CN102379043A - 双面接触的太阳能电池及其制造方法 - Google Patents
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Abstract
本发明涉及一种用于制造正面和背面接触的太阳能电池的方法。该方法基于具有介电层的晶圆的微结构化和被微结构化的区域的掺杂。随后沉积含金属的成核层，并且电镀加固这些接触。本发明还涉及能够使用所述方法制造的太阳能电池。
Description
技术领域
本发明涉及一种用于制造双面接触的太阳能电池的方法，该方法基于具有介电层的晶圆的微结构化和被微结构化的区域的掺杂。随后实现含金属的成核层的沉积以及接触的电镀加固。本发明还涉及能够以这种方式制造的太阳能电池。
背景技术
太阳能电池的制造与用于精密加工晶圆的大量工序相关联。这里包括发射极扩散、介电层的施加及其微结构化、晶圆的掺杂、接触、成核层的施加及其加厚。
关于正面接触的微结构化，目前常见的应用是薄氮化硅层(SiNx)的微结构化。这些层就商业电池而言目前形成标准减反射涂层。由于该减反射涂层还部分地起到太阳能电池的正面钝化作用，并且该层在正面金属化之前被施加，因此必须通过相应的微结构化使此非导电层局部开口，以便将金属接触直接施加到硅衬底上。
因此，现有技术是利用含玻璃粉的金属膏印刷SiNx层。首先进行干燥以驱除有机溶剂，然后在高温下(大约900℃)烧成。由此玻璃粉破坏SiNx层，使SiNx层局部溶解，因此能够形成硅-金属接触。这种方法的缺陷是由玻璃粉产生的高接触电阻(＞10-3Ωcm2)以及能够降低钝化层质量和硅衬底质量的必需的高工艺温度。
用于使SiNx层局部开口的已知的温和方法是应用光刻法结合湿化学蚀刻工艺。首先，将光刻胶层施加在晶圆上，并且经由UV曝光和显影使该光刻胶层结构化。随后，在含氢氟酸或含磷酸的化学体系中执行湿化学蚀刻步骤，以去除在光刻胶的已开口位置处的SiNx。这种方法的一个很大的缺陷是极大的复杂性以及与此相关的成本。此外，利用该方法制造太阳能电池不能实现足够的生产量。就某些氮化物而言，由于蚀刻速率太低，因此不能再应用此处描述的方法。
此外，根据目前的技术发展水平已知，借助激光束，完全通过热烧蚀(干式激光烧蚀)去除由SiNx制成的钝化层。
关于晶圆掺杂，在微电子学中，通过外延生长的SiO2掩模的光刻结构化以及随后在扩散炉内的全表面扩散来进行局部掺杂是目前的技术发展水平。通过在光刻限定的抗蚀剂掩模上真空蒸发以及随后在有机溶剂内溶解抗蚀剂实现金属化。该方法的缺陷是具有非常大的复杂性、时间长和成本要求高，并且整个表面加热元件，这还会改变可能存在的扩散层并且也能损坏衬底的电学性质。
通过自掺杂(如含铝的)金属膏的丝网印刷以及随后在约900℃的温度下干燥和烧成也可以实现局部掺杂。该方法的缺陷是元件的高机械负荷、昂贵的耗材以及整个元件经受的高温。此外，仅大于100μm的结构宽度在此是可以使用的。
另一种方法(“埋入式基极接触”)使用全表面SiNx层，利用激光辐射使该层局部开口，然后在扩散炉中扩散掺杂层。由于SiNx层的遮蔽，仅在被激光开口的区域形成高度掺杂区。在对产生的磷硅酸盐玻璃(PSG)进行再蚀刻之后，通过在含金属的液体内无电流沉积形成金属化。该方法的缺陷是激光所造成的损伤以及去除PSG所需的蚀刻步骤。此外，该方法包括一些单独的步骤，这些单独的步骤又需要很多处理步骤。
发明内容
由此，本发明的目的是提供一种制造太阳能电池的更加有效的方法，该方法可以减少工序的数量且在本质上可以无需昂贵的平板印刷步骤。另外，也设法减少用于接触的金属的量。
通过具有权利要求1的特性的方法和据此制造的具有权利要求18的特性的太阳能电池实现该目的。进一步的多个从属权利要求揭示了一些优势发展。
根据本发明，提供了一种制造双面接触的太阳能电池的方法，其中：
a)晶圆的正面和背面的至少一些区域内涂敷至少一个介电层；
b)实现所述至少一个介电层的微结构化；
c)通过引导至少一个液体射流在待掺杂表面的一些区域上方，实现被微结构化的表面区域的掺杂，该至少一个液体射流指向实体的表面且包括至少一种掺杂剂，并利用激光束提前或同时局部加热该待掺杂表面；
d)在该晶圆的背面上的至少一些区域内沉积含金属的成核层；以及
e)为了该晶圆的双面接触，实现在晶圆的正面和背面上金属化的至少一些区域内的电镀沉积。
优选用干式激光器、或水射流引导激光器、或包含蚀刻剂的液体射流引导激光器处理表面以实现微结构化。因此，实现包含蚀刻剂的液体射流引导激光器的使用，以使得指向晶圆表面并且包括用于晶圆的至少一种蚀刻剂的液体射流被引导在待结构化的表面的多个区域上方，该待结构化的表面被激光束提前或同时局部加热。
