CN102782869A - 使用三维半导体吸收器的高效光伏背触点太阳能电池的结构和制造方法 - Google Patents

使用三维半导体吸收器的高效光伏背触点太阳能电池的结构和制造方法 Download PDF

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CN102782869A
CN102782869A CN2010800634967A CN201080063496A CN102782869A CN 102782869 A CN102782869 A CN 102782869A CN 2010800634967 A CN2010800634967 A CN 2010800634967A CN 201080063496 A CN201080063496 A CN 201080063496A CN 102782869 A CN102782869 A CN 102782869A
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M·M·穆斯利赫
P·卡普尔
K·J·克拉默
D·X·王
S·苏特
V·V·雷纳
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Abstract

提供了背结背触点三维太阳能电池及其制造方法。背结背触点三维太阳能电池包括三维衬底。该衬底包括具有钝化层的光捕获正面表面，掺杂的基极区域，和极性与掺杂的基极区域相反的掺杂的背面发射极区域。背面钝化层置于掺杂的背面发射极区域上。背面发射极触点和背面基极触点，其连接至金属互连件且选择性地在三维太阳能电池背面的三维特征上形成。

Description

使用三维半导体吸收器的高效光伏背触点太阳能电池的结构和制造方法
相关申请
本申请要求2009年12月9日提交的临时专利申请61/285140的权益，其通过引用并入本文中。
技术领域
本发明大体涉及光伏和太阳能电池技术领域，更具体地涉及背结背触点薄太阳能电池及其制造方法。
背景技术
目前，晶体硅在光伏(PV)产业的市场份额最大，占整个PV市场的80%以上。尽管制造更薄的晶体硅太阳能电池长期以来被认为是降低PV成本最有效的策略之一(因为太阳能电池中使用的晶体硅晶片的相对较高的材料成本占了PV模块总成本的一部分)，但是由于衬底尺寸较大较薄，这使得使用较薄的晶体的过程中存在很多机械破损问题。其他问题包括在薄结构中存在光捕获不充分，这是由于硅是一种间接能隙半导体材料。另外，在PV工厂中，在制造量较高的情况下很难以一种有效节约成本的方式取得高机械产量和降低的晶片破损率之间的平衡。
对于无支撑的独立式晶体硅太阳能电池而言，比当前的厚度范围140μm-250μm再稍微降低一点也会在制造过程中严重危害到机械产量。薄膜硅尤其具有机械脆性，会造成制造和处理困难。因此，任何处理非常薄的太阳能电池结构的方案可采用在整个电池工艺中电池完全由主载体支撑的电池工艺，或者是采用新颖的自支撑、独立、具有结构创新的衬底的电池工艺。
尽管过去太阳能电池行业很多人尝试使用诸如玻璃的载体来支撑薄衬底，然而这些载具有很严重的缺陷，包括最高处理温度很低(在玻璃情况下)，这会潜在地影响太阳能电池的效率。还有人尝试制造小面积薄的电池，这样就不会有严重的破损问题了；然而，商业可行性要求大的电池面积。
以较低制造成本获得较高的电池和模组效率对于太阳能电池发展和制造而言很关键。背结/背触点电池体系结构非常高效，主要是由于电池正面无金属遮挡，前面无发射极，无由此导致的高蓝光响应，并且还因为背面可能较低的金属电阻。本领域的技术人员知道背触点电池要求少数载流子扩散长度与衬底厚度的比值要非常高(同时任何太阳能电池都要有好的标准，包括正面触点电池，这对背触点电池尤其重要)该比值典型地应大于五。
由于在不影响机械产量的情况下很难降低电池的厚度，因此目前的背结背触点太阳能电池的重点在于使用寿命很长的材料。虽然这会产生较大的扩散长度，但是使用寿命长的材料也会增加衬底的成本。然而，使用较薄的电池，其扩散长度不一定要要求如此高，这就使得材料质量的要求很容易满足，因此电池的成本也会降低。除这种成本降低之外，使用较少的硅成本会明显降低。因此，在非常薄的晶体硅衬底上的背结/背触点电池具有大的成本和性能优势。
发明内容
根据本发明，提供了用于制造超薄晶体硅、大面积(适合于商业应用）的、背结背触点太阳能电池的方法及其创新结构。
本发明提供了背结背触点三维太阳能电池及其制造方法。背结背触点三维太阳能电池包括三维衬底。该衬底包括具有钝化层的光俘获正面表面，掺杂的基极区域，和极性与掺杂的基极区域相反的掺杂的背面发射极区域。背面钝化层置于掺杂的背面发射极区域上。背面发射极触点和背面基极触点，其连接至金属互连件且选择性地在三维太阳能电池背面的三维特征上形成。
由于此处提供的描述，本发明以及其它新颖特征会很明显。本简要内容不是要对权利要求的主题进行综合描述，而是对本发明的功能性进行简短的概述。在查阅以下图表和详细描述时，此处提供的其它系统、方法、特征和优点对于本领域的技术人员来说将变得明显。本简要内容的意图是将所有包含在本描述内的这些其它的系统、方法、特征和优点包括在伴随的权利要求的范围内。
附图说明
现参考以下结合附图的描述，以便对本发明及其优点有一个更全面的理解，附图中相似的标号表示相似的特征，其中：
