CN105723520A - 用于制造太阳能电池的方法 - Google Patents
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Abstract
本发明涉及一种用于由晶体半导体材料制造太阳能电池(1)的方法，其中，在半导体衬底(3)的第一表面(3a)中通过向内热扩散第一掺杂剂构成第一掺杂区域(5)并且在半导体衬底的第二表面(3b)中通过离子注入和向内热扩散第二掺杂剂构成第二掺杂区域(7)。
Description
技术领域
本发明涉及一种用于由晶体半导体材料制造太阳能电池的方法，其中，在半导体衬底的第一表面中通过向内热扩散第一掺杂剂构成第一掺杂区域并且在半导体衬底的第二表面中利用第二掺杂剂构成第二掺杂区域。
背景技术
基于单晶体的或多晶体的半导体材料、特别是硅的太阳能电池提供绝大部分由光伏能量转换获得的电能，尽管新型的太阳能电池种类、如薄层太阳能电池和有机太阳能电池得以研发并引入市场。在晶体硅太阳能电池中，最近也有重要的新发展，上述类型的太阳能电池(特别是所谓的N-PERT太阳能电池)属于所述晶体硅太阳能电池。
为了提高工业太阳能电池的效率，目前更多地推进具有磷和硼掺杂区域的太阳能电池的研发。一个突出的实例是双面n型太阳能电池，其中，硼掺杂的发射极位于电池的正面并且磷掺杂的背面场(BSF)位于背面。
特别是当所述掺杂区域与丝网印刷金属化部接触时，希望的是，针对两种掺杂剂调节掺杂轮廓，所述掺杂轮廓考虑市场常见的金属化膏剂的不同接触特性。因此，当利用传统的扩散工艺工作时，至少需要两个高温步骤以及附加的用于掩盖扩散的步骤。
这些不同的要求对于工艺控制构成很大挑战，因为磷和硼的扩散常数几乎相等。在一种具有两个扩散工艺的示例性的实施方案中，所述工艺互相影响，因为它们必须依次进行。
如果磷扩散在硼扩散之前进行，则硼扩散的热预算使磷扩散的深度变大。在这种情况下，磷扩散比硼扩散进行得深，正好与设计目标相反。如果磷扩散在硼扩散之后进行，则能够呈现希望的掺杂轮廓。然而，现在面对在磷向内扩散之前保护硼发射极的挑战。这在工业上特别是在结构化(texturiert)的太阳能电池正面上很难以良好的收益实现。具有两个扩散工艺的实施方案的另一缺点在于工艺复杂度高，因为必需多个高温步骤和覆盖层。
几种具有减小的工艺复杂度的方案尝试在一个高温步骤中同时进行硼和磷的扩散、亦即所谓的共扩散。该共扩散例如可以通过来自掺杂玻璃的扩散或者通过离子注入两种物质连同随后的扩散步骤得以进行。显然的是，利用该方案，两种扩散轮廓也同样深。
发明内容
通过本发明提供一种具有权利要求1所述特征的方法。本发明构思的适宜的扩展方案是从属权利要求的主题。
本发明实现一种混合方案，其中，仅磷掺杂的区域(或总体上：第二掺杂区域)通过离子注入制成并且在硼掺杂(或总体上：利用第一掺杂剂的掺杂)时仍采用既定方案、如来自气相或来自掺杂玻璃的扩散。在该方案计的范围内，主要作为扩散阻碍层起作用的覆盖层在构成第二掺杂区域的表面上构成，以便在这里禁止并且至少大大地防止第一掺杂剂向内扩散。
当然，有效的转化方案带来一系列问题，这些问题的解决方案基于所提及的方案最终导致本发明从这方面看的最佳实施方案。一方面，另外上面已经阐述的希望是针对两种掺杂剂调节出不同的掺杂轮廓。此外，存在如下问题：来自气相或掺杂玻璃的第一掺杂剂的扩散在半导体衬底的两面上构成掺杂区域，因此，在仅允许在所述表面的一个表面上具有包括第一掺杂剂的掺杂区域的太阳能电池结构中，需要附加步骤来避免或消除不希望的掺杂区域。
本发明的优选工艺顺序的特征在于，硼扩散(或者说第一掺杂剂的向内扩散)的热预算同时用于活化注入的磷区域(或总体上：第二掺杂剂的掺杂剂沉积层)。
