CN113013293A - 一种异质结电池的制备方法 - Google Patents
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Abstract
本发明公开一种异质结电池的制备方法：(1)对硅片进行预清洗；(2)对硅片进行碱制绒形成金字塔结构；(3)对硅片正面激光修饰，在金字塔上形成光斑缺陷；(4)用硝酸和氢氟酸对金字塔结构的底部以及光斑缺陷进行圆润处理；(5)在硅片正面依次沉积本征非晶硅薄膜和P型非晶硅薄膜；在硅片背面依次沉积本征非晶硅薄膜和N型非晶硅薄膜形成背表面场，在硅片正反面沉积TCO；(6)在TCO上印刷电极并烘干。本发明方法增加了激光对制绒后硅片进行修饰，极大的增加硅片的有效比表面积，增强硅片的陷光、提高光的利用率；在激光后进行RCA清洗，对硅片表面金字塔及激光区域进行圆润处理，提高非晶硅薄膜在绒面上的沉积均匀性。
Description
技术领域
本发明涉及太阳能光伏领域，具体涉及一种异质结电池的制备方法。
背景技术
晶体硅太阳能光伏电池技术近年来发展迅速，尤其是HJT(Hereto-junctionwithIntrinsic Thin layer)作为新一代高效光伏电池中的佼佼者，异质结HJT电池具备转换效率高、提效空间大、发电能力强、工艺流程短等多重优势，目前正受到产业资本的高度关注。在HJT电池转换效率23.5％、25年功率衰减8％、4％发电增益的假设下，判断HJT电池非硅成本的临界范围约0.4-0.5元/W，预计当异质结电池性价比优势逐步显现之后有望实现对主流路线的替代。
在HJT异质结电池结构中，异质结界面决定电池的最终特性，硅衬底是异质结界面的一部分，其品质是决定电池性能的关键因素之一。因此，制绒绒面结构清洗工序，需要优化电池的陷光性能，有效绒面结构可使入射光在表面进行多次反射和折射，延长光程，增加光生载流子；需要形成洁净表面，减少硅片表面不洁净而引入的缺陷和杂质，从而降低结界处载流子的复合损伤。
发明内容
本发明的目的在于提供一种异质结电池的制备方法，本发明的方法可以进一步增加硅片的陷光性能，提高光的利用率，本发明的方法既可以提升光生载流子，又能保证降低对非晶硅薄膜沉积的影响。
本发明是通过如下技术方案实现的：
一种异质结电池的制备方法，包括如下步骤：
(1)预清洗：对硅片进行预清洗；
(2)制绒：预清洗后对所述硅片进行碱制绒(各向异性)，在所述硅片表面形成金字塔结构；
(3)修饰：制绒后对所述硅片正面进行激光修饰，在所述金字塔结构上腐蚀形成光斑缺陷；使用激光在所述金字塔结构上进行开孔，增加硅片的比表面积；
(4)RCA清洗：使用硝酸和氢氟酸的混合溶液对所述硅片进行各向同性腐蚀，对所述金字塔结构的底部以及所述光斑缺陷进行圆润处理；
(5)沉积：在所述硅片正面依次沉积本征非晶硅薄膜(i-a-Si:H)和P型非晶硅薄膜(p-a-Si:H)；在所述硅片背面依次沉积本征非晶硅薄膜(i-a-Si:H)和N型非晶硅薄膜(n-a-Si:H)形成背表面场，再在所述硅片正面和背面沉积透明氧化物导电薄膜(TCO)；
(6)在所述透明氧化物导电薄膜上印刷电极并烘干，完成异质结(HJT)电池片的制备。具体地，本发明的方法首先对单晶硅片进行预清洗去除有机物，然后对单晶硅片进行碱制绒，形成金字塔结构；在硅片表面形成金字塔结构后，使用激光在金字塔结构上进行开孔，增加硅片的比表面积；然后进行RCA清洗，使用HNO3、HF的各向同性腐蚀对硅片进行圆润处理；在硅片表面沉积非晶硅薄膜，形成良好的钝化效果及异质结界面；在硅片正反两面沉积透明导电氧化物薄膜，实现导电、减反射、保护非晶硅薄膜；丝网印刷制备电极，与PN结两端形成良好的欧姆接触及导电性能和高效的电流收集。
