CN103038897A - 具有微晶吸收体层和钝化层的薄膜太阳能电池以及制造这种电池的方法 - Google Patents
具有微晶吸收体层和钝化层的薄膜太阳能电池以及制造这种电池的方法 Download PDFInfo
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Abstract
光伏电池60包括衬底31、透明导电氧化物的前或第一电极42以及微晶硅的至少一个p-i-n结43，所述p-i-n结43包括第一n掺杂硅子层44和第二p掺杂硅子层46以及具有基本上本征微晶硅的第三子层45。包括基本上本征非晶硅的钝化层45布置成：a)位于微晶本征子层45和n掺杂硅层46之间，或者b)成为嵌在微晶本征子层45中的层，或者c)这二者。用于制造这种光伏薄膜硅太阳能电池的方法包括：提供在其上具有TCO前电极42的透明衬底41；沉积p掺杂Si层44、微晶硅本征层45、来自基本上本征非晶硅的钝化层55、n掺杂Si层46以及后电极层48。
Description
本发明涉及太阳能光伏转换器件，太阳能电池，特别是由于在器件的光活性微晶部分内结合(多个)钝化层而具有改进性能的薄膜硅光伏器件。
发明领域
图4A示出本领域中已知的串联结硅薄膜太阳能电池。这种薄膜太阳能电池50通常包括依次堆叠在衬底41上的第一或前电极42，一个或多个半导体薄膜p-i-n结(52-54，51，44-46，43)，以及第二或后电极47。每个p-i-n结51、43或薄膜光电转换单元包括夹置于p型层52、44和n型层54、46之间的i型层53、45(p型=正掺杂，n型=负掺杂)。基本上为本征半导体层的i型层53、45占据薄膜p-i-n结的厚度的大部分。在此上下文中，基本上本征被理解为"表现出基本上没有结果得到的掺杂"。光电转换主要发生在此i型层中；它因此也称为吸收体层。
依据i型层53、45的晶体分数(结晶度)，太阳能电池或光电(转换)器件被表征为非晶(a-Si，53)或微晶(μc-Si，45)太阳能电池，与相邻p和n层结晶类型无关。如本领域公知，微晶层被理解为在非晶基体中包括显著比例的结晶硅(所谓的微晶体)的层。
p-i-n结的堆叠被称为串联或三结光伏电池。如图4A所示，非晶和微晶p-i-n结的组合也称为非微晶叠层（micromorph）串联电池。
发明背景
在结合微晶硅作为光活性(本征)i层的单结和多结太阳能电池中，μc-i层的两个关键物理参数为：1)其结晶度和2)其电子质量(缺陷密度)。为了得到器件的最佳性能，光活性层的结晶度的选择一方面必须考虑(对于标准PECVD沉积条件)，当靠近非晶-微晶硅过渡区被沉积时，微晶硅层具有更好的电子质量(低缺陷密度)，这导致器件的高的开路电压(Voc)。另一方面，在远超过非晶-微晶过渡区处，通过增大结晶度而获得高电流密度(Jsc)。因此，为了得到最佳器件，必须找到高Voc和高Jsc之间的折衷。通常是针对"中等"i层结晶度而找到最适宜条件。已知PECVD工艺当前使用分步或连续调适微晶i层沉积期间的沉积参数(诸如硅烷浓度分布图和/或功率分布图)，从而获得i-μc-Si:H层的最佳结晶度和最高电子质量。
i-μc-Si:H层中的缺陷密度不是仅仅与其结晶度有关。当使用粗糙前透明导电氧化物(TCO)层作为前电极("前TCO"，前电极)时，附加缺陷被引入。这种TCO主要用于通过增加器件中光的光学路径来增大薄膜硅太阳能电池的Jsc。然而，使用粗糙前TCO通常引起Voc和填充因子(FF)减小。此效应归因于存在附加的与形貌有关的缺陷(多孔i-μc-Si:H的区域)，所述缺陷引起FF的减小和Voc的减小。
现有技术中的不足
通常，i-μc-Si:H层的所选择的器件结晶度源于针对高Jsc的高结晶度和针对高Voc的中等结晶度之间的折衷。现有技术PECVD沉积工具和工艺不允许用于μc-Si:H i层制作的具有高结晶度(高Jsc)和低缺陷密度(高Voc)的理想μc-Si:H材料。但是利用缺陷钝化层，利用典型标准PECVD沉积参数，有可能得到高结晶度(高Jsc)和良好Voc。
附图说明
图1：具有变化的钝化a-Si:H i层(测试厚度：10、50和150nm，粗糙LPCVD-ZnO衬底)的非微晶叠层顶部受限制电池的I(V)特性。参照电池平均Voc为1347mV，Jsc为12.2mA/cm2以及FF为70.2%。利用10nm i-a:Si:H钝化的电池具有下述平均更高的电学性能：Voc为1356mV，Jsc为12.4mA/cm2以及FF为72.4%。
图2A和B：在MM电池的Voc和FF的绝对值上引入变化厚度的a-Si:H钝化层的效应。
图3：与不具有钝化层的参照电池相比，具有10nm钝化层的非微晶叠层串联电池的总外量子效率(EQE)。
图4A：现有技术串联结薄膜硅光伏电池。厚度不是按比例。
