CN110085683A - 无掺杂晶体硅异质结太阳能电池及其制备方法 - Google Patents
无掺杂晶体硅异质结太阳能电池及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种无掺杂晶体硅异质结太阳能电池以及其制备方法，衬底为n型c‑Si，空穴选择材料为WO3，电子选择材料为CsF；其特征在于：在c‑Si层两侧各生长有一层本征a‑Si:H薄膜层。本发明在硅片的两侧都实现了本征氢化非晶硅(a‑Si:H)薄膜的钝化，通过钝化夹层界面处理表面复合，提高电池的整体性能。
Description
技术领域
本发明属于太阳能电池技术领域，特别是涉及一种无掺杂晶体硅异质结太阳能电池及其制备方法。
背景技术
在工业和实验室中，大多数太阳能电池使用掺杂的同质结来分离光能产生的电子和空穴，为了研究掺杂同质结，科研人员面临着无数与之相互关联的光学、载流子传输、复合损耗、寄生吸収和其他重掺杂效应的问题。此外，与掺杂有关的复杂技术问题，例如较高的工艺温度(＞800℃)、较小的接触分数(＜0.5％)、结的隔离，都必须加以考虑。这些问题可以通过转换到一组不对称载流子选择性接触异质结来解决，这种方法长期以来被认为是突破晶体硅(c-Si)电池内在效率限制的关键技术。载流子选择性异质接触对所收集的载流子形成一个可忽略的电阻，同时阻止另一种载流子，等效于低接触复合。这可以通过许多可能的方法在异质接触面实现这种载流子选择性接触的效果，在硅基电池的能带中形成带阶，增大或降低对不同载流子运输的势垒，使不同载流子的电导率差异巨大，达到收集层对载流子选择性抽取的作用。
近年来，非对称异质结的优势已经显现，最典型的例子是硅异质结太阳能电池结构(SHJ，有时称为HIT，带有本征非晶硅薄层的异质结)，它在效率方面已经超过了同质结太阳能电池。然而，到目前为止，包括SHJ技术在内的所有非对称异质结结构，仍然依赖于掺杂硅层，这将引入复杂的沉积优化问题和寄生光学损耗问题。非对称载流子选择性接触异质结的概念是用可选择的材料完全替代掺杂的硅层。一些载流子选择性材料目前已经在c-Si上得到证明，包括过渡金属氧化物、有机薄膜、金属绝缘体结构(应用于太阳电池的MOS反型层)，其中许多材料已经在一些太阳能电池中实现。与掺杂硅层的局限性相比，载流子选择性材料大大提高了光学特性、电学特性，解耦了太阳能电池不同组件的相互作用。此外，它们可以通过更简单的技术在低温下沉积，比如热蒸发、旋转涂层等，大大降低成本和工艺的复杂性。然而，c-Si无掺杂非对称异质结太阳电池的效率比较低，主要在于c-Si与异质结界面的载流子复合严重。
发明内容
本发明的目的是提供一种先进的无掺杂晶体硅异质结太阳能电池，以及其制备方法。
本发明的思路是，通过钝化夹层界面处理表面复合，可提高电池的开路电压和整体性能。就像在HIT太阳电池中一样，在硅片的两侧都实现了本征氢化非晶硅(a-Si:H)薄膜的钝化，不同于掺杂的a-Si:H薄膜会导致100％的寄生吸收，而具有较少缺陷的本征非晶硅薄膜有利于光生电流的产生，更重要的是，这些钝化层大大减少了在c-Si表面的载流子复合率，提高少数载流子的浓度，这对电池开路电压的增大至关重要。这种薄层必须保持适当的厚度，以避免过大的电阻和吸收损失。我们注意到本征a-Si:H薄膜并不是无掺杂异质结太阳电池的组成部分，因此这种a-Si:H薄膜可以用其他非吸收性、寿命更长的有机或无机钝化膜来代替。理想情况下，当一种功函数很低的材料被用于轻掺杂的c-Si时，电子的积累(空穴的排斥)会发生在表面附近，这种表面的高浓度电子降低了异质结接触的电阻率，相应的表面低空穴浓度降低了异质结接触界面发生Shockley-Read-Hall复合概率。同理，这个论断适用于空穴和高功函数的材料。通过这种方式，在硅片两侧使用功函数差异较大的材料，可以有效实现光生载流子的分离。经过研究，这些材料基本是Ⅲ-Ⅴ族过渡金属氧化物和Ⅱ-Ⅵ族碱金属氟化物，它们对空穴或电子能有效地选择性抽取。已经被研究被过的金属氧化物，例如氧化钨(WO3)，由于具有的宽带隙(～2.7ev)、良好的载流子选择性、高的功函数(～5.6ev)等特性，常作为有机和无机薄膜太阳能电池的窗口层。利用高功函数的WO3来收集和传导空穴，利用低功函数的CsF作为缓冲层与背电极Al形成复合阴极来增强电子的收集，可以得到一种结构为Ag/ITO/WO3/c-Si/CsF/Al的无掺杂晶体硅异质结太阳能电池(如图1所示)，但这种结构电池的开路电压比较低。
