CN113161446A - 一种铸造单晶或多晶类硅片的两步扩散预处理方法 - Google Patents
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Abstract
本发明涉及一种铸造单晶或多晶类硅片的两步扩散预处理方法，它包括如下步骤，A.酸洗；B.高温沉积PSG；C.一次除杂；D.低温沉积PSG；E.二次除杂。本发明的目的在于提供一种铸造单晶或多晶类硅片的两步扩散预处理方法，其适合与铸造单晶或多晶类硅片的有效钝化，能够减少硅片体内和表面的缺陷密度，减少载流子的复合，提升钝化水平和载流子的传输水平，使得铸造单晶或多晶类硅片能按照现有的高效电池片制作流程进行太阳能电池生产，获得高效的电池转换效率。
Description
技术领域
本发明涉及太阳能电池领域，尤其涉及一种铸造单晶或多晶类硅片的两步扩散预处理方法。
背景技术
太阳能作为新兴能源，已成为21世纪大力发展的产业。太阳电池的研发与制作，主要围绕着降本增效方向展开，提高太阳电池的转换效率是发展太阳能事业的根本，降低太阳电池的制作成本是壮大太阳能事业的基础，是满足大规模生产的先决条件。
硅片是生产硅基太阳电池片所用的载体，一般分为单晶硅片、铸造单晶硅硅片和多晶硅片。采用低成本的硅片材料是降低太阳电池制造成本的有效方式之一。在高效异质结太阳电池制作中，采用铸造单晶太阳能硅片来取代传统单晶硅片，有利降低生产成本，提高企业竞争力。铸造单晶(cast mono crystalline silicon)是近年来新开发的定向铸造技术，其利用置于坩埚底部的仔晶进行定向生长，铸造出类似于单晶的硅锭。相对于传统的单晶硅片，铸造单晶硅具有制造成本低，铸锭硅片尺寸灵活，电阻率分布窄，氧含量低等优势。
但铸造单晶，由于铸造工艺的特点，在同一硅片表面上既存在单晶区域也存在多晶区域，因此硅片内部一般存在着位错、小角度晶界、缺陷密度大等缺点，这给太阳电池的钝化带来了一定的难度，现有的铸造单晶硅异质结太阳电池制备方法和传统的异质结太阳电池制备流程相似，即使施加了高质量的表面清洁和表面钝化，总体少子寿命依旧不高，以致影响最终电池的转换效率。
发明内容
本发明的目的在于提供一种铸造单晶或多晶类硅片的两步扩散预处理方法，其适合与铸造单晶或多晶类硅片的有效钝化，能够减少硅片体内和表面的缺陷密度，减少载流子的复合，提升钝化水平和载流子的传输水平，使得铸造单晶或多晶类硅片能按照现有的高效电池片制作流程进行太阳能电池生产，获得高效的电池转换效率。
本发明的目的通过如下技术方案实现：
一种铸造单晶或多晶类硅片的两步扩散预处理方法，它包括如下步骤，
A.酸洗：用酸性溶液对硅片进行酸洗，之后清洗烘干；
B.高温沉积PSG：在经步骤A酸洗处理后的硅片表面高温沉积磷硅玻璃层，并进行退火处理；
C.一次除杂：经步骤B高温沉积PSG处理后的硅片用溶剂进行清洗并抛光，去除表面反应层和吸附的杂质；
D.低温沉积PSG：在经步骤C一次除杂处理后的硅片表面低温沉积磷硅玻璃层，并进行退火处理；
E.二次除杂：经步骤D低温沉积PSG处理后的硅片用溶剂进行清洗。
较之现有技术而言，本发明的优点在于：
(1)针对不同金属杂质在不同温度的活跃性差异，采用两次不同温度的磷扩散吸杂，能够更为充分的将金属杂质从位错、晶界等晶体缺陷处释放，并扩散到铸造单晶硅表面而被捕获，最终达到清除杂质的目的。
(2)利用酸性溶液清洗表面油污以及杂质，并最大程度的保留其表面粗糙度，提高吸杂效果。
(3)采用高温退火方式，将铸造单晶中晶粒位错进行重整，减少晶格缺陷，最终达到提高铸造单晶异质结太阳电池的电池效率。