图4B：具有钝化层的根据本发明的实施例。厚度不是按比例。
发明内容
如图4B所示，本发明包括在PV电池60(非微晶叠层串联电池中的底部电池)的微晶i层45中或者毗邻其引入缺陷钝化层55。此附加钝化层55包括a-Si:H i层，其对于撞击在其上的光(即通过顶部+p-i μc-Si:H子电池之后到达的光)是光学透明的。沉积在i-μc-Si:H层顶部上的此附加a-Si:H i层增大整个非微晶叠层器件电学性能(Voc、FF和Jsc，测量为外量子效率EQE)。
具体实施方式
在下述说明示例中，在原生粗糙TCO(LPCVD-ZnO)上制备顶部受限制非微晶叠层电池。用于比较的参照器件50提供了i层53厚度为250nm的顶部pin a-Si:H电池51以及具有中等结晶度(用780nm激光测量的体拉曼结晶度为50-55%)的2000nm光活性i层45的底部μc-Si:H电池43。钝化器件60对于顶部和底部电池具有相同的i层厚度，除了根据本发明μc-Si:H i层45的沉积之后是沉积变化厚度的完全非晶i层55(钝化层)。钝化器件60表现出改进的电学性能(见图1)。这表明底层微晶硅层的某些缺陷的有害效应因而被减轻。特别地，诸如悬挂键的复合中心可以用a-Si:H高效地钝化，并且光载流子的相应的减小的复合导致增大的Voc、FF和总(顶部+底部子电池)Jsc(由EQE测量)，如在我们的说明示例中所观察到。
通过在i-μc-Si:H层生长结束时引入钝化层，还减小了形貌引起的缺陷，即与生长有的缺陷的有害效应。
对于诸如此说明示例中使用的底部电池，在微晶i层结束时引入非晶钝化层而获得的效率中的相对增益约为5%。
钝化层的适当厚度必须通过考虑其对电池的Voc和FF的效应来选择，如图1所说明。此图表明需要某一厚度的钝化层，以同时获得FF和Voc的增大值。然而，当钝化层太厚时，双二极管行为出现在I(V)曲线中，这显著地降低器件性能。图2示出限制增益与层厚度的关系。
在我们的说明示例中，出现了在μc-Si:H i层结束时沉积的附加层引起的缺陷密度减小，还出现了底部电池光电流增大(见图3，在Jsc_总=Jsc_顶部_电池+Jsc_底部_电池中，约+0.5mA/cm2)。因为非微晶叠层电池是顶部受限制的，在I(V)曲线中看不到这种增大。
也可以使用纯a-Si:H以外的基于硅的钝化i层，可以使用诸如a-SiC:H、a-Si:O:H或a-SiN:H等的合金。它们的最佳厚度必须针对每个TCO粗糙度根据它们的导电性以及在650nm-1100nm波长范围中的光学透明度来选择。
预期当以更高结晶度(即更多缺陷的)应用到μc-Si:H i层时，钝化a-Si:H i层将甚至更有效。因此预期，由于这些层的较低电子级别引起的Voc中通常观察到的损失至少部分地被附加的完全非晶钝化层所补偿。
最后，不是强制在本征微晶层的沉积结束时应用此钝化层。如果随后的结晶层具有足够的结晶度，此层在本征微晶层生长期间可以应用在变化的位置。在生长微晶i层期间也可能引入超过一个钝化层。
实验：
根据本发明的钝化层可以如下所述制备。在本领域中已知的PECVD处理腔(例如从Oerlikon Solar商业上可获得的KAI-M)中使用下述工艺参数。衬底尺寸约为500x400mm2。利用0.1-2mbar，优选地0.2-0.5mbar的压力，5-500W(2.5mW/cm2-250mW/cm2衬底尺寸)，优选地30-100W(15mW/cm2-50mW/cm2衬底尺寸)的功率，以及氢气和硅烷之间1:1的比例，可实现高质量a-Si:H钝化层。处理温度选择为100℃-250℃，优选地约200℃。50-2000sccm，优选地50-500sccm的气流被应用，然而也将取决于所使用的处理工具和衬底尺寸。
可替换地，可以应用1-5mbar的处理压力、100-600W的功率以及氢气和硅烷之间10:1至200:1的比例。沉积速率取决于所使用的处理工具；处理持续时间因此将改变，直至已经实现根据本发明5nm-50nm的层厚度。
总结
光伏电池60包括衬底31、透明导电氧化物的前或第一电极42以及包括微晶硅的至少一个p-i-n结43，所述p-i-n结43包括包括硅和n-掺杂剂的第一子层44，包括硅和p-掺杂剂的第二子层46，以及包括基本上本征微晶硅的第三子层45，其中包括基本上本征非晶硅的至少一个钝化层45布置成：a)位于微晶本征子层45和n掺杂硅层46之间，或者b)作为嵌在微晶本征子层45中的层，或者c)这二者。
在其它实施例中，可以存在若干嵌入层。钝化层45具有5nm-200nm，优选地为10-50nm的厚度。钝化层55可以例如下述来实现：基本上本征硅或硅化合物/合金，诸如a-SiC:H、a-Si:O:H或a-SiN:H或类似物。