图1A和1B是可重复使用的模板的侧视图和俯视图；
图2A和2B是硅衬底的照片；
图3是示出制造背结背触点薄太阳能电池的工艺流程；
图4A-4C是制造可重复使用的模板的剖面图；
图5A至5D是制造衬底的剖面图
图6A至6H是经过图3流程中的关键制造工艺步骤后太阳能电池的剖面图；
图7是制造示例性太阳能电池的工艺流程；
图8A至8H是经过图7中制造工艺流程的关键处理步骤后太阳能电池的剖视图；
图9是制造另一种示例性太阳能电池的工艺流程；
图10是图9中电池的最终结构的剖面图；
图11是制造另一种示例性太阳能电池的工艺流程；
图12A-12H是图示经过图11中工艺流程的关键制造步骤后电池的剖面图；
图13图示了制造另一种示例性太阳能电池的工艺流程；
图14是图13中电池的最终结构的剖面图；
图15图示了制造另一种示例性太阳能电池的工艺流程；
图16是图15中电池的最终结构的剖面图；
图17图示了制造另一种示例性太阳能电池的工艺流程；
图18A-18F是经过图17中流程的关键处理步骤后太阳能电池的剖视图；
图19图示了制造另一种示例性太阳能电池的工艺流程；
图20是图19中电池的最终结构的剖面图；
图21图示了制造另一种示例性太阳能电池的工艺流程；
图22是图21中电池的最终结构的剖面图；
图23图示了制造另一种示例性太阳能电池的工艺流程；和
图24是图23中电池的最终结构的剖面图。
具体实施方式
以下描述没有限制意义，其目的是为了描述本发明的一般原理。本发明的范围应该根据权利要求而定。本发明的示例性实施例在附图中图示，相同标号在在附图中表示相同或相应部件。
本发明提供了背结背触点薄半导体电池的结构方案和制造工艺方案。尽管以上描述是针对硅这种薄膜硅衬底(TFSS)，但也可以使用其它半导体材料如锗或砷化镓，而不脱离本发明的结构和方法的范围。使用硅或其它半导体材料的异质结和多结太阳能电池也在本发明的范围内。另外，三维背结背触点太阳能电池及其制造方法适用于衬底上任何三维形状/结构或微观结构，但是所显示并描述的是倒金字塔结构。术语“PyCell”此处指的是倒金字塔型结构的背结触点太阳能电池。
在操作中，首先使用外延生长在可重复使用的模板顶面制造一般厚度小于100um(尤其是在15um至50um范围内)的大面积(在156mmX156mm的范围内)薄太阳能电池衬底，且随后该衬底被移出。该可重复使用的模板可具有三维结构，或在另一种实施例中大体上是平面的。它可重复使用多次用于外延生长，这样便可分摊模板成本。TFSS可利用牺牲层从模板上分离，该牺牲层不仅可以将结晶性从模板传送到TFSS，而且与TFSS和可重复使用的模板相比还可以容易地、可选择性地被去除。牺牲层的一个例子是多孔硅，其孔隙率可被调整或分级以便获得上述两个重要功能。使用上述方法制造薄太阳能电池衬底之后，关键挑战是在制造太阳能电池的过程中处理这些TFSS，且不造成破损和分裂。从经营成本的角度来看，沉积非常薄的硅层是可取的。随着层逐渐变薄，应对薄层衬底进行增强以保证通过此工艺流程可获得较高的机械产量，例如带有超薄(1um到30um)硅层的大(156mmx156mm近似方形)三维TFSS。以下结构和方法用于解决TFSS加工问题并可增大总效率。
图1A和1B分别为PyCell可重复使用的硅模板的剖面图和俯视图。图1A图示了可重复使用的倒金字塔型模板的部分剖面图，该金字塔型模板剖面由大金字塔型空腔和小金字塔型空腔组成。由于是通过各向异性硅蚀刻对金字塔型空腔进行化学蚀刻，所以侧壁和顶部横向平面之间的角度是54.7度，即(111)和(100)硅结晶平面之间的角度是54.7度。图1B图示了本发明中所制造的模板的俯视图。结构化的硅模板由各向异性蚀刻的大金字塔型空腔和小金字塔型空腔组成。大空腔的顶部开口尺寸在10μm到1mm的范围内，小空腔的顶部开口尺寸是大空腔开口尺寸的一部分。例如，大空腔开口大约是200μm，而小空腔开口大约是100μm。在这种情况下，大空腔的深度大约是140μm，而小空腔的深度大约是70μm。
图2A和2B是PyCell硅衬底背面视图和正面视图的照片。图2A图示了衬底背面，所有的基极和发射极触点、结、金属指状电极和汇流条都在衬底背面上制造。由于背面表面不是平面，优选地将触点和金属指状电极放置在顶部表面，比如放置在脊的顶部。图2B图示了衬底正面，也就是太阳能电池的向阳面。规则的金字塔型结构可提供有效的光捕获效果。
图3是示出制造背结背触点薄太阳能电池，PyCell-1的制造工艺的工艺流程。工艺流程包括三个竖栏：模板、衬底和电池，分别与模板、衬底和电池处理步骤相对应。图4A至4C是当根据图3中的模板制造工艺制造可重复使用的模板时在关键制造工艺步骤后制造可重复使用的模板的剖视图。
