CN101350377B - 硅多结太阳能电池及其制备方法 - Google Patents
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Abstract
硅多结太阳能电池，其具有至少两个子电池(1，2)，每个子电池具有p-型层(p1，p2)、本征层(i1，i2)和磷掺杂的n-型层(n1，n2)。与置于其前的子电池(1)的n-型层(n1)接触的p-型层(p2)被构造为至少部分纳米-或微晶的。
Description
技术领域
本发明包括至少两个子电池的硅多结太阳能电池(multiple solar cell)，并涉及其制备方法。
背景技术
硅太阳能电池通常具有p-i-n的层序，即p-型层或p-层、本征层(intrinsiclayer)或i-层和n-型层或n-层，电场产生在整个i-层上。多电池包括各自具有p-i-n层序的多个子电池，容许电场显著地放大。
为了制备多电池，通常使用化学汽相沉积(CVD)，尤其是等离子体增强(PE)CVD方法。
单个子电池的多个层是通过在分级(fractionate)等离子体中含硅气体而产生的。所用沉积气体通常是硅烷(SiH4)或二硅烷(Si2H6)。除了(未掺杂的)i-层，掺杂的p-和n-层被沉积，即，光进入i-层所经由的p层通常通过混合硼(尤其通过混合二硼烷(B2H6)或三甲基硼(B(CH3)3))到沉积气体中而沉积的，而n-层通过添加磷(例如通过混合磷化氢到沉积气体中)而沉积的。
为了经济地制备硅多结太阳能电池，已经证实使用尤其是单室法是特别适合的，通过单室法，多结太阳能电池的所有层的沉积在一个且相同的反应器内依次以p-i-n-p-i-n的层序来进行，也就是说，在沉积掺杂层和本征层之间不清洗反应器。因此，在PECVD法中，单个层的沉积可以在不运输基底或也不中断等离子体的情况下进行。
由于很快的沉积速率，p-、i-和n层优选由非晶硅沉积。
p-i-n型硅多结太阳能电池的质量基本上由本征层的质量来决定。因此，必须保持硅多结太阳能电池的本征层的缺陷密度尽可能低。
发明内容
因此，本发明的目的是大大地减低硅多结太阳能电池的本征层的缺陷密度。
这是根据本发明通过一种硅多结太阳能电池来实现的，该硅多结太阳能电池包括至少两个子电池，每个子电池包括p-型层、本征层和磷掺杂的n-型层，光经由p-型层落入特定子电池的本征层，p-型层具有在与置于其前的子电池的n-型层的界面处的第一子层，以及具有非晶第二子层，其特征在于p-型层的第一子层包括纳米晶硅，该纳米晶硅包括尺寸为1-100nm的晶体，并且具有至少2nm的层厚度，所述n-型层具有比与其接触的位于其后的子电池的p-型层的层厚度更小的层厚度。
本发明的硅多结太阳能电池包括至少两个子电池，每个子电池包括p-层、沉积于p-层上的i-层、以及沉积于i-层上的磷掺杂的n-层.
