CN104393121A - 掺氧非晶硅锗薄膜、异质结晶体硅太阳能电池及制备方法 - Google Patents

掺氧非晶硅锗薄膜、异质结晶体硅太阳能电池及制备方法 Download PDF

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CN104393121A
CN104393121A CN201410581435.XA CN201410581435A CN104393121A CN 104393121 A CN104393121 A CN 104393121A CN 201410581435 A CN201410581435 A CN 201410581435A CN 104393121 A CN104393121 A CN 104393121A
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张丽平
孟凡英
刘正新
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Tongwei Solar Chengdu Co Ltd
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Shanghai Institute of Microsystem and Information Technology of CAS
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Abstract

本发明提供一种用于钝化晶体硅表面的掺氧非晶硅锗薄膜、异质结晶体硅太阳能电池及制备方法，所述用于钝化晶体硅表面的掺氧非晶硅锗薄膜的制备方法包括步骤：提供一晶体硅衬底，采用化学气相沉积工艺于所述晶体硅衬底表面沉积掺氧非晶硅锗薄膜。本发明通过调节反应气体流量中氧和锗浓度可以得到带隙连续可调的致密掺氧非晶硅锗薄膜材料，该材料利用氧、锗元素可以抑制界面外延和调节材料带隙的作用，实现空穴载流子的有效收集，从而有效提高异质结晶体硅太阳电池的效率。

Description

掺氧非晶硅锗薄膜、异质结晶体硅太阳能电池及制备方法
技术领域
本发明属于太阳能电池及制造领域，特别是涉及一种用于钝化晶体硅表面的掺氧非晶硅锗薄膜、异质结晶体硅太阳能电池及制备方法。
背景技术
能源是一个国家赖以生存和发展的动力。在化石能源日益枯竭和环境问题凸显的时代，新型可替代能源的研究将为国民经济持续发展提供有力的保障。本发明涉及一种新型非晶薄膜钝化层，在晶体硅表面形成突变界面且有效降低晶体硅表面的载流子复合速率，从而提升非晶硅/晶体硅异质结太阳电池的性能。该层是实现高效异质结太阳电池的必要条件，属于新能源中薄膜在太阳电池中应用的技术领域。
目前，晶体硅异质结太阳电池用钝化层多为非晶硅薄膜，且利用非晶硅薄膜钝化晶体硅表面后的载流子复合速率低于10cm/s.如果晶体硅表面不做任何工艺处理，非晶硅薄膜极易在晶体硅表面外延形成多晶硅薄层，导致表面钝化性能被弱化，最终制成器件的性能开路电压不高，性能没有进一步提升的空间。
针对这个问题，现有技术中，一般是通过在界面处融入氧以有效抑制晶体硅表面外延层的生长，提高钝化性能。然而，融入氧后非晶钝化层的带隙增宽，导致带隙不连续性增大，特别是在p-a-Si:H/c-Si界面价带带阶ΔEV的增大会影响空穴载流子的收集，如图1所示，其中，图1中由左至右为：发射极p-a-Si:H103、普通钝化层i-a-Si(Ox):H102、晶体硅c-Si101、普通钝化层i-a-Si(Ox):H102和背场层n-a-Si:H104；下方对应各层能带为：导带EC、价带EV、费米能级EF、以及发射极p侧的价带带阶ΔEV。
发明内容
