CN111900232A - 一种shj电池生产中不良返工方法 - Google Patents

一种shj电池生产中不良返工方法 Download PDF

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CN111900232A
CN111900232A CN202010775191.4A CN202010775191A CN111900232A CN 111900232 A CN111900232 A CN 111900232A CN 202010775191 A CN202010775191 A CN 202010775191A CN 111900232 A CN111900232 A CN 111900232A
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hydrofluoric acid
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孙林
孟凡英
杜俊霖
刘正新
陈功兵
何堂贵
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Tongwei Solar Chengdu Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
    • H01L31/072Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
    • H01L31/0745Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells
    • H01L31/0747Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells comprising a heterojunction of crystalline and amorphous materials, e.g. heterojunction with intrinsic thin layer or HIT® solar cells; solar cells
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1876Particular processes or apparatus for batch treatment of the devices
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy

Abstract

本发明公开一种SHJ电池生产中不良返工方法,包括以下步骤:S1.将收集的不良电池片放入专门返工片清洗机,清洗掉硅片表面的薄膜:S1.1酸洗:用酸洗液对不良电池片清洗,所述酸洗液为盐酸溶液,或者盐酸溶液与氢氟酸溶液的混合液;S1.2漂洗:用纯水对经酸洗后的硅片进行漂洗,洗去硅片表面残留的酸洗洗液;S1.3 SC1液洗:用SC1液将S1.2所得硅片洗;S1.4漂洗:用纯水洗进行漂洗;S1.5烘干:在90℃进行烘干;S2.将经S1所得的硅片,进行重新制绒,制绒时,制绒辅助剂为正常制绒的用量的1‑2倍。本发明将不良电池片经过返工处理,返工后A级率95%,且所得电池片效率与正常相当,不良返工可实现规模化生产,提升整个生产的A级率。