因此，优选在所述至少一个介电层上比在衬底上具有更强的蚀刻效果的制剂作为蚀刻剂。该蚀刻剂尤其优选自H3PO4、H3PO3、PCl3、PCl5、POCl3、KOH、HF/HNO3、HCl、氯化合物、硫酸以及它们的混合物构成的组。
所述液体射流尤其优选是由纯的或高浓度磷酸或稀释的磷酸形成。磷酸可以例如在水中或别的合适溶剂中稀释，或者以不同的浓度使用。也可以添加改变pH值(酸或碱溶液)、润湿特性(如表面活性剂)或粘度(如乙醇)的添加剂。当使用包括重量百分比为50％到85％的磷酸的液体时，会达到特别良好的效果。特别地，可以完成表面层的迅速处理而不损坏衬底以及周边区域。
借助于根据本发明的微结构化，能够以非常低的复杂性实现两点。
一方面，因为所述液体对衬底具有较弱的(最好是根本没有)蚀刻效果，所以可以在不损坏衬底的情况下在所述的区域中完全去除表面层。同时，由于局部加热待去除区域内的表面层，优选是仅加热这些区域，所以能够很好地局部去除被限制在这些区域内的表面层。这由这样的事实造成：液体的蚀刻效果通常随着温度的升高而增加，因此大范围地避免了由于部分可能到达相邻的、未加热区域内的蚀刻液体对这些区域内的表面层的损坏。
沉积在晶圆上的介电层作为钝化和/或减反射层。所述介电层优选自SiNx、SiO2、SiOx、MgF2、TiO2、SiCx和Al2O3构成的组。
多个这样的层沉积层叠也是可能的。
优选地，在步骤c)中利用激光束耦合的含H3PO4、H3PO3和/或POCl3的液体射流实施所述掺杂。
掺杂剂优选自磷、硼、铝、铟、镓和它们的混合物构成的组，尤其是磷酸、亚磷酸、磷酸盐和磷酸氢盐的溶液、硼砂、硼酸、硼酸盐和过硼酸盐、硼化合物、镓化合物以及它们的混合物构成的组。
另一优选变型例提供，利用液体射流引导激光器同时实施所述微结构化和掺杂。
根据本发明的又一变型例包括在精密处理并且处理试剂包括掺杂剂的情况下，继微结构化之后，实现被微结构化的硅晶圆的掺杂。
这可以通过使用包括至少一种蚀刻固体材料的化合物的液体代替包括至少一种掺杂剂的液体来实现。该变型例尤其优选，因为可以在同一装置内先实施微结构化，通过液体交换，随后实施掺杂。或者，也可以利用气溶胶射流来实施微结构化。由于可以通过提前加热气溶胶或其组分实现相似的结果，因此在该变型例中，不是绝对地需要激光辐射。
根据本发明的优选用于微结构化和掺杂的方法使用一种技术体系，在该技术体系中，可以配各种化学体系的液体射流作为用于激光束的液体光导管。激光束经由特殊耦合装置耦合入液体射流中且由内部全反射进行引导。这样，确保了在同一时间和地点向工艺炉供应化学制剂和激光束。因此激光承担不同的任务：一方面能够在其撞击点局部加热衬底表面，从而可选择地熔化衬底表面，并且在极端情况下使其蒸发。因为一些化学过程受动力学限制或从热力学观点来看是不适宜的，在标准条件下不发生所述化学过程，但是由于被加热的衬底表面上化学制剂的同时撞击，所以可以激活这些化学过程。除了激光的热效应外，关于激光在衬底表面上产生例如电子空穴对方面，还能够实现光化活化，这些电子空穴对可以促进该区域内氧化还原反应的过程或使得氧化还原反应成为可能。
除了集中激光束和化学制剂供应，液体射流还确保了工艺炉的边缘区域的冷却以及反应产物的迅速移除。最后提到的这方面是促进和加速迅速进行化学(平衡)过程的一个重要的前提条件。射流的冷却作用可以保护不参与反应、最重要的是不经过材料去除的边缘区域，使其免于受到热应力的损伤和由此产生的晶体损坏，这使太阳能电池能够低损伤或无损伤的结构化。此外，由于液体射流的高流速，它赋予供应的材料明显的机械动力，当射流撞击在熔化的衬底表面上时，该机械动力尤其显著。
激光束和液体射流共同形成新的工艺工具，原则上，这种组合优于它们各自构成的***。
优选通过真空蒸发、溅射或通过从水溶液还原沉积所述含金属的成核层。优选同时在晶圆的正面和背面实现该沉积。因此该含金属的成核层优选包括选自铝、镍、钛、铬、钨、银和它们的合金构成的组的金属。
施加所述成核层之后，优选例如利用激光退火进行热处理。
在沉积所述含金属的成核层之后，优选地，在晶圆的正面上的至少一些区域中沉积用以增加粘着度的层。
用于增加粘着度的该层优选包括选自镍、钛、铜、钨和它们的合金构成的组的金属或由这些金属构成。
施加所述含金属的成核层之后，优选地，通过金属化，尤其是银或铜的电镀沉积实现至少一些区域内的成核层的加厚，从而实现晶圆的正面和背面的接触。