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种用于钝化晶体硅表面的掺氧非晶硅锗薄膜、异质结晶体硅太阳能电池及制备方法，用于解决现有技术中晶体硅表面融入氧后非晶钝化层的带隙增宽，导致带隙不连续性增大，特别是在p-a-Si:H/c-Si界面价带带阶ΔEV的增大会影响空穴载流子收集的问题。
为实现上述目的及其他相关目的，本发明提供一种用于钝化晶体硅表面的掺氧非晶硅锗薄膜的制备方法，所述制备方法包括步骤：
提供一晶体硅衬底，于所述晶体硅衬底表面沉积掺氧非晶硅锗薄膜。
作为本发明的用于钝化晶体硅表面的掺氧非晶硅锗薄膜的制备方法的一种优选方案，采用化学气相沉积工艺于所述晶体硅衬底表面沉积掺氧非晶硅锗薄膜。
进一步地，所述化学气相沉积工艺包括等离子体化学气相沉积工艺及热丝化学气相沉积工艺。
作为本发明的用于钝化晶体硅表面的掺氧非晶硅锗薄膜的制备方法的一种优选方案，所述化学气相沉积工艺采用的反应气体包括锗源气体、硅源气体、氧源气体及稀释气体。
进一步地，所述锗源气体包括GeH4、GeF4及GeH3CH3的一种或组合，所述硅源气体包括SiH4、Si2H6、SiHCl3及SiH3CH3的一种或组合，所述氧源气体包括CO2及N2O的一种或组合、所述稀释气体包括H2、N2、Ar及He的一种或组合。
作为本发明的用于钝化晶体硅表面的掺氧非晶硅锗薄膜的制备方法的一种优选方案，包括步骤：
1)提供一晶体硅衬底，将所述晶体硅衬底置于反应室中，并使所述反应室具有预设的本底真空度；
2)向所述反应室中通入锗源气体、硅源气体、氧源气体及稀释气体，采用化学气相沉积法于所述晶体硅衬底表面形成掺氧非晶硅锗薄膜，其中：
所述化学气相沉积法采用的晶体硅衬底的表面温度为100～400℃；反应气体压强为20～1000Pa；采用的等离子体辉光功率密度为0.01～0.5W/cm2，或采用的热丝温度为300～2000℃；反应气体流量中氧浓度为1％～20％；反应气体流量中锗浓度为1％～20％；反应气体流量中锗氧浓度为1％～40％；反应气体流量中硅锗氧浓度为1％～50％。
本发明还提供一种异质结晶体硅太阳电池的制备方法，包括步骤：
1)采用如上所述的任意一项方案所述的用于钝化晶体硅的表面的掺氧非晶硅锗薄膜的制备方法于晶体硅衬底的上表面及下表面沉积掺氧非晶硅锗薄膜；
2)于所述晶体硅衬底的上表面的掺氧非晶硅锗薄膜表面制备P型硅基发射层、结合于所述P型硅基发射层表面的透明导电薄膜及结合于所述透明导电薄膜的前金属栅极；于所述晶体硅衬底的下表面的掺氧非晶硅锗薄膜表面制备N型硅基背场层、结合于所述N型硅基背场层的透明导电薄膜及结合于所述透明导电薄膜的后金属栅极。
本发明还提供一种用于钝化晶体硅表面的掺氧非晶硅锗薄膜，包括晶体硅衬底以及结合于所述晶体硅衬底至少一个表面的掺氧非晶硅锗薄膜。
作为本发明的用于钝化晶体硅表面的掺氧非晶硅锗薄膜的一种优选方案，所述掺氧非晶硅锗薄膜结合于所述晶体硅衬底的上表面及下表面。
本发明还提供一种异质结晶体硅太阳电池，包括所述晶体硅衬底、分别结合于所述晶体硅衬底上表面及下表面的掺氧非晶硅锗薄膜、分别结合于所述掺氧非晶硅锗薄膜表面的P型硅基发射层及N型硅基背场层、分别结合于所述P型硅基发射层及N型硅基背场层表面的透明导电薄膜、以及分别结合于所述透明导电薄膜的前金属栅极及后金属栅极。
如上所述，本发明提供一种用于钝化晶体硅表面的掺氧非晶硅锗薄膜、异质结晶体硅太阳能电池及制备方法，所述用于钝化晶体硅表面的掺氧非晶硅锗薄膜的制备方法包括步骤：提供一晶体硅衬底，于所述晶体硅衬底表面沉积掺氧非晶硅锗薄膜。
本发明公开了低温沉积高质量本征非晶硅锗氧(i-a-SiGeyOx:H)薄膜钝化层的技术方案，改善p-a-Si:H/c-Si界面能带连续的问题，以降低价带带阶，提高空穴载流子收集。本薄膜材料综合了两个特性：一、氧融入可以有效抑制晶体硅表面外延层的生长；二、锗融入可以减小因氧而导致的带隙展宽，抑制带阶的增加。与常规的i-a-Si:H钝化层相比，i-a-SiGeyOx:H有致密的非晶网络、带隙匹配且有较小的价带带阶。