Description

一种SHJ电池生产中不良返工方法
技术领域
本发明涉及太阳能电池领域,具体涉及一种SHJ电池生产中不良返工方法。
背景技术
SHJ(Silicon Herterojunction)硅异质结电池,又被称作HIT(Heterojunctionwith intrinsic thin layer)电池,该电池具有高效率、高Voc等特点,该电池一般以N型硅片为基底,对硅基底界面要求特别严格(对比脏污残留敏感),一般制程工序为:制绒、非晶硅、TCO、丝网&测试。现目前,SHJ规模化生产中,实际产生中经常会出现的外观或者电性能表征不良的电池片,但是这些不良还未有完备可行的返工工艺,或是不良直接下流造成最终电池片降级或是效率低,或是返工后达不到清洁的表面状况(还是存在明显外观不良),或是返工后效率较之前差(效率较正常生产片效率低)等问题。
发明内容
为了解决上述问题,本发明提供一种SHJ电池生产中不良返工方法。
为了实现上述目的,本发明采用如下技术方案:
一种SHJ电池生产中不良返工方法,包括以下步骤:
S1.将收集的不良电池片放入专门返工片清洗机,清洗掉硅片表面的薄膜:
S1.1酸洗:用酸洗液对不良电池片清洗,所述酸洗液为盐酸溶液,或者盐酸溶液与氢氟酸溶液的混合液;
S1.2漂洗:用纯水对经酸洗后的硅片进行漂洗,洗去硅片表面残留的酸洗洗液;
S1.3 SC1液洗:用SC1液洗S1.2所得硅片;
S1.4漂洗:用纯水洗进行漂洗;
S1.5烘干:将所得硅片烘干;
S2.将经S1所得的硅片,进行重新制绒,制绒时,制绒辅助剂为正常制绒的用量的1-2倍。
进一步的,S1.1酸洗液中,当酸洗液为盐酸溶液与氢氟酸溶液的混合液时,氢氟酸溶液的体积不超过90%,其中盐酸溶液中的HCl的质量浓度为36-38%,氢氟酸溶液中的HF的质量浓度为45-50%。
进一步的,S1中,酸洗时间为7200s,漂洗时间为150s,SC1液洗时间为300s,烘干时间为600s。
进一步的,S1.1中,酸洗液中,盐酸溶液与氢氟酸溶液的体积比为99:1。
进一步的,S1.3中,
S1.3中,SC1液中,双氧水的体积占1-50%,碱溶液的体积占0.1-5%,余量为水,其中,双氧水中H2O2的质量浓度为28-35%,碱溶液中碱的质量浓度为42-48%。
进一步的,S2包括以下步骤:
S2.1预清洗:使用预清洗液对S1所得硅片进行清洗,所述预清洗液为氢氟酸溶液,或者氢氟酸与臭氧的混合溶液,或者氢氟酸与盐酸混合溶液;再用纯水清洗;
S2.2 SC1液清洗:用SC1液处理后,再用纯水清洗;
S2.3制绒:进行制绒处理,制绒辅助剂为正常制绒的用量的1-2倍,制绒时间少于正常制绒时间,然后用纯水漂洗;
S2.4后清洗:采用常规后清洗工艺进行后清洗处理,然后用纯水漂洗;
S2.5氢氟酸洗:采用氢氟酸洗液洗,然后用纯水漂洗;
S2.6烘干:将所得硅片烘干。
进一步的,S2.1中,当预清洗液为氢氟酸与臭氧的混合溶液时,O3浓度为0-100ppm,氢氟酸溶液所占体积比为0.3-10%,盐酸溶液所占体积比为0.01-10%,余量为水,其中氢氟酸溶液的中HF的质量浓度为45-50%。
进一步的,S2.5中,氢氟酸洗液中,质量浓度为45-50%的氢氟酸溶液所占体积为10-15%,余量为水。
一种SHJ电池,所述电池的硅片采用上述方法制得。
与现有技术相比,本发明的有益效果在于:
本发明将不良电池片经过返工处理,返工后A级率95%,且所得电池片效率与正常相当,不良返工可实现规模化生产,提升整个生产的A级率,按照5%返工率测算,每瓦因降级带来损失0.2元,返工后A级率95%,那么每GW产能每年可增加收益=0.2元*1000000000*5%*95%=950万元,增加了利润,且本发明适用于TCO不良返工,且本发明中S2可单独用于非晶硅不良返工或者制绒不良返工。
具体实施方式
下面结合实施例对本发明作进一步的描述,所描述的实施例仅仅是本发明一部分实施例,并不是全部的实施例。基于本发明中的实施例,本领域的普通技术人员在没有做出创造性劳动前提下所获得的其他所有实施例,都属于本发明的保护范围。
