CN101681936A - 清洗由太阳能蚀刻浆料制造的太阳能电池表面开口的方法 - Google Patents
清洗由太阳能蚀刻浆料制造的太阳能电池表面开口的方法 Download PDFInfo
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Abstract
本发明描述了一种薄硅太阳能电池,其具有背表面介电钝化层以及具有局部背面场的后接触。特别地,该太阳能电池可由厚度为50至500微米的晶体硅制成。阻挡层和介电层至少施加到硅晶片的背表面,以避免硅晶片在形成后接触时变形。对介电层形成至少一个开口。提供背面场的铝接触形成在开口中和介电层上。铝接触可通过丝网印刷含1~12原子%的硅的铝浆料,并接着在750摄氏度的温度下对其进行热处理来施加。
Description
政府利益
本发明由美国能源部的合同号为DE-FC36-07GO17023的项目资助,美国政府享有本发明的已付费的非独占的、世界范围内的许可,且在特定的情况下有权基于合理的理由要求专利权人许可给他人。
技术领域
本发明一般性地涉及硅太阳能电池。更具体地,本发明涉及背接触或后接触的形成,其提供背表面钝化和光学限制性能。
背景技术
太阳能电池是将光能转化为电能的装置。这些装置也常常称为光伏(PV)电池。太阳能电池可由各种半导体制造。一种常用的半导体材料是晶体硅。
太阳能电池具有三个主要元件:(1)半导体;(2)半导体结;以及(3)导电接触。诸如硅的半导体可掺杂为n-型或p-型。如果n-型硅和p-型硅形成为彼此接触,则它们在太阳能电池中接触的区域就是半导体结。半导体吸收光。来源于光的能量传输到硅层中的原子的价电子,使得价电子逃逸其束缚态,从而留下空穴。与p-n结有关的电场将这些光生电子和空穴分离。导电接触使得电流从太阳能电池流到外电路。
图1示出了现有技术中太阳能电池的基本元件。太阳能电池可以在硅晶片上制造。太阳能电池5包括p-型硅基板10、n-型硅发射体20、底部导电接触40以及顶部导电接触50。p-型硅基板10和n-型硅发射体20彼此接触形成结。n-型硅20接合至顶部导电接触50。p-型硅10接合到底部导电接触40。顶部导电接触50和底部导电接触40接合到负载75,为其供电。
由银构成的顶部导电接触50(“前接触”)使电流流入太阳能电池5。但是,因为银不完全透光,所以顶部导电接触50没有覆盖电池5的整个表面。因此,顶部导电接触50具有栅格图案,使得光进入太阳能电池5。电子从顶部导电接触50流出,并穿过负载75,然后经由底部导电接触40与空穴结合。
底部导电接触40(“后接触”或“背接触”)通常由铝-硅共晶体构成。这种导电接触40通常覆盖p型硅10的整个底部,以使导电最大化。铝和硅在约750摄氏度的高温下形成合金,这大大高于铝-硅共晶温度577摄氏度。这种合金化反应在基板底部产生重掺杂p-型区域,并在该处产生强电场。该电场有助于防止光生电子与空穴在背接触处复合,使得它们可在p-n结处被更有效地收集。
硅和导电接触之间的界面典型地是具有高复合的区域。例如,在整个背表面的铝背面场的背表面复合速率是500厘米每秒或更快。高的背表面复合速率会降低电池效率。
发明内容
已经使用的一种降低背接触处的复合的方法是在硅晶片的后表面上形成二氧化硅的介电层。这种介电层改善钝化,但会引发其他问题,例如如何形成从介电层到硅的开口以及如何优化各个窗口的尺寸和间距。而且,介电层无法在接触形成期间保护硅晶片免受可使硅晶片变形的铝-硅合金化。薄膜硅晶片特别容易变形。现有技术中用于减少背表面处的复合的方案未充分解决其他问题,例如防止薄膜硅的变形、确定介电开口的尺寸和间距、清洁介电开口以及在介电开口处形成高质量的背面场。
本文提出的方案包括一种太阳能电池结构,其具有介电钝化层以及具有局部铝背面场的后接触。提供一种形成后接触的方法。在一个实施方案中,介电层在具有n区域和p区域的薄的结晶晶片的后面上形成。通过丝网印刷蚀刻浆料在介电层中形成开口,接着进行第一热处理。氢氟酸溶液可用于移除由蚀刻浆料留下的任何残留物。通过在整个背表面上丝网印刷接触浆料接着进行第二热处理形成后接触。接触浆料由铝和1~12原子%的硅构成。接触浆料中硅的存在使得第二热处理期间铝对硅的需要得到满足,并在局部开口处提供高质量的背面场接触。在铝中使用少量或不使用玻璃粉有助于避免使装置性能降低的明显的铝穿透介电层。