如图4A所示，模板制作过程从使用单晶硅晶片(100)开始。起始的晶片可以是圆形、正方形或近似方形的形状。此步骤包括在暴露的晶片表面形成薄而硬的掩蔽层。硬掩蔽层用于掩蔽后续步骤中不需要蚀刻的硅表面区域。硬度适当的掩蔽层包括，但不局限于，热生长的硅氧化物和低压汽相沉积的(LPCVD)氮化硅。下一个步骤包括光刻步骤，其光刻涂胶、烘焙、在光掩模上方进行紫外线曝光、后烘焙、光刻胶显影以及晶片清洗和干燥构成。经过这些步骤，光掩模上的图案，比如错开的正方形开口，被转移到光刻层。图案化的光刻层在后续步骤中作为软掩蔽层用于硬掩蔽层蚀刻。下一个步骤包括通过化学蚀刻将光刻图案进一步转移到下面的硬掩蔽层，比如用缓冲HF溶液蚀刻薄硅氧化层。也可以使用其它已知的用于半导体和MEMS晶片处理的湿蚀刻方法和干蚀刻方法。在下一个步骤中，去除剩余的软掩蔽层即光刻层，并清洁晶片。光刻去除工艺的例子包括湿法，如使用丙酮或食人鱼溶液(硫酸和过氧化氢的混合液)，或干法，如氧等离子体灰化。在下一个步骤中，晶片被批量装入各向异性的硅液体蚀刻剂中，如KOH溶液。典型的蚀刻温度在50°C到80°C之间，蚀刻速率大约是0.2μm/min-1μm/min。在一个实施例中，大金字塔型空腔的蚀刻深度在50μm-200μm的范围内。TMAH(四甲基氢氧化铵）是另一种选择性的各向异性硅蚀刻化学品。KOH或TMAH硅蚀刻速率取决于对晶体硅平面的取向。结晶平面(111)族的蚀刻速率都非常慢，且对于用图案化的硬掩膜对硅晶片(100)进行各向异性蚀刻而言，这些结晶平面通常是“停止（stop）”面。结果，交叉的水平面(111)形成具有尖头空腔底部和四个平面侧壁(111)的金字塔型空腔，如图4B所示。在制造模板的最后一个步骤中，如图4C所示，除去硬蚀刻掩膜。
图5A至5D为根据图3中的衬底制造工艺，关键制造工艺步骤后制造衬底的剖面图。图5A至5D中的剖面图描述的结构特征是一致的，除非另行标注。
第一个步骤以预结构化的模板开始，通过对模板表面的正面和背面的硅进行电化学阳极HF蚀刻，在该模板上形成多孔硅层。在HF/IPA(或HF/醋酸)溶液中形成多孔硅的过程中，周期性地将电流极性在正电流和负电流之间转换，使得每一个模板面/表面都能被顺序地蚀刻，以在模板的正面和背面形成双层或多层多孔硅结构。除了周期性的电流极性转换，电流强度也以一种受控的方式被改变以形成优选地由两个孔隙率不同的(低和高)薄层组成的多孔硅层。第一薄多孔硅层在顶部，且首先由块状硅晶片制成。第一薄层优选地具有较低的孔隙率，其孔隙率在15%到30%之间。第二薄多孔硅层被直接蚀刻到块状硅中，且位于第一薄多孔硅层下面。第二薄多孔硅层优选地具有较高孔隙率，其孔隙率在40%到80%的范围内。顶部较低孔隙率多孔硅层用作为晶体种子层，以获得高质量的外延硅生长，下面的较高孔隙率多孔硅层由于其物理连接(在外延硅和块状硅界面之间)密度较低以及机械强度弱，因此被用于促进TFSS的分离。选择性地，也可使用孔隙率从顶部到底部逐渐增大的单多孔分离层。在这种情况下，多孔硅层顶部的孔隙率较低，在15%到30%之间，而多孔硅层下部的孔隙率较高，在40%以80%之间。在下一个步骤中，在外延硅生长之前，将晶片放入外延硅沉积反应器内，在高温(950度到1200度，且优选地在1050度到1150度的范围内)氢环境下烘焙，以便在较高孔隙率掩埋的多孔硅层内形成联合结构(空隙相对较大)，同时在孔隙率较低的多孔硅层顶部形成连续的晶体硅表面种子层。接下来，在模板上沉积单晶外延硅层，优选地在生产量高，批量大的外延火炉中进行。外延层可原位掺杂。在该工艺流程中，外延层的块状基极是N(磷)型掺杂，内层可以是掺杂等级比n-型基极高的n+(磷)型掺杂，如此形成前表面场(FSF)，并且外层可以是P(硼)掺杂以形成太阳能电池的发射极区域。外延层是薄的，优选地100μm。更具体地，除了硅掺入(三氯氢硅-TCS)和其它必要的气体外，基极掺杂可通过使用磷化氢(磷掺入)气体获得，且在外延工艺最后发射极生长结束时，可按程序控制反应器将其切换到乙硼烷(硼掺入)替代磷化氢。应优化基极和发射极区域的厚度以获得最佳的太阳能电池性能。在一个实施例中，优选地基极厚度小于100μm，掺杂在5e14和1e17cm-3之间，发射极厚度小于3μm，掺杂在1e18和3e20cm-3之间。发射极也可以分很多步骤，每一个步骤产生一个不同的浓度。这种外延结构有利于太阳能电池产生高的开路电压，从而实现更高的效率。在下一个步骤中，薄氧化层在外延表面热生长。薄氧化层用于太阳能电池表面钝化，以及用于后续选择性表面开口的掩蔽层。图5A图示了薄氧化步骤后的剖面图。
在下一个步骤中，施加增强层以填充空腔且覆盖整个顶部表面。增强层的材料须能承受高温，比如200-300度，以用于后续的前表面PECVD氮化硅钝化工艺。作为例子，聚酰亚胺可用于所述增强目的。增强层可通过喷雾涂覆，之后进行固化或进行薄膜真空分层工艺来施加。选择性地，增强可通过夹紧载板来实现。夹紧可通过使用真空力来完成，或由静电夹头(ESC)或可移动静电载具(MESC)辅助或实现。图5B示出背面增强后的剖面图。在如图3所示，在下一个步骤中，对模板边缘顶部表面以及斜表面进行机械抛光以便在模板边缘将外延硅层与模板进行物理分离。通过进行局部浅层激光切割穿越外延层而不损害下面模板的表面可进一步在模板上限定PyCell TFSS的边界。在下一个步骤中，被强化的硅外延层从模板上分离/分开。在一个公开的方法中，TFSS是在超声波DI-水浴中被分离。然而在另一种公开的方法中，在晶片背面和顶部外延被真空吸紧的情况下，通过直接拉拔分离TFSS。分离的三维TFSS的厚度在50μm到200μm的范围内(取决于可重复使用的模板上倒金字塔型空腔的深度)而无需考虑增强层。强化的三维TFSS的厚度在0.2mm到1mm的范围内。在下一个步骤中，通过使用KOH或TMAH溶液进行短硅蚀刻来清洁被分离的TFSS背面表面以便去除硅碎片且完整地或局部地去除近似单晶硅(QMS)层。与此同时，且在边缘外延硅层从模板上被去除后，使用稀释的HF和稀释的湿硅蚀刻溶液清洁模板，比如使用TMAH和/或KOH去除剩余的多孔硅层和硅粒子。然后，通过传统的硅晶片清洗方法进一步清洗模板，比如使用SC1和SC2湿法净化(或所谓的RCA清洗工艺)去除可能的有机污染和金属污染。最后，用去离子水进行适当的冲洗且干燥后，该模板便可用于另一个重复使用循环。如图5C所示，强化的PyCell衬底，被称为三维TFSS，已制成，并且准备好进行后续的电池制造工艺。