具体地，本发明采用的技术方案是这样的：无掺杂晶体硅异质结太阳能电池，衬底为n型c-Si，空穴选择材料为WO3，电子选择材料为CsF；其特征在于：在c-Si层两侧各生长有一层本征a-Si:H薄膜层。
为实现第二个发明目的，所采用的技术方案是这样的：无掺杂晶体硅异质结太阳能电池的制备方法，包括以下步骤：
1)硅片清洗：将利用激光切割的方法把硅片分割成4×4cm2的尺寸，然后采用标准RCA法清洗；
2)沉积本征a-Si:H钝化层：硅片清洗后，立即置于等离子体增强化学气相沉积(PECVD)中双面生长厚度10nm的本征a-Si:H层，硅烷与氢气的比例为1:3～10；沉积腔体的本底真空优于5×10-4Pa，沉积功率20～75W，沉积压强为90～120Pa，沉积温度为200℃；
3)沉积WO3：立即将硅片置于蒸发镀膜机内，真空度优于5×10-4Pa，调节电源电流，以0.05nm/s的速率，在硅片正面生长一层10nm厚的WO3薄膜，硅片的背面利用掩模板覆盖；
4)沉积CsF：与步骤3)相同操作，以0.05nm/s的速率，在硅片的背面生长0.8～1.2nm厚的CsF薄膜；
5)沉积背面铝背极：在不破真空条件下以0.5nm/s的速率在CsF上蒸镀800nm厚的Al；
6)溅射ITO：用磁控溅射沉积80nm的ITO薄膜，当腔室本底真空到5×10-4Pa，加热硅片使其温度为250℃，设定Ar与O2流量比为40:1；调节气压为1.0Pa，直流溅射电流为0.1A，预溅射3min后，开始溅射，溅射时间为8min，沉积的ITO厚度为80nm；
7)制作栅线电极：利用栅线掩膜版，以0.5nm/s的速率蒸镀800nm Ag，形成银栅线电极。
附图说明
以下结合附图和本发明的实施方式来作进一步详细说明
图1为现有的电池结构示意图；
图2为本发明的电池结构示意图；
图3为有、无非晶硅钝化层电池的性能参数图，曲线S1有本征a-Si:H钝化层，曲线S2无本征a-Si:H钝化层。
具体实施方式
如图1所示，现有的电池结构为由上到下依次为Ag电极1、ITO薄膜2、WO3薄膜3、c-Si层4、CsF薄膜5、Al电极6。
如图2所示，本实施例所示电池结构，衬底为n型c-Si层4，空穴选择材料为WO3薄膜3，电子选择材料为CsF薄膜5；在c-Si层4两侧各生长有一层本征a-Si:H薄膜层7。由上到下依次为Ag电极1、ITO薄膜2、WO3薄膜3、本征a-Si:H薄膜层7、c-Si层4、本征a-Si:H薄膜层7、CsF薄膜5、Al电极6。
制备时：
1.实验材料
(1)n型单晶硅片(直拉法生长，双面非抛光，190μm，0.8-5Ω·cm)
(2)氟化铯(纯度＞99.5％)
(3)三氧化钨(纯度99.99％)
2.太阳能电池制备步骤
A.硅片清洗：将利用激光切割的方法把硅片分割成4×4cm2的尺寸，然后采用标准RCA法清洗，每一步之间均用去离子水(DIW)超声清洗2min，具体步骤如下：
1)丙酮超声清洗10min；
2)无水乙醇超声清洗10min；
3)配制浓度为25％的NaOH溶液，80℃水浴加热20min；
4)以(29％)NH4OH:(30％)H2O2:DIW＝1:1:5配制清洗溶液，80℃水浴加热10min；
5)以(37％)HCl:(30％)H2O2:DIW＝1:1:5配制清洗溶液，80℃水浴加热10min；
6)浸泡于1％HF溶液中180s；
7)氮气吹干。
B.沉积本征a-Si:H钝化层：硅片清洗后，立即置于等离子体增强化学气相沉积(PECVD)中双面生长厚度10nm的本征a-Si:H层，硅烷与氢气的比例为1:3～10。沉积腔体的本底真空优于5×10-4Pa，沉积功率20～75W，沉积压强为90～120Pa，沉积温度为200℃。
