多晶硅表面金属催化化学腐蚀法制绒研究现状

doi:10.15541/jim20200361

无机材料学报 ›› 2021, Vol. 36 ›› Issue (6): 570-578.DOI: 10.15541/jim20200361

所属专题：能源材料论文精选(2021)；【虚拟专辑】太阳能电池(2020~2021)；【能源环境】太阳能电池

多晶硅表面金属催化化学腐蚀法制绒研究现状

武晓玮¹^,²(), 李佳艳¹^,²()

1.大连理工大学三束材料改性教育部重点实验室, 大连 116024
2.大连理工大学材料科学与工程学院, 大连 116024

收稿日期:2020-06-30 修回日期:2020-08-30 出版日期:2021-06-20 网络出版日期:2020-10-10
通讯作者: 李佳艳, 副教授. E-mail: lijiayan@dlut.edu.cn
作者简介:武晓玮(1991-), 男, 博士研究生. E-mail: wuxiaowei261@163.com
基金资助:
国家自然科学基金(51574057)

Texturing Technology on Multicrystalline Silicon Wafer by Metal-catalyzed Chemical Etching: a Review

WU Xiaowei¹^,²(), LI Jiayan¹^,²()

1. Key Laboratory of Materials Modification by Laser, Ion, and Electron Beams, Dalian University of Technology, Dalian 116024, China
2. School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, China

Received:2020-06-30 Revised:2020-08-30 Published:2021-06-20 Online:2020-10-10
Contact: LI Jiayan, associate professor. E-mail: lijiayan@dlut.edu.cn
About author:WU Xiaowei(1991-), male, PhD candidate. E-mail: wuxiaowei261@163.com
Supported by:
National Natural Science Foundation of China(51574057)

摘要/Abstract

摘要：

在多晶硅太阳能电池的生产过程中, 金刚线切割技术(Diamond wire sawn, DWS)具有切割速度快、精度高、原材料损耗少等优点, 受到了广泛关注。金刚线切割多晶硅表面形成的损伤层较浅, 与传统的酸腐蚀制绒技术无法匹配, 金属催化化学腐蚀法应运而生。金属催化化学腐蚀法制绒具有操作简单、结构可控且易形成高深宽比的绒面等优点, 具有广阔的应用前景。本文总结了不同类型的金属催化剂在制绒过程中的腐蚀机理及其形成的绒面结构, 深入分析和讨论了具有代表性的银、铜的单一及复合催化腐蚀过程及绒面结构和电池片性能。最后对金刚线切割多晶硅片表面的金属催化化学腐蚀法存在的问题进行了分析, 并展望了未来的研究方向。

关键词: 金刚线切割, 多晶硅, 金属催化化学腐蚀法, 制绒, 综述

Abstract:

In the production process of multicrystalline silicon solar cells, diamond wire sawn (DWS) cutting technology attracts wide attention because of its advantages of high cutting speed, high precision and less loss of raw materials. But the traditional acid etching technology cannot match the shallow damage layer formed on the surface of diamond wire sawn cut multicrystalline silicon wafer to make the texture surface. On the contrary, the metal-catalyzed chemical etching method owns the advantages of simple operation, controllable structure and easy to form the structure with high aspect ratio, indicating a wide range of application on diamond wire sawn cut multicrystalline silicon wafer. This paper systematically summarizes the work of the etching mechanisms and the structures of textures by different metal catalysts in the process of making texture surface, and deeply discusses the single and composite catalytic etching process of Ag and Cu, the structure of texture surface, and the performance of solar cells. Finally, the problems of metal-catalyzed chemical etching on the surface of diamond wire sawn cut multicrystalline silicon are analyzed, and their future research directions are prospected.

Key words: diamond wire sawn cut, multicrystalline silicon, metal-catalyzed chemical etching, texturization, review

中图分类号:

TM914

武晓玮, 李佳艳. 多晶硅表面金属催化化学腐蚀法制绒研究现状[J]. 无机材料学报, 2021, 36(6): 570-578.

WU Xiaowei, LI Jiayan. Texturing Technology on Multicrystalline Silicon Wafer by Metal-catalyzed Chemical Etching: a Review[J]. Journal of Inorganic Materials, 2021, 36(6): 570-578.

图/表 12

图1 (a)砂浆切割和(b)金刚线切割示意图

Fig. 1 Schematic diagram of (a) MWSS cut technique and (b) DWS cut technique

图2 (a, b)砂浆切割和(c, d)金刚线切割后多晶硅片表面形貌SEM照片

Fig. 2 SEM images of (a, b) MWSS cut and (c, d) DWS cut multicrystalline silicon wafer surface

图3 酸腐蚀法制绒后硅片表面SEM形貌和反射率曲线

Fig. 3 Surface SEM morphology and reflectivity for texture surface of silicon wafer by acid etching

图4 MCCE法原理示意图[18]

Fig. 4 Schematic diagram of MCCE[18]

图5 (a)纳米绒面、(b)微米绒面及(c)纳米-微米复合绒面SEM表面形貌照片[31]