用于沉积光伏薄膜太阳能电池中的钝化层55的工艺包括：在展示待处理衬底的PECVD处理腔中引入包括硅烷和氢气的气体混合物；建立0.1-2mbar，优选地0.2-0.5mbar的处理压力，5-500W，优选地30-100W的RF功率(40MHz或更高)，以及1:1的氢气和硅烷之间的比例，或者建立1-5mbar的处理压力，100-600W的RF功率(40MHz或更高)，以及10:1至200:1的氢气和硅烷之间的比例；将衬底保持在100℃-250℃，优选地160℃的温度，以及沉积厚度为5nm-100nm，优选地20-40nm的包括非晶本征硅的层。
一种用于制造光伏薄膜硅太阳能电池的方法包括：
提供在其上具有透明导电前电极42的透明衬底41；沉积p掺杂Si层44、微晶硅本征层45、包括基本上本征非晶硅的钝化层55、n掺杂Si层46和后电极层48。
Claims (7)
1.一种光伏电池，包括：
衬底；
透明导电氧化物的前或第一电极；
包括微晶硅的至少一个p-i-n结，所述p-i-n结包括第一n掺杂硅子层和第二p掺杂硅子层以及布置在所述第一和第二子层之间的第三基本上本征微晶硅子层，
其中包括基本上本征非晶硅的至少一个钝化层布置成：a)位于微晶本征子层和n掺杂硅子层之间，或者b)成为嵌在微晶本征子层中的层，或者c)这二者。
2.根据权利要求1的光伏电池，其中所述钝化层具有5nm-200nm，优选地为10-50nm的厚度。
3.根据权利要求1-2的光伏电池，其中所述钝化层包括基本上本征硅或硅化合物/合金，诸如a-SiC:H、a-Si:O:H或a-SiN:H或类似物。
4.一种用于制造光伏薄膜硅太阳能电池的方法，包括：
-提供透明衬底，在其上具有透明导电前电极；
-沉积p掺杂Si层，
-沉积微晶硅本征层，
-沉积具有基本上本征非晶硅的钝化层，
-沉积n掺杂Si层和后电极层。
5.根据权利要求4的方法，其中沉积钝化层的步骤包括：
-引入具有硅烷和氢气的气体混合物到展示衬底的PECVD处理腔，
-将衬底保持在100℃-250℃，优选地160℃的温度；
-沉积厚度为5nm-100nm，优选地20-40nm的包括非晶本征硅的层。
6.根据权利要求4-5的方法，其中沉积钝化层的步骤包括：
-建立0.1-2mbar，优选地0.2-0.5mbar的处理压力，
-在40MHz或更高的2.5mW-250mW每cm2衬底尺寸，优选地15mW-50mW每cm2衬底尺寸的RF功率，以及
-氢气和硅烷之间1:1的比例。
7.根据权利要求4-5的方法，其中沉积钝化层的步骤包括：
-建立1-5 mbar的处理压力，
-在40MHz或更高的50mW-300mW每cm2衬底尺寸的RF功率，以及
-氢气和硅烷之间10:1至200:1的比例。
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| PCT/CH2011/000139 WO2011160246A1 (en) | 2010-06-25 | 2011-06-10 | Thin film solar cell with microcrystalline absorpber layer and passivation layer and method for manufacturing such a cell |
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| CN104362184A (zh) * | 2014-09-26 | 2015-02-18 | 中国科学院上海光学精密机械研究所 | 基于减反结构和导模谐振的薄膜非晶硅太阳能电池 |
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| CN103280846B (zh) * | 2013-03-27 | 2016-08-03 | 上海空间电源研究所 | 一种柔性光伏一体化电源系统 |
| CN103606589A (zh) * | 2013-07-25 | 2014-02-26 | 昆明铂阳远宏能源科技有限公司 | 非晶硅薄膜太阳能电池及其制造方法 |
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| EP2887406A1 (en) * | 2013-12-23 | 2015-06-24 | CSEM Centre Suisse d'Electronique et de Microtechnique SA - Recherche et Développement | Semiconductor device and method for fabricating said semiconductor device |
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