本发明通过调节气体流量中氧和锗浓度可以得到带隙连续可调的致密掺氧非晶硅锗薄膜材料，该材料可以分别利用氧和锗的抑制外延、调窄带隙作用，实现空穴载流子的有效收集，从而有效提高异质结晶体硅太阳电池的效率。
附图说明
图1显示为现有技术中晶体硅衬底上形成融入氧后非晶钝化层的结构示意图及价带带阶示意图。
图2显示为本发明的晶体硅衬底上形成用于钝化晶体硅表面的掺氧非晶硅锗薄膜的结构示意图以及价带带阶示意图。
图3显示为本发明的带有掺氧非晶硅锗薄膜钝化层的异质结晶体硅太阳电池结构示意图。
元件标号说明
101    晶体硅衬底
202    掺氧非晶硅锗薄膜
103    P型硅基发射层
104    N型硅基背场层
105    透明导电薄膜
106    前金属栅极
107    后金属栅极
具体实施方式
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。
请参阅图2～图3。需要说明的是，本实施例中所提供的图示仅以示意方式说明本发明的基本构想，遂图式中仅显示与本发明中有关的组件而非按照实际实施时的组件数目、形状及尺寸绘制，其实际实施时各组件的型态、数量及比例可为一种随意的改变，且其组件布局型态也可能更为复杂。
实施例1
如图2所示，本实施例提供一种用于钝化晶体硅表面的掺氧非晶硅锗薄膜202的制备方法，所述制备方法包括步骤：提供一晶体硅衬底101，于所述晶体硅衬底101表面沉积掺氧非晶硅锗薄膜202。
作为示例，采用化学气相沉积工艺于所述晶体硅衬底101表面沉积掺氧非晶硅锗薄膜202。其中，所述化学气相沉积工艺包括等离子体化学气相沉积工艺及热丝化学气相沉积工艺。
作为示例，所述化学气相沉积工艺采用的反应气体包括锗源气体、硅源气体、氧源气体及稀释气体。进一步地，所述锗源气体包括GeH4、GeF4及GeH3CH3的一种或组合，所述硅源气体包括SiH4、Si2H6、SiHCl3及SiH3CH3的一种或组合，所述氧源气体包括CO2及N2O的一种或组合、所述稀释气体包括H2、N2、Ar及He的一种或组合。
具体地，在本实施例中，所述用于钝化晶体硅表面的掺氧非晶硅锗薄膜202的制备方法，包括步骤：
1)提供一晶体硅衬底101，将所述晶体硅衬底101置于反应室中，并使所述反应室具有预设的本底真空度。在本实施例中，可以将光滑或带有绒度的晶体硅衬底101置于反应室内，并使所述反应室的本底真空不大于0.1Pa。
2)向所述反应室中通入锗源气体、硅源气体、氧源气体及稀释气体，采用等离子体增强化学气相沉积法于所述晶体硅衬底101表面形成掺氧非晶硅锗薄膜202，在本实施例中，反应气体为硅烷SiH4、锗烷GeH4、及二氧化碳，稀释气体为采用为氢气，其中：
所述化学气相沉积法采用的晶体硅衬底101的表面温度为100～400℃；反应气体压强为20～1000Pa；
采用的等离子体辉光功率密度为0.01～0.5W/cm2。当然，也可以采用热丝化学气相沉积法制备，采用热丝温度为300～2000℃。
反应气体流量中氧浓度为1％～20％；反应气体流量中锗浓度为1％～20％；反应气体流量中锗氧浓度为1％～40％；反应气体流量中硅锗氧浓度为1％～50％。
如图2所示，本实施例提供一种用于钝化晶体硅表面的掺氧非晶硅锗薄膜202，包括晶体硅衬底101以及结合于所述晶体硅衬底101至少一个表面的掺氧非晶硅锗薄膜202。在本实施例中，所述掺氧非晶硅锗薄膜202结合于所述晶体硅衬底101的上表面及下表面，另外，在本实施例中，所述掺氧非晶硅锗薄膜202的厚度为10nm，其钝化的效果与20nm非晶硅钝化层效果相当。
如图2所示，图2中由左至右为：发射极p-a-Si:H103、本征掺氧非晶硅锗(i-a-SiGeyOx:H)薄膜202钝化层、晶体硅衬底101、本征掺氧非晶硅锗(i-a-SiGeyOx:H)薄膜202钝化层和背场层n-a-Si:H104；下方对应各层能带为：导带EC、价带EV、费米能级EF、以及发射极p侧的价带带阶ΔEV，本实施例采用界面处融入锗调节硅氧层的带隙，实现连续变化的p-a-Si:H/c-Si界面，起到降低界面带阶的作用，促进空穴载流子收集。本实施例的制备方法可以低温沉积致密的掺氧非晶硅锗薄膜202、带隙从1.5eV～2.1eV连续可调。
