CN1981376B - 带有自掺杂触点的埋入触点太阳能电池 - Google Patents

带有自掺杂触点的埋入触点太阳能电池 Download PDF

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CN1981376B
CN1981376B CN2005800041566A CN200580004156A CN1981376B CN 1981376 B CN1981376 B CN 1981376B CN 2005800041566 A CN2005800041566 A CN 2005800041566A CN 200580004156 A CN200580004156 A CN 200580004156A CN 1981376 B CN1981376 B CN 1981376B
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P·哈克
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Abstract

一种埋入触点太阳能电池，加工过程中的埋入触点太阳能电池的组件以及制备埋入触点太阳能电池的方法，其中自掺杂触点材料放置在多个埋入触点表面凹槽内。通过结合凹槽掺杂和金属化的步骤，所得太阳能电池对于制造来说更简单且更经济。

Description

带有自掺杂触点的埋入触点太阳能电池
相关申请的交叉引用
本申请要求在2004年2月5日提交的美国临时专利申请序号60/542,454的优先权，该申请的名称为″Process for Fabrication ofBuried-Contact Cells Using Self-Doping Contacts″，以及在2004年2月5日提交的美国临时专利申请序号60/542,390的优先权，该申请的名称为″Fabrication of Back-Contact Silicon Solar Cells″。本申请涉及Peter Hacke和James M.Gee的、同时与其一起提交的美国实用专利申请AttorneyDocket No.31474-1005-UT，该申请的名称为″Contact Fabrication ofEmitterWrap-Through Back Contact Silicon Solar Cells″，并且涉及也是James M.Gee和Peter Hacke的、同时与其一起提交的美国实用专利申请AttorneyDocket No.31474-1006-UT，该申请的名称为″Back-Contact Solar Cells andMethods for Fabrication″。所有所述申请的说明书都通过引用结合在此。
发明背景
发明领域(技术领域)：
本发明涉及用于直接从光产生电源的光电太阳能电池，而无论该光是自然的太阳光还是人造光，更具体地说，涉及太阳能电池以及制备太阳能电池的方法，所述的包含太阳能电池凹入到电池的前和/或背表面内的触点。
背景技术：
注意，下列讨论参考了大量的出版物和参考文献。此处的这样出版物的讨论是为科学原理的更完全背景而给出的，它不应当认为是承认这样的出版物是用于确定可专利性目的的现有技术。
在典型的“埋入触点”硅太阳能电池中，电流收集栅极凹入到前表面的凹槽内。通过对被栅极触点所占据的表面面积最小化(即，栅极隐蔽)，得到更大的可用于电流收集的面积。然而，即使表面接触面积较小，串联电阻损耗也不会增加，因为接触面积相对于触点深度而增加，而且导体存在有较大的横截面面积。埋入触点电池的其它优势包括只在埋入触点凹槽内的大量扩散(因电子和空穴在接触时复合而降低了接触电阻和损耗)，并且触点金属化被选择性只沉积在凹槽内。埋入触点电池以及制备该电池的方法例如在美国专利4,726,850和4,748,130中有描述。高效大面积埋入触点电池已经同时在单晶和多晶硅衬底上被证实。