进一步地，步骤(1)预清洗：在80-90℃下使用混合液清洗所述硅片90-150秒；所述的混合液由氨水、双氧水和水按体积比1：1：(6-8)配制而成。
进一步地，步骤(2)中所述碱为10-20wt％氢氧化钾溶液或10-20wt％氢氧化钠溶液；所述金字塔结构尺寸为1-3μm。
进一步地，步骤(3)修饰：制绒后将所述硅片正面置于激光下，通过激光在所述硅片金字塔结构表面形成光斑缺陷(即激光腐蚀坑)；且所述光斑缺陷的直径为0.05-0.5μm、深度为0.05-1μm。
进一步地，步骤(4)RCA清洗：所述腐蚀温度为20-30℃，腐蚀时间为90-120秒。
进一步地，步骤(4)RCA清洗：所述硝酸的浓度为1-40wt％；所述氢氟酸的浓度为1-40wt％。
进一步地，步骤(6)通过丝网印刷方式在所述透明氧化物导电薄膜上印刷电极并在80-90℃下烘干120-150秒。
本发明的方法利用碱(KOH或NaOH腐蚀液)对N型硅片进行各项异性腐蚀，将Si(100)晶面腐蚀为Si(111)晶面的四方椎体结构(“金字塔结构”)，即在硅片表面形成绒面，可将硅片表面反射率降低至12.5％以下，从而产生更多的光生载流子。本发明的制绒清洗工序可以形成洁净硅片表面，由于HJT电池片中硅片衬底表面直接为异质结界面的一部分，故需形成洁净硅片表面，从而避免不洁净引进的缺陷和杂质而带来的结界面初载流子的复合。激光修饰绒面在制绒结束之后，RCA之前，可以大幅加强电池片的陷光、增加光的利用率从而增加光生载流子，便于应用到HJT电池上。其中激光修饰技术的关键步骤，激光光斑控制在0.05-0.5微米、深度控制0.05-0.5微米，以实现在金字塔上进行激光开孔而不破坏金字塔整体形貌，提升陷光。激光修饰后，进行RCA清洗，经过此步骤后，硅片表面金字塔及光斑处将形成圆润无棱角的易于非晶硅沉积的陷光结构。
本发明的有益效果：
本发明的方法在原有的工艺基础上增加激光对制绒后硅片进行修饰工序，极大的增加硅片的有效的比表面积的同时，增强硅片的陷光、提高光的利用率；在激光后进行RCA清洗，对硅片表面金字塔及激光区域进行圆润处理，提高非晶硅薄膜在绒面上的沉积均匀性。本发明的异质结电池制备方法简单，用以解决异质结(HJT)电池中金字塔形貌陷光低，该方法既可以提升光生载流子，又能保证降低对非晶硅薄膜沉积的影响。
附图说明
为了更清楚地说明本发明实施例的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域的技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他附图。
图1为本发明实施例1制造方法的激光开孔的侧面示意图；
图2为本发明实施例1制造方法的激光修饰后绒面微观效果图。
图中：1激光头、2绒面金字塔结构。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明的一部分实施例，而不是全部的实施例。以下对至少一个示例性实施例的描述实际上仅仅是说明性的，决不作为对本发明及其应用或使用的任何限制。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
一种异质结电池的制备方法，用以解决HJT电池中，金字塔形貌陷光低，该方法既可以提升光生载流子，又能保证降低对非晶硅薄膜沉积的影响，具体包括如下步骤：