附图说明
图1是以常规流程的铸造单晶硅为衬底的异质结电池片的EL图。
图2是以铸造单晶或多晶类硅片的两步扩散预处理方法处理后的铸造单晶硅为衬底的异质结电池片的EL图。
图3是一种采用铸造单晶或多晶类硅片的两步扩散预处理方法的铸造单晶硅异质结太阳电池的制造流程示意图。
具体实施方式
下面结合说明书附图和实施例对本发明内容进行详细说明：
如图2至图3所示为本发明提供的一种铸造单晶或多晶类硅片的两步扩散预处理方法的实施例示意图。
一种铸造单晶或多晶类硅片的两步扩散预处理方法，它包括如下步骤，
A.酸洗：用酸性溶液对硅片进行酸洗，之后清洗烘干；
B.高温沉积PSG：在经步骤A酸洗处理后的硅片表面高温沉积磷硅玻璃层，并进行退火处理；
C.一次除杂：经步骤B高温沉积PSG处理后的硅片用溶剂进行清洗并抛光，去除表面反应层和吸附的杂质；
D.低温沉积PSG：在经步骤C一次除杂处理后的硅片表面低温沉积磷硅玻璃层，并进行退火处理；
E.二次除杂：经步骤D低温沉积PSG处理后的硅片用溶剂进行清洗。
所述步骤A酸洗的具体方法为，用酸性溶液对硅片浸洗180-300s，然后用去离子水浸洗片表面120-240s，之后烘干至表面无水迹残留，烘干温度为50-90℃，烘干时间为3-5min。
所述酸性溶液为氢氟酸、盐酸、硝酸中的一种以上与水配置而成，酸的总质量百分比为5-15％。
所述步骤B高温沉积PSG中高温沉积磷硅玻璃层的具体方法为，采用三氯氧磷扩散法进行高温沉积磷硅玻璃层；扩散温度为800℃-1100℃，扩散压力为50mbar-300mbar，扩散时间为5min-30min，在高温扩散过程中通入POCL3、O2、N2，POCL3气体流量为50sccm-500sccm，O2气体流量为200sccm-2000sccm，N2气体流量为500sccm-5000sccm。
所述步骤B高温沉积PSG中退火的具体方法为，退火温度为700℃-1000℃，降温速率为2-10℃/min；退火压力为100mbar-500mbar，退火时间为60min-180min；在退火过程中通入O2和N2，O2和N2的气体流量分别为500sccm-5000sccm。
所述步骤C一次除杂的具体方法为，用酸性溶液对硅片进行浸洗，清洗时间为5-10分钟，清洗温度为20℃-30℃；之后进行抛光，抛光时使用氢氧化钾溶液或氢氧化钠溶液，抛光时间为2-5min；所述酸性溶液为氢氟酸溶液，氢氟酸的质量百分比为5-20％，其余为水；所述氢氧化钾或氢氧化钠的质量百分比为0.5％-3％。PSG(磷硅玻璃层)是含有磷的二氧化硅层，在硅片表面的磷硅玻璃层用HF去除，但是磷会扩散到磷硅玻璃层下面的体硅内，体硅中含有磷的杂质层通常称为扩散层需要用抛光去除，分两次去除的原因是PSG中含有大量的金属元素，直接抛光容易污染体硅。
所述步骤D低温沉积PSG中低温沉积磷硅玻璃层的具体方法为，采用三氯氧磷扩散法进行低温沉积磷硅玻璃层；扩散温度为400℃-600℃，扩散压力为50mbar-300mbar，扩散时间为5min-30min，在低温扩散过程中通入POCL3、O2、N2，POCL3气体流量为50sccm-500sccm，O2气体流量为200sccm-2000sccm，N2气体流量为500sccm-5000sccm。
所述步骤D低温沉积PSG中退火的具体方法为，退火温度为300℃-500℃，降温速率为2-10℃/min；退火压力为100mbar-500mbar，退火时间为60min-180min；在退火过程中通入O2和N2，O2和N2的气体流量分别为500sccm-5000sccm。