制备埋入触点电池的代表性工艺步骤如下：
1.碱蚀刻
2.少量磷扩散(60到100Ω/sq)
3.HF蚀刻
4.将氮化硅沉积在前表面或两个表面上
5.在前表面激光划割和蚀刻凹槽
6.大量磷在凹槽内扩散(<20Ω/sq)
7.将铝沉积在背表面上
8.使穿过背部介电层的铝合金化
9.HF蚀刻
10.由化学浸镀在凹槽内沉积Ni薄层
11.烧结Ni层
12.由化学浸镀在凹槽内沉积Cu
如图1A所示，根据现有技术方法，由硅衬底10制备的埋入触点太阳能电池包含在照明表面之上的少量磷扩散12、在前表面之上沉积或热生长的介电层18以及随后采用的凹槽20。如图1B所示，在制备凹槽20之后，采用大量磷扩散30，比如通过优选使用三氯氧化磷(POCl3)、膦(PH3)、三溴化磷(PBr3)或其它气态磷前体的气体扩散进行，以及在随后步骤中被覆铝层并使其合金化，从而在电池背表面上形成铝合金化连接50。随后，被大量扩散的凹槽20用金属填充，比如用无电沉积Ni薄层42，再将该Ni层烧结，然后无电沉积Cu层40。如图1C所示，最终结构得到具有被大量掺杂(例如，具有大量磷扩散)的内表面30的凹槽，从而降低了接触电阻和接触复合，以及得到金属栅极或触点40，42。备选地，如美国专利4,748,130公开的那样，可以将银(Ag)金属膏状物施用于被大量掺杂后的凹槽，随后进行烧制。
现有技术的埋入触点电池具有大量的优点，包括为高收集效率而在发光表面之上的少量磷扩散、为低接触电阻和低接触复合而在凹槽内的大量磷扩散，以及向凹槽的大量磷扩散和化学镀金属层化的自动调整。现有技术方法中有一些简单的变化，比如使用切割或金刚石锯而不是使用激光划片器切割凹槽(尽管激光图案可提供更精细线的几何形状)。现有技术的工艺步骤的首要缺点是工艺相对复杂、耗时且昂贵。删去一些工艺步骤获得相同或改进的设备结构是有利的，例如删去了气态磷第二次扩散进入凹槽内这一步骤。此外，删去化学浸镀也是有利的，因为化学浸镀涉及使用需要在废水处理过程中严格控制的有害化学品。
Meier等人在美国专利6,180,869中已经描述了在太阳能电池表面上使用自掺杂金属触点。也可以参见DanielL Meier等，″Self-doping contactsto silicon using silver coated with a dopant source，″28th IEEE PhotovoltaicSpecialists Conference，69页(2000)。为了制备掺杂硅层并且同时提供触点，Ag：掺杂剂的膏状物可以直接放置在硅表面上或穿过氮化硅层烧制，尽管在后一种的情况下，膏状物必需包含溶解氮化物的组分(参见M.Hilali，等，″Optimization of self-doping Ag paste firing to achieve high fill factors onscreen-printed silicon solar cells with a 100 ohm/sq.emitter，″29th IEEEPhotovoltaic Specialists Conf.，New Orleans，LA，2002年5月)。然而，该自掺杂金属触点方法只是应用于表面，并且遭受了因自掺杂膏状物在电池表面上扩散出去引起的高遮蔽损耗。
发明概述
本发明是一种制备太阳能电池的方法，该方法包括以下步骤：在电池衬底内划割至少一个凹槽的步骤，在凹槽内放置自掺杂触点材料的步骤以及加热自掺杂触点材料的步骤，由此同时进行掺杂和金属化凹槽。自掺杂触点材料优选包含硅掺杂剂，优选含有磷的硅掺杂剂。自掺杂触点材料优选包含银，并且优选为包含银粒子和磷的膏状物。电池衬底优选包含p-型硅衬底并且自掺杂触点材料优选包含银和n-型硅掺杂剂。备选地，电池衬底包含n-型硅衬底并且自掺杂触点材料包含银和p-型硅掺杂剂。