实施例2
如图3所示，本实施例提供一种异质结晶体硅太阳电池的制备方法，包括步骤：
1)提供一N型的晶体硅衬底101，将所述晶体硅衬底101置于反应室中，并使所述反应室具有预设的本底真空度。在本实施例中，可以将光滑或带有绒度的晶体硅衬底101c-Si置于反应室内，并使所述反应室的本底真空不大于0.1Pa。
向所述反应室中通入锗源气体、硅源气体、氧源气体及稀释气体，采用等离子体增强化学气相沉积法于分别所述晶体硅衬底101的上表面及下表面形成掺氧非晶硅锗薄膜202，在本实施例中，反应气体为硅烷SiH4、锗烷GeH4、及二氧化碳，稀释气体为采用为氢气，其中：
所述化学气相沉积法采用的晶体硅衬底101的表面温度为100～400℃；反应气体压强为20～1000Pa；
采用的等离子体辉光功率密度为0.01～0.5W/cm2。当然，也可以采用热丝化学气相沉积法制备，采用热丝温度为300～2000℃。
反应气体流量中氧浓度为1％～20％；反应气体流量中锗浓度为1％～20％；反应气体流量中锗氧浓度为1％～40％；反应气体流量中硅锗氧浓度为1％～50％。
在本实施例中，所述掺氧非晶硅锗薄膜202的厚度为5nm。
2)于所述晶体硅衬底101的上表面的掺氧非晶硅锗薄膜202表面制备P型硅基发射层103、结合于所述P型硅基发射层103表面的透明导电薄膜105及结合于所述透明导电薄膜105的前金属栅极106；于所述晶体硅衬底101的下表面的掺氧非晶硅锗薄膜202表面制备N型硅基背场层104、结合于所述N型硅基背场层104的透明导电薄膜105及结合于所述透明导电薄膜105的后金属栅极107。
如图3所示，本实施例提供一种异质结晶体硅太阳电池，包括所述晶体硅衬底101、分别结合于所述晶体硅衬底101上表面及下表面的掺氧非晶硅锗薄膜202、分别结合于所述掺氧非晶硅锗薄膜202表面的P型硅基发射层103及N型硅基背场层104、分别结合于所述P型硅基发射层103及N型硅基背场层104表面的透明导电薄膜105、以及分别结合于所述透明导电薄膜105的前金属栅极106及后金属栅极107。
本发明中涉及到的异质结晶体硅太阳电池，是以c-Si为基底、新型掺氧非晶硅锗薄膜202SGOF作为钝化层，分别由p侧和n+侧的透明导电薄膜105-金属栅极(TCO/M)实现光生载流子的收集。掺氧非晶硅锗薄膜202可以降低载流子在晶体硅表面的复合，提高有效载流子寿命，使两侧实现最大限度的收集光生载流子。本发明的掺氧非晶硅锗薄膜202钝化层比常规非晶硅钝化层厚度薄1～5nm。并且，本发明的异质结晶体硅太阳电池的开路电压可达730mV。
本发明采用新型掺氧非晶硅锗薄膜202来改善晶体硅异质结太阳电池的钝化并解决界面载流子输运的问题。一是利用氧融入前驱物融入抑制界面外延改善钝化，是保证钝化性能的必要条件；二是利用锗前驱物融入抑制外延层的同时缩小因氧融入带来的带隙展宽问题，实现带隙连续且带阶降低，是保证界面特别是p侧载流子输运的充分条件，二者缺一不可。
如上所述，本发明提供一种用于钝化晶体硅表面的掺氧非晶硅锗薄膜、异质结晶体硅太阳能电池及制备方法，所述用于钝化晶体硅表面的掺氧非晶硅锗薄膜的制备方法包括步骤：提供一晶体硅衬底101，于所述晶体硅衬底101表面沉积掺氧非晶硅锗薄膜202。本发明通过调节气体流量中氧和锗浓度可以得到带隙连续可调的致密掺氧非晶硅锗薄膜202材料，该材料可以分别利用氧和锗的抑制界面外延作用、调窄带隙作用，实现空穴载流子的有效收集，从而有效提高异质结晶体硅太阳电池的效率。所以，本发明有效克服了现有技术中的种种缺点而具高度产业利用价值。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (10)