所述步骤E二次除杂的具体方法为，用酸性溶液对硅片进行清洗，清洗时间为5-10分钟，清洗温度为20℃-30℃；所述酸性溶液为氢氟酸溶液，氢氟酸的的质量百分比为5-20％。
在进行步骤A酸洗处理之前，硅片先后浸入SCI、SCII溶液中漂洗；SCI溶液为氨水双氧水溶液，即氨水、双氧水、水；SCII为盐酸双氧水溶液，即盐酸、双氧水、水。
所述SCI溶液配比为VNH3.H2O∶VH2O2∶VDI-water＝1∶1∶6，所述SCII溶液配比为VHCl∶VH2O2∶VDI-water＝1∶1∶5；每种溶液的漂洗温度为80℃，每种溶液的漂洗时间为10min。
对比实验：本发明中铸造单晶为衬底的异质结电池与常规流程铸造单晶为衬底的异质结电池相比，其制备工艺的差别仅在于：前者的预处理采用本发明进行，后者的预处理仅是去除机械损伤层。本发明中铸造单晶为衬底的异质结电池与常规流程铸造单晶为衬底的异质结电池相比，少子寿命以及电性能中转换效率、开路电压、短路电流及填充因子均有较大程度的提升，具体如下表1，表2所示：
表1、非晶硅镀膜后的少子寿命及Implied Voc对比
| 实验名称 | IN/IP少子寿命(us) | Implied Voc(V) |
| 常规流程铸造单晶为衬底的异质结电池 | 86 | 0.641 |
| 本发明中铸造单晶为衬底的异质结电池 | 2423 | 0.736 |
表2、电性能中转换效率、开路电压、短路电流及填充因子对比
| 方案 | Isc(A) | Uoc(V) | FF(％) | Eta(％) |
| 常规流程铸造单晶为衬底的异质结电池 | 8.178 | 0.631 | 79.98 | 16.89 |
| 本发明中铸造单晶为衬底的异质结电池 | 9.535 | 0.733 | 80.83 | 23.13 |
对比本发明优化的异质结流程及常规异质结流程的铸造单晶电池片所测试的EL，本发明优化的电池片，铸造单晶的晶界缺陷已明显改善，如图二。而无经过处理流程的铸造单晶硅片，可以明显看出晶界缺陷，如图一。
本发明中将铸锭单晶或多晶进行两步磷扩散吸杂和后续退火处理，因为不同金属杂质在不同温度的活跃性差异，采用两次不同温度的磷扩散吸杂，能够更为充分的将金属杂质从位错、晶界等晶体缺陷处释放，这有利于降低铸造单晶硅片体内和表面的缺陷密度，减少载流子的体内复合，提高整体的钝化水平；同时铸造单晶硅片在高温中进行有利于将铸造单晶中晶粒位错进行重整，减少晶格缺陷；将两步吸杂处理的硅片进行本征非晶硅钝化，少子寿命最高可以提升20倍以上，这极大地提高了铸造单晶异质结太阳电池的转换效率。
本发明在前处理过程中完整保留的硅片的表面粗糙度，吸杂效果显著提高，大大减少载流子的体内复合，提高整体的钝化水平。
Claims (11)
1.一种铸造单晶或多晶类硅片的两步扩散预处理方法，其特征在于：它包括如下步骤，
A.酸洗：用酸性溶液对硅片进行酸洗，之后清洗烘干；
B.高温沉积PSG：在经步骤A酸洗处理后的硅片表面高温沉积磷硅玻璃层，并进行退火处理；
C.一次除杂：经步骤B高温沉积PSG处理后的硅片用溶剂进行清洗并抛光，去除表面反应层和吸附的杂质；
D.低温沉积PSG：在经步骤C一次除杂处理后的硅片表面低温沉积磷硅玻璃层，并进行退火处理；
E.二次除杂：经步骤D低温沉积PSG处理后的硅片用溶剂进行清洗。
2.根据权利要求1所述的一种铸造单晶或多晶类硅片的两步扩散预处理方法，其特征在于：所述步骤A酸洗的具体方法为，用酸性溶液对硅片浸洗180-300s，然后用去离子水浸洗片表面120-240s，之后烘干至表面无水迹残留，烘干温度为50-90℃，烘干时间为3-5min。