优选地，使用尽可能层流的液体射流来实施该方法。于是可以通过液体射流内的全反射特别有效地引导该激光束，由此液体射流实现光导管的功能。例如通过在喷嘴单元内与液体射流射束方向垂直的窗口来实现激光束的耦合。因此该窗口可以配置成聚焦激光束的透镜。选择地或附加地还可以使用独立于该窗口的透镜用于聚焦或形成激光束。因此可以在本发明的特别简单的实施例中设计所述喷嘴单元，这样可以在射流方向的径向上从一侧或多侧供应液体。
优选作为可用类型的激光器是：
各种固体激光器，尤其是商业上经常使用的波长为1064nm、532nm、355nm、266nm和213nm的Nd-YAG激光器、波长＜1000nm的二极管激光器、波长为514nm到458nm的氩离子激光器和准分子激光器(波长：157nm到351nm)。
因为在表面层内由激光引入的能量逐渐越来越好地集中在表面，这易于减小热影响区以及相应的减少材料内、尤其是钝化层下面的掺磷硅内的晶体损坏，所以趋势是随着波长减小微结构化的质量更好。
由于这个原因，具有飞秒到纳秒范围脉冲宽度的蓝色激光器和近紫外线(UV)范围(如355nm)内的激光器已被证明特别有效。尤其使用短波激光，还存在在硅内直接产生电子/空穴的选择，这些电子/空穴可以用于镍沉积(光化活化)期间的电化工艺。因此，例如由激光产生的硅内的自由电子除了有助于以上已经描述的镍离子和磷酸的氧化还原过程，还直接有助于表面上镍的减少。可以在结构化工艺期间通过具有规定波长(尤其是近UV内，λ≤355nm)样品的永久照明而永久保持产生该电子/空穴，并且可以以持续的方式促进金属成核过程。
为此，可以利用太阳能电池性能，经由p-n结分离多余的电荷载体，由此对n型传导表面充负电。
根据本发明的所述方法的再一优选变型例提供，激光束以时间和/或空间脉冲形式主动调整。这里包括平顶形式、M形轮廓或矩形脉冲。
根据本发明，还提供了能够根据前述方法制造的太阳能电池。
附图说明
参照附图和随后的实例将更加详细地解释根据本发明的主题，而不希望将所述主题限于这里所示的特殊实施例。
图1示出根据本发明制造的太阳能电池的实施例。
具体实施方式
图1中根据本发明的太阳能电池1具有硅基上的晶圆2，其背面涂有平的全表面发射极3。在发射极层上布置钝化层4。在一些规定的区域中，这里示出背面上的电场5(背面场)和背面接触6。在晶圆2的正面上，布置平的全表面发射极7以及钝化层8。在表面区域中，在一些规定的位置处布置具有高度掺杂发射极(n+)9和正面接触10的区域。
实例1
被锯开的p型晶圆首先经过损伤蚀刻以便去除线锯损伤，该损伤蚀刻在40％KOH溶液中80℃下进行20分钟。接着晶圆在1％KOH溶液中98℃下(持续约35分钟)被单面纹理化。接下来的一步，将三氯氧化磷(POCl3)用作磷源在管式炉内进行光发射极扩散。发射极的层电阻在100到400ohm/sq的范围内。随后，通过在其上方流过水蒸气而在管式炉内制造薄热氧化层。氧化层的厚度据此在6到15nm的范围内。接下来的一步，在正面实现氮化硅(折射率n＝2.0到2.1，层的厚度：约60nm)的等离子体增强化学气相沉积(PECVD)以及在背面实现二氧化硅层(厚度：约200nm)。随后利用液体射流使这样处理后的晶圆结构化。借助于耦合到液体射流的激光(所谓的激光化学加工，LCP)同时实现沟道壁的切割和掺杂。85％磷酸用作射流介质。结构的线宽约为30μm且两线之间的间距为1到2mm。因此使用532nm(P＝7W)的Nd:YAG激光器。行进速度为400mm/s。随后，利用LCP工艺，对由此被结构化和掺杂的晶圆执行镍的无电流沉积。这里，使用具有NiSO4(c＝3mol/l)和H3PO3(c＝3mol/l)的水溶液作为射流介质。激光参数和行进速度与上述方法步骤相同。随后，通过使用硼酸(c＝40g/l)的LCP形成局部背面电场(BSF)。线宽约为30μm且两线之间的间距为200μm到2mm。这里的激光参数和行进速度也和前两个方法步骤是相同的。随后，在背面实现铝的蒸汽蒸发(厚度：约50nm)，然后在背面实现接触金属的真空蒸发(例如，钛，厚度：约30nm)。接着，可选择地，在合成气体气氛(N2H2)中300℃到500℃温度下实现正面和背面接触的烧结。最后，为了加厚正面和背面接触达约为10μm的接触厚度，实现银或铜的光诱导沉积。对于电镀浴，在这里氰化银(c＝1mol/l)用作银源。镀浴温度为25℃，施加到晶圆背面的电压为0.3V。使用具有波长为253nm的卤素灯用于该光诱导。
Claims (18)
1.用于制造双面接触的太阳能电池的方法，其中
a)晶圆的正面和背面的至少一些区域内涂敷至少一个介电层；
b)实现所述至少一个介电层的微结构化；
c)通过引导至少一个液体射流在待掺杂表面的一些区域上方，实现被微结构化的表面区域的掺杂，该至少一个液体射流指向实体的表面且包括至少一种掺杂剂，并利用激光束提前或同时局部加热该待掺杂表面；
