CN1057735A - 一种制造半导体元件的方法和由此方法制成的太阳能电池 - Google Patents

一种制造半导体元件的方法和由此方法制成的太阳能电池 Download PDF

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CN1057735A
CN1057735A CN91104372A CN91104372A CN1057735A CN 1057735 A CN1057735 A CN 1057735A CN 91104372 A CN91104372 A CN 91104372A CN 91104372 A CN91104372 A CN 91104372A CN 1057735 A CN1057735 A CN 1057735A
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Abstract

半导体元件上的掺杂区是按下述方法制成的，在 半导体衬底表面的一部分涂敷形成掩蔽层并含有掺 杂剂的氧化物，加温使掺杂剂向半导体衬底扩散，在 掺杂过程中半导体衬底的未被保护的表面的不希望 的自掺杂也发生了，为此，通过碱腐蚀或等离子体腐 蚀将半导体衬底的自掺杂区域腐蚀掉，所述掩蔽层构 成对其下的掺杂区的保护阻挡层。在制造带有分别 为P和N导电型的两个掺杂区的太阳能电池时，两 掺杂区之间的距离司用于通过在阻塞(blocking)方 向偏置的二极管调节暗电流的变化率，

Description

本发明涉及在半导体元件特别是太阳能电池上制造掺杂区的方法。本发明还涉及根据本发明制造的带有旁路二极管的太阳能电池。
一个太阳能电池基本包括一薄硅晶片，在该晶片的面对光源的一面上覆盖单个的大面积的典型Pn结。光致激发的电荷载流子分别流向前面和背面的金属连接区，前者具有能完成基本上最大限度地收集电荷载流子的几体形状，而覆盖电池表面的金属连接区的面积和由此形成的对光的阻挡被降至最小。上述太阳能电池是单面的，即该太阳能电池仅仅对于入射在电池前面的光来说是光敏的。在电池背面另设一薄的结层，该层也做成光敏的，以便形成一个双面太阳能电池。太阳能电池可具有本征的P或N型衬底，而掺杂的一层或多层可以是N+或P+。
使用含掺杂剂的氧化物在本领域是公知的。美国专利说明书第4101351号描述了一种氧化物在晶体上如何生长，然后晶体的该部分再次曝光使氧化物限定有源区的方法。这种曝光较典型地是通过向该氧化物覆盖的晶体上加上耐氢氟酸的掩蔽层来实现的，在晶体上涂覆光致抗蚀剂的区域中氧化层被氢氟酸腐蚀掉、由此曝光的晶体区域在光致抗蚀剂层除去后被掺杂、这种掺杂是通过适当的物质在高温下向晶体的扩散实现的，所说的高温的典型范围为约1000℃。掺杂源材料是通过在晶体的曝光区域沉积一层例如含掺杂源材料的二氧化硅而被添加的。因为晶体的剩余部分有氧化层保护，所以不会发生不希望的掺杂。氧化、加光致抗蚀剂掩蔽、腐蚀和掺杂过程要多次重复，以便使晶体具有所希望的数目的掺杂区。所述的该方法具有许多缺点，包括例如多个复杂的工序，如氧化物在晶体表面上的生成需要约1000℃的高温处理以及在纯氧或水蒸气中的洁净环境。晶体表面的部分区域的曝光通常需要使用氢氟酸，由于其毒性，氢氟酸是极其难于处理的化学物质。
本发明的目的是要提出一种在半导体元件特别是太阳能电池上制造掺杂区的方法。