图6A到6H是当根据图3中的制造工艺制造太阳能电池时在关键的电池制造工艺步骤后太阳能电池PyCell-1的剖面图。图6A至6H中的剖面图描述的结构特征是一致的，除非另行标注。图6A至6H中，太阳能电池的剖面图显示其正面(向阳面)朝下，背面(非-向阳/触点面)朝上以便更好地图示处理步骤。
如图6A所示，厚度优选地在60nm到100nm之间的PECVD氮化硅层在正面沉积，该正面是PyCell衬底的金字塔面(向阳面)。PECVD氮化硅层用作为表面钝化层和抗反射涂层(ARC)。对于晶体硅太阳能电池而言，降低表面载流子复合是获得高效率的一项重要要求，且由于较大的面容比，这对于薄而大的硅衬底而言更加关键。用介电层进行表面钝化是一种降低表面载流子复合速率的有效方法，因为好的表面钝化层不仅降低表面状态的密度，使介电层产生固定绝缘体电荷，还可提供能将少数载流子从表面逐走的有源场，因此进一步减低表面载流子复合率。氮化硅层也可在正面表面作为抗反射涂层(ARC)，以及作为增强物的内部光学反射层以在前表面更好地捕获光。在下一个步骤中，如图6B所示，PyCell衬底正面通过施加一层支撑材料，比如PV-级EVA、Z68或硅树脂而被强化。施加方法包括，但不局限于，热喷涂和真空层压。正面增强后，可完全去除背面增强层，比如通过松开MESC或MOVAC载板，或去除沉积层，如所示的聚酰亚胺层。在另一种实施例中，可局部去除背面增强层(如聚酰亚胺层)以局部暴露衬底背面表面,以便形成结、触点和金属化。
在下一个步骤中，使用对准的激光烧蚀从背面的脊打开发射极触点开口。要求激光烧蚀波长、脉宽和能量剂量能选择性地去除介电层(这种情况下为薄氧化层)而不损伤到下面的硅表面或造成最低损伤。背面增强层去除后且发射极触点开口后的剖面图在图6C中示出。
在下一个步骤中，通过覆盖式喷涂或对准印刷，在表面沉积磷液体掺杂物。在将磷液体掺杂物进行固化后，将激光束指向基极触点区域。通过在基极触点区域顶部烧蚀介电层，受控的激光束将基极触点打开并且驱入磷掺杂物来形成n++基极结。激光处理步骤的剖面图在图6D中示出。在下一个步骤中，在湿蚀刻工艺中，比如使用稀释的HF蚀刻剂除去剩余的磷掺杂物。图6E图示了形成的发射极触点开口、基极触点开口和n++基极结。应注意，在PyCell-1流程中发射极和基极触点开口是离散的，这意味着这些开口没有被连接起来以形成连续的交叉指状线条开口。在下一个步骤中，在脊表面喷墨印刷金属，比如镍((Ni)纳米粒子墨汁以将触点开口连接到交叉指状发射极和基极电极图案。烧结后，印刷的镍薄图案也用作为种子层用于后续的较厚金属电镀工艺。印刷镍的剖面图在图6F中示出，电镀的厚Ni+Cu+Sn的剖面图在图6G中示出。
在这个阶段，太阳能电池(PyCell-1)已完成，并可以接着进行后续的测试和模块组装步骤。然而，在选择性的实施例中，通过实施改良的钝化层堆叠和背反射镜来进一步增大电池效率，背面增强层可被完整地除去，且可选择性地在没有金属触点的背面表面按顺序沉积薄铝氧化物钝化层和薄PVD铝镜层。由于PECVD三氧化二铝层内部存在固定的电荷，该固定电荷可有效降低少数载流子表面复合率，因此PECVD沉积的三氧化二铝层改善了背面表面钝化效果。PVD铝薄层被用作为背反射镜以将光线反射回硅中。沉积PECVD氧化铝和PVD铝之前可使用荫罩，将荫罩适当对准地覆盖到电镀的发射极和基极汇流条触点区域以避免氧化铝和铝层覆盖。可在实施正面增强层之后，随即去除整个背面增强层。图6H示出具有改善的背面表面钝化和增加的PVD铝背反射镜的PyCell-1太阳能电池的剖面图。
图7是根据本发明的制造PyCell太阳能电池另一种示例(PyCell-2)的工艺流程。PyCell-2的可重复使用的模板和PyCell衬底的制作过程可与PyCell-1的模板和衬底的制作过程相同。电池工艺步骤在发射极触点开口步骤之前也可以是相同的。然后，PyCell-2设计包括用于发射极和基极触点的连续的交叉指状线条开口，而非形成非连续的发射极和基极触点开口。结果，喷墨印刷金属纳米粒子墨汁的步骤被取消，因为在PyCell-1中，喷墨印刷镍的目的是用非连续的触点开口来形成连续的交叉指状线条基极和发射极图案。
图8A至8H是经过PyCell-2电池工艺流程的关键制造步骤后，太阳能电池的剖面图。图8A至8C中的处理步骤和结构设计与图6A到6C中的相同。然而，如图8D所示，用对准的激光束扫描连续的交叉指状线条以形成连续的交叉指状线条基极和发射极触点开口(如图8E所示)。所示的基极结也具有连续的交叉指状线条形状。形成触点开口和基极结之后，在暴露的硅表面对镍进行化学镀，然后电镀Cu和Sn以形成发射极和基极金属指状电极和汇流条，如图8G所示。如图6H所示的那样，图8H图示了选择性的实施例PyCell-2，其包括PECVD氧化铝钝化层和PVD铝背反射镜层。PECVD氧化铝钝化层和PVD铝背反射镜层未覆盖发射极和基极汇流条触点区域，此并未在图8(h)中示出。