在此，一个十分重要的特征在于，在磷离子注入之后和在硼扩散之前在磷区域上沉积出多功能覆盖层。在此，该覆盖层至少具有如下特性：用作用于第一掺杂剂(例如硼)的(向内)扩散阻碍并且因此防止该第一掺杂剂侵入第二掺杂剂(特别是磷)的掺杂剂沉积层中。
在优选实施方式中，覆盖层还具有其他特点/功能：
1.覆盖层作为用于氧的扩散阻碍起作用。
2.覆盖层可以作为用于磷(或总体上第二掺杂剂)的(向外)扩散阻碍。
3.覆盖层作为在第二表面、特别是亦即磷掺杂区域上的电钝化层起作用。
4.覆盖层作为在太阳能电池、特别是双面太阳能电池背面上的防反射层。
在本方法的一种目前看来适宜的设计方案中，作为半导体材料使用硅并且作为第一掺杂剂使用包括硼、铟、镓、铝的组中的元素、特别是硼，并且作为第二掺杂剂使用包括磷、砷、锑的组中的元素、特别是磷。鉴于近期的、效率提高的太阳能电池发展，特别地，上面一再具体要求保护的硼/磷掺杂剂组合具有重大的实践意义。
所提出的方法可构造为用于制造具有正面发射极的双面接触的太阳能电池或具有背面发射极的太阳能电池或MWT(金属贯穿孔技术)太阳能电池或IBC(交指背接触)太阳能电池的方法。特别地，所述第一掺杂区域可以构成为在n型硅衬底的正面表面中的发射极区域并且所述第二掺杂区域可以构成为在n型硅衬底的背面表面中的背面场。
在另一种实施方式中，所述第二掺杂区域的掺杂轮廓相对于所述第一掺杂区域的掺杂轮廓是较扁平的和/或通过所述第二掺杂剂比所述第一掺杂剂高的表面浓度来表征。更特别地，该方法这样设计，使得所述第一掺杂区域的构成包括以含有所述第一掺杂剂的玻璃覆盖所述第一表面和可选的所述第二表面或者在工艺气氛中所述第一掺杂剂以气态提供。
本发明的主要优点在于，相对于现有技术在成本方面明显优化的包括仅一个高温步骤的工艺顺序。这通过使用扩散阻碍层来实现，该扩展阻碍层能实现用于所述第一掺杂剂的向内热扩散步骤同时用于活化预先借助离子注入引入的第二掺杂剂，而不对希望的掺杂轮廓产生不利影响，并且该扩展阻碍层在适宜的设计方案中还具有其他优点，例如能实现含氧的工艺气氛的使用，其提高工艺速度并且因此降低工艺成本。
附图说明
下面借助实施例参考示意性的附图详细解释本发明。
唯一一个附图示出根据本发明的太阳能电池的示意性横剖图。
具体实施方式
唯一一个附图以横剖图示意性地示出太阳能电池1，该太阳能电池包括n型晶体硅衬底3和相应棱锥形结构化的第一(正面)表面3a和第二(背面)表面3b。在第一表面3a中，通过硼扩散构成第一掺杂区域(发射极区域)5，并且在第二表面中通过磷注入和随后的退火(Ausheilung)/活化构成扁平的背面场(BackSurfaceField)7作为第二掺杂区域。
在第一和第二表面3a、3b上分别作为防反射层沉积出密封的氮化硅层或含氮化硅的双层9a或9b。由此，背面的氮化硅层9b是在向背面表明3b中进行磷注入之后、但在向半导体衬底中进行硼扩散步骤之前构成的和在热扩散步骤之后保留在那里的层。防反射层可以通过由氧化物(如氧化硅)制成的附加的子层进行补充，该子层改善层钝化特性，但在图中未示出。在太阳能电池正面(第一表面)3a上设置正面金属化结构11a并且在太阳能电池背面(第二表面)3b上设置背面金属化结构11b。
下面示例性地描述用于制造双面接触的具有正面发射极的n型电池的顺序。对于本领域技术人员而言，用于制造不同类型的太阳能电池的变化方案是明显的。该太阳能电池的制造顺序包括下面提到的以该顺序的工艺模块，其中，每个工艺模块包括一个或多个工艺步骤。
工艺模块1：晶片的结构化
在该工艺步骤中，可以进行工业常见的结构化连同随后的净化。可选地可以在背面平面化晶片。为此，多种方法由现有技术公开并且对于阐述本发明是不重要的。
工艺模块2：构成掺杂剂沉积层(磷注入)