这个目的是这样实现的，在半导体衬底的表面的一部分上涂敷形成掩蔽层的含掺杂剂的氧化物，将所说的涂有掩蔽层的半导体衬底加热到是以实现掺杂物的部分从掩蔽层向半导体衬底扩散的温度，同时在掺杂过程中也会发生半导体衬底的裸露表面的不希望的自掺杂。半导体衬底的自掺杂区可通过例如碱腐蚀或等离子腐蚀被腐蚀掉，所说的碱包括胆碱、氢氧化钾或氢氧化钠，而对于掩蔽层下的掺杂区来说，掩蔽层构成一保护阻挡层。这使得光致抗蚀剂掩蔽成为不必要的，因为所用氧化物掺杂源层具有多种功能，在以后的掺杂过程中它也起对掺杂区的阻挡层作用。进一步高温工序的次数减少，以便它能与掺杂过程的次数基本对应，如果采用一掺杂源层作为对气相源的阻挡层，高温工序次数甚至可少于掺杂过程次数。这是一个显著的优点，因为重复的高温工序会破坏晶片的晶体结构。
本发明的特征是，在半导体衬底上沉积一掺杂源层，当自掺杂区被腐蚀掉时，该层作为掩蔽层和保护层。本发明的特征在于，仅通过一个单独的高温工序就可制造出多个相互隔离的不同类型和浓度的掺杂区。合适的细节限定在权利要求2-7中。权利要求8和10限定了一种带有与光电二极管反向的旁路二极管的太阳能电池，以便在部分被遮盖或破坏时，该太阳能电池能起导电二极管作用而不切断太阳能电池板。
根据本发明的制造太阳能电池的方法优越性在于，完全避免了使用氨氟酸和光致抗蚀剂，因此，该方法对环境是非常有益的。进一步，流程工序和高温处理工序的数目显著减少，从经济观点看这也是一个优点。具有合适的效率的太阳能电池的制造以前，只能限于实验室环境，因为涉及到清洁环境，使用多种危险的化学物质和先进设备等高要求。本发明对环境没有这样的要求，因此，它特别适用在不能利用高技术的企业中。
本发明将通过结合优选实施例并参考附图得到更充分地阐述，其中，
图1显示出本发明的方法的流程图的一个例子。
图2-8示意表示根据图1的流程图制备的双面太阳能电池的一个优选实施例的制造过程中的各种状态。
图1显示出制造本发明的太阳能电池的工序流程。在基片上形成掺杂区之前，要进行一些已知的处理工序，其中，例如，除去锯痕，使反射特性改变，为完整起见，所述工序只是被简单地说明。对于如何实现已制成的半导体/太阳能电池的连接也将举例说明。
要根据要制成的太阳能电池的需要来选择衬底材料，在图示的例子中，选择电阻率为100Ωcm的N型硅衬底。该衬底是具有（100）取向和处理前厚350μm的单晶晶片、因为是从硅棒上锯下的，该晶片表面具有较小的锯痕。
为了最后的连接，在101工序中采用例如厚膜印刷技术可印制二氧化硅网络图案，在111工序中采用如koH通过连续的表面腐蚀形成一系列邻接凹槽，其中连接可能发生，以便有源区不被遮罩。另外，所述凹槽也可通过激光刻槽形成。对于双面太阳能电池，该工序是在晶片的两面进行的。
为改善太阳能电池的效率，在112工序中采用例如胆碱溶液更好地实施另一种已知的腐蚀，以便形成具有约5μm的锥峰的锥形结构表面，然后停止该腐蚀工序，象其它腐蚀工序那样，将晶片置于水中洗涤并接着使之干燥，同时由此对晶片进行化学清洁处理。如果太阳能电池的表面未构成，可另外涂敷一抗反射层，它能任意地与后面将提到的掺杂源材料层之一结合。抗反射层通常具有大约1/4波长的厚度。
工序121使得有可能在晶片的前面沉积出具有很高的克分子百分比的含磷的薄的图案化二氧化硅层，这可通过厚膜技术实现。使图案适于覆盖在子工序101和111中形成的凹槽，以便降低金属连接区和硅材料之间的接触电阻。由于高掺杂破坏了晶体结构，将图案的分布限制在连接区域是重要的，层厚最好限制在0.05μm，在图案中线宽通常比上述凹槽宽1/3。当制造过程结束时将用于连接的金属材料沉积在高掺杂硅线的顶部，以防止通过弱掺杂区可能产生的短路。此外，可能淀积除用于连接线之外的多余线，由于这些多余线可作为对连接网的补充并也允许光通过，因而它们降低了对金属化的连接网的要求。
