CN109537058A - 湿法黑硅制备工艺 - Google Patents
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Abstract
本发明涉及一种湿法黑硅制备工艺,包括:用氢氧化钾溶液去除硅片表面损伤层;用含有有机掩膜的A1溶液处理上述抛光硅片两次;用氢氟酸和双氧水以及不含金属的B1混合溶液反应,形成纳米结构;用氢氧化钾溶液清洗,去除上述过程中的残留酸液;用氢氟酸、硝酸以及B2的混合溶液,将步骤4所形成的黑硅纳米结构进行扩大化处理;用氢氧化钾溶液,去除上述步骤反应后形成的多孔硅;用氢氟酸和盐酸的混合溶液清洗硅片;将上述清洗后硅片,进行烘干处理,流入后道工序。本发明解决了多晶金刚线制绒困难的问题;可有效降低硅片表面反射率;可有效提高电池转换效率,增加收益;添加剂成分不含重金属,有效避免环保污染问题。
Description
技术领域
本发明涉及太阳能电池技术领域,尤其是一种湿法黑硅制备工艺。
背景技术
随着电池行业降本增效高速发展,硅片全部转为金刚线切割,但是相对于传统砂线切割,采用金刚线切割硅片表面损伤层少。
传统的多晶制绒均是采用HF/HNO3的各项同性腐蚀,生成凹坑绒面。但是传统的HF/HNO3制绒工艺难以形成绒面,导致反射率较高,电池转换效率偏低;并且工艺中采用的添加剂成分含有重金属,会造成环保污染问题。
发明内容
本发明要解决的技术问题是:提出一种湿法黑硅制备工艺。
本发明所采用的技术方案为:一种湿法黑硅制备工艺,包括以下步骤:
1)将45wt%的氢氧化钠溶液与纯水以体积比1:6-12混合,在温度75-85℃去除硅片表面损伤层,时间200-400S,然后水洗;
2)用A1溶液对上述抛光硅片进行预清洗,温度为温度20-30℃,时间100-200S,然后水洗;
3)重复步骤2);
4)用氢氟酸和双氧水以及不含金属的B1混合溶液反应,其中氢氟酸:双氧水:纯水=1:3-6:2-10;B1溶液为0.5%-4%;温度30-40℃,时间180S-300S,最终形成纳米结构,即黑硅,然后水洗;
5)用45wt%氢氧化钾溶液与纯水以体积比例1:40-80混合,温度20-30℃,清洗上述酸液,时间60-150S;
6)将49%wt的氢氟酸与纯水以体积比例1:40-80混合,温度20-30℃,时间60-150S;
7)将步骤4)所形成的黑硅纳米结构进行扩大化处理;然后水洗;
8)用碱性溶液在温度20-30℃下去除上述步骤反应后形成的多孔硅,时间100-200S,然后水洗;
9)用酸性清洗硅片,温度20-30℃,时间100-300S,然后水洗;
10)将上述清洗后硅片,进行烘干处理,流入后道工序。
进一步的说,本发明所述的步骤2)中A1溶液由0.5%-5%的聚乙烯吡咯烷酮,0.5%-5%的聚季铵盐,2%-10%柠檬酸混合制成。
再进一步的说,本发明所述的步骤4)中,B1溶液由0.5%-5%PEG400,1%-10%PVA混合制成。
再进一步的说,本发明所述的步骤7)中,用49%wt氢氟酸、66%wt硝酸的混合溶液,将步骤4)所形成的黑硅纳米结构进行扩大化处理;氢氟酸:硝酸:纯水=1:3-5:1-3,温度6-12℃,时间80-150S。
再进一步的说,本发明所述的步骤8)中的碱性溶液为49%wt氢氧化钾溶液,占纯水比例3%-5%。
再进一步的说,本发明所述的步骤9)中酸性溶液为49%wt氢氟酸和36%wt盐酸的混合溶液,与纯水比例1:1-3:1-5。
本发明的有益效果是:
1、解决了多晶金刚线制绒困难的问题;
2、可有效降低硅片表面反射率;