d)在该晶圆的背面上的至少一些区域内沉积含金属的成核层；以及
e)为了该晶圆的双面接触，实现在晶圆的正面和背面上金属化的至少一些区域内的电镀沉积。
2.根据权利要求1所述的方法，其中，通过用干式激光器、或水射流引导激光器、或包含蚀刻剂的液体射流引导激光器处理表面以实现所述微结构化，所述液体射流指向固体的表面且包括用于晶圆的至少一种蚀刻剂，该液体射流被引导在待结构化的表面的多个区域上方，该待结构化的表面被激光束提前或同时局部加热。
3.根据前述权利要求之一所述的方法，其中，所述蚀刻剂在所述至少一个介电层上比在衬底上具有更强的蚀刻效果，并且该蚀刻剂尤其选自H3PO4、H3PO3、PCl3、PCl5、POCl3、KOH、HF/HNO3、HCl、氯化合物、硫酸以及它们的混合物构成的组。
4.根据前述权利要求之一所述的方法，其中，所述介电层选自SiNx、SiO2、SiOx、MgF2、TiO2、SiCx和Al2O3构成的组。
5.根据前述权利要求之一所述的方法，其中，利用激光束耦合的含H3PO4、H3PO3和/或POCl3的液体射流实施所述掺杂。
6.根据前述权利要求之一所述的方法，其中，所述至少一种掺杂剂选自磷、硼、铝、铟、镓和它们的混合物构成的组，尤其是磷酸、亚磷酸、磷酸盐和氢磷酸盐的溶液、硼砂、硼酸、硼酸盐和过硼酸盐、硼化合物、镓化合物以及它们的混合物构成的组。
7.根据前述权利要求之一所述的方法，其中，利用液体射流引导激光器同时实施所述微结构化和掺杂。
8.根据前述权利要求之一所述的方法，其中，所述含金属的成核层通过蒸发沉积、溅射或通过从水溶液还原来沉积，优选同时在该晶圆的正面和背面实现该沉积。
9.根据前述权利要求之一所述的方法，其中，所述含金属的成核层包括选自铝、镍、钛、铬、钨、银和它们的合金构成的组的金属。
10.根据前述权利要求之一所述的方法，其中，施加所述成核层之后，尤其通过激光退火进行热处理。
11.根据前述权利要求之一所述的方法，其中，在沉积所述含金属的成核层之后，在所述正面上的至少一些区域中沉积用以增加粘着度的层。
12.根据前述权利要求之一所述的方法，其中，用于增加粘着度的该层包括选自镍、钛、铜、钨和它们的合金构成的组的金属或由合金构成。
13.根据前述权利要求之一所述的方法，其中，施加所述含金属的成核层之后，通过金属化，尤其是银或铜的电镀沉积实现至少一些区域内的成核层的加厚，从而实现晶圆的正面和背面的接触。
14.根据前述权利要求之一所述的方法，其中，所述激光束被在液体射流内全反射引导。
15.根据前述权利要求之一所述的方法，其中，所述液体射流是层流的。
16.根据前述权利要求之一所述的方法，其中，所述液体射流具有10到500μm的直径。
17.根据前述权利要求之一所述的方法，其中，所述激光束以时间和/或空间脉冲形式，尤其是平顶形式、M形轮廓或矩形脉冲主动调整。
18.根据如前述权利要求之一所述的方法可以制造的太阳能电池。
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| DE102009011306.1 | 2009-03-02 | ||
| DE102009011306A DE102009011306A1 (de) | 2009-03-02 | 2009-03-02 | Beidseitig kontaktierte Solarzellen sowie Verfahren zu deren Herstellung |
| PCT/EP2010/000921 WO2010099863A2 (de) | 2009-03-02 | 2010-02-15 | Beidseitig kontaktierte solarzellen sowie verfahren zu deren herstellung |
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| CN102379043A true CN102379043A (zh) | 2012-03-14 |
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| EP (1) | EP2404324A2 (zh) |
| KR (1) | KR20110122214A (zh) |
| CN (1) | CN102379043A (zh) |
| DE (1) | DE102009011306A1 (zh) |
| WO (1) | WO2010099863A2 (zh) |