在工序122中，在图2所示的硅片1上，设置了一低掺杂二氧化硅层3，该层3是通过任何适当的技术，比如厚膜印刷技术，旋涂，喷涂和化学气相淀积（CVD）等制成的。不过，这里选择旋涂技术，将二氧化硅溶液施加于旋转的晶体1上，从而在该晶片的表面2上沉积出一薄层3。通过控制各种参数;例如晶片的旋转速度和二氧化硅（溶液）的粘度，可以控制层3的分布、包括它在晶片的背面或下面的延伸。层3具有多种功能，但主要是作掺杂源用。此外，层3可防止来自下面的高掺杂层或图案的自掺杂，该图案是在工序121中有选择地沉积成的，它还能使下层防止不希望的掺杂以及连续腐蚀效应。此外，层3的厚度应使之能在成品太阳能电池上作为防反射层用。因此，当在1000℃干燥之后，层3可能具有0.15μm的厚度。
为获得18-25%量级的电池效率，层3的沉积和其组分是起非常决定性的作用的，因为这种效率取决于低的表面浓度。对于一个太阳能电池来说，光电流（在入射光的PN结中形成的电流）是与反向电流（暗电流）叠加的，因此要努力限制后者。引起大的暗电流的重要原因是在表面（高表面复合速率）上的许多复合中心，它们可通过采用一薄的SiO2层-所谓的钝化层，使表面钝化而被中和，不过、只有当掺杂杂质（这里是磷原子）的表面浓度相当低，即低于约2.5×1018Cm-3时，钝化层方是有效的。
在晶片1的表面2的部分被涂敷掺杂源层后，电池被高温处理，在工序131中该处理是在约1000℃温度，最好，在干燥的氮气气氛中进行，该工序持续的时间为15分钟。这种处理的用途是通过从所沉积的层3向位于晶片1的表面正下方的区域扩散，在该晶片上形成掺杂区。如此调整这个工序131，即提供有效吸收以便使晶片中的不希望的杂质被除去。如果不需要吸收，高温工序131可延长并省去工序132。使用纯氮（不含氧）气流可避免在电池背面形成SiO2遮盖层，另外还可防止在工序132中来自PoCl3源的气相磷扩散。
图3示出的掺杂结区4的形成，发生在工序131中，这里用于形成N区的磷杂质来自工序122中沉积成的二氧化硅层，二氧化硅层3在工序131中硬化，以便另外在前面提供一种掩蔽效果来防止在工序132中大量的磷原子的不希望的进入。本发明的特殊性在于，在一个单独的高温工序中制备出不同类型和浓度的相互分离的掺杂区。
在向工序132过渡时，温度保持1100℃，晶片被移到炉中的另一区域，该区域的气氛包含氧和来自PoCl3源的运载气体。这部分高温处理耗时15分钟并随慢慢冷却结束，在此过程中PoCl3源是不接通的。为了从吸收过程中得到充分的好处，慢慢冷却是必需的。此外，快速冷却对保持晶体结构是不合适的，因为可能发生晶体破裂，这会降低少数电荷载流子的扩散长度并因此降低电池效率。因此，工序131和132在没有中间冷却和在相同的扩散室或炉中进行是很重要的。每次冷却和加热都会发生新的晶体破裂。1100℃温度可在宽的界限内变化，但为清楚起见，选它作为一个典型的例子。
如从图3中将看到的，一掺杂区5将由气相源形成，其上有一氧化层6在扩散过程中形成。
尤其是在扩散过程中，一坚固的磷掺杂二氧化硅层形成于背面，不过、该层会在工序141中通过腐蚀被除去。一个扩散层可借助参数，结深和表面电阻（单位面积的欧姆数），来表征结深度是从表面到一点的距离，在该点处第一种杂质的浓度等于第二种杂质的浓度，也即被分别称为受主和施主原子之间的平衡。
