CN105449014A - 具有电镀的金属格栅的太阳能电池 - Google Patents

具有电镀的金属格栅的太阳能电池 Download PDF

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CN105449014A
CN105449014A CN201510778132.1A CN201510778132A CN105449014A CN 105449014 A CN105449014 A CN 105449014A CN 201510778132 A CN201510778132 A CN 201510778132A CN 105449014 A CN105449014 A CN 105449014A
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傅建明
徐征
游晨涛
王君俊
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Abstract

本发明涉及具有电镀的金属格栅的太阳能电池。本发明的一个实施例提供一种用于制造太阳能电池的方法。在操作期间，在半导体结构的顶上淀积抗反射层以形成光伏结构，并且在光伏结构的顶上形成包括金属堆叠的正面电极格栅。该金属堆叠包括含Ti或Ta的金属粘合层以及位于金属粘合层之上的含Cu或Ag的传导层。

Description

具有电镀的金属格栅的太阳能电池
本申请是申请日为2011年9月13日、申请号为201110276380.8、发明名称为“具有电镀的金属格栅的太阳能电池”的中国发明专利申请的分案申请。
相关申请的交叉引用
本申请要求2010年9月10日提交的、发明人为JianmingFu、ZhengXu、ChentaoYu和JiunnBenjaminHeng、题为“SOLARCELLWITHMETALGRIDSFABRICATEDBYUSINGELECTROPLATING”、代理人案卷号为SSP10-1010PSP的美国临时申请No.61/381,659的权益。
技术领域
本公开总体上涉及太阳能电池的设计。更具体而言，本公开涉及包括通过电镀技术制造的金属格栅的太阳能电池。
背景技术
由于使用化石燃料造成的负面环境影响及其增加的成本已经导致了对更洁净、更便宜的备选能源的极度需求。在不同形式的备选能源中，太阳能因其洁净度和广泛的可用性已经很受欢迎。
太阳能电池使用光伏效应将光转换成电。存在若干基本的太阳能电池结构，包括单个p-n结太阳能电池、p-i-n/n-i-p太阳能电池以及多结太阳能电池。典型的单个p-n结结构包括p型掺杂层和n型掺杂层。具有单个p-n结的太阳能电池可以是同质结太阳能电池或异质结太阳能电池。如果p掺杂层和n掺杂层二者均由类似的材料(具有相等带隙的材料)制成，则太阳能电池称为同质结太阳能电池。相比之下，异质结太阳能电池至少包括具有不同带隙的两层材料。p-i-n/n-i-p结构包括p型掺杂层、n型掺杂层以及夹在p层和n层之间的本征(未掺杂)半导体层(i层)。多结结构包括堆叠在彼此顶上的具有不同带隙的多个单结结构。
在太阳能电池中，光在p-n结附近被吸收，从而产生载流子。载流子扩散进入到p-n结中并由内建电场分开，从而产生跨器件和外部电路的电流。确定太阳能电池的质量的重要衡量标准是其能量转换效率，该能量转换效率定义为当太阳能电池连接到电路时所转换的能量(从吸收的光到电能)和所收集的能量之间的比率。
图1呈现了图示基于晶体-Si(c-Si)衬底的示例性同质结太阳能电池(现有技术)的示意图。太阳能电池100包括正面Ag电极格栅102、抗反射层104、发射极层106、衬底108以及铝(Al)背面电极110。图1中的箭头指示入射太阳光。