图9是用于制造PyCell太阳能电池的另一种示例，PyCell-3A的工艺流程。与PyCell-1相比，PyCell-3A的一个不同之处在于背面增强层也用作为背面漫反射镜。背面漫反射镜将透过的光线在各个方向反射回硅材料中。例如，热喷涂的PTFE背面增强层同时也可用作为漫反射镜层。图10是图9中PyCell-3A电池工艺流程的最终结构的剖面图，示出有背面增强和漫反射镜层。
图11是用于制造PyCell太阳能电池的另一种示例，PyCell-3B的工艺流程。PyCell-3B的可重复使用的模板和PyCell衬底的制作过程可与PyCell-1的模板和衬底的制作过程相同。PyCell-3B的关键实施例为其具有选择性发射极，且背面增强层也用作为背面漫反射镜层。基极和发射极触点开口是离散的；因此需要喷墨印刷镍纳米粒子墨汁的步骤以便用离散的触点开口形成连续的交叉指状线条基极和发射极图案。
图12A-12H是图示经过图11PyCell-3B电池的工艺流程的关键制造步骤后，电池的剖面图。剖面图图12A到-12H中描述的结构特征是一致的，除非另行标注。
电池PyCell-3B的工艺从背面强化的衬底开始，且背面增强层也用作为背反射镜。如图12A所示，在电池正面沉积厚度在60nm至100nm之间的PECVD氮化硅层，它是PyCell衬底的金字塔型面。PECVD氮化硅层用作为表面钝化层和抗反射涂层(ARC)。在下一个步骤中，如图12B所示，PyCell衬底正面通过施加一层支撑材料，比如PV-级EVA、Z68或硅树脂而被强化。沉积方法包括但不局限于热喷涂和真空层压。正面增强后，可局部去除背面增强层，比如PTFE层，以局部暴露可以形成结、触点和金属化的衬底背面表面。可通过选择性激光烧蚀来部分去除背面增强层。如图12C所示，在下一个步骤中，通过覆盖式喷涂或对准印刷在表面沉积硼液体掺杂物。在将硼液体掺杂物进行固化后，将激光束指向发射极触点区域。通过烧蚀发射极区域顶部的介电层(薄硅氧化物)受控的激光束可打开发射极触点，以及驱入硼掺杂物以便同时形成p++选择性发射极结。在下一个步骤中，使用湿蚀刻工艺，比如使用稀释的HF蚀刻剂，除去剩余的硼掺杂物，且制造了选择性发射极结，在图12D中示出。选择性发射极p++结比p+外延发射极层的掺杂浓度高，且选择性发射极结的深度可以比外延发射极层更深。
接下来，如图12E所示，进行相似的工艺以形成选择性基极结。这一工艺从通过覆盖式喷涂或对准印刷而在表面沉积磷液体掺杂物开始。将磷液体掺杂物进行固化后，将激光束指向基极触点区域。通过烧蚀基极发射极区域顶部的介电层(薄硅氧化物)使用受控的激光束打开基极触点，以及驱入磷掺杂物以便同时形成n++选择性发射极结。在下一个步骤中，使用湿蚀刻工艺，比如使用稀释的HF蚀刻剂，除去剩余的硼掺杂物，并且制造了选择性基极结，在图12F中示出。通过反掺杂外延p+发射极层形成选择性基极n++结，且基极结深度比外延发射极层更深。图12F图示了形成的发射极触点开口、基极触点开口、p++选择性发射极结和n++基极结。应注意，在PyCell-3B流程中发射极和基极触点开口也是离散的，这意味着这些开口没有被连接起来以形成连续的交叉指状线条开口。
在下一个步骤中，在脊表面喷墨印刷金属，比如镍((Ni)纳米粒子墨汁以将触点开口连接到交叉指状发射极和基极电极图案。烧结后，印刷的镍薄图案也用作为种子层用于后续的较厚金属电镀工艺。印刷镍的剖面图在图12G中示出，电镀的厚Ni+Cu+Sn的剖面图在图12H中示出。在此阶段，PyCell-3B太阳能电池已完成(在图12H中示出)，并且可开始进行后续的测试和模块组装步骤。
图13图示了制造PyCell太阳能电池的另一种示例，PyCell-4A的工艺流程。PyCell-4A的可重复使用的模板和PyCell衬底的制作过程大体上与PyCell-1的模板和衬底的制作过程相同。不同的是，在PyCell-4A中，背面增强层也用作为背面漫反射镜。背面漫反射镜将透过的光线在各个方向反射回硅材料中。例如，热喷涂的PTFE背面增强层同时也可用作为漫反射镜层。电池工艺步骤在发射极触点开口步骤之前也可以是相同的。然后，PyCel l-4A设计制造用于发射极和基极触点的连续的交叉指状线条开口，而非制造非连续的发射极和基极触点开口。结果，喷墨印刷镍纳米粒子墨汁的步骤被取消，因为在PyCell-1中，喷墨印刷镍的目的是用非连续的触点开口来形成连续的线条交叉的基极和发射极图案。也就是说，除了触点开口是连续的线条交叉的图案，且取消了喷墨印刷镍纳米粒子的步骤之外，电池PyCell4A的工艺流程可与图7和8中描述的相同。此外，由于背面增强层具有背反射镜效果，因此在PyCell-4A设计中免去了在背面施加PECVD氧化铝钝化层和PCD铝层的需要。
图14是根据本发明的PyCell-4A电池工艺流程的最终结构的剖面图。图中示出了背面增强和漫反射镜层，且发射极和基极触点开口和基极结为连续的线条交叉的图案。