工序141中的腐蚀，最好用胆碱来实现，如何将背面的磷氧化物薄层6腐蚀掉，以便将埋置于其中的杂质连同最外层的厚度5μm的硅一起除去。腐蚀停止后，前面二氧化硅层同样也变薄了，此时具有的0.1μm的厚度。最好腐蚀是选择性的，以便保持锥形结构，但这包含一种冒险，即（表面）结构将不如腐蚀前那样均匀，因为一些锥体腐蚀得比其它锥体更快。腐蚀后背面的锥体比前面的锥体高5μm。特别是与（111）方面相比，在（100）方向腐蚀速率要高许多倍，因此，保证腐蚀深度（这里是5μm）大于在132工序中来自气相外界源的磷原子在背面的浸透深度（这里是3μm）是重要的。
就象在工序121中那样，在工序151中将具有很高的硼克分子百分比的二氧化硅层沉积在晶片背面，这可通过厚膜印刷技术来实现。在150℃干燥后该层厚为0.1μm，它除了作为高掺杂连接区的一个掺杂源外，它还作为阻止不希望的金属材料进入的一个附加保护层。另外，与工序121中使用的图案相对应，使该图案以相同的方式覆盖在工序101中形成的连接槽上。
如果该电池装配后面将要提到的旁路二极管，那么沿背面的周边涂敷具有高的磷克分百分比的二氧化硅层，这适合借助于厚膜技术来实现，它是在工序152中完成的。然后，具有低克分子百分比的二氧化硅层9（图5）沉积在背面，这是在工序153中进行的，并且适合借助于厚膜印刷技术来实现。层9（图5）覆盖在除沿晶片周边的环形区域之外的整个背面上。在100℃干燥后，该层的厚度约为0.1μm。低克分子百分比保证在连接区域之外表面浓度不超过8×1018硼原子/厘米3。硼的浓度高于前面提到的磷的浓度，原因是硼的扩散比磷慢，因而为保持相同的低表面电阻必须增高浓度。此外，应当考虑到，在工序161的高温处理中，磷通过扩散更深地向晶片渗透。解决这个问题的方法是先沉积一硼层（工序121-122）然后沉积一磷层（工序151-153）。
工序161中的扩散是在1000℃干燥的氮和氧气氛中进行的，时间为30分钟。高温工序是在富氧气氛中非常慢地冷却而结束的，以便形成0.01μm厚的表面钝化层，这最好通过干式氧化来实现。应当注意，氧化物生长在硅晶体表面而不是生长在掺杂的二氧化硅上。在这里冷却是非常重要的，最好的结果是采用非常缓慢地冷却（2℃/秒）得到的。
在工序161中，硼从二氧化硅层9向晶片的渗透是在二氧化硅层9正下面的区域10中。在处于两二氧化硅层之间的无保护区域中，区域11的自掺杂将发生，并且氧化物12将在其顶面形成。在扩散过程中，掺杂区4将轻微地扩展。
在图7将看到工序171中的腐蚀如何除去自掺杂区11和其上形成的氧化物12。腐蚀采用热胆碱溶液，以便从二氧化硅层之间的区域的表面除去2μm厚的硅。在腐蚀过程中，二氧化硅层3和10的厚度降至0.01μm，使得有可能在以后的工序中涂上较多数目的反射层。二氧化硅层被腐蚀掉是有益的，因为在这种情况下它主要含有低折射率（典型值为1.45）的SiO2。采用高折射率（的材料）可得到较好的抗反射层。换句话说，为了层3和9，或许能决定采用具有折射率为2.1的TiO2并保持之。另外，也许能决定将这层和其它抗反射层结合使用，比如Ta2O5、ZnS或MgF2，以便提供产生较好的抗反射效果的双层结构。
然后，以已知方式制备连接区，这将是本领域技术从员所熟知的，因而不再给予更详细说明，已参照一个双面太阳能电池，对流程图作了解释，但也要理解，在工序141的腐蚀之后就可中止而提供给以后准备连接的单面太阳能电池。
因此可以说，掺杂源和掩蔽层均采用二氧化硅层会产生一系列好的效果。在制造单面太阳能电池时，衬底晶片的一面涂敷二氧化硅层，该二氧化硅层部分地作为源材料而又部分地作为掩蔽层。在高温工序中，原子从掺杂源直接向晶片的下面部分扩散，并经气体以自掺杂的方式向未保护的晶片背面扩散。晶片的自掺杂部分通过后面的腐蚀被除去，而二氧化硅层保护下面的掺杂区。然后晶片被连接并可作用单面太阳能电池使用。