在此，向电池背面中注入磷(例如剂量在0.5和7e151/cm2之间并且能量为1-40keV、优选在1.5和4e151/cm2之间并且能量为10keV)。磷层的层电阻在退火(步骤4)之后为10-300Ohm/Sq、优选30-120Ohm/Sq。在一种扩展实施方式中，注入可以可选择地进行，使得金属化区域下方的剂量较高。附加地，注入可以被掩盖，使得在晶片边缘和磷掺杂之间产生50-1000μm宽的未掺杂区域，以确保BSF和发射极之间的电隔离。
在磷注入之后，可选地进行晶片的净化，以便去除不希望的磷残留物和污染。在一种实施方式中，这可以通过湿化学工艺进行，该湿化学工艺包括一个或多个在水、稀释的HF、HNO3或H2O2/HCl中的步骤。在另一种实施方式中，净化可以通过利用含氢、含氧和/或含氟的气氛的等离子体工艺进行。
在该工艺步骤之后，磷以电的非活性的形式处于晶片的基体中，而不处于晶片表面上。
工艺模块3：产生扩散阻碍层
第二衬底表面上的覆盖层(扩散阻碍层)防止硼向内扩散到该层中并且是氧不可通过的。此外，扩散阻碍层应确保良好的钝化，以及在双面太阳能电池的使用中用作防反射层。
在最简单的实施方式中，作为覆盖层使用纯SiN层(折射率为n＝1.8-2.2、优选为1.9-2)。层厚度为在1nm至250nm之间、优选在30-80nm之间。通常，覆盖层通过PECVD(等离子体增强化学气相沉积法)利用由组SiH4、N2、NH3、H2、Ar的一种或多种气体构成的工艺化学物沉积出。备选地，覆盖层可以利用其他方法、如LPCVD(低压力化学气相沉积法)、APCVD(常压化学气相沉积法)或PVD(物理气相沉积)施加。
为了优化所有要求，也可以使用层堆叠，在该层堆叠中，在硅和SiN之间嵌入SiO2、Al2O3、TiO或SiON层，该层可以改善钝化特性(0.5-50nm、优选5nm)。
为了改善阻碍特性，可以在层堆叠中附加地插入一个由非结晶硅或多晶硅制成的层(0.5-30nm、优选20nm)。
工艺模块4：硼扩散和同时磷活化
硼扩散通过炉工艺实施，在该炉工艺中，晶片首先在含硼的气氛中以硼质玻璃覆盖。在此，常见的前体有BBr3和BCl3，其他工艺气体有N2和O2。在覆盖步骤之后，在原处在惰性的或含氧的气氛中进行向内扩散步骤。在优选变型方案中，覆盖步骤和向内扩散步骤至少部地分在含氧的气氛中进行，以便实现加速的硼扩散。
另一种可能性在于将硼质玻璃沉积到电池正面上(例如通过APCVD或PECVD)并且随后在分开的工艺步骤中进行向内扩散。
硼扩散区域主要通过层电阻表征，层电阻特别是在30至200Ohm/Sq之间、优选在45至100Ohm/Sq之间。
如上所示，硼扩散同时引起磷掺杂区域的退火和活化。在此，磷也更深地扩散到衬底中，但通过利用多功能层的工艺控制比硼进行得慢。
扩散区域的深度在30nm至2500nm、优选在400至1000nm之间，在此，硼的深度优选比磷大。
工艺模块5：正面钝化
在现有技术中已知不同的用于钝化硼发射极的实施方案。在这里，钝化主要与由SiO2/SiN或Al2O3/SiN构成的层堆叠有关。所述层堆叠可以通过组合PECVD和热氧化工艺得以产生。确切的实施方案与本发明无关。
在钝化之前必须从正面去除在工艺模块4中可能构成的硼质玻璃，这可以根据现有技术利用稀释的HF溶液进行。
工艺模块6：可选的附加的背面钝化
如果在工艺模块3中构成的扩散阻碍层不同时作为电池背面的电钝化层起作用，则该层必须被去除并且由附加的钝化层取代。覆盖层的去除可以通过延长的HF步骤与步骤5中的硼质玻璃的去除共同进行。
作为钝化层可以根据现有技术使用SiO/SiN层或SiN层。
工艺模块7：金属化
金属化可以利用工业常见的方法进行并且对本发明是不重要的。正面金属化通常利用银栅格进行。背面金属化也借助银格栅或具有局部触点的整面铝金属化部进行，该铝金属化部例如通过激光烧蚀和PVD制成。