(1)预清洗：在80℃下使用混合液清洗单晶硅片120秒；且所述的混合液由氨水、双氧水和水按体积比1：1：6配制而成；
(2)制绒：预清洗后用15wt％的氢氧化钾溶液对所述硅片进行碱制绒，在所述硅片表面形成尺寸2微米的金字塔结构2；
(3)修饰：如图1所示，制绒后对所述硅片正面进行激光修饰，在所述金字塔结构上腐蚀形成直径0.05微米、深度0.05微米的光斑缺陷；具体的是将所述硅片的正面置于激光头1下，通过激光头1发出激光在所述硅片金字塔结构表面形成激光腐蚀坑；在本实施例中将制绒后硅片正面置于激光下并使激光全覆盖正面制绒硅片，共需打激光[L/(D+R)]2个光斑(其中L为硅片尺寸,R为光斑直径，D为相邻光斑距离)；
(4)RCA清洗：使用20wt％的硝酸(HNO3)和40wt％的氢氟酸(HF)的混合溶液对所述硅片进行各向同性腐蚀，且腐蚀温度为25℃，腐蚀时间为100秒，对所述金字塔结构的底部以及所述光斑缺陷进行圆润处理；如图2所示(即激光修饰后进行RCA圆润处理效果图)；
(5)沉积：在所述硅片正面依次沉积本征非晶硅薄膜(i-a-Si:H)和P型非晶硅薄膜(p-a-Si:H)；在所述硅片背面依次沉积本征非晶硅薄膜(i-a-Si:H)和N型非晶硅薄膜(n-a-Si:H)形成背表面场，再在所述硅片正面和背面沉积透明氧化物导电薄膜(TCO)；
(6)通过丝网印刷方式在所述的透明氧化物导电薄膜上印刷电极并在85℃下烘干120秒，完成异质结(HJT)电池片的制备。
实施例2
一种异质结电池的制备方法，用以解决HJT电池中，金字塔形貌陷光低，该方法既可以提升光生载流子，又能保证降低对非晶硅薄膜沉积的影响，具体包括如下步骤：
(1)预清洗：在90℃下使用混合液清洗单晶硅片90秒；且所述的混合液由氨水、双氧水和水按体积比1：1：8配制而成；
(2)制绒：预清洗后用10wt％的氢氧化钠溶液对所述硅片进行碱制绒，在所述硅片表面形成尺寸1微米的金字塔结构；
(3)修饰：制绒后对所述硅片正面进行激光修饰，在所述金字塔结构上腐蚀形成直径0.2微米、深度0.5微米的光斑缺陷；
(4)RCA清洗：使用1wt％的硝酸和20wt％的氢氟酸的混合溶液对所述硅片进行各向同性腐蚀，且腐蚀温度为30℃，腐蚀时间为90秒，对所述金字塔结构的底部以及所述光斑缺陷进行圆润处理；
(5)沉积：在所述硅片正面依次沉积本征非晶硅薄膜(i-a-Si:H)和P型非晶硅薄膜(p-a-Si:H)；在所述硅片背面依次沉积本征非晶硅薄膜(i-a-Si:H)和N型非晶硅薄膜(n-a-Si:H)形成背表面场，再在所述硅片正面和背面沉积透明氧化物导电薄膜(TCO)；
(6)通过丝网印刷方式在所述的透明氧化物导电薄膜上印刷电极并在80℃下烘干150秒，完成异质结(HJT)电池片的制备。
实施例3
一种异质结电池的制备方法，用以解决HJT电池中，金字塔形貌陷光低，该方法既可以提升光生载流子，又能保证降低对非晶硅薄膜沉积的影响，具体包括如下步骤：
(1)预清洗：在85℃下使用混合液清洗单晶硅片150秒；且所述的混合液由氨水、双氧水和水按体积比1：1：7配制而成；
(2)制绒：预清洗后用10wt％的氢氧化钠溶液对所述硅片进行碱制绒，在所述硅片表面形成尺寸3微米的金字塔结构；
(3)修饰：制绒后对所述硅片正面进行激光修饰，在所述金字塔结构上腐蚀形成直径0.5微米、深度1微米的光斑缺陷；
(4)RCA清洗：使用40wt％的硝酸和1wt％的氢氟酸的混合溶液对所述硅片进行各向同性腐蚀，且腐蚀温度为20℃，腐蚀时间为120秒，对所述金字塔结构的底部以及所述光斑缺陷进行圆润处理；