以上内容为发明概要,因此根据需要包含简述、概括和细节的省略;因此,本领域技术人员应理解上述发明内容仅仅是说明性的,且不旨在以任何方式对本发明进行限制。仅仅由权利要求限定的本发明的其他方面、创造性特征和优点将通过下文的非限制性的详述变得显而易见。
附图说明
图1是现有技术的太阳能电池的截面图。
图2是形成具有局部背面场的背接触的工艺的一个实施方案的流程图。
图3A是线状背接触的DESSIS模拟区域。
图3B是点状背接触的DESSIS模拟区域。
图4A是DESSIS输出图,其示出了宽度为75微米的接触的间距与效率的关系。
图4B是DESSIS输出图,其示出了宽度为150微米的接触的间距与效率的关系。
图5A至5D是不同的铝接触浆料的局部背面场在电子显微镜下的截面图。
图6A至6E是在背接触制造工艺的各个阶段的硅晶片的一个实施方案的截面图。
图7A是对具有点状图案的硅的窗开口的一个实施方案的底视图。
图7B是对具有线状图案的硅的窗开口的一个实施方案的底视图。
图8是用丝网印刷蚀刻浆料处理的介电层的开口在电子显微镜下的顶视图。
发明详述
在以下详述中,阐述了许多具体细节以便全面理解本发明。但是,本领域技术人员应理解,本发明可以在没有这些具体细节的情况下实施。在其他情况下,公知的方法、程序、组件和电路并未详细说明,以免混淆本发明的主旨。
图2描述的是形成高质量后接触的流程图,该后接触保护硅晶片在合金化过程中免受损伤并提供局部背面场。希望产生局部背面场(BSF),因为其有助于减少在太阳能电池背表面处的电子复合。如果太阳能电池具有高质量的局部BSF,则由此可提高太阳能电池的效率。
在操作200中,p-型或n-型层在硅晶片上形成。该硅晶片可以是结晶的。该硅晶片可具有200至250微米的厚度。对于另一实施方案,硅晶片可具有50至500微米的厚度。在硅晶片整个背表面的铝-硅合金化会使薄硅晶片变形。因此,在操作210中,在硅晶片的前表面和背表面上生长阻挡层和介电层,而不是在硅晶片上直接形成全部区域的接触。介电层可同步或同时地生长。对于本发明的一个实施方案,介电层是二氧化硅。对于本发明的另一实施方案,介电层可以是氧化铝。
通过旋涂工艺可形成二氧化硅以在各个面上达到1000至5000埃的厚度。在旋涂工艺期间,液态电介质沉积在旋转的晶片上。旋涂前体可以是二氧化硅溶胶凝胶。二氧化硅溶胶凝胶可从Filmtronics Inc.购买,商品名为“20B”。旋涂工艺之后,晶片在150至250摄氏度的温度下干燥10至20分钟。二氧化硅可在常规管式炉中、在875至925摄氏度的温度下、在氧气气氛中进行固化。旋涂工艺可形成较厚的、更均匀的二氧化硅层,这使得电介质成为用于单侧扩散的扩散掩模。
可替代地,二氧化硅可通过化学气相沉积或等离子体增强化学气相沉积(PECVD)工艺形成。这些工艺可利用硅烷和氧气作为前体,并在300至500摄氏度的温度下进行10至20分钟。可使用反应室来控制用于该工艺的反应物。
在操作215中,在晶片的前表面和背表面上形成阻挡层。该阻挡层可由厚度为100至700埃的氮化硅构成。氮化硅层可利用PECVD来形成。硅烷和氨可分别作为硅和氮的PECVD前体。可替代地,氮化硅层可利用低压化学气相沉积工艺在合适的反应室中形成。前表面上的阻挡层提供了抗反射涂层以有助于吸收光。阻挡层还保护介电层。若背表面没有阻挡层,则背表面介电层可能会受到铝的穿透和由空气引入杂质的影响。而且,在没有阻挡层的情况下,在丝网印刷接触的焙烧期间,介电层更容易为高温所损伤。
在操作220中,在硅晶片的背表面上的介电和阻挡层中形成至少一个开口。如果形成多个开口,则开口可在硅晶片的整个表面上均匀分布。对于本发明的一个实施方案,通过将太阳能蚀刻浆料施加到阻挡层而制造开口。示例性的太阳能蚀刻浆料由Merck&Co.,Inc.制造,其商品名为“SolarEtch AX M1”。太阳能蚀刻浆料还可用于在前表面介电层中制造开口。该蚀刻浆料可包括磷酸、氢氟酸、氟化铵或氟化氢铵。操作220中形成的开口可为点状或线状。