在常规的基于c-Si的太阳能电池中，电流通过正面Ag格栅102收集。为了形成Ag格栅102，常规方法包括将Ag浆(其通常包括Ag颗粒、有机粘结剂和玻璃粉)印刷到晶片上并且然后在700℃和800℃之间的温度下对Ag浆进行烧结。Ag浆的高温烧结保证了Ag和Si之间的良好接触，并且降低了Ag线的电阻率。烧结的Ag浆的电阻率典型地在5×10-6欧姆厘米和8×10-6欧姆厘米之间，这比体银(bulksilver)的电阻率高得多。
除了高的串联电阻之外，通过丝网印刷Ag浆得到的电极格栅还具有其它缺陷，包括较高的材料成本、较宽的线宽以及受限的线高。随着银成本的升高，银电极的材料成本已经超过用于制造太阳能电池的加工成本的一半。利用现有技术中的印刷工艺，Ag线典型地具有在100微米和120微米之间的线宽，并且难以进一步减小线宽。尽管喷墨印刷可以产生较窄的线，但喷墨印刷存在其它问题，诸如低的生产率。Ag线的高度也受到印刷方法的限制。一次印刷可以产生高度小于25微米的Ag线。尽管多次印刷可以产生具有增加的高度的线，但它还会增加线宽，这对于高效率太阳能电池而言是不希望的。类似地，将Ag或Cu电镀到印刷的Ag线上可以在增加线宽的代价下增加线高。此外，这种Ag线的电阻仍然太高以至于无法满足高效率太阳能电池的要求。
另一个解决方案是将Ni/Cu/Sn金属堆叠直接电镀在Si发射极上。该方法可以产生具有较低电阻的金属格栅(镀覆的Cu的电阻率典型地在2×10-6欧姆厘米和3×10-6欧姆厘米之间)。然而，Ni到Si的粘合不够理想，并且来自金属堆叠的应力可能导致整个金属线的剥离。
发明内容
本发明的一个实施例提供了一种用于制造太阳能电池的方法。在操作期间，在光伏结构的顶上淀积抗反射层，并且在抗反射层的顶上形成包括金属堆叠的正面电极格栅。金属堆叠包括含Ti或Ta的金属粘合层以及位于金属粘合层之上的含Cu或Ag的传导层。
在该实施例的变体中，金属粘合层还包括以下中的一个或更多：TiN、TiW、TiSi、TaN和Co。
在该实施例的变体中，金属粘合层使用物理气相淀积(PVD)技术形成，所述物理气相淀积技术包括以下中的一个：蒸发和溅射淀积。
在该实施例的变体中，在传导层的顶上形成包括Sn或Ag的焊接层。
在该实施例的变体中，金属粘合层具有在1nm和1000nm之间的厚度。
在另一变体中，金属粘合层具有在5nm和50nm之间的厚度。
在该实施例的变体中，传导层通过在金属粘合层之上淀积金属种子层以及在金属种子层之上淀积体金属层来形成。
在另一变体中，金属种子层使用物理气相淀积(PVD)技术形成，所述物理气相淀积技术包括以下中的一个：蒸发和溅射淀积。
在另一变体中，体金属层通过在金属种子层上淀积图案化的掩膜层以及在图案化的掩膜层之上镀覆金属层来形成。掩膜层的开口对应于正面电极格栅的位置，并且镀覆的金属与金属种子层具有类似的材料构成。
在另一变体中，该方法包括去除掩膜层以及执行刻蚀工艺以去除未被镀覆的金属覆盖的金属粘合层和金属种子层的部分。
在另一变体中，体金属层通过在金属种子层上淀积图案化的掩膜层、执行刻蚀工艺以去除未被所镀覆的金属覆盖的金属粘合层和金属种子层的部分、去除图案化的掩膜层以露出金属种子层的未刻蚀部分以及在金属种子层的未刻蚀部分之上镀覆金属层来形成。由图案化的掩膜层覆盖的区域对应于正面电极格栅的位置，并且所镀覆的金属与金属种子层具有类似的材料构成。
附图说明
图1呈现了图示示例性太阳能电池(现有技术)的示意图。
图2呈现了图示根据本发明实施例的用于制造太阳能电池的示例性工艺的示意图。
图3呈现了图示根据本发明实施例的用于制造太阳能电池的示例性工艺的示意图。
在附图中，类似的附图标记指代相同的附图元件。
具体实施方式
下面的描述是为了使任何本领域技术人员都能制作和使用这些实施例而呈现的，并且下面的描述是在特定应用及其要求的上下文中提供的。对所公开的实施例的各种修改对于本领域技术人员而言将是容易明白的，并且这里限定的通用原理可以适用于其它实施例和应用，而不脱离本公开的精神和范围。因而，本发明并不限于所示出的实施例，而是将被赋予与这里公开的原理和特征一致的最广范围。
概述