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| CN103681903A (zh) * | 2012-09-21 | 2014-03-26 | 财团法人工业技术研究院 | 太阳能电池 |
| CN114175278A (zh) * | 2019-05-29 | 2022-03-11 | 韩华Qcells有限公司 | 晶片太阳能电池、太阳能模块以及用于制造晶片太阳能电池的方法 |
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| US9508886B2 (en) | 2007-10-06 | 2016-11-29 | Solexel, Inc. | Method for making a crystalline silicon solar cell substrate utilizing flat top laser beam |
| US8399331B2 (en) | 2007-10-06 | 2013-03-19 | Solexel | Laser processing for high-efficiency thin crystalline silicon solar cell fabrication |
| US9455362B2 (en) | 2007-10-06 | 2016-09-27 | Solexel, Inc. | Laser irradiation aluminum doping for monocrystalline silicon substrates |
| KR20110086098A (ko) | 2008-10-23 | 2011-07-27 | 알타 디바이씨즈, 인크. | 광전지 장치 |
| US9691921B2 (en) | 2009-10-14 | 2017-06-27 | Alta Devices, Inc. | Textured metallic back reflector |
| US9502594B2 (en) | 2012-01-19 | 2016-11-22 | Alta Devices, Inc. | Thin-film semiconductor optoelectronic device with textured front and/or back surface prepared from template layer and etching |
| US20170141256A1 (en) | 2009-10-23 | 2017-05-18 | Alta Devices, Inc. | Multi-junction optoelectronic device with group iv semiconductor as a bottom junction |
| US20150380576A1 (en) * | 2010-10-13 | 2015-12-31 | Alta Devices, Inc. | Optoelectronic device with dielectric layer and method of manufacture |
| US11271128B2 (en) | 2009-10-23 | 2022-03-08 | Utica Leaseco, Llc | Multi-junction optoelectronic device |
| DE102010026331A1 (de) * | 2010-07-07 | 2012-02-02 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zum Materialabtrag an Festkörpern |
| DE202011100178U1 (de) | 2011-04-29 | 2012-07-31 | 3D-Micromac Ag | Vorrichtung zur direkten Energieeinkopplung in organisches Halbleitermaterial für Solarzellen |
| KR20120140026A (ko) * | 2011-06-20 | 2012-12-28 | 엘지전자 주식회사 | 태양전지 |
| DE102011052256B4 (de) * | 2011-07-28 | 2015-04-16 | Hanwha Q.CELLS GmbH | Verfahren zur Herstellung einer Solarzelle |