该浆料应当仅施加到介电层中需要形成开口的区域。可利用丝网印刷机来施加该浆料。基板的开口的最佳尺寸和间距是晶片电阻率的函数。诸如Device Simulations for Smart Integrated System(DESSIS)的计算机程序可用于确定开口的最佳尺寸和间距。DESSIS基于如下参数来计算最佳间距,这些参数包括接触类型(点或线)、接触尺寸(75微米或150微米)以及横向BSF(存在或不存在)。模拟区域源于最小单位电池,其可周期性延伸而表示整个结构。为了简化模拟问题,可限定前接触参数使得前接触均匀分布。在这种情况下,在DESSIS模拟中,单位电池的尺寸由背接触的几何结构来控制。
图3A示出线接触的模拟区域。图3A的模拟区域包括p型硅300、n型硅310、介电层320、第一导电接触330、第二导电接触360和局部BSF370。p型硅300接合至n型硅310、介电层320和局部BSF370。局部BSF370接合至第二导电接触360。n型硅310接合至第一导电接触330。
类似地,图3B中示出点接触的模拟区域。图3B的模拟区域包括p型硅300、n型硅310、介电层320、第一导电接触330、第二导电接触360和局部BSF370。p型硅300接合至n型硅310、介电层320和局部BSF370。局部BSF370接合至第二导电接触360。n型硅310接合至第一导电接触330。
光产生参数可设定为假设均匀光入射到具有54.7度晶面角、2.0的抗反射指数层以及75纳米厚的织构硅表面上。入射光还可减少约8.5%,以说明实际器件中被前接触所遮蔽的情况。内部前表面反射可设定为92%。背表面反射可设定为85%。
发射体的分布可以是高斯分布,其在表面具有1.14×1020每立方厘米的n型掺杂浓度峰值,且具有0.3微米的结深,其对应于具有约80欧姆每平方的片电阻的发射体。可替代地,发射体的片电阻可在70至90欧姆每平方的范围内变化。
背接触处的局部BSF可限定为具有1×1019每立方厘米的恒定的p型掺杂浓度,厚度为1.47微米。这导致在2.0欧姆-厘米的基板上的接触处的有效表面复合速率为约300厘米每秒。为模拟横向BSF,BSF层可横向延伸至接触边缘外至少1.3微米。为模拟无横向BSF,BSF层可限定为仅覆盖接触区域。
其他的参数设定可包括50至200微米的电池厚度、1.5至2.5欧姆-厘米的电阻率、50000至70000厘米每秒的前表面复合速率、40至60厘米每秒的介电层处的背表面复合速率以及零欧姆-平方厘米的接触电阻。利用这些参数,图4A示出了说明宽度为75微米的接触的接触间距与太阳能电池效率的关系的DESSIS输出图,图4B示出了说明宽度为150微米的接触的接触间距与太阳能电池效率的关系的图。
在施加蚀刻浆料之后,蚀刻浆料暴露于温度为300至380摄氏度的热源30至45秒。该热源与太阳蚀刻浆料一起使浆料下的阻挡层和介电层溶解,从而为基板留下开口。可利用氢氟酸溶液来移除开口中或开口周围的任何所得残留物。
对于本发明的另一实施方案,可利用激光或机械划线来形成介电层中的开口。开口可覆盖后表面区域的1%~10%。在操作220之后,介电层仍然保留在后表面的剩余部分上。
在操作230中,将包含了1~12原子%的硅的铝浆料施加至后接触层。对于本发明的一个实施方案,铝浆料的商品号可为:AL 53-090、AL 53-110、AL 53-120、AL 53-130、AL 53-131或AL 5540,均可由Ferro公司购买。对于本发明的另一实施方案,铝浆料可以是购自由DuPont Corporation、Cermet Materials,Inc.、Chimet Chemicals、Cixi Lvhuan HealthyProducts、Daejoo Electronic Materials、Exojet Electronic、HamiltonPrecision Metals,Inc.、Metalor Technologies、PEMCO Corporation、Shanghai Daejoo、Young Solar或Zhonglian Solar Technology生产的市售铝浆料。铝浆料可包括分散于有机介质中的微细铝颗粒。有机介质可还包括诸如乙基纤维素或甲基纤维素的粘合剂以及诸如松油醇或卡必醇的溶剂。将硅组分添加到铝浆料中使所得“接触浆料”包含1~12原子%的硅。