在用于背面发射极电池的这个工艺顺序(硼在背面上、磷在正面上)的一种可能的变化方案中也可以改变掺杂顺序。在这种情况下，取代磷而注入硼并且取代硼扩散而实施磷扩散。
在本领域技术人员的技术手段范围内得到在这里仅示例性地描述的方法和设备的其他设计方案和实施方式。
Claims (12)
1.用于由晶体半导体材料制造太阳能电池(1)的方法，其中，在半导体衬底(3)的第一表面(3a)中通过向内热扩散第一掺杂剂构成第一掺杂区域(5)并且在半导体衬底的第二表面(3b)中通过离子注入和向内热扩散第二掺杂剂构成第二掺杂区域(7)，
其中，通过离子注入第二掺杂剂在第二表面上和附近构成掺杂剂沉积层并且在第二表面上产生扩散阻碍层(9b)，用以阻碍第二掺杂剂从第二表面扩散出并且此后实施至少一个热工艺步骤，用以构成第一和第二掺杂区域。
2.根据权利要求1所述的方法，其中，作为半导体材料使用硅并且作为第一掺杂剂使用包括硼、铟、镓、铝的组中的元素、特别是硼，并且作为第二掺杂剂使用包括磷、砷、锑的组中的元素、特别是磷。
3.根据权利要求1或2所述的方法，其中，所述第一掺杂区域(5)构成为在n型硅衬底(3)的正面表面(3a)中的发射极区域并且所述第二掺杂区域构成为在n型硅衬底的背面表面(3b)中的背面场(7)。
4.根据上述权利要求中任一项所述的方法，其中，所述第二掺杂区域(7)的掺杂轮廓相对于所述第一掺杂区域(5)的掺杂轮廓是较扁平的和/或通过所述第二掺杂剂比所述第一掺杂剂高的表面浓度来表征。
5.根据上述权利要求中任一项所述的方法，其中，为了构成第一和第二掺杂区域(5；7)仅实施一个热工艺步骤，在该热工艺步骤中，用于向内扩散所述第一掺杂剂的热预算同时引起事先构成的掺杂剂沉积层中的第二掺杂剂的活化，为此，在所述第二表面(3b)上构成所述扩散阻碍层(9b)之后实施所述第一掺杂剂的向内扩散，并且其中，所述扩散阻碍层构造为向内扩散阻碍，用以防止所述第一掺杂剂向内扩散到所述第二表面中。
6.根据权利要求5所述的方法，其中，所述扩散阻碍层(9b)同时也构造为氧扩散阻碍并且所述第一掺杂剂的向内扩散至少部分地在含氧的气氛中实施。
7.根据上述权利要求中任一项所述的方法，其中，所述第一掺杂区域(5)的构成包括以含有所述第一掺杂剂的玻璃覆盖所述第一表面(3a)和可选的所述第二表面(3b)或者在工艺气氛中所述第一掺杂剂以气态提供。
8.根据上述权利要求中任一项所述的方法，其中，在所述第二表面构成太阳能电池(1)的背面的太阳能电池结构中，所述第二表面(3b)上的扩散阻碍层(9b)作为背面钝化层和/或背面防反射层保留在所述第二表面上。
9.根据上述权利要求中任一项所述的方法，该方法构造为用于制造具有正面发射极的双面接触的太阳能电池(1)或具有背面发射极的太阳能电池或MWT(金属贯穿孔)太阳能电池或IBC(指状组合型背接触)太阳能电池的方法。
10.根据上述权利要求中任一项所述的方法，其中，作为扩散阻碍层(9b)使用SiN层，该SiN层的折射率特别是n＝1.8...2.2、更特别是n＝1.9...2.0并且该SiN层的厚度特别是在1至250nm之间、更特别是在30至80nm之间。
11.根据权利要求10所述的方法，其中，作为扩散阻碍层使用层堆叠，该层堆叠除了SiN层外还包括SiO2层、Al2O3层、TiO层和/或SiON层，并且在该层堆叠中，该附加层或这些附加层特别是具有在0.5至50nm之间的范围内的厚度。
12.根据权利要求10或11所述的方法，其中，所述扩散阻碍层(9b)借助PECVD工艺、LPCVD工艺、APCVD工艺或PVD工艺产生。