一种SHJ电池生产中不良返工方法,包括以下步骤:S1.将收集的不良电池片放入专门返工片清洗机,清洗掉硅片表面的薄膜:S1.1酸洗:用酸洗液对不良电池片清洗,所述酸洗液为盐酸溶液,或者盐酸溶液与氢氟酸溶液的混合液;S1.2漂洗:用纯水对经酸洗后的硅片进行漂洗,洗去硅片表面残留的酸洗洗液;S1.3 SC1液洗:用SC1液洗S1.2所得硅片;S1.4漂洗:用纯水洗进行漂洗;S1.5烘干:将所得硅片烘干;S2.将经S1所得的硅片,进行重新制绒:S2.1预清洗:使用预清洗液对S1所得硅片进行清洗,所述预清洗液为氢氟酸溶液,或者氢氟酸与臭氧的混合溶液,或者氢氟酸与盐酸混合溶液;再用纯水清洗;S2.2 SC1液清洗:用SC1液处理后,再用纯水清洗;S2.3制绒:进行制绒处理,制绒辅助剂为正常制绒的用量的1-2倍,制绒时间少于正常制绒时间,然后用纯水漂洗;S2.4后清洗:采用常规后清洗工艺进行后清洗处理,然后用纯水漂洗;S2.5氢氟酸洗:采用氢氟酸洗液洗,然后用纯水漂洗;S2.6烘干:将所得硅片烘干。本发明首先利用盐酸和氢氟酸溶液对不良电池片进行清洗,HCl与可与电池片表面的薄膜反应,可除去电池片表面蓝膜,而HF可与电池片表面的磷硅玻璃及硼硅玻璃反应,清除电池片表面的阻档均匀反应的物质,达到均匀反应;S1步骤中,经S1.1的酸洗后,可立即进行SC1清洗;经过S1步骤的处理,不良电池片表面还存在非晶硅层5-20nm,非晶硅层由Si-H构成的致密非晶硅层,如果该非晶硅层不进行去除或者疏松,重新制绒时会出现不均匀的现象,造成硅片外观异常,从而返工失败,因此,在制绒前,本发明采用臭氧氢氟酸混合体系进行预清洗处理,O3的强氧化性可以对Si起到氧化作用,形成SiO2,而HF可以与SiO2反应,将SiO2从硅片表面剥离,由于O3是气体,经O3/HF体系处理的不良电池片表面的致密非晶硅层被疏松,本发明的所得返工片Eta值甚至比正常片有所提高;在制绒步骤,本发明采用制绒辅助剂为正常制绒的用量的1-2倍,减短制绒时间,达到去除减重较正常低,绒面反射率又未增加的目的,同时,在制绒槽中添加过氧化氢溶液或者硝酸溶液能氧化溶液,可以加快反应速率;例如通常正常使用制绒辅助剂的量为140ml/L溶液,增加1-2倍就是用280ml/L到420ml/L的量,制绒辅助剂对反应起到抑制作用,增加制绒辅助剂的量主要起到减少腐蚀量、减少绒面大小的作用,正常绒面金字塔大小为1-5um,增加添加剂后绒面大小会在2-6um,由于返工的电池片本身已经形成完整的金字塔,因此不会存在部分区域因制绒辅助剂的抑制能力强无法形成金字塔,造成外观的问题,于此同时,由于制绒辅助剂的用量加大,缩短了二次制绒时间,减少返工时的去重,保证硅片的去重,返工减重控制在0.3-0.6g。
实施例1
一种SHJ电池生产中不良返工方法,包括以下步骤:
S1.1酸洗:将挑选不良电池片至杆槽花篮中备返工,挑选操作中尽量避免摩擦和手直接接触硅片,每200pcs为一批,在常温条件下,用酸洗液对不良电池片清洗7200s,所述酸洗液为盐酸与氢氟酸的混合液;酸洗液中,质量浓度为36-38%的盐酸溶液与质量浓度为49%的氢氟酸溶液的体积比为99:1;
S1.2漂洗:常温下,用纯水对经酸洗后的硅片进行漂洗150s,洗去硅片表面残留的酸洗洗液;
S1.3 SC1液洗:在65℃下,用SC1液将S1.2所得硅片洗300s,清除S1.2所得硅片的表面有机脏污和颗粒脏污,使硅片表面清洁;SC1液中,质量浓度为30%的双氧水的体积占10%,质量浓度为45%的氢氧化钾溶液的体积占1.6%,余量为水;
S1.4漂洗:室温下用纯水洗进行漂洗;
S1.5慢提拉:在60℃下进行慢提拉30s;
S1.6烘干:在90℃进行烘干处理600s;
S2.1预清洗:在15-40℃下,使用O3与HF混合溶液对S1所得片子进行清洗150-600s,其中O3浓度为30ppm,质量浓度为49%的氢氟酸溶液所占体积为体积比0.5%,余量为水;再在常温下用纯水漂洗150s;
S2.2SC1液清洗:在85℃下用SC1液洗300s,再在室温下用纯水漂洗150s;SC1液中,质量浓度为30%的双氧水的体积占10%,质量浓度为45%的氢氧化钾溶液的体积占1.6%,余量为水;
S2.3制绒:在75-85℃下制绒360-600s,制绒辅助剂ADD(市面购买)的添加量为正常制绒的用量的2倍,制绒时间360-600s较正常制绒的制绒时间短,然后在室温下用纯水漂洗150s;
S2.4后清洗:在65℃下采用常规后清洗工艺进行后清洗300s,然后在室温下用纯水漂洗150s;
S2.5氢氟酸洗:在室温下采用氢氟酸洗150s,然后用纯水漂洗150s;其中质量浓度为49%的氢氟酸溶液所占体积为10%,余量为水;
S2.6慢提拉:在55-60℃下进行慢提拉40s;
S2.7烘干:在45℃下进行烘干处理600s。
实际安装该返工方式生产900片,与正常片效率对比如表1所示:
类型 数量 Eta Voc Isc FF
返工片 887 22.98 0.7398 9.3022 81.58
正常片 900 22.78 0.7393 9.3187 80.78
经统计,返工片A级率:95.43%,正常生产片A级率:96.00%。由实际生产测试可以看出,本发明的返工的方法所得电池片,效率较正常不差,A级率略低,综合评估与正常片持平,有效解决了不良直接下流造成最终电池片降级或是效率低,或是返工后达不到清洁的表面状况(还是存在明显外观不良),或是返工后效率较之前差(效率较正常生产片效率低)等问题。