本发明的实施例提供一种太阳能电池，其包括通过电镀形成的金属格栅。太阳能电池包括晶体-Si(c-Si)衬底、发射极层、钝化层、金属粘合层以及正面电极金属格栅和背面电极金属格栅。金属粘合层使用诸如溅射或蒸发的物理气相淀积(PVD)技术来形成。正面金属格栅通过在金属粘合层上选择性地电镀金属堆叠来形成，该金属堆叠可以是单层或多层结构。背面电极通过丝网印刷、电镀或气流喷射印刷金属格栅来形成。
制造工艺
图2呈现了图示根据本发明实施例的用于制造太阳能电池的示例性工艺的示意图。
在操作2A中，制备Si衬底200。在一个实施例中，Si衬底200可以是p型晶体-Si(c-Si)晶片。在另一实施例中，制备Si衬底200包括标准的切割损坏层刻蚀(其去除Si的受损伤的外层)和表面纹理化。
在操作2B中，在Si衬底200的顶上形成轻掺杂的发射极层202。取决于Si衬底200的掺杂类型，发射极层202可以是n型掺杂的或者p型掺杂的。在一个实施例中，发射极层202轻掺杂有n型掺杂剂。在另一实施例中，发射极层202通过扩散磷来形成。注意到，如果使用磷扩散形成发射极层202，则需要磷硅玻璃(PSG)刻蚀和边缘隔离。
在操作2C中，在发射极层202的顶上形成抗反射层204。在一个实施例中，抗反射层204包括但不限于：氮化硅(SiNx)、氧化硅(SiOx)、氧化钛(TiOx)、氧化铝(Al2O3)及其组合。在一个实施例中，抗反射层204包括透明导电氧化物(TCO)材料的层，该透明导电氧化物(TCO)材料诸如氧化铟锡(ITO)、氧化铝锌(AZO)、氧化镓锌(GZO)、掺钨氧化铟(IWO)及它们的组合。
在操作2D中，在Si衬底200的背面上形成背面电极206。在一个实施例中，形成背面电极206包括印刷全Al层以及随后通过烧结进行合金化。在一个实施例中，形成背面电极206包括印刷Ag/Al格栅以及随后进行炉烧结。
在操作2E中，在抗反射层204中形成大量接触窗口，包括窗口208和窗口210。在一个实施例中，分别在接触窗口208和接触窗口210正下方的发射极层202中形成诸如区域212和区域214的重掺杂区域。在另一实施例中，通过在抗反射层204上进行磷溅射，之后进行激光刻槽局部扩散工艺来形成接触窗口208和接触窗口210以及重掺杂区域212和重掺杂区域214。注意到，操作2E是可选的，并且当抗反射层为电绝缘时是需要的。如果抗反射层204是电传导的(例如，当抗反射层204使用TCO材料形成时)，不需要形成接触窗口。
在操作2F中，在抗反射层204上形成粘合层216。在一个实施例中，用于形成粘合层216的材料包括但不限于：Ti、氮化钛(TiNx)、钨化钛(TiWx)、硅化钛(TiSix)、氮化硅钛(TiSiN)、Ta、氮化钽(TaNx)、氮化硅钽(TaSiNx)、镍钒(NiV)、氮化钨(WNx)、Co、W、Cr、Mo、Ni以及它们的组合。在另一实施例中，粘合层216使用诸如溅射或蒸发的物理气相淀积(PVD)技术形成。粘合层216的厚度可以在从几纳米到100nm的范围。注意到，Ti及其合金倾向于与Si材料形成非常好的粘合，并且它们可以与重掺杂区域212和重掺杂区域214形成良好的欧姆接触。
在操作2G中，在粘合层216上形成金属种子层218。金属种子层218可以包括Cu或Ag。金属种子层218的厚度可以在5nm和500nm之间。在一个实施例中，金属种子层218具有100nm的厚度。类似于粘合层216，金属种子层218可以使用PVD技术形成。
在操作2H中，在金属种子层218的顶上淀积图案化的掩膜层220。掩膜层220的开口(诸如开口222和开口224)对应于接触窗口208和接触窗口210的位置，并且因而它们位于重掺杂区域212和重掺杂区域214之上。注意到，开口222和开口224可以比接触窗口208和接触窗口210稍大。掩膜层220可以包括图案化的光致抗蚀剂层，该层可以使用光刻技术来形成。在一个实施例中，光致抗蚀剂层通过在晶片的顶上丝网印刷光致抗蚀剂来形成。然后对光致抗蚀剂进行烘焙以去除溶剂。将掩膜板放置于光致抗蚀剂上，并且使晶片暴露于UV光。在UV曝光之后，去除掩膜板，并在光致抗蚀剂显影剂中对光致抗蚀剂进行显影。在显影之后形成了开口222和开口224。光致抗蚀剂还可以通过溅射、浸渍涂覆或幕帘式涂覆来施加。还可以使用干膜光致抗蚀剂。备选地，掩膜层220可以包括图案化的氧化硅(SiO2)的层。在一个实施例中，掩膜层220通过使用低温等离子体增强化学气相淀积(PECVD)技术首先淀积SiO2的层来形成。在另一实施例中，掩膜层220通过使用二氧化硅浆液(silicaslurry)浸渍涂覆晶片的正表面、之后丝网印刷包括氢氟酸或氟化物的刻蚀剂来形成。其它掩膜材料也是可能的，只要该掩膜材料是电绝缘的即可。