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| KR20130062775A (ko) * | 2011-12-05 | 2013-06-13 | 엘지전자 주식회사 | 태양 전지 및 이의 제조 방법 |
| KR101860919B1 (ko) * | 2011-12-16 | 2018-06-29 | 엘지전자 주식회사 | 태양 전지 및 이의 제조 방법 |
| DE102012200559A1 (de) * | 2012-01-16 | 2013-07-18 | Deutsche Cell Gmbh | Verfahren zur Herstellung eines Emitters einer Solarzelle und Solarzelle |
| EP2654090B1 (en) * | 2012-04-17 | 2020-07-08 | LG Electronics, Inc. | Solar cell |
| KR101872786B1 (ko) * | 2012-06-22 | 2018-06-29 | 엘지전자 주식회사 | 태양 전지의 불순물층 형성 방법 및 태양 전지의 제조 방법 |
| DE102013210092A1 (de) * | 2013-05-29 | 2014-12-04 | Robert Bosch Gmbh | Verfahren zur Herstellung einer Solarzelle |
-
2013
- 2013-09-27 DE DE102013219603.2A patent/DE102013219603A1/de not_active Withdrawn
-
2014
- 2014-09-26 CN CN201480062121.7A patent/CN105723520A/zh active Pending
- 2014-09-26 EP EP14776652.1A patent/EP3050118A1/de not_active Withdrawn
- 2014-09-26 KR KR1020167010999A patent/KR20160061409A/ko not_active Application Discontinuation
- 2014-09-26 US US15/024,879 patent/US20160240724A1/en not_active Abandoned
- 2014-09-26 WO PCT/EP2014/070613 patent/WO2015044342A1/de active Application Filing
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109301031A (zh) * | 2018-09-12 | 2019-02-01 | 江苏林洋光伏科技有限公司 | N型双面电池的制作方法 |
| CN109301031B (zh) * | 2018-09-12 | 2021-08-31 | 江苏林洋光伏科技有限公司 | N型双面电池的制作方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015044342A1 (de) | 2015-04-02 |
| KR20160061409A (ko) | 2016-05-31 |
| EP3050118A1 (de) | 2016-08-03 |
| DE102013219603A1 (de) | 2015-04-02 |
| US20160240724A1 (en) | 2016-08-18 |
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