本发明基于以下发现：除了由不饱和连接电子引起的缺陷尤其意外的掺杂导致本征层的缺陷。使用单室法尤其存在危险，因为掺杂元素可因而由先前沉积的掺杂层扩展到本征层内。可能的源是例如以与基底上的多电池的相同方式在PECVD法中沉积在反应器壁上、在单室法中还沉积在PECVD反应器的电极上的不充分结合的掺杂元素。
这里尤其重要的部分是展开掺杂n-层所需的磷。
现在根据本发明已经发现，如果沉积在第一个或在前的子电池的磷掺杂的n-层上的第二个或随后的每个子电池的p-层构建为至少部分纳米晶或微晶，则可极大地排除磷展开到本征层内。所述纳米或微晶硅在这里应理解为含有尺寸为1nm-1μm、尤其是10-100nm晶体的硅。
本发明的太阳能电池可以是例如具有两个子电池的串叠电池(tandemcell)或者具有三个子电池的三结电池，每个子电池都具有p-i-n层序，光经由p-层落入特定子电池的本征层。
本发明的硅多结太阳能电池的制备优选通过CVD在单室法中实施，即以第一子电池和每个另外子电池的p-i-n层序沉积是通过CVD在一个且相同反应器中实施。优选使用PECVD法。
所用沉积气体优选为硅烷、二硅烷或其他硅烷氢气体，而沉积气体可以具有混合在其中的氢气(H2)或惰性气体。在PECVD法中分级气体的等离子体可以通过施加直流电压或交流电压来产生。交流电场的频域由低频千赫范围经由MHz范围的放射频率延伸到GHz的微波范围。优选使用1-100MHz范围频率的交流电场。
为了将与先前沉积的子电池的n-层接触的p-层构造为至少部分纳米或微晶的，具有高含量氢气(H2)的沉积气体用于在沉积气体中形成反应性氢原子。也经常增加气体压力，并且在使用交流电场的PECVD法中增加频率来活化沉积气体中的氢气。
根据本发明的所述至少部分纳米-或微晶p-层与预先在入射光方向放置的子电池的先前沉积的n-层接触，构成防止磷由先前沉积的n-层展开的阻挡层。
本发明的多结太阳能电池的本征层优选包括比纳米或微晶硅沉积快很多的非晶硅。
与位于其后子电池的p-层接触的n-层可包括非晶硅，但是n-层优选在与p-层的界面上具有纳米-或微晶硅的子层，而n-层的保留部分是非晶的。这使得能够得到n/p接触上的低系列阻力，并且因而在太阳能电池内能得到高的填充系数。
与置于其前的子电池的n-层接触的p-层可完全包括纳米-或微晶硅。然而，对于仅p-层的子层，其优选为纳米-或微晶的，同时其余部分是非晶的，以便更快地沉积n-层。
在此情况下对于p-层的子层优选在与n-层的界面上为纳米-或微晶的，而p-层的其余部分为非晶的。在与n-层的界面上p-层的纳米-或微晶子层减小了在n/p接触上的系列阻力，并且因而提高了填充因数。
也就是说，本发明的多电池优选包括例如以下层序：非晶p-层、非晶i-层，非晶n-层或非晶n-子层、作为第一子电池的纳米或微晶n-子层以及纳米或微晶p-子层、非晶p-子层、非晶i-层、作为最后子电池的非晶n-层，而在第一和最后子层之间的其他子层优选各自包括以下层序：纳米或微晶p-子层、非晶p-子层、非晶i-层和非晶n-层或非晶n-子层和纳米或微晶n-子层。
与置于其前的子电池n-层接触的p-层的层厚度优选总共为5-30nm，尤其是8-10nm。P-层的纳米或微晶子层优选在这里具有的层厚度为至少2纳米，尤其是3-5nm。
与位于其后子电池的p-层接触的n-层的层厚度优选为5-30nm，尤其是8-15nm。
与先前放置的子电池的n-型层接触的p-型层优选与碳、氧或氮合金化，也任选为与所述元素的混合物合金化，以便增加带隙。
为此目的，在p-层的制备中可将含所述元素的气体混合到沉积气体中。这将少了p-层的吸光度，光经由所述p-层落入本征层中。
当n-层的掺杂使用混合到沉积气体中的磷气体(尤其是磷化氢)进行时，p-层通常通过将二硼烷或三甲基硼混合到沉积气体中进行。
另外，本发明的硅多结太阳能电池对应于现有技术，即其通常具有在光入射侧上的第一子电池的正面p-层上的透明电极层，和背面n-层上的电极层，还具有例如在光入射侧上的透明载盘，该透明载盘同时构成用于沉积多结太阳能电池的基底。
附图说明
图1是本发明的普通硅串叠电池的示意结构；
图2是根据以下实施例1的普通串叠电池的特征谱图；
图3是本发明的硅串叠电池的示意性示例结构；
图4是根据实施例2的本发明的串叠电池的特征图。
具体实施方式
根据图1，常规串叠电池具有第一子电池1和第二子电池2，光落在第一子电池1上。第一和第二子电池1、2各自构造为p-i-n电池，即他们各自在正面侧(即光入射侧)具有p-层p1、p2，并在背面侧具有n-层n1、n2，其中第一子电池1的n-层n1和第二子电池2的p-层p2彼此接触。每个子电池1、2的p-层p-1、p-2和n-层n1、n2之间在每种情况下都提供有本征层或i-层i1、i2。p-层p-1、p-2和本征层i1、i2各自包括非晶硅，n-层n1、n2也是如此。