3.根据权利要求2所述的一种铸造单晶或多晶类硅片的两步扩散预处理方法，其特征在于：所述酸性溶液为氢氟酸、盐酸、硝酸中的一种以上与水配置而成，酸的总质量百分比为5-15％。
4.根据权利要求1所述的一种铸造单晶或多晶类硅片的两步扩散预处理方法，其特征在于：所述步骤B高温沉积PSG中高温沉积磷硅玻璃层的具体方法为，采用三氯氧磷扩散法进行高温沉积磷硅玻璃层；扩散温度为800℃-1100℃，扩散压力为50mbar-300mbar，扩散时间为5min-30min，在高温扩散过程中通入POCL3、O2、N2，POCL3气体流量为50sccm-500sccm，O2气体流量为200sccm-2000sccm，N2气体流量为500sccm-5000sccm。
5.根据权利要求4所述的一种铸造单晶或多晶类硅片的两步扩散预处理方法，其特征在于：所述步骤B高温沉积PSG中退火的具体方法为，退火温度为700℃-1000℃，降温速率为2-10℃/min；退火压力为100mbar-500mbar，退火时间为60min-180min；在退火过程中通入O2和N2，O2和N2的气体流量分别为500sccm-5000sccm。
6.根据权利要求1所述的一种铸造单晶或多晶类硅片的两步扩散预处理方法，其特征在于：所述步骤C一次除杂的具体方法为，用酸性溶液对硅片进行浸洗，清洗时间为5-10分钟，清洗温度为20℃-30℃；之后进行抛光，抛光时使用氢氧化钾溶液或氢氧化钠溶液，抛光时间为2-5min；所述氢氧化钾或氢氧化钠的质量百分比为0.5％-3％。
7.根据权利要求1所述的一种铸造单晶或多晶类硅片的两步扩散预处理方法，其特征在于：所述步骤D低温沉积PSG中低温沉积磷硅玻璃层的具体方法为，采用三氯氧磷扩散法进行低温沉积磷硅玻璃层；扩散温度为400℃-600℃，扩散压力为50mbar-300mbar，扩散时间为5min-30min，在低温扩散过程中通入POCL3、O2、N2，POCL3气体流量为50sccm-500sccm，O2气体流量为200sccm-2000sccm，N2气体流量为500sccm-5000sccm。
8.根据权利要求7所述的一种铸造单晶或多晶类硅片的两步扩散预处理方法，其特征在于：所述步骤D低温沉积PSG中退火的具体方法为，退火温度为300℃-500℃，降温速率为2-10℃/min；退火压力为100mbar-500mbar，退火时间为60min-180min；在退火过程中通入O2和N2，O2和N2的气体流量分别为500sccm-5000sccm。
9.根据权利要求1所述的一种铸造单晶或多晶类硅片的两步扩散预处理方法，其特征在于：所述步骤E二次除杂的具体方法为，用酸性溶液对硅片进行清洗，清洗时间为5-10分钟，清洗温度为20℃-30℃。
10.根据权利要求1-9任意一项所述的一种铸造单晶或多晶类硅片的两步扩散预处理方法，其特征在于：在进行步骤A酸洗处理之前，硅片先后浸入SCI、SCII溶液中漂洗。
11.根据权利要求10所述的一种铸造单晶或多晶类硅片的两步扩散预处理方法，其特征在于：所述SCI溶液配比为VNH3.H2O∶VH2O2∶VDI-water＝1∶1∶6，所述SCII溶液配比为VHCl∶VH2O2∶VDI-water＝1∶1∶5；每种溶液的漂洗温度为80℃，每种溶液的漂洗时间为10min。
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