Fig. 5 SEM images of silicon surfaces with (a) nano-texture, (b) micro-texture and (c) nano-micro-texture[31]

图6 (a)DWS多晶硅片表面制备亚微米级(SIM)绒面的过程示意图和(b)三种绒面结构的反射率结果[33]

Fig. 6 (a) Schematic illustration of the main steps to prepare the submicron-in-micron (SIM) texture on the DWS mc-Si wafer and (b) experimental reflectance (curves) and simulated reflectance (scatter points) of three samples[33]

图7 碱、Ag-MCCE和后腐蚀处理获得的不同晶面的硅片表面和截面SEM照片[34]

Fig. 7 Surface and cross-sectional SEM images of mc-Si grains after etching by alkali, Ag-MCCE and post-etching with different orientations[34] (a) (100); (b) (110); (c) (111)

图8 Cu-MCCE制绒后采用后处理工艺(a, b)前和(c, d)后的硅片形貌图以及(e)后处理工艺示意图[41]

Fig. 8 SEM images of Si nanostructures produced by Cu-MCCE method (a,b) before and (c,d) after the post-processing treatment and (e) schematic diagram of post-processing treatment[41]

图9 (a)Ag-MCCE和(b)Cu-MCCE处理后的硅片截面形貌SEM照片, 以及(c)单独的Cu-MCCE、Ag-MCCE和Ag-Cu复合制绒过程的原理图[45]

Fig. 9 Cross-sectional SEM images of Si wafers after (a) Ag-MCCE and (b) Cu-MCCE, and (c) schematics of etching process by single Cu- and Ag-catalyzed chemical etching and Ag/Cu-cocatalyzed chemical etching[45]

表1 金刚线切割多晶硅片表面不同MCCE方法制绒后的性能对比

Table 1 Performances for texture surfaces of DWS cut multicrystalline silicon prepared via different MCCE methods

Catalyst	Method	R^a	η^b	Ref.
Ag	Ag-MCCE + HF/HNO₃+NaOH	15.9%	18.45%	[31]
Ag	Artificial defects (HF/HNO₃/AgNO₃)+HF/HNO₃	19%	19.07%	[33]
Ag	Alkali etching+Ag-MCCE+post etching	16.85%	19.4%	[34]
Ag	Ag deposition (additive)+etching	16.04%	19.51%	[35]
Ag	Ag deposition+etching (additive)	18.17%	19.56%	[36]
Ag	HF/HNO₃+Ag-MCCE+RIE	-	20.69%	[56]
Ag	Ag-MCCE	23.7%	20.89%	[57]
Ag	Ag-MCCE+Modification by acid etching	19.46%	19.07%	[58]
Ag	HF/HNO₃+Ag-MCCE+NSR process	8.26%	17.96%	[59]
Ag	HF/HNO₃+Ag-MCCE+HF/HNO₃	18.4%	18.7%	[60]
Cu	Cu-MCCE+post etching (HF/HNO₃/H₃PO₄)	-	18.88%	[41]
Cu	Cu-MCCE+HF/HNO₃	18.21%	19.06%	[42]
Cu	Cu-MCCE	22.4%	19.03%	[61]
Ag-Cu	Cu/Ag-MCCE	12.08%	19.49%	[45]
Ag-Cu	Alkali pretreatment (additive)+Cu/Ag-MCCE+post etching	15.52%	18.91%	[62]
Ag-Cu	Cu/Ag-MCCE + NSR (H₂O₂/NaF)	16.50%	18.71%	[63]
Ag-Cu	Cu/Ag-MCCE + NSR (H₂O₂/NaF)	16.85%	19.10%	[64]
Ni	Ni-MCCE	-	16.60%	[47]
Cu-Ni	Cu/Ni-MCCE (Cu(NO₃)₂+NiSO₄+HF+H₂O₂)	18.53%	-	[48]

图10 电池片光电转换效率与绒面反射率之间的关系图[31,33-36,42,45,58-65]

Fig. 10 Relation between η of solar cells and reflectivity of texture surface[31,33-36,42,45,58-65]

表2 金刚线切割多晶硅片表面不同MCCE方法的对比

Table 2 Comparison of making texture surface on DWS cut multicrystalline silicon by different MCCE methods

Method	Advantages	Disadvantages	η
Ag-MCCE	Mature technology, easy to form nanostructure, stable performance	High cost, difficult to recycle waste liquid	20.89%
Cu-MCCE	Low cost, easy to remove residual Cu, significantly reduce the impact of saw marks	Easy to form the dense film, decreased etching rate, essential oxidants	19.06%
MCCE-additive	Uniform size, stable performance	Organic compounds increasing the cost of waste liquid treatment	19.56%
Composite MCCE	Composite structure	Complicated process, and difficult to recycle the waste liquid	19.49%
Other metal-MCCE	Low cost, composite structure	Inmature	16.60%

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多晶硅表面金属催化化学腐蚀法制绒研究现状

Texturing Technology on Multicrystalline Silicon Wafer by Metal-catalyzed Chemical Etching: a Review

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