CSS沉积CdTe-层。
7.根据权利要求1至5中任一项所述的方法，其特征在于，借助于VTD沉积CdTe-层。
8.根据前述权利要求中任一项所述的方法，其特征在于，借助于等离子体活化CdTe-蒸气。
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