1.一种用于钝化晶体硅表面的掺氧非晶硅锗薄膜的制备方法，其特征在于，所述制备方法包括步骤：
提供一晶体硅衬底，于所述晶体硅衬底表面沉积掺氧非晶硅锗薄膜。
2.根据权利要求1所述的用于钝化晶体硅表面的掺氧非晶硅锗薄膜的制备方法，其特征在于：采用化学气相沉积工艺于所述晶体硅衬底表面沉积掺氧非晶硅锗薄膜。
3.根据权利要求2所述的用于钝化晶体硅表面的掺氧非晶硅锗薄膜的制备方法，其特征在于：所述化学气相沉积工艺包括等离子体化学气相沉积工艺及热丝化学气相沉积工艺。
4.根据权利要求2或3所述的用于钝化晶体硅表面的掺氧非晶硅锗薄膜的制备方法，其特征在于：所述化学气相沉积工艺采用的反应气体包括锗源气体、硅源气体、氧源气体及稀释气体。
5.根据权利要求4所述的用于钝化晶体硅表面的掺氧非晶硅锗薄膜的制备方法，其特征在于：所述锗源气体包括GeH4、GeF4及GeH3CH3的一种或组合，所述硅源气体包括SiH4、Si2H6、SiHCl3及SiH3CH3的一种或组合，所述氧源气体包括CO2及N2O的一种或组合、所述稀释气体包括H2、N2、Ar及He的一种或组合。
6.根据权利要求4所述的用于钝化晶体硅表面的掺氧非晶硅锗薄膜的制备方法，其特征在于：包括步骤：
1)提供一晶体硅衬底，将所述晶体硅衬底置于反应室中，并使所述反应室具有预设的本底真空度；
2)向所述反应室中通入锗源气体、硅源气体、氧源气体及稀释气体，采用化学气相沉积法于所述晶体硅衬底表面形成掺氧非晶硅锗薄膜，其中：
所述化学气相沉积法采用的晶体硅衬底的表面温度为100～400℃；反应气体压强为20～1000Pa；采用的等离子体辉光功率密度为0.01～0.5W/cm2，或采用的热丝温度为300～2000℃；反应气体流量中氧浓度为1％～20％；反应气体流量中锗浓度为1％～20％；反应气体流量中锗氧浓度为1％～40％；反应气体流量中硅锗氧浓度为1％～50％。
7.一种异质结晶体硅太阳电池的制备方法，其特征在于：包括步骤：
1)采用如权利要求1～6任意一项所述的用于钝化晶体硅的表面的掺氧非晶硅锗薄膜的制备方法于晶体硅衬底的上表面及下表面沉积掺氧非晶硅锗薄膜；
2)于所述晶体硅衬底的上表面的掺氧非晶硅锗薄膜表面制备P型硅基发射层、结合于所述P型硅基发射层表面的透明导电薄膜及结合于所述透明导电薄膜的前金属栅极；于所述晶体硅衬底的下表面的掺氧非晶硅锗薄膜表面制备N型硅基背场层、结合于所述N型硅基背场层的透明导电薄膜及结合于所述透明导电薄膜的后金属栅极。
8.一种用于钝化晶体硅表面的掺氧非晶硅锗薄膜，其特征在于：包括晶体硅衬底以及结合于所述晶体硅衬底至少一个表面的掺氧非晶硅锗薄膜。
9.根据权利要求8所述的用于钝化晶体硅表面的掺氧非晶硅锗薄膜的制备方法，其特征在于：所述掺氧非晶硅锗薄膜结合于所述晶体硅衬底的上表面及下表面。
10.一种异质结晶体硅太阳电池，其特征在于，包括所述晶体硅衬底、分别结合于所述晶体硅衬底上表面及下表面的掺氧非晶硅锗薄膜、分别结合于所述掺氧非晶硅锗薄膜表面的P型硅基发射层及N型硅基背场层、分别结合于所述P型硅基发射层及N型硅基背场层表面的透明导电薄膜、以及分别结合于所述透明导电薄膜的前金属栅极及后金属栅极。
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CN110923660A (zh) * 2019-12-16 2020-03-27 上海华虹宏力半导体制造有限公司 改善掺杂非晶硅薄膜方块电阻面内均一性的方法
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CN111952381B (zh) * 2020-08-24 2024-02-09 中国科学院上海微系统与信息技术研究所 一种硅异质结太阳电池及其制备方法

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