根据图3的本发明的串叠电池不同于图1之处基本上在于：与第一子电池1的n-层n1接触的第二子电池的p-层p2包括与第一子电池1的n-层n1接触的纳米-或微晶硅的第一子层p21，以及与第二子电池2的本征层i2接触的非晶硅的第二子层p22。另外，相对于n-层n1的层厚度Dn1，与第一子电池1的n-层n1接触的第二子电池2的p-层p2具有更大的层厚度Dp2。
实施例1(对比)
在交流电场中(频率13.56MHz)中通过PECVD于单室法中制备了根据图1的常规硅串叠太阳能电池。碳合金化的、硼掺杂的非晶p-层p1和p2的层厚度在每个情况下为8nm，磷掺杂的非晶n-层n1和n2在每个情况下为10nm，非晶本征层i1和i2的层厚度在每个情况下为300nm。
图2显示串叠太阳能电池的特征。MPP代表最大功率点，ISC为短路电流，VOC为开路电流。
填充因数为53％。在第二子电池2的本征层的开始，通过二次离子质谱(SIMS)检测的磷浓度超过1×108cm-3。
实施例2
重复实施例1，不同之处在于所制备的串叠太阳能电池的第一子电池1的n-层n1的层厚度为5nm，而在与第一子电池1的n-层n1的界面处的第二子电池2的正面p-层p2包括层厚度为5nm的纳米-或微晶硅的第一子层p21，以及层厚度为8nm的非晶硅的相邻第二子层p22。
图4所示为该串叠太阳能电池的特征。其填充系数为76％。
Claims (8)
1.硅多结太阳能电池，其包括至少两个子电池(1，2)，每个子电池包括p-型层(p1，p2)、本征层(i1，i2)和磷掺杂的n-型层(n1，n2)，光经由p-型层(p1，p2)落入特定子电池(1，2)的本征层(i1，i2)，p-型层(p2)具有在与置于其前的子电池(1)的n-型层(n1)的界面处的第一子层(p-21)，以及具有非晶第二子层(p22)，其特征在于p-型层(p2)的第一子层(p21)包括纳米晶硅，该纳米晶硅包括尺寸为1-100nm的晶体，并且具有至少2nm的层厚度，所述n-型层(n1)具有比与其接触的位于其后的子电池(2)的p-型层(p2)的层厚度(Dp2)更小的层厚度(Dn1)。
2.权利要求1的硅多结太阳能电池，其特征在于本征层(i1，i2)包括非晶硅。
3.上述权利要求之一的硅多结太阳能电池，其特征在于与位于其后子电池(2)的p-型层(p2)接触的n-型层(n1)被构造为至少部分非晶的。
4.权利要求3的硅多结太阳能电池，其特征在于n-型层(n1)具有非晶子层和在与位于其后子电池(2)的p-型层(p2)的界面处的纳米-或微晶子层。
5.权利要求1的硅多结太阳能电池，其特征在于与位于其后子电池(2)的p-型层(p2)接触的n-型层(n1)的层厚度为20nm或以下。
6.权利要求2的硅多结太阳能电池，其特征在于与位于其后子电池(2)的p-型层(p2)接触的n-型层(n1)的层厚度为20nm或以下。
7.权利要求3的硅多结太阳能电池，其特征在于与位于其后子电池(2)的p-型层(p2)接触的n-型层(n1)的层厚度为20nm或以下。
8.权利要求1的硅多结太阳能电池，其特征在于通过与碳、氧或氮合 金化，与置于其前的子电池(1)的n-型层(n1)接触的p-型层(p2)具有增加的带隙。
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| DE102007033444.5 | 2007-07-18 | ||
| DE102007033444A DE102007033444A1 (de) | 2007-07-18 | 2007-07-18 | Silizium-Mehrfachsolarzelle und Verfahren zu deren Herstellung |
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| DE102009008371A1 (de) * | 2009-02-11 | 2010-08-12 | Schott Solar Ag | Integraler Prozeß von Waferherstellung bis Modulfertigung zur Herstellung von Wafern, Solarzellen und Solarmodulen |
| DE102010006314A1 (de) | 2010-01-29 | 2011-08-04 | EWE-Forschungszentrum für Energietechnologie e. V., 26129 | Photovoltaische Mehrfach-Dünnschichtsolarzelle |