加热步骤优选还包括合金化在电池背表面上的背触点，并且该背触点优选包含铝。在该方法中，划割至少一个凹槽优选包括划割多个凹槽，其中凹槽的深度是凹槽宽度的倍数。
本发明也是一种通过前述方法制备的太阳能电池。
本发明还是一种用于制备太阳能电池的衬底，所述衬底包含具有前表面和背表面的平面半导体衬底、在所述半导体衬底表面内划割的至少一个凹槽、位于凹槽内的自掺杂触点材料。自掺杂触点材料优选包含膏状物，并且优选包含银。半导体衬底优选包含晶体硅，并且自掺杂触点材料包含优选含有磷的硅掺杂剂。半导体衬底优选包含p-型硅衬底并且自掺杂触点材料优选包含银和n-型硅掺杂剂。半导体衬底优选还包含在凹槽表面上的磷扩散层。本发明的衬底优选还包含在与凹槽表面相反的表面上的铝层。
本发明还是一种太阳能电池，它包含至少一个凹槽以及基本上位于凹槽内的触点，该触点含有掺杂剂。触点优选包含银，掺杂剂优选包含硅掺杂剂，优选含有磷的硅掺杂剂。
本发明的一个主要目的是简化制备埋入触点太阳能电池的方法。
本发明的另一个目的是提供在埋入触点太阳能电池内的金属触点的同时掺杂并形成。
本发明的一个主要优点是它提供了不太昂贵的、带有最小量栅极隐蔽的太阳能电池。
本发明的另一个优点是它用于删去在制备埋入触点太阳能电池中的多个步骤，包含删去了大量磷扩散步骤以及用于化学浸镀或其它引入一种或多种金属形成埋入触点的单独步骤。
本发明的其它目的、优点和新特征以及进一步的适用性范围将在下面的详述中部分内容结合附图进行描述，并且部分内容对于本领域的技术人员在验证下面内容之后，将变得明显或者可以通过实践本发明而获悉。借助尤其是在所附权利要求中指出的手段和结合，可以实现并获得本发明所述的目的和优点。
附图几种视图的简述
并入本说明书中并成为其一部分的附图与说明书一起解释本发明的一个或多个实施方案，用于解释本发明的原理。附图只是用于解释本发明的一个或多个优选实施方案的目的，而不是被解释为对本发明的限制。在附图中：
图1A描述现有技术硅衬底在切割有凹槽的制备方法中的横截面；
图1B描述将磷大量扩散进入凹槽之后的现有技术硅衬底；
图1C描述与加入化学镀金属层一起形成埋入触点太阳能电池的现有技术硅衬底；        
图2A描述在少量磷扩散和形成凹槽的情况下的硅衬底的横截面；
图2B描述根据本发明自掺杂金属触点材料在凹槽内的放置；以及
图2C描述本发明退火之后的埋入触点太阳能电池的横截面。
发明详述
通过使用自掺杂触点，本发明允许删去化学浸镀步骤以及提供用于制备埋入触点太阳能电池结构的简单方法，其中埋入触点结构可以在前面电池表面和背面电池表面中的之一或两者上，所述自掺杂触点包含但不限制于Ag：掺杂剂的膏状物。
硅衬底典型地为多结晶或多晶硅，但可以使用其它种类的硅衬底，它包含但不限制于在玻璃或其它衬底上的单晶、三晶以及薄晶体硅膜。典型地，硅为p-型半导体衬底。然而，如下面所述，本发明也可以使用n-型半导体衬底。
本发明的一个优选实施方案提供一种用于制备埋入触点电池结构的方法，该方法删去了大量扩散步骤，并且用单一的印刷和烧制步骤代替了化学浸镀步骤(两次电镀和一次烧结)。主要通过使用自掺杂触点材料填充凹槽，使该方法能够实施。自掺杂触点材料同时包含：元素金属或合金，以及在触点形成过程中掺杂硅表面的硅掺杂剂。为制备n-型层，硅掺杂剂为n-型掺杂剂，比如磷(P)、锑(Sb)或砷(As)。备选地，为制备p-型层，如果衬底为n-型，则掺杂剂优选为p-型掺杂剂，比如铟(In)、铝(Al)、硼(B)或镓(Ga)。金属载体在相对低的温度下优选与硅合金化，并且是良好的导体。后一种性质允许使用该金属载体作为用于传导来自太阳能电池的电流的栅极线。备选材料包含例如Ag、Al、Cu、Sn和Au，其中Ag由于它的惰性性质(它可以在具有最小氧化的情况下在空气中烧制)、良好的传导性以及与Si材料加工的相容性(Ag在能够降低太阳能电池效率的Si中不是强复合中心)而是优选的。