(5)沉积：在所述硅片正面依次沉积本征非晶硅薄膜(i-a-Si:H)和P型非晶硅薄膜(p-a-Si:H)；在所述硅片背面依次沉积本征非晶硅薄膜(i-a-Si:H)和N型非晶硅薄膜(n-a-Si:H)形成背表面场，再在所述硅片正面和背面沉积透明氧化物导电薄膜(TCO)；
(6)通过丝网印刷方式在所述的透明氧化物导电薄膜上印刷电极并在90℃下烘干130秒，完成异质结(HJT)电池片的制备。
本发明提供的HJT制绒金字塔激光修饰制造方法，包括：对单晶硅片进行碱制绒，形成金字塔结构；硅片表面形成金字塔后，使用激光在金字塔上进行开孔，增加硅片比表面积；进行RCA清洗，使用HNO3、HF的各向同性腐蚀对硅片进行圆润处理；在硅片表面沉积非晶硅薄膜，形成良好的钝化效果及异质结界面；在硅片正反两面沉积透明导电氧化物薄膜，实现导电、减反射、保护非晶硅薄膜；丝网印刷制备电极，与PN结两端形成良好的欧姆接触及导电性能和高效的电流收集。本发明方法在原有的工艺基础上增加激光对制绒后硅片进行修饰，极大的增加硅片的有效的比表面积的同时，增强硅片的陷光、提高光的利用率；在激光后进行RCA清洗，对硅片表面金字塔及激光区域进行圆润处理，提高非晶硅薄膜在绒面上的沉积均匀性。
上述为本发明的较佳实施例仅用于解释本发明，并不用于限定本发明。凡由本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之中。
Claims (7)
1.一种异质结电池的制备方法，其特征在于，该方法包括如下步骤：
(1)预清洗：对硅片进行预清洗；
(2)制绒：预清洗后对所述硅片进行碱制绒，在所述硅片表面形成金字塔结构；
(3)修饰：制绒后对所述硅片正面进行激光修饰，在所述金字塔结构上腐蚀形成光斑缺陷；
(4)RCA清洗：使用硝酸和氢氟酸的混合溶液对所述硅片进行各向同性腐蚀，对所述金字塔结构的底部以及所述光斑缺陷进行圆润处理；
(5)沉积：在所述硅片正面依次沉积本征非晶硅薄膜和P型非晶硅薄膜；在所述硅片背面依次沉积本征非晶硅薄膜和N型非晶硅薄膜形成背表面场，再在所述硅片正面和背面沉积透明氧化物导电薄膜；
(6)在所述透明氧化物导电薄膜上印刷电极并烘干。
2.根据权利要求1所述的一种异质结电池的制备方法，其特征在于，步骤(1)预清洗：在80-90℃下使用混合液清洗所述硅片90-150秒；所述的混合液由氨水、双氧水和水按体积比1：1：(6-8)配制而成。
3.根据权利要求1所述的一种异质结电池的制备方法，其特征在于，步骤(2)中所述碱为10-20wt％氢氧化钾溶液或10-20wt％氢氧化钠溶液；所述金字塔结构尺寸为1-3μm。
4.根据权利要求1所述的一种异质结电池的制备方法，其特征在于，步骤(3)修饰：制绒后将所述硅片正面置于激光下，通过激光在所述硅片金字塔结构表面形成光斑缺陷；且所述光斑缺陷的直径为0.05-0.5μm、深度为0.05-1μm。
5.根据权利要求1所述的一种异质结电池的制备方法，其特征在于，步骤(4)RCA清洗：所述腐蚀温度为20-30℃，腐蚀时间为90-120秒。
6.根据权利要求1所述的一种异质结电池的制备方法，其特征在于，步骤(4)RCA清洗：所述硝酸的浓度为1-40wt％；所述氢氟酸的浓度为1-40wt％。
7.根据权利要求1所述的一种异质结电池的制备方法，其特征在于，步骤(6)通过丝网印刷方式在所述透明氧化物导电薄膜上印刷电极并在80-90℃下烘干120-150秒。
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