| DE102011115028A1 (de) | 2011-10-07 | 2013-04-11 | Ewe-Forschungszentrum Für Energietechnologie E. V. | Photovoltaische Mehrfach-Solarzelle |
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| US4737196A (en) * | 1984-10-29 | 1988-04-12 | Mitsubishi Denki Kabushiki Kaisha | Amorphous solar cell |
| US4875944A (en) * | 1987-09-17 | 1989-10-24 | Fuji Electric Corporate Research And Development, Ltd. | Amorphous photoelectric converting device |
| CN1697201A (zh) * | 2005-06-20 | 2005-11-16 | 南开大学 | 硅薄膜太阳电池用p型窗口层及其制备方法 |
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| US4776894A (en) * | 1986-08-18 | 1988-10-11 | Sanyo Electric Co., Ltd. | Photovoltaic device |
| US5246506A (en) * | 1991-07-16 | 1993-09-21 | Solarex Corporation | Multijunction photovoltaic device and fabrication method |
| JPH05243596A (ja) * | 1992-03-02 | 1993-09-21 | Showa Shell Sekiyu Kk | 積層型太陽電池の製造方法 |
| JP3437386B2 (ja) * | 1996-09-05 | 2003-08-18 | キヤノン株式会社 | 光起電力素子、並びにその製造方法 |
| JP3754815B2 (ja) * | 1997-02-19 | 2006-03-15 | キヤノン株式会社 | 光起電力素子、光電変換素子、光起電力素子の製造方法及び光電変換素子の製造方法 |
| JPH11354820A (ja) * | 1998-06-12 | 1999-12-24 | Sharp Corp | 光電変換素子及びその製造方法 |
| US20080048102A1 (en) * | 2006-08-22 | 2008-02-28 | Eastman Kodak Company | Optically enhanced multi-spectral detector structure |
| US20080188062A1 (en) * | 2007-02-02 | 2008-08-07 | Chi-Lin Chen | Method of forming microcrystalline silicon film |
| US20080271675A1 (en) * | 2007-05-01 | 2008-11-06 | Applied Materials, Inc. | Method of forming thin film solar cells |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4737196A (en) * | 1984-10-29 | 1988-04-12 | Mitsubishi Denki Kabushiki Kaisha | Amorphous solar cell |
| US4875944A (en) * | 1987-09-17 | 1989-10-24 | Fuji Electric Corporate Research And Development, Ltd. | Amorphous photoelectric converting device |
| CN1697201A (zh) * | 2005-06-20 | 2005-11-16 | 南开大学 | 硅薄膜太阳电池用p型窗口层及其制备方法 |
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| CN101350377A (zh) | 2009-01-21 |
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