在一个优选实施方案中，自掺杂触点材料是膏状物，优选含有被P掺杂的Ag粒子的膏状物。该膏状物通过任何可行的方式涂覆于凹槽上，所述的方式包括丝网印刷、涂刷器涂敷或者其它印刷或沉积方式。在涂敷Ag:P的膏状物之后，太阳能电池在高于Ag:Si共晶温度(845℃)的温度下烧制，以制备具有掺杂触点的Ag栅极。当温度超过共晶温度时，Ag溶解在界面上的部分Si，并且当温度降低时，析出的硅被磷掺杂。可以使用除P之外的N-型掺杂剂，比如Sb或As，尤其是但是不排除地，与Ag的结合中时。类似地，尽管优选使用自掺杂的膏状物，但是可以使用Ag的其它形式，并且可以优选使用Ag：掺杂剂。
在一个备选实施方案中，再通过任何可行方式，包括丝网印刷、涂刷器涂敷或其它印刷或包括溅射或蒸发的沉积方式，在凹槽内涂敷Ag膏状物或其它Ag层。随后，Ag层用含n-型掺杂剂的材料比如含有磷化合物的层涂布。备选地，如果在衬底为n-型的情况下需要p-型层，则再通过任何可行方式，包含丝网印刷或者其它印刷或包括溅射或蒸发的沉积方式，使上覆层能够包含含有p-型掺杂剂比如硼(B)、铟(In)、镓(Ga)或铝(Al)的材料。备选地，含有掺杂剂的层可以放置在载体金属(在这种情况下，Ag)和Si之间。在温度升高到金属-Si共晶温度之上后，通过该方法使得含掺杂剂的层溶解在金属-Si液相线中。
膏状物可以通过粒子形式Ag与液相形式掺杂剂的结合进行制备，由此制备出自掺杂、可丝网印刷的膏状物。为制备可丝网印刷的膏状物，膏状物配方还可以包含在本领域中已知并使用的粘合剂、溶剂等。也可以并且考虑使用烧结的膏状物配方，比如含有玻璃粉的膏状物，这尤其是可在需要渗过氮化硅层之处应用。
自掺杂Ag金属化只用一个步骤—印刷或者相反将自掺杂触点材料放置在凹槽内代替现有方法的大量磷扩散步骤以及三次电镀金属并烧结的步骤。所得的工艺步骤因此要求更少的步骤，并且比常规埋入触点电池的步骤要简单得多，同时又提供了所有的或实质上所有的相同高效率优点。
根据本发明，图2A描述了未掺杂凹槽20，该凹槽20是具有预先涂敷在前表面上的少量磷扩散12层的硅衬底10内切割而成的。所述少量磷扩散层12优选在凹槽形成之前被介电层18覆盖，该介电层18起着用于太阳能电池的抗反射涂层的作用，并且使印刷在凹槽外部表面上的任何过量金属与扩散层12之间的冶金反应最小。硅衬底10优选包含p-型半导体硅，但是，可以使用其它衬底，包括n-型硅和具有任何导电类型的镓或硅-镓衬底。少量磷扩散12层通过常规方式涂敷，所述的方式优选包括使用液体POCl3的气相扩散。然而，可以使用其它扩散源或方法，包含通过常规方法比如涂布、浸涂或旋涂涂覆液体源，或比如采用将固体源材料如P2O5加热到高温而涂覆固体源。然而，通常，优选常规的气相POCl3扩散。
凹槽20可以被可以产生所需尺寸凹槽的任何方法切割或划割。尽管优选使用激光划割，但是也可以使用其它方法，包括蚀刻、机械铣削等。凹槽20是在表面的相对边缘之间基本相互平行的纵向凹口。
注意在附图中，尤其是在图2A到2C中，凹槽20的尺寸、各层的厚度以及其它尺寸都没有按比例绘制，而是为了解释和易于识别的目的示意性表示的。通常，埋入触点凹槽20具有大于其宽度的深度，并且在一个优选实施方案中，深度为宽度的倍数。例如，凹槽20的宽度可以在约10μm和约50μm之间，优选约20μm，并且凹槽20的深度在约20μm和约60μm之间(某种程度上取决于衬底10的厚度)，优选约40μm。因此，如图2A所示，凹槽20可以不具有线性横截面，但是可以具有圆底、斜侧壁等。平行的多个凹槽20隔开一定距离，该距离在某种程度上取决于电池的设计考虑。但是，可以是任何可行的分隔，因此相邻平行的凹槽20可以隔开约1000μm到约3500μm的距离(从中心线到中心线)，优选隔开约1500μm到约2500μm的距离。在完成后的太阳能电池中的介电层18的厚度(如果使用折射率约为2的氮化硅)优选为约80nm，并且扩散层12的厚度优选为约200到1500nm。