Claims (10)

1.一种SHJ电池生产中不良返工方法,其特征在于,包括以下步骤:
S1.将收集的不良电池片放入专门返工片清洗机,清洗掉硅片表面的薄膜:
S1.1 酸洗:用酸洗液对不良电池片清洗,所述酸洗液为盐酸溶液,或者盐酸溶液与氢氟酸溶液的混合液;
S1.2漂洗:用纯水对经酸洗后的硅片进行漂洗,洗去硅片表面残留的酸洗洗液;
S1.3 SC1液洗:用SC1液洗S1.2所得硅片;
S1.4漂洗:用纯水洗进行漂洗;
S1.5烘干:将所得硅片烘干;
S2.将经S1所得的硅片,进行重新制绒,制绒时,制绒辅助剂为正常制绒的用量的1-2倍。
2.根据权利要求1所述的一种SHJ电池生产中不良返工方法,其特征在于,S1.1酸洗液中,当酸洗液为盐酸溶液与氢氟酸溶液的混合液时,氢氟酸溶液的体积不超过90%,水的体积不超过90%;其中盐酸溶液中的HCl的质量浓度为36-38%,氢氟酸溶液中的HF的质量浓度为45-50%。
3.根据权利要求1所述的一种SHJ电池生产中不良返工方法,其特征在于,S1.3中,SC1液中,双氧水的体积占1-50% ,碱溶液的体积占0.1-5% ,余量为水,其中,双氧水中H2O2的质量浓度为28-35%,碱溶液中碱的质量浓度为42-48%。
4.根据权利要求1所述的一种SHJ电池生产中不良返工方法,其特征在于,S2包括以下步骤:
S2.1预清洗:使用预清洗液对S1所得硅片进行清洗,所述预清洗液为氢氟酸溶液,或者氢氟酸与臭氧的混合溶液,或者氢氟酸与盐酸混合溶液;再用纯水清洗;
S2.2 SC1液清洗:用SC1液处理后,再用纯水清洗;
S2.3制绒:进行制绒处理,制绒辅助剂为正常制绒的用量的1-2倍,制绒时间少于正常制绒时间,然后用纯水漂洗;
S2.4后清洗:采用常规后清洗工艺进行后清洗处理,然后用纯水漂洗;
S2.5氢氟酸洗:采用氢氟酸洗液洗,然后用纯水漂洗;
S2.6烘干:将所得硅片烘干。
5.根据权利要求4所述的一种SHJ电池生产中不良返工方法,其特征在于,S2.1中,当预清洗液为氢氟酸与臭氧的混合溶液时,O3浓度为0-100ppm,氢氟酸溶液所占体积比为0.3-10%,盐酸溶液所占体积比为0.01-10%,余量为水,其中氢氟酸溶液的中HF的质量浓度为45-50%。
6.根据权利要求4所述的一种SHJ电池生产中不良返工方法,其特征在于,S2.5中,氢氟酸洗液中,质量浓度为45-50%的氢氟酸溶液所占体积为10-15%,余量为水。
7.根据权利要求4所述的一种SHJ电池生产中不良返工方法,其特征在于,S2可用于非晶硅不良返工或者制绒不良返工。
8.一种非晶硅不良或者制绒不良的返工方法,其特征在于,包括以下步骤:
(1)预清洗:使用预清洗液对S1所得硅片进行清洗,再用纯水清洗,所述预清洗液为氢氟酸溶液,或者氢氟酸与臭氧的混合溶液,或者氢氟酸与盐酸混合溶液;
(2)SC1液清洗:用SC1液洗后,再用纯水漂洗;
(3)制绒:制绒辅助剂为正常制绒的用量的1-2倍,制绒时间少于正常制绒时间,然后用纯水漂洗;
(4)后清洗:采用常规后清洗工艺进行后清洗,然后用纯水漂洗;
(5)氢氟酸洗:采用氢氟酸洗液洗,然后用纯水漂洗;
(6)烘干。
9.根据权利要求8所述一种非晶硅不良或者制绒不良的返工方法,其特征在于,步骤(1)中,当预清洗液为氢氟酸与臭氧的混合溶液时,臭氧浓度为0-100ppm,氢氟酸溶液所占体积比为0.3-10%,盐酸溶液所占体积比为0.01-10%,余量为水,其中氢氟酸溶液的中HF的质量浓度为45-50%。
10.一种SHJ电池,其特征在于,所述电池的硅片采用如权利要求1-7任一项所述的方法制得,或者如权利要求8-9任一项所述的方法制得。
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