3、可有效提高电池转换效率,增加收益;
4、添加剂成分不含重金属,有效避免环保污染问题。
附图说明
图1是本发明的工艺流程图;
图2为黑硅反射率对比金刚线曲线图;
图3为黑硅绒面SEM图。
具体实施方式
现在结合附图和优选实施例对本发明作进一步详细的说明。这些附图均为简化的示意图,仅以示意方式说明本发明的基本结构,因此其仅显示与本发明有关的构成。
实施例1
1、用45wt%氢氧化钾溶液,与纯水体积比例1:6-12,温度75-85℃去除硅片表面损伤层,时间200-400S,然后纯水清洗90S;
2、用0.5%-2%A1溶液处理上述抛光硅片,A1主要成分0.5%-5%聚乙烯吡咯烷酮,0.5%-5%聚季铵盐,2%-10%柠檬酸等,温度20-30℃,时间100-200S,然后水洗90S;
3、用0.5%-2%A1溶液处理上述抛光硅片,A1主要成分0.5%-5%聚乙烯吡咯烷酮,0.5%-5%聚季铵盐,2%-10%柠檬酸等,温度20-30℃,时间100-200S,然后水洗90S;
4、用氢氟酸和双氧水以及不含金属的B1混合溶液反应,氢氟酸:双氧水:纯水=1:3-6:2-10,B1占比0.5%-4%,B1主要成分0.5%-5%PEG400,1%-10%PVA,温度30-40℃,时间180S-300S,最终形成纳米结构,然后水洗90S;
5、用45wt%氢氧化钾溶液,与纯水体积比例1:40-80,温度20-30℃,清洗上述酸液,时间60-150S;
6、49%wt氢氟酸,与纯水比例1:40-80,温度20-30℃,时间60-150S;
7、用49%wt氢氟酸、66%wt硝酸的混合溶液,将步骤4所形成的黑硅纳米结构进行扩大化处理,更容易后道工艺匹配,氢氟酸:硝酸:纯水=1:3-5:1-3,温度6-12℃,时间80-150S,然后水洗90S;
8、用49%wt氢氧化钾溶液,占纯水比例3%-5%,温度20-30℃,时间100-200S,去除上述步骤反应后形成的多孔硅,然后水洗90S;
9、用49%wt氢氟酸和36%wt盐酸的混合溶液,与纯水比例1:1-3:1-5,温度20-30℃,时间100-300S,清洗硅片,然后水洗120S;
10、将上述清洗后硅片,进行烘干处理,烘干时间600S,硅片反射率10%-20%。
实施例2
1、用45wt%氢氧化钾溶液,与纯水体积比例1:6-12,温度75-85℃去除硅片表面损伤层,时间200-400S,然后纯水清洗90S;
2、用0.5%-2%A1溶液处理上述抛光硅片,A1主要成分0.5%-5%聚乙烯吡咯烷酮,0.5%-5%聚季铵盐,2%-10%柠檬酸等,温度20-30℃,时间100-200S,然后水洗90S;
3、用0.5%-2%A1溶液处理上述抛光硅片,A1主要成分0.5%-5%聚乙烯吡咯烷酮,0.5%-5%聚季铵盐,2%-10%柠檬酸等,温度20-30℃,时间100-200S,然后水洗90S;
4、用氢氟酸和双氧水以及不含金属的B1混合溶液反应,氢氟酸:双氧水:纯水=1:3-6:2-10,B1占比0.5%-4%,B1主要成分0.5%-5%PEG400,1%-10%PVA,温度30-40℃,时间180S-300S,最终形成纳米结构,然后水洗90S;
5、用45wt%氢氧化钾溶液,与纯水体积比例1:40-80,温度20-30℃,清洗上述酸液,时间60-150S;
6、49%wt氢氟酸,与纯水比例1∶40-80,温度20-30℃,时间60-150S;
7、用49%wt氢氟酸、66%wt硝酸的混合溶液,将步骤4所形成的黑硅纳米结构进行扩大化处理,更容易后道工艺匹配,氢氟酸∶硝酸∶纯水=1∶3-5∶1-3,温度6-12℃,时间80-150S,然后水洗90S;