图2B描述了填充有自掺杂触点材料60的凹槽20。该自掺杂材料60可以是上面所述的任一种，优选包含含Ag和硅掺杂剂的膏状物，硅掺杂剂优选含有P。然而，自掺杂触点材料60可以备选为涂敷有P或其它掺杂剂、再涂敷Ag和掺杂剂(可以是先Ag再掺杂剂或者是先掺杂剂再Ag)的Ag粒子的干制品，或者可以简单且廉价地选择性涂敷到凹槽内的自掺杂触点材料的其它配方。
涂敷自掺杂触点材料60之后，自掺杂触点材料与硅合金化，优选通过在高于Ag:Si共晶(845℃)温度的温度下加热或烧制而合金化，以制备具有自掺杂触点的Ag栅极，从而产生了图2C所示的结构。当温度超过共晶温度时，Ag溶解了在界面上的部分Si，并且当温度降低时，析出的硅被磷掺杂，从而得到了在凹槽内表面上的硅掺杂层70，其中Ag触点80占据凹槽。
本发明使用单一磷扩散步骤和栅极所用的自掺杂膏状物的工艺步骤的一个实例如下：
1.碱蚀刻
2.少量磷扩散(60到100Ω/sq)
3.HF蚀刻
4.将氮化硅沉积在前表面上
5.在前表面上划割凹槽，优选使用激光划割凹槽
6.将自掺杂膏状物(例如Ag:P)沉积在前表面上的凹槽内
7.将铝沉积在背表面上
8.炉子退火，以使Ag和Al触点同时合金化
在前述步骤中，碱蚀刻用于清洁表面。可以使用任何适当的碱蚀刻材料，比如热或温的氢氧化钠。作为举例，可以使用在约2重量％与50重量％之间的氢氧化钠水溶液，优选在约60℃和约95℃之间的温度下进行。
少量磷扩散如上面所述那样。扩散之后，使用酸蚀刻步骤，比如用氢氟酸(HF)水溶液，优选用2到50重量％的HF酸。可以使用任何常规的方法，包含将晶片浸渍在含HF酸的溶液中。源自少量磷扩散的氧化物优选但任选地用酸比如HF除去，因为氧化物可能导致可靠性问题，尤其是对于封装的光电模件。HF蚀刻之后，裸露的硅表面优选但任选地通过沉积介电层而钝化。氮化硅(SiN)可以常规地由等离子体增强的化学气相沉积(PECVD)或由低压化学气相沉积(LPCVD)、用于钝化太阳能电池结构中的硅表面的熟知技术进行沉积。然而，如果需要，可以使用其它用于钝化的方法和材料，比如例如热生长SiO2层或通过各种方式如印刷、喷涂、PECVD等沉积其它介电材料如SiO2、TiO2、Ta2O5等。
如果需要，钝化之后，比如用SiN钝化之后，在前表面内划割出凹槽。优选使用激光器，比如Q-交换的Nd:YAG激光器。然而，可以使用如上所述的机械划割或其它方式。任选划割之后，可以使用清洁步骤，比如使用含有氢氧化钠或氢氧化钾的化学溶液的清洁步骤。
然后，凹槽20用自掺杂触点材料比如Ag:P的膏状物填充。这样的填充可以借助丝网印刷进行，但是也可以使用其它方式。尽管图2B所示是只填充凹槽并且只达到衬底10上表面水平的自掺杂触点材料60，但是可以且考虑使自掺杂触点材料60和所得的触点80(如图2C所出)可以延伸超过表面并且可以任选是半球形的。
对于常规的电池，可以使用任意的金属背触点。在一个优选实施方案中，如上所述，使用Al背触点。在Ag:P的膏状物退火之前涂敷Al是一个特别优选的实施方案，因为可以使用单一炉子退火的步骤，以使在形成部分埋入触点的Ag:P膏状物中的Ag和形成背触点的Al同时合金化。例如，Al背触点可以通过电子束汽化、溅射、丝网印刷或其它技术进行涂敷。
为了使可以受到高金属化温度影响的SiN层保持钝化，在金属化之后可以任选进行步骤4，外加另外的掩模和剥离步骤。步骤5可以备选在过程开始时进行。如果凹槽20被钝化，如用SiN钝化，则自掺杂触点材料60任选且优选包含玻璃料。
在一个实施方案中，可以在划割凹槽20之后应用少量磷扩散。典型地但不是必需采用这种方法，比如使用SiN钝化，要在涂覆自掺杂触点材料60之前进行，因而优选使用玻璃料。然而，这种方法具有的优点是在凹槽20内提供n-型掺杂剂的相加效应，即，采用通过使用自掺杂触点材料60的基本上另外的n-型掺杂，少量磷扩散会在凹槽壁表面内部产生部分掺杂。如此，由于连续掺杂步骤的相加效应，在凹槽侧壁内的掺杂基本上大于表面掺杂。