图15图示了制造PyCell太阳能电池的另一种示例，PyCell-4B的工艺流程。PyCell-4B的可重复使用的模板和PyCell衬底的制作过程大部分与PyCell-1的模板和衬底的制作过程相同。不同的是，背面增强层也用作为背面漫反射镜。背面漫反射镜将透过的光线在各个方向反射回硅材料中。例如，热喷涂的PTFE背面增强层同时也可用作为漫反射镜层。除了发射极和基极触点开口和结是连续的线条交叉的图案之外，电池PyCell-4B的工艺流程大部分与电池PyCell-3B的工艺流程相同。PyCell-4B也具有选择性发射极(p++)结，除了PyCell-4B的选择性发射极设计是连续的线条交叉的图案外，其制造方法与PyCell-3B电池工艺中选择性发射极结的制造方法相同。
图16是图15中PyCell-4B电池工艺流程的最终结构的剖面图。PyCell-4B电池具有形成的选择性发射极。背面增强层也用作为漫反射镜层。发射极和基极触点开口和基极结为连续的线条交叉的图案。
图17图示了制造PyCell太阳能电池的另一种示例，PyCell-4C的工艺流程。PyCell-4C的可重复使用的模板和PyCell衬底的制作过程大部分与PyCell-1的模板和衬底的制作过程相同。不同的是，背面增强层也用作为背面漫反射镜。背面漫反射镜将透过的光线在各个方向反射回硅材料中。例如，热喷涂的PTFE背面增强层同时也可用作为漫反射镜层。除了发射极和基极触点开口和结是在单个激光烧蚀和掺杂工艺中形成的之外，电池PyCell-4C的工艺流程大部分与电池PyCell-4B的工艺流程相同。PyCell-4C也具有选择性发射极(p++)结，其制造方法与PyCell-4B电池工艺中的选择性发射极结的制造方法相同。
图18A-18F是经过根据本发明的电池PyCel l-4C工艺流程的关键处理步骤后的剖面图。电池PyCell-4C的工艺从背面强化的衬底开始，且背面增强层也用作为背反射镜。如图18A所示，在正面沉积厚度在60nm至100nm之间的PECVD氮化硅层，它是PyCell衬底的金字塔型面。PECVD氮化硅层用作为表面钝化层和抗反射涂层(ARC)。在下一个步骤中，如图18B所示，PyCell衬底正面通过沉积一层支撑材料，比如PV-级EVA、Z68或硅树脂而被强化。沉积方法包括，但不局限于，热喷涂和真空层压。正面增强后，可局部去除背面增强层，比如PTFE层，以局部暴露形成结、触点和金属化的衬底背面表面。可通过选择性激光烧蚀来部分去除背面增强层。如图18C所示，在下一个步骤中，通过喷墨工艺在电池表面沉积硼液体掺杂物和磷液体掺杂物。印刷磷和硼液体可在单个印片(print load)上一次完成，其中，所述两种液体分别从两个分离的印刷喷嘴喷出。选择性地，这两种液体可以在先后两个印片中印刷，中间有可选择的干燥步骤。接下来，印刷的磷和硼掺杂物完全干燥和固化，比如在对流烘箱中进行干燥和固化。
在下一个步骤中，如图18D所示，将对准的激光束指向发射极触点区域。通过烧蚀触点区域顶部的介电层(薄硅氧化物)受控的激光束将发射极触点打开，以及驱入硼掺杂物用于同时形成p++选择性发射极结和n++基极结。在下一个步骤中，剩余的硼和磷掺杂物在湿蚀刻工艺中，比如使用稀释的HF蚀刻剂，被去除，且形成了选择性发射极结和基极结，在图18E中示出。结和触点开口为连续的交叉指状线条图案。选择性发射极p++结比p+外延发射极层的掺杂浓度高，且选择性发射极结的深度可以比外延发射极层更深。接下来，如图18F所示，电镀厚的Ni+Cu+Sb金属层，且电镀的金属电极形成交叉指状金属线条以及基极和发射极汇流条。在此阶段，PyCell-4C太阳能电池已完成，在图18F中示出，并且可进行后续的测试和模块组装步骤。
图19图示了制造PyCell太阳能电池的另一种示例，PyCell-5A的工艺流程。PyCell-5A的可重复使用的模板和PyCell衬底的制作过程大部分与PyCell-1的模板和衬底的制作过程相同。例外的是，背面增强层也用作为背面漫反射镜。背面漫反射镜将透过的光线在各个方向反射回硅材料中。例如，热喷涂的PTFE背面增强层同时也可用作为漫反射镜层。电池PyCell-5A的工艺流程大部分与电池PyCell-4A的工艺流程相同。然而，为了进一步改善背面漫反射镜的效果，在电池背面施加了额外的漫反射镜堆叠。在制造出所描述的电池PyCell-4A之后，喷涂低密度的PTFE层并且覆盖除发射极和基极汇流条触点区域以外的背面表面，那些区域由荫罩覆盖。接下来，在背面和增加的PTFE层顶部沉积薄PVD铝层，该PVD铝用作为背反射镜。在PVD铝的沉积工艺过程中，发射极和基极汇流条触点区域也被荫罩覆盖以便发射极和基极金属不会因为PVD铝而产生分流。
图20是图19中描述的PyCell-5A电池工艺流程的最终结构的剖面图。PyCell-5A电池背面具有连续的交叉指状发射极和基极触点线条开口、具有额外低密度PTFE层的增强型背面漫反射镜，以及PVD铝层。PTFE和PVD铝层未覆盖发射极和基极汇流条触点区域，此并未在图20中示出。PyCell-5A电池没有选择性发射极。
图21是用于制造PyCell太阳能电池的另一种示例，PyCell-5B的工艺流程。PyCell-5B的可重复使用的模板和PyCell衬底的制作过程大部分与PyCell-1的模板和衬底的制作过程相同。例外的是，背面增强层也用作为背面漫反射镜。背面漫反射镜将透过的光线在各个方向反射回硅材料中。例如，热喷涂的PTFE背面增强层同时也可用作为漫反射镜层。电池PyCell-5B的工艺流程大部分与电池PyCell-4B的工艺流程相同。然而，为了进一步改善背面漫反射镜的效果，在电池背面施加了额外的漫反射镜堆叠。在制造出所描述的电PyCell-4B之后，喷涂低密度的PTFE层并且覆盖除发射极和基极汇流条触点区域以外的背面表面，那些区域由荫罩覆盖。接下来，在背面且在增加的PTFE层顶部沉积薄PVD铝层，该PVD铝用作为背反射镜。在PVD铝的沉积工艺过程中，发射极和基极汇流条触点区域也被荫罩覆盖以便发射极和基极金属不会因为PVD铝而产生分流。