在图8中可以看到，由气相掺杂源掺杂的区域11通过工序171中的最终腐蚀为何不能被完全除去。这样，在工序152中在底部形成一个带结层的环形沟槽。该沟槽的宽度正好大于掺杂区4和4的相应浸透深度。二氧化硅层3和9之间的距离入可用于调节暗电流的变化率，这种调节是通过由在阻塞（blocking）方向偏置的半导体层形二极管来实现的，由此可降低热点危险。对于N+和P+区之间的漏电流，距离入是起决定性作用的，当太阳能电池由此而具有二极管效应时，即使一个或多个独立的太阳能电池失效或被遮盖，太阳能电池板也能连续工作。所提到的二极管效应可通过采用选择性腐蚀除去结合图6说明的自掺杂区来得到，以便使环形沟槽暴露于晶片1，同时沿有源区4和10边缘仍有层11的剩余部分。由于层11是通过来自源层9的自掺杂形成的，因而它具有和有源区10相同的导电类型，层11的面对区域10的一个组成部分将因此被认为是这区域10的一个组成部分，而面对区域4的剩余部分将被认为是一个与有源区4导电类型不同的掺杂区16（图8）。与区域4导电类型相同的区域15在沟槽中与区域10连接，以便提供一个Pn结或PIN结。区域15可能，例如，与连接区相连而形成，因此它可以是铝的。这个半导体结形成一个与太阳能电池形成的“光电二极管”反向的二极管，因此可保证，即使是太阳能电池不能工作，例如被破坏，被遮盖或类似的情况，安装太阳能电池的面极也能继续工作。采用单晶原材料，二极管垂直于环形沟槽延伸，而采用多晶硅原材料，二极管由垂直于沟槽的多个部分组成，因而，它包括一系列并连的二极管。
在前面对具有硼或磷的二氧化硅层作为源层进行了说明，但应当理解，掺杂剂可任意从例如锑和砷中选择。二氧化硅通常包括通过强加热和添加氧形成石英晶体的含硅和氧材料，但它可由例如氮化硅，氧化钛或其它具有作为阻挡层所必须的特性的材料替代。前面描述的例子中的原材料为单晶硅片，但也可由多晶片甚至非晶片替代，这些材料的选择取决于太阳能电池的所希望的特性。
正如从前所述能理解的，晶片被涂覆多个不同导电类型的源层，它们共同扩散并且既作为源层又作为阻止不希望的自掺杂的掩蔽层。这些层可通过例如CVD、旋涂或厚膜印刷技术按普通方式被设置。从而使得有可能在一个单独的高温工序中制成双面太阳能电池，而自掺杂区可由以后的腐蚀除去，还应理解，这里描述的技术适用于包括闸流晶体管在内多种不同半导体类型的制造。因此，可在半导体上形成任意结构的渗杂区。
在前面对以碱溶液作为腐蚀剂作了说明，但是腐蚀工序由等离子腐蚀来代替是有利的，这样扩散工序和腐蚀工序就可在一个相同的炉室中进行，而不必在工序之间移动晶片。因此这种方法的显著优点是在腐蚀过程中炉管道是清洁的，并且可省去以后的晶片洗涤、化学清洁处理和干燥等工序。

Claims (10)

1、一种在半导体元件特别是太阳能电池上制造掺杂区的方法，其特征在于，在半导体衬底表面的一部分涂敷带有第一种掺杂剂的一个源层；将带源层的半导体衬底加热到足以使掺杂剂的部分从源层向半导体衬底扩散的温度，同时在掺杂过程中，半导体衬底的未被保护的表面的不希望的自掺杂也发生了；以后腐蚀掉半导体衬底的自掺杂区，所述源层构成对下面的掺杂区的保护阻挡层。
2、根据权利要求1的方法，其特征在于，腐蚀之后，在半导体衬底表面的另一部分，涂敷带有第二种掺杂剂的第二源层;将带有源层的半导体衬底加热到足以使第二种掺杂剂的部分从第二源层向半导体衬底扩散的温度，同时在掺杂过程中，半导体衬底的未被保护的表面的不希望的自掺杂也发生了;以后腐蚀掉半导体衬底的自掺杂区，所述源层构成对下面的掺杂区的保护阻挡层。