在操作2I中，在掩膜层220的开口处淀积一个或多个金属层，以形成正面金属格栅226。正面金属格栅226可以使用电镀技术形成，该电镀技术可以包括电淀积、光诱发镀覆和/或无电淀积。在一个实施例中，金属种子层218和/或粘合层216经由电极耦合到镀覆电源(可以是直流(DC)电源)的阴极。金属种子层218和包括开口的掩膜层220被淹没在允许电流的电解液中。注意到，由于仅掩膜层220内的开口是电传导的，所以金属将被选择性地淀积到开口中，从而形成金属格栅，该金属格栅具有的图案对应于先前在抗反射层204上形成的接触窗口的图案。取决于形成金属种子层218的材料，正面金属格栅226可以使用Cu或Ag来形成。例如，如果金属种子层218使用Cu形成，则正面金属格栅226也使用Cu形成。此外，正面金属格栅226可以包括多层结构，诸如Cu/Sn双层结构或Cu/Ag双层结构。淀积Sn或Ag顶层以有助于随后的焊接工艺。当淀积Cu时，在阳极处使用Cu极板，并且将太阳能电池淹没在适于Cu镀覆的电解液中。对于尺寸为125mm×125mm的晶片，用于Cu镀覆的电流在0.1安培和2安培之间，并且Cu层的厚度近似为几十微米。
在操作2J中，去除掩膜层220。
在操作2K中，刻蚀掉最初被掩膜层220覆盖的金属种子层218和粘合层216的部分，只留下在正面金属格栅226之下的部分。在一个实施例中，使用湿法化学刻蚀工艺。注意到，由于正面金属格栅226比粘合层216和金属种子层218厚得多(厚若干数量级)，所以刻蚀对于正面金属格栅226具有可忽略的影响。
图3呈现了图示根据本发明实施例的用于制造太阳能电池的另一示例性工艺的示意图。
在操作3A中，使用类似于操作2A中使用的工艺，制备Si衬底300。
在操作3B中，使用类似于操作2B中使用的工艺，在Si衬底300的顶上形成轻掺杂的发射极层302。
在操作3C中，使用类似于操作2C中使用的工艺，在发射极层302的顶上形成抗反射层304。
在操作3D中，使用类似于操作2D中使用的工艺，在Si衬底300的背面上形成背面电极306。
在操作3E中，使用类似于操作2E中使用的工艺，形成大量接触窗口，包括窗口308和窗口310。在一个实施例中，在发射极层302中形成重掺杂区域312和重掺杂区域314。
在操作3F中，使用类似于操作2F中使用的工艺，在抗反射层304上形成粘合层316。
在操作3G中，使用类似于操作2G中使用的工艺，在粘合层316上形成金属种子层318。
在操作3H中，使用类似于操作2H中使用的工艺，在金属种子层318的顶上形成图案化的掩膜层320。然而，与图案化的掩膜层220不同，图案化的掩膜层320在仍位于重掺杂区域312和重掺杂区域314之上的同时，覆盖对应于接触窗口308和接触窗口310的位置的区域。注意到，覆盖的区域比接触窗口308和接触窗口310稍大。
在操作3I中，使用类似于操作2K中使用的工艺，刻蚀掉未被掩膜层320覆盖的金属种子层318和粘合层316的部分。
在操作3J中，去除掩膜层320以露出金属种子层318的剩余部分。
在操作3K中，使用类似于操作2I中使用的工艺，在金属种子层318的剩余部分上淀积一个或多个金属层，以形成正面金属格栅326。注意到，由于仅金属种子层318的剩余部分是电传导的，所以镀覆工艺可以选择性地在金属种子层318的剩余部分的顶上淀积金属。
对各种实施例的以上描述仅出于图示和描述的目的而呈现。它们并不旨在于是穷尽的或者并不旨在于将本发明限制到所公开的形式。因此，对于本领域技术人员而言，许多的修改和变化将是显而易见的。此外，上述公开并不旨在于限制本发明。