图22是图21中PyCell-5B电池工艺流程的最终结构的剖面图。如所示，PyCell-5B电池背面具有连续的交叉指状线条发射极和基极结以及触点开口、具有额外低密度PTFE层的增强型背面漫反射镜，以及PVD铝层。PTFE和PVD铝层未覆盖发射极和基极汇流条触点区域，此并未在图22中示出。PyCell-5B电池没有选择性发射极。
图23是制造PyCell太阳能电池的另一种示例，PyCell-5C的工艺流程。PyCell-5C的可重复使用的模板和PyCell衬底的制作过程大部分与PyCell-1的模板和衬底的制作过程相同。例外的是，背面增强层也用作为背面漫反射镜。背面漫反射镜将透过的光线在各个方向反射回硅材料中。例如，热喷涂的PTFE背面增强层同时也可用作为漫反射镜层。电池PyCell-5C的工艺流程大部分与电池PyCell-4C的工艺流程相同。然而，为了进一步改善背面漫反射镜的效果，在电池背面施加了额外的漫反射镜堆叠。在制造出所描述的电PyCell-4C之后，喷涂低密度的PTFE层并且覆盖除发射极和基极汇流条触点区域以外的背面表面覆盖，那些区域由荫罩覆盖。接下来，在背面且在增加的PTFE层顶部沉积薄PVD铝层，PVD铝用作为背反射镜。在PVD铝的沉积工艺过程中，发射极和基极汇流条触点区域也被荫罩覆盖以便发射极和基极金属不会因为PVD铝而产生分流。
图24图示了图23中的PyCell-5C电池工艺流程的最终结构的剖面图。如所示，PyCell-5C电池背面具有连续的交叉指状线条发射极和基极结以及触点开口、具有额外低密度PTFE层的增强型背面漫反射镜，以及PVD铝层。PTFE和PVD铝层未覆盖发射极和基极汇流条触点区域，此并未在图24中示出。PyCell-5C电池没有选择性发射极。
在操作中，本发明描述了背结背触点晶体三维太阳能电池的结构，该电池沉积在具有三维结构的可重复使用的模板上，该模板作为耐高温的载具可以使工艺在模板上进行，且随后通过使用分离层可使得三维晶体太阳能电池与模板分离。进一步，本发明描述了用于三维电池的增强结构以及施加该增强结构的方法，这使得可将超薄半导体层用于三维电池，从而降低总成本并降低该层的整块（bulk）寿命要求。此外，本发明描述了使用具有亚纳秒脉冲宽度的短激光脉冲来完成以上描述的三维背结背触点太阳能电池触点的至少一个极性，优选地两个极性的触点开口。此外，描述了使用激光脉冲来完成以上描述的背结背触点太阳能电池触点区域至少一个极，优选地两个极的触点区域的掺杂。本发明描述了一些工艺流程，作为如何获得增强、用于隔离的介电层形成、钝化、反射镜的形成、分离和金属化的建议。该领域的技术人员可从所建议的示例的方法可推导出其它方法，推导出的方法也被认为是在本发明的范围内。
在一个实施例中，提供了使用外延硅层制造各种类型PyCell太阳能电池的方法。术语“超薄（ultra-thin）”指的是在1μm到50μm的范围内的生长材料的厚度。与同样是由超薄硅层制成的，大体上是平面的太阳能电池相比，PyCell具有两个优点：(1)在给定特定范围的厚度的话，PyCell衬底在机械上比具有相同厚度、大体上是平面的硅衬底更加坚固。(2)PyCell微观结构提供自然光捕获效果，因此不需要进行正面表面织构化工艺。事实上，进行有效的表面织构化(比如平均为5μm，平均金字塔高度)，在平面硅表面上，会消耗一些平面硅衬底中硅的厚度。因此，与大体上是平面的超薄外延硅太阳能电池相比，超薄PyCell衬底节省了外延硅材料。
提供了各种具有背结和背触点的PyCell太阳能电池的制造方法和结构的描述。更具体地，PyCell的金字塔型面用作为向阳面，被称为正面；而PyCell的脊型面用作为触点、结和金属化面，被称为背面。此外，所有的基极和发射极触点、结、金属指状电极以及金属汇流条都在PyCell太阳能电池的背面上制造。
本发明的其它方面包括在外延硅生长期间进行原位掺杂步骤以形成原位掺杂的正面表面场(FSF)和发射极掺杂层。原位掺杂浓度分布可以是台阶形或梯形。短脉冲(比如亚纳秒)激光烧蚀，用于产生离散的或连续的电介质触点开口。激光表面处理，用于对以上描述的三维背结背触点太阳能电池触点区域至少一个极性，优选地两个极性的触点区域进行掺杂。背面和增强层用作为扩散的背反射镜。形成选择性发射极(在发射极触点区域内部具有较高的发射极掺杂)以增大电池效率。使用喷墨印刷液体掺杂物以及直写激光掺杂工艺，用于制造选择性发射极和基极触点。除了以上组合以外，本发明提供了使用脉冲激光的新颖制造方法。描述了一些工艺流程，作为如何获得增强、用于隔离的介电层、钝化、反射镜的形成、分离和金属化的建议。
提供上述优选地实施例的描述是为了使本领域的任何技术人员制造或使用所请求保护的主题。这些实施例的各种修改对本领域中的技术人员来说是很明显的，且此处确定的基本原则可应用于其它实施例，无需创造性劳动。因此，所要求保护的主题不是要限于此处展示的实施例，而是要覆盖与此处公开的原理和新颖特征相一致的最广的范围。