图5A至5D示出铝浆料中的硅组分改善了局部BSF的形成。BSF的质量由BSF区域的均匀性和厚度所限定。图5A至5D是扫描电子显微镜的截面视图。图5A是由烧结的铝浆料形成的局部BSF。图5B是由无烧结的铝浆料形成的局部BSF。图5C是由具有7原子%的硅的无烧结的铝浆料形成的局部BSF。图5D是由具有12原子%的硅的无烧结的铝浆料形成的局部BSF。从图5A至5D中可见,与不含硅的铝浆料相比,具有1~12原子%的硅的铝浆料产生较高质量的BSF。局部BSF可有助于特别是在具有高电阻率的基板上实现良好的欧姆接触。
而且,局部BSF有助于使金属界面处的高复合的影响最小化。在整个背表面的铝BSF的背表面复合速率为约500厘米每秒。与之相比,具有由含12%的硅的铝浆料形成的局部铝BSF的介电层背表面钝化,使得背表面复合速率降至125厘米每秒或更小。
具有铝和硅的接触浆料可利用丝网印刷机施加。对于本发明的一个实施方案,接触浆料是未烧结的。对于本发明的另一实施方案,接触浆料是低烧结的。未烧结或低烧结的铝不会蚀刻或干扰介电层。
接着,对接触浆料进行热处理。在操作240中,“升温”至700至900摄氏度的温度。升温至峰值温度的时间是1~5秒。硅在高于共晶温度的温度下溶解于铝中,这形成了熔融的铝和硅合金。快速升温时间有助于形成更均匀的BSF。一旦达到峰值温度,在操作250中,保持该温度3秒或更短。例如,峰值温度可保持1~3秒。峰值温度保持这么短的时间段有助于避免结泄漏电流,这是因为杂质扩散至结的几率更小。
最后,在操作260中,温度“降温”至400摄氏度或更低。降温时间为3~6秒。该快速降温时间可通过强制冷却来实现。例如,风扇或将晶片从热源快速移出的传送带可用于使温度快速降温至400摄氏度或更低。
快速降温为主体区提供了钝化。在本发明的一个实施方案中,阻挡层可包含4×1021~7×1022原子每立方厘米的氢浓度。可通过PECVD前体将氢引入氮化硅层。因此,在热处理期间,氢可从阻挡层中解离。接着,氢原子可通过附着于硅中的缺陷而有助于硅晶片主体区中的钝化。
硅在铝中的溶解度与合金的温度成正比。因此,在冷却期间,合金中硅的百分比下降。过量的硅从熔体中析出并在液体硅界面处外延再生长。根据固化温度下铝在硅中的有限固溶度,该再生长层被铝掺杂。因此该再生长层变为p+BSF层。
如果使用纯铝而不是铝和硅的组合的话,那么在高温下,铝嗜硅。因此,减少了开口中硅析出到硅表面上。这使得后表面钝化的质量降低和使得电池性能降低。
与含硅的铝后接触接合的介电层还用于改善绝对电池效率。绝对电池效率用于衡量太阳能电池将输入的光转化成能量的能力。全区域铝共晶背接触具有约60%的背表面反射率。背表面反射率定义为由背表面反射回进入硅的入射光的百分比。本发明公开的背接触产生大于85%的背表面反射率。接合至铝和硅后接触的介电层将电池效率提升1~2%。
接触浆料中1~12原子%的硅添加剂用于使铝为硅所饱和。因为铝具有硅富集,所以在冷却期间更多的硅从熔体中析出到开口。析出的硅具有铝富集,并在液体硅界面处外延再生长,从而形成p+BSF层。图5A至5D示出实验室测试的结果,表明借助于硅添加剂,可以实现6~15微米深度的局部BSF。
后接触通常直接施加到硅晶片的整个背表面上。如果硅添加到铝浆料并施加到基板的整个背表面,则因为会从硅基板中溶解更少的硅,所以可观察到BSF层厚度的减小。因此,这与将硅添加到铝浆料的常识相反。但是发明者披露,将硅添加到铝浆料会增加局部开口几何结构的BSF的深度。在铝浆料中没有硅的情况下,远离开口的铝层在冷却期间需要大于12原子%的硅来保持平衡状态。这使得开口中用于再生长的硅的量减少,从而产生较薄的局部BSF。在铝浆料中添加硅满足铝中对硅的需求。因此,开口中的熔融铝-硅合金中的大部分硅可用于再生长,从而产生较厚的局部BSF。
除了改善BSF之外,具有硅的接触浆料有助于避免铝穿透。硅在铝中的溶解度随着温度升高而增加。随着硅扩散入铝中,铝进而会填充由离去的硅所产生的空隙。如果铝穿透硅晶片的p-n或p+-p结,则会使性能降低。
如上所述,因为接触浆料具有1~12原子%的硅,所以铝已经被硅原子饱和。因此,在热处理期间,可以避免来自于基板的硅原子扩散入铝层中。因此,由于在基板中不存在由离去的硅产生的空隙,所以避免铝穿透。
图6A至6D示出了处于制造工艺中不同阶段的硅晶片的一个实施方案的截面图。图6A示出了硅晶片,其具有接合至扩散层610的掺杂基板600。