8、用49%wt氢氧化钾溶液,占纯水比例3%-5%,温度20-30℃,时间100-200S,去除上述步骤反应后形成的多孔硅,然后水洗90S;
9、用49%wt氢氟酸和36%wt盐酸的混合溶液,与纯水比例1∶1-3∶1-5,温度20-30℃,时间100-300S,清洗硅片,然后水洗120S;
10、将上述清洗后硅片,进行烘干处理,烘干时间600S,硅片反射率10%-20%。
电池效率对比如下所示:
comment | output | Voc | Isc | FF | Eff |
baseline | 1449 | 0.6405 | 8.872 | 81.69 | 18.896% |
实施例1 | 1093 | 0.6404 | 9.052 | 81.21 | 19.162% |
实施例2 | 1638 | 0.6372 | 9.059 | 81.70 | 19.195% |
以上说明书中描述的只是本发明的具体实施方式,各种举例说明不对本发明的实质内容构成限制,所属技术领域的普通技术人员在阅读了说明书后可以对以前所述的具体实施方式做修改或变形,而不背离本发明的实质和范围。
Claims (6)
1.一种湿法黑硅制备工艺,其特征在于包括以下步骤:
1)将45wt%的氢氧化钠溶液与纯水以体积比1:6-12混合,在温度75-85℃去除硅片表面损伤层,时间200-400S,然后水洗;
2)用A1溶液对上述抛光硅片进行预清洗,温度为温度20-30℃,时间100-200S,然后水洗;
3)重复步骤2);
4)用氢氟酸和双氧水以及不含金属的B1混合溶液反应,其中氢氟酸:双氧水:纯水=1:3-6:2-10;B1溶液为0.5%-4%;温度30-40℃,时间180S-300S,最终形成纳米结构,即黑硅,然后水洗;
5)用45wt%氢氧化钾溶液与纯水以体积比例1:40-80混合,温度20-30℃,清洗上述酸液,时间60-150S;
6)将49%wt的氢氟酸与纯水以体积比例1:40-80混合,温度20-30℃,时间60-150S;
7)将步骤4)所形成的黑硅纳米结构进行扩大化处理;然后水洗;
8)用碱性溶液在温度20-30℃下去除上述步骤反应后形成的多孔硅,时间100-200S,然后水洗;
9)用酸性清洗硅片,温度20-30℃,时间100-300S,然后水洗;
10)将上述清洗后硅片,进行烘干处理,流入后道工序。
2.如权利要求1所述的湿法黑硅制备工艺,其特征在于:所述的步骤2)中A1溶液由0.5%-5%的聚乙烯吡咯烷酮,0.5%-5%的聚季铵盐,2%-10%柠檬酸混合制成。
3.如权利要求1所述的湿法黑硅制备工艺,其特征在于:所述的步骤4)中,B1溶液由0.5%-5%PEG400,1%-10%PVA混合制成。
4.如权利要求1所述的湿法黑硅制备工艺,其特征在于:所述的步骤7)中,用49%wt氢氟酸、66%wt硝酸的混合溶液,将步骤4)所形成的黑硅纳米结构进行扩大化处理;氢氟酸:硝酸:纯水=1:3-5:1-3,温度6-12℃,时间80-150S。
5.如权利要求1所述的湿法黑硅制备工艺,其特征在于:所述的步骤8)中的碱性溶液为49%wt氢氧化钾溶液,占纯水比例3%-5%。
6.如权利要求1所述的湿法黑硅制备工艺,其特征在于:所述的步骤9)中酸性溶液为49%wt氢氟酸和36%wt盐酸的混合溶液,与纯水比例1:1-3:1-5。
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