Claims (23)

1.一种背结背触点三维薄太阳能电池,包括：
具有正面和背面的三维沉积的半导体层，包括：
具有钝化层的光俘获正面表面，
掺杂的基极区域，和
掺杂的背面发射极区域，其极性与所述掺杂的基极区域相反；
在所述掺杂的背面发射极区域上的背面钝化层；
背面发射极触点和背面基极触点，其连接至金属互连件且选择性地在所述三维沉积的半导体层背面的三维特征上形成；和
在所述背结背触点三维薄太阳能电池的正面设置的透明正面永久性支撑增强物。
2.如权利要求1所述的背结背触点三维薄太阳能电池，其中，所述沉积的半导体层是厚度在1到30微米范围内的外延硅层。
3.如权利要求1所述的背结背触点三维薄太阳能电池，其中，所述掺杂的背面发射极区域是外延原位掺杂发射极区域。
4.如权利要求1所述的背结背触点三维薄太阳能电池，其中，所述背面发射极触点和背面基极触点离散地位于所述三维沉积的半导体层背面的三维特征上。
5.如权利要求1所述的背结背触点三维薄太阳能电池，其中，所述背面发射极触点和背面基极触点在所述三维沉积的半导体层背面的三维特征上以连续的交叉指状图案形成。
6.如权利要求1所述的背结背触点三维薄太阳能电池，其中，所述具有钝化层的光俘获正面表面用作抗反射涂层。
7.如权利要求1所述的背结背触点三维薄太阳能电池，其中，所述具有钝化层的光俘获正面表面提供场辅助钝化。
8.如权利要求1所述的背结背触点三维薄太阳能电池，还包括填充所述三维沉积的薄半导体层背面上的三维特征的空腔的背面增强层。
9.一种背结背触点三维薄太阳能电池,包括：
具有正面和背面的三维沉积的半导体层，所述沉积的半导体层具有倒金字塔型结构，其中，背面表面脊限定倒金字塔型空腔的开口，包括：
具有钝化层的光俘获正面表面，
掺杂的基极区域，和
掺杂的背面发射极区域，其极性与所述掺杂的基极区域相反；
在所述掺杂的背面发射极区域上的背面钝化层；和
背面发射极触点和背面基极触点，其选择性地在所述三维沉积的半导体层的背面表面脊上形成且连接至金属互连件。
10.如权利要求9所述的背结背触点三维薄太阳能电池，其中,在所述背结背触点三维薄太阳能电池的正面上有透明永久性正面支撑增强物。
11.如权利要求9所述的背结背触点三维薄太阳能电池，其中，所述沉积的半导体层是厚度在1到30微米范围内的外延硅层。
12.如权利要求9所述的背结背触点三维薄太阳能电池，其中，所述掺杂的背面发射极区域是外延原位掺杂发射极区域。
13.如权利要求9所述的背结背触点三维薄太阳能电池，其中，所述倒金字塔型空腔包括多个尺寸不同的倒金字塔型空腔。
14.如权利要求9所述的背结背触点三维薄太阳能电池，其中，所述倒金字塔型空腔包括一组较大的倒金字塔型空腔和一组较小的倒金字塔型空腔。
15.如权利要求9所述的背结背触点三维薄太阳能电池，其中，所述背面发射极触点和背面基极触点离散地位于所述三维沉积的薄半导体层背面的倒金字塔型空腔的背面表面脊上。
16.如权利要求9所述的背结背触点三维薄太阳能电池，其中，所述背面发射极触点和背面基极触点在所述三维沉积的薄半导体层背面的倒金字塔型空腔的脊上以连续的线条图案形成。
17.如权利要求9所述的背结背触点三维薄太阳能电池，还包括背面增强层，其至少部分填充所述三维沉积的薄半导体层背面上的倒金字塔形空腔。
18.从晶体半导体层制造三维背结背触点薄太阳能电池的方法，所述方法为所述晶体半导体层提供连续的结构性支撑，所述方法包括：
在三维模板上形成保形多孔半导体层，所述三维模板具有倒金字塔型结构，其具有背面表面脊，所述背面表面脊限定倒金字塔型空腔的开口，其中，所述模板提供结构性支撑，且在背结背触点太阳能电池的背面处理步骤中充当高温临时载具，所述背面处理步骤包括：
在所述多孔半导体层上沉积保形的掺杂的基极晶体半导体层；
在所述掺杂的基极晶体半导体层上形成保形掺杂的发射极层；
沿着所述多孔半导体层将所述掺杂的基极晶体半导体层与所述模板分离，其中，在分离之前将电池背面增强层附着到所述太阳能电池背面以为电池正面处理步骤提供支撑，所述正面处理步骤包括在所述晶体半导体层正面形成具有钝化和抗反射层的光捕获正面表面；
将透明永久性正面增强物附着到电池正面；
在所述掺杂的发射极层上沉积背面钝化介电层；
在所述倒金字塔型空腔的脊上形成穿越所述介电层的选择性背面基极和发射极触点开口；
掺杂暴露的区域以形成发射极区域和基极区域；和
将所述电池背面金属化以在所述倒金字塔型空腔的脊上形成背面基极和发射极触点。
19.如权利要求18所述的方法，其中，所述电池背面增强层充当所述背结背触点三维薄太阳能电池的背面漫反射镜。
20.如权利要求18所述的方法，其中，所述沉积掺杂的基极晶体半导体层的步骤包括沉积厚度在1到30微米范围内的掺杂的基极外延硅层。
21.如权利要求18所述的方法，其中，在所述掺杂的基极晶体半导体层上形成掺杂的发射极层的所述步骤还包括形成原位掺杂的发射极外延层。
22.如权利要求18所述的方法，其中，使用脉冲宽度激光烧蚀在所述倒金字塔型空腔的脊上形成穿越所述介电层的选择性背面基极和发射极触点开口。
23.如权利要求18所述的方法，其中，使用亚纳秒脉冲宽度的激光烧蚀在所述倒金字塔型空腔的脊上形成穿越所述介电层的选择性背面基极和发射极触点开口。
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