| KR101838278B1 (ko) * | 2011-12-23 | 2018-03-13 | 엘지전자 주식회사 | 태양 전지 |
| AU2012362505B2 (en) * | 2011-12-26 | 2015-08-20 | Solexel, Inc. | Systems and methods for enhanced light trapping in solar cells |
| US11038080B2 (en) | 2012-01-19 | 2021-06-15 | Utica Leaseco, Llc | Thin-film semiconductor optoelectronic device with textured front and/or back surface prepared from etching |
| KR101940074B1 (ko) * | 2012-04-30 | 2019-04-10 | 주성엔지니어링(주) | 태양 전지 및 그 제조 방법 |
| DE102012211161A1 (de) | 2012-06-28 | 2014-02-06 | Robert Bosch Gmbh | Verfahren zum Ausbilden einer elektrisch leitenden Struktur an einem Trägerelement, Schichtanordnung sowie Verwendung eines Verfahrens oder einer Schichtanordnung |
| DE102013106272B4 (de) * | 2013-06-17 | 2018-09-20 | Hanwha Q Cells Gmbh | Wafersolarzelle und Solarzellenherstellungsverfahren |
| US9653638B2 (en) | 2013-12-20 | 2017-05-16 | Sunpower Corporation | Contacts for solar cells formed by directing a laser beam with a particular shape on a metal foil over a dielectric region |
| EP2993699B1 (en) * | 2014-09-04 | 2018-03-21 | IMEC vzw | Method for fabricating crystalline photovoltaic cells |
| DE102018105438A1 (de) * | 2018-03-09 | 2019-09-12 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur Herstellung einer photovoltaischen Solarzelle und photovoltaische Solarzelle |
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- 2010-02-15 WO PCT/EP2010/000921 patent/WO2010099863A2/de active Application Filing
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- 2010-02-15 KR KR1020117022811A patent/KR20110122214A/ko not_active Application Discontinuation
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2010099863A3 (de) | 2010-12-29 |
| US20120055541A1 (en) | 2012-03-08 |
| WO2010099863A2 (de) | 2010-09-10 |
| EP2404324A2 (de) | 2012-01-11 |
| KR20110122214A (ko) | 2011-11-09 |
| DE102009011306A1 (de) | 2010-09-16 |
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