3、根据权利要求1或2的方法，其特征在于，为对于涂敷了带有掺杂剂的源层，加热前涂敷一层或多层带掺杂剂的源层。
4、根据权利要求1或2的方法，其特征在于，半导体衬底为晶体硅。
5、根据权利要求1或2的方法，其特征在于，含有掺杂剂的源层为二氧化硅。
6、根据权利要求1或2的方法，其特征在于，含有掺杂剂的源层从下面一组中选择：TiO，TiO2，ALO2，SnO2氮化硅。
7、根据权利要求1-5的方法，其特征在于，掺杂剂从磷、硼、砷和锑中选择。
8、一种根据权利要求1或2所述方法制造的太阳能电池，其特征在于，它包括一个半导体衬底的晶片（1），晶片一面的部分具有第一导电型的第一有源区（10），晶片的另一面，晶片的边缘和晶片的第一面的周边具有第二导电型的第二有源区（4），两个有源区（4，10）隔开的距离为入。
9、根据权利要求8的太阳能电池，其特征在于，有源区（4，10）涂敷有抗反射层。
10、根据权利要求8或9的太阳能电池，其特征在于，位于第一（10）和第二（4）有源区之间的区域包括一个与第一区（10）相连的第二种导电型的第三有源区（15）和一个与第二有源区（4）相连的第一导电型的第四有源区（16），以便提供一个相对于由第一和第二有源区（4，10）形成的PN结反向的PN结。
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CN111344872A (zh) * 2017-11-22 2020-06-26 法国原子能源和替代能源委员会 光伏电池的改进的制造方法

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EP0531430A1 (en) 1993-03-17
NO924568D0 (no) 1992-11-26
RO111230B1 (ro) 1996-07-30
US5461002A (en) 1995-10-24
HU9203773D0 (en) 1993-04-28
CA2084089A1 (en) 1991-12-01
DK133890A (da) 1991-12-01
NO924568L (no) 1992-11-26
DK133890D0 (da) 1990-05-30
JPH05508742A (ja) 1993-12-02
DK170189B1 (da) 1995-06-06
AU7976591A (en) 1991-12-31
EP0531430B1 (en) 1996-04-03
HUT63711A (en) 1993-09-28
AU646263B2 (en) 1994-02-17
CN1025392C (zh) 1994-07-06
DE69118530D1 (de) 1996-05-09
PL167243B1 (pl) 1995-08-31
FI925409A (fi) 1992-11-27
ES2088793T3 (es) 1996-09-16
FI925409A0 (fi) 1992-11-27
DE69118530T2 (de) 1996-11-21
ATE136402T1 (de) 1996-04-15
US5665175A (en) 1997-09-09
WO1991019323A1 (en) 1991-12-12
BR9106519A (pt) 1993-05-25

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