图6B中,介电层620接合至掺杂基板600。而且,介电层630接合至扩散层610。该介电层620可以是二氧化硅。介电层620可由上述旋涂工艺制成。
图6C示出了接合至介电层620的阻挡层640和接合至介电层630的阻挡层650。阻挡层640和650可由通过PECVD形成的氮化硅构成。阻挡层640和650为介电层提供保护。而且,阻挡层650可为太阳能电池的前表面提供抗反射涂层。
图6D示出了介电层620和阻挡层640中的开口625。在介电层630和阻挡层650中也可形成开口635。对于本发明的一个实施方案,开口625和开口635可通过将太阳能蚀刻浆料施加到介电层并接着对介电层实施热处理而形成。热处理可包括300~380摄氏度的温度。热处理使浆料下的介电层溶解,形成至介电层805中的硅810的开口,如图8所示。图8示出了具有至硅810的开口的介电层805的底视平面图。对于本发明的另一实施方案,开口625和开口635可通过激光形成。对于本发明的又一实施方案,开口625和开口635可由机械划线形成。
开口625可为点状或线状。图7A示出阻挡层740的底视平面图,其具有至硅的点状开口725。点状开口可为矩形或圆形。图7B示出阻挡层740的底视平面图,其具有至硅的线状开口725。
图6E示出了后接触660,其接合至介电层620、阻挡层640,且通过开口625接合至掺杂的基板600。这种后接触可由具有1~12原子%的硅的铝构成。在铝中添加硅获得了具有6~15微米的深度的高质量的BSF670。
在以上说明书中,已经参照本发明的特定示例性实施方案描述了本发明。但是显而易见的是,在不脱离由所附权利要求设定的本发明的较宽的精神和范围的情况下,可对本发明进行各种改进和改变。因此,说明书和附图应视为说明性的而不是限制性的。
Claims (9)
1.一种方法,包括:
在厚度为50~200微米的薄硅晶片的掺杂基板上形成扩散层,其中所述硅晶片具有前表面和背表面;
在所述硅晶片的背表面上形成旋涂介电层;
在所述旋涂介电层上形成阻挡层;
对所述阻挡层的1~10%的表面区域施加蚀刻浆料;
在300~380摄氏度的温度下对所述蚀刻浆料进行第一热处理;以及
利用含氢氟酸的溶液从开口移除残留物。
2.权利要求1的方法,其中所述第一热处理实施30~45秒。
3.权利要求1的方法,还包括:
在所述第一热处理之后,对所述硅晶片的背表面施加接触浆料。
4.权利要求3的方法,其中所述接触浆料是含1~12原子%的硅的铝浆料。
5.权利要求3的方法,还包括:
在700~900摄氏度的峰值温度下对所述接触浆料进行第二热处理。
6.权利要求5的方法,其中所述第二热处理在所述峰值温度下实施1~3秒。
7.权利要求1的方法,还包括:
利用Device Simulation for Smart Integrated System(DESSIS)来确定对所述介电层的部分表面区域施加蚀刻浆料。
8.权利要求7的方法,还包括:
将参数输入DESSIS以确定蚀刻浆料施加,其中所述参数包括发射体片电阻、电池厚度、电阻率、前表面复合速率、介电层处的背表面复合速率以及接触电阻。
9.权利要求8的方法,其中所述发射体片电阻为70~90欧姆每平方,所述电池厚度为90~200微米,所述电阻率为1.5~2.5欧姆-厘米,所述前表面复合速率为50000~70000厘米每秒,所述介电层处的背表面复合速率为40~60厘米且所述接触电阻是零欧姆-平方厘米。
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2008
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CN104115286A (zh) * | 2012-03-06 | 2014-10-22 | 应用材料公司 | 用于背面钝化的图案化的铝背触点 |
CN102709335A (zh) * | 2012-05-08 | 2012-10-03 | 常州天合光能有限公司 | 一种利用SiN薄膜针孔形成局部掺杂或金属化的方法 |
CN104966761A (zh) * | 2015-07-08 | 2015-10-07 | 四川银河星源科技有限公司 | 一种晶体硅太阳能电池的制造方法 |
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