Claims (18)

1.一种太阳能电池，包括：
光伏结构，包括发射极层，其中所述发射极层包括重掺杂区域；
透明导电氧化物TCO层，位于所述光伏结构的第一侧上；以及
第一金属格栅，位于所述TCO层的第一侧上，其中所述第一金属格栅包括多个金属层，并且其中所述多个金属层至少包括：
金属粘合层，所述金属粘合层包括Cu，与所述TCO层接触，以及
传导层，包括Cu，位于所述金属粘合层的第一侧上。
2.根据权利要求1所述的太阳能电池，其中所述金属粘合层还包括以下中的一个或更多：Ti、Ta、Co、W、Cr、Mo、Ni、氮化钛(TiNx)、钨化钛(TiWx)、硅化钛(TiSix)、氮化硅钛(TiSiN)、氮化钽(TaNx)、氮化硅钽(TaSiNx)、镍钒(NiV)、氮化钨(WNx)以及它们的组合。
3.根据权利要求1所述的太阳能电池，其中所述金属粘合层使用物理气相淀积(PVD)技术形成，所述物理气相淀积技术包括以下中的一个：蒸发和溅射淀积。
4.根据权利要求1所述的太阳能电池，其中所述第一金属栅格还包括含Sn或Ag的焊接层。
5.根据权利要求1所述的太阳能电池，其中所述金属粘合层具有在1nm和1000nm之间的厚度。
6.根据权利要求5所述的太阳能电池，其中所述金属粘合层具有在5nm和50nm之间的厚度。
7.根据权利要求1所述的太阳能电池，其中所述传导层还包括使用电镀技术形成的体金属层。
8.根据权利要求1所述的太阳能电池，其中所述TCO层包括以下中的至少一个：
氧化铟锡(ITO)；
氧化铝锌(AZO)；
氧化镓锌(GZO)；以及
掺钨氧化铟(IWO)。
9.一种用于制造太阳能电池的方法，包括：
在半导体结构的第一表面上形成发射极层并在所述发射极层的第一表面上形成透明导电氧化物TCO层，以形成光伏结构；
在所述TCO层的第一表面上形成包括金属堆叠的第一电极格栅，其中形成所述第一电极格栅包括：
在所述TCO层的所述第一表面上淀积包括Cu的金属粘合层，以及
在所述金属粘合层的第一表面上淀积包括Cu的金属接触层。
10.根据权利要求9所述的方法，其中所述金属粘合层还包括以下中的一个或更多：Ti、Ta、Co、W、Cr、Mo、Ni、氮化钛(TiNx)、钨化钛(TiWx)、硅化钛(TiSix)、氮化硅钛(TiSiN)、氮化钽(TaNx)、氮化硅钽(TaSiNx)、镍钒(NiV)、氮化钨(WNx)以及它们的组合。
11.根据权利要求9所述的方法，其中形成所述金属粘合层包括物理气相淀积(PVD)技术，所述物理气相淀积技术包括以下中的一个：蒸发和溅射淀积。
12.根据权利要求9所述的方法，其中形成所述第一电极格栅还包括在所述金属接触层的第一表面上形成包括Sn或Ag的焊接层。
13.根据权利要求9所述的方法，其中所述金属粘合层具有在1nm和1000nm之间的厚度。
14.根据权利要求13所述的方法，其中所述金属粘合层具有在5nm和50nm之间的厚度。
15.根据权利要求9所述的方法，其中形成所述金属接触层还包括：
使用电镀技术形成体金属层。
16.根据权利要求15所述的方法，其中形成所述体金属层包括：
在所述金属粘合层的所述第一表面上淀积图案化的掩膜层，其中所述掩膜层的开口对应于所述第一电极格栅的位置；以及
在所述图案化的掩膜层的开口之上镀覆金属层。
17.根据权利要求16所述的方法，还包括：
去除所述掩膜层；以及
执行刻蚀工艺以去除未被所镀覆的金属覆盖的所述金属粘合层的部分。
18.根据权利要求17所述的方法，其中形成所述体金属层包括：
在所述金属种子层的所述第一表面上形成图案化的掩膜层，其中由所述图案化的掩膜层覆盖的区域对应于所述第一电极格栅的位置；
执行刻蚀工艺以去除未被所述图案化的掩膜层覆盖的所述金属粘合层的部分；
去除所述图案化的掩膜层以露出所述金属粘合层的未刻蚀部分；以及
在所述金属种子层的未刻蚀部分之上镀覆金属层。
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