尽管本发明已经具体参照这些优选实施方案进行了详细描述，但是其它实施方案也可以获得相同结果。本发明的变化和修改对于本领域技术人员而言是显而易见的，其意在覆盖所有这样的修改和等价形式。上面引用的所有参考文献、申请、专利和出版物，以及相应申请的全部公开内容均通过引用结合在此。

Claims (23)

1.一种用于制备太阳能电池的方法，所述方法包括如下步骤：
在电池衬底内划割至少一个凹槽；
将自掺杂触点材料放置在所述凹槽内；以及
加热自掺杂触点材料，由此同时掺杂和金属化所述凹槽。
2.根据权利要求1的方法，其中所述自掺杂触点材料包含硅掺杂剂。
3.根据权利要求2的方法，其中所述硅掺杂剂包含磷。
4.根据权利要求1的方法，其中所述自掺杂触点材料包含银。
5.根据权利要求1的方法，其中所述自掺杂触点材料是包含银粒子和磷的膏状物。
6.根据权利要求1的方法，其中所述电池衬底包含p-型硅衬底并且所述自掺杂触点材料包含银和n-型硅掺杂剂。
7.根据权利要求1的方法，其中所述电池衬底包含n-型硅衬底并且所述自掺杂触点材料包含银和p-型硅掺杂剂。
8.根据权利要求1的方法，其中所述加热步骤还包括将在电池背表面上的背触点合金化。
9.根据权利要求8的方法，其中背触点包含铝。
10.根据权利要求1的方法，其中划割至少一个凹槽包含划割多个凹槽，其中所述凹槽的深度大于所述凹槽宽度。
11.一种太阳能电池，其由根据权利要求1的方法制备。
12.一种用于制备太阳能电池的衬底，所述衬底包含：
具有前表面和背表面的平面半导体衬底；
在所述半导体衬底的表面内划割的至少一个凹槽；以及
放置在所述凹槽内的自掺杂触点材料。
13.根据权利要求12的衬底，其中所述自掺杂触点材料包含膏状物。
14.根据权利要求12的衬底，其中所述自掺杂触点材料包含银。
15.根据权利要求12的衬底，其中所述半导体衬底包含晶体硅并且所述自掺杂触点材料包含硅掺杂剂。
16.根据权利要求15的衬底，其中所述硅掺杂剂包含磷。
17.根据权利要求12的衬底，其中所述半导体衬底包含p-型硅衬底并且所述自掺杂触点材料包含银和n-型硅掺杂剂。
18.根据权利要求12的衬底，其中所述半导体衬底还包含在所述凹槽表面上的磷扩散层。
19.根据权利要求18的衬底，所述的衬底还包含在与所述凹槽表面相反的表面上的铝层。
20.一种太阳能电池，其包含：
至少一个凹槽；以及
位于所述凹槽内的触点，所述触点包含掺杂剂。
21.根据权利要求20的太阳能电池，其中所述触点包含银。
22.根据权利要求20的太阳能电池，其中所述掺杂剂包含硅掺杂剂。
23.根据权利要求22的太阳能电池，其中所述掺杂剂包含磷。
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CN1981376A (zh) 2007-06-13
US20050172998A1 (en) 2005-08-11
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WO2005086633A3 (en) 2006-10-19
EP1733426A2 (en) 2006-12-20
CA2596961A1 (en) 2005-09-22
US7335555B2 (en) 2008-02-26
AU2005220701A1 (en) 2005-09-22
WO2005086633A2 (en) 2005-09-22
JP2007521669A (ja) 2007-08-02

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