C.沉积WO3：立即将硅片置于蒸发镀膜机内，真空度优于5×10-4Pa，调节电源电流，以0.05nm/s的速率，在硅片正面生长一层10nm厚的WO3薄膜，硅片的背面利用掩模板覆盖；
D.沉积CsF：与上述相同操作，以0.05nm/s的速率，在硅片的背面生长0.8～1.2nm厚的CsF薄膜；
E.沉积背面铝背极：在不破真空条件下以0.5nm/s的速率在CsF上蒸镀800nm厚的Al；
F.溅射ITO：用磁控溅射沉积80nm的ITO薄膜，主要步骤为：
1)当腔室本底真空到5×10-4Pa，加热硅片使其温度为250℃，设定Ar与O2流量比为40:1；
2)调节气压为1.0Pa，直流溅射电流为0.1A，预溅射3min后，开始溅射，溅射时间为8min，沉积的ITO厚度为80nm；
G.制作栅线电极：利用栅线掩膜版，以0.5nm/s的速率蒸镀800nm Ag，形成银栅线电极。
3.实验结果
在标准测试条件(AM1.5，100mW/cm2，25℃)下，两种不同结构电池的电流-电压(I-V)曲线如图3所示，相应的电学参数如表1所示。
表1有无非晶硅钝化层电池的性能参数
| 电池结构 | 开路电压/V | 短路电流/mA·cm<sup>-2</sup> | 填充因子/％ | 转换效率/％ |
| 无钝化层 | 0.31 | 22.51 | 49.10 | 3.32 |
| 有钝化层 | 0.55 | 26.32 | 60.12 | 8.75 |
通过比较发现，有本征a-Si钝化层的电池开路电压有较大提高，这是因为WO3/c-Si/CsF异质结界面存在大量的界面态，这些界面态是有效载流子复合中心，由不同结构的悬挂键缺陷引起，使晶体硅表面的少数载流子寿命大大降低。通过在硅表面两侧沉积本征a-Si钝化薄层，可以饱和硅片表面的悬挂键，降低少数载流子在硅表面的复合。开路电压可以看出Voc取决于太阳能电池的饱和电流I0和光生电流IL，光生电流的变化很小，而饱和电流的大小可以改变几个数量级，所以Voc关键影响在于饱和电流，而I0主要取决于有效载流子的复合效应。因此，通过降低少数载流子在硅表面的复合可以提高开路电压，提升器件性能。
Claims (2)
1.无掺杂晶体硅异质结太阳能电池，衬底为n型c-Si，空穴选择材料为WO3，电子选择材料为CsF；其特征在于：在c-Si层两侧各生长有一层本征a-Si:H薄膜层。
2.权利要求1所述太阳能电池的制备方法，其特征在于：包括以下步骤：
1)硅片清洗：将利用激光切割的方法把硅片分割成4×4cm2的尺寸，然后采用标准RCA法清洗；
2)沉积本征a-Si:H钝化层：硅片清洗后，立即置于等离子体增强化学气相沉积(PECVD)中双面生长厚度10nm的本征a-Si:H层，硅烷与氢气的比例为1:3～10；沉积腔体的本底真空优于5×10-4Pa，沉积功率20～75W，沉积压强为90～120Pa，沉积温度为200℃；
3)沉积WO3：立即将硅片置于蒸发镀膜机内，真空度优于5×10-4Pa，调节电源电流，以0.05nm/s的速率，在硅片正面生长一层10nm厚的WO3薄膜，硅片的背面利用掩模板覆盖；
4)沉积CsF：与步骤3)相同操作，以0.05nm/s的速率，在硅片的背面生长0.8～1.2nm厚的CsF薄膜；
5)沉积背面铝背极：在不破真空条件下以0.5nm/s的速率在CsF上蒸镀800nm厚的Al；
6)溅射ITO：用磁控溅射沉积80nm的ITO薄膜，当腔室本底真空到5×10-4Pa，加热硅片使其温度为250℃，设定Ar与O2流量比为40:1；调节气压为1.0Pa，直流溅射电流为0.1A，预溅射3min后，开始溅射，溅射时间为8min，沉积的ITO厚度为80nm；
7)制作栅线电极：利用栅线掩膜版，以0.5nm/s的速率蒸镀800nm Ag，形成银栅线电极。
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