CN113161447A - 一种铸造单晶或多晶类硅片的磷氢退火预处理方法 - Google Patents
一种铸造单晶或多晶类硅片的磷氢退火预处理方法 Download PDFInfo
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Abstract
本发明涉及一种铸造单晶或多晶类硅片的磷氢退火预处理方法，它包括如下步骤，A.酸洗；B.高温沉积PSG；C.一次除杂；D.高温氢气退火。本发明的目的在于提供一种铸造单晶或多晶类硅片的磷氢退火预处理方法，其适合于铸造单晶或多晶类硅片的有效钝化，能够将金属杂质从位错、晶界等晶体缺陷处释放，减少载流子的体内复合，提高整体的钝化水平，并且有利于促进硅中氧的外扩散，将晶粒位错进行重整，减少晶格缺陷。
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磷氢退火预处理方法。
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磷氢退火预处理方法，其适合于铸造单晶或多晶类硅片的有效钝化，能够将金属杂质从位错、晶界等晶体缺陷处释放，减少载流子的体内复合，提高整体的钝化水平，并且有利于促进硅中氧的外扩散，将晶粒位错进行重整，减少晶格缺陷。
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磷氢退火预处理方法，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.高温氢气退火：将经步骤C一次除杂处理后的硅片置于高纯氢气氛中进行高温退火处理。
较之现有技术而言，本发明的优点在于：
(1)磷扩散吸杂能够将金属杂质从位错、晶界等晶体缺陷处充分释放，减少载流子的体内复合，提高整体的钝化水平；并且进行高温氢气退火处理有利于促进硅中氧的外扩散，将铸造单晶中晶粒位错进行重整，减少晶格缺陷；实验发现，处理后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或多晶异质结太阳电池的转换效率。
(2)本发明的预处理方法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。
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是以本发明铸造单晶或多晶类硅片的磷氢退火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磷氢退火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磷氢退火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磷氢退火预处理方法，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.高温氢气退火：将经步骤C一次除杂处理后的硅片置于高纯氢气氛中进行高温退火处理。
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。
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。
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。
所述步骤D高温氢气退火的具体方法为，将经步骤C一次除杂处理后的硅片置于高纯氢气氛中进行高温退火处理，氢气纯度为99.999％，退火温度范围为1100℃-1350℃，退火气体流量为200sccm-100sccm，退火压力为100mbar-400mbar，退火时间为30min-120min。
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。
经相应预处理后，后续的制造工艺一般如下：
E、将预处理后的硅片进行表面制绒，制绒所用的碱性溶液为KOH或NaOH中的一种，质量百分比为0.5％-3％，硅片在碱性溶液中制绒时间为15-40分钟，处理温度为75℃-85℃。
F、在E制绒清洗之后，是PECVD(等离子化学气相沉积)镀膜制备表面钝化膜层(非掺杂型)和掺杂膜层。硅片的背面镀膜顺序是本征型非晶硅，然后是N型掺杂的非晶硅。PECVD设备电源采用13.56MHz、26MHz或40MHz，优选地采用13.56MHz。本征型非晶硅膜层的工艺气体包含硅烷(SiH4)、氢气(H2)、CO2和CH4的全部或几种组合。制备N型掺杂的非晶硅的工艺气体包含SiH4、H2和磷烷(PH3)。硅片的正面镀膜顺序是本征型非晶硅，然后是P型掺杂的宽能隙材料。正面(入光面)本征型非晶硅的工艺气体包含硅烷(SiH4)、氢气(H2)、CO2和CH4的全部或几种组合。制备P型掺杂膜层的工艺气体包含SiH4、H2、CO2、CH4、乙硼烷(B2H6)、TMB的全部或几种组合。正面的P型掺杂膜层优选地可以是含氧型微晶μc-SiOx:H或者非晶态的碳化硅a-SiC。含氧型微晶μc-SiOx:H(P)的成膜速度控制在0.2-1.5埃/秒，优选地在0.6-0.8埃/秒。含氧型微晶μc-SiOx:H(P)在制绒面上的厚度为40-200埃，优选地为60-120埃。
G、在F非晶硅薄膜沉积工艺之后施加PVD(物理气相沉积)磁控溅射制备透明导电膜(TCO).TCO的材料可以是含氧化锡、氧化钛、氧化锌或氧化镓掺杂的氧化铟薄膜。其中氧化铟(In2O3)是主体材料，按重量比占比90％以上。优选地，掺杂材料至少含有氧化锡、氧化钛、氧化锌或氧化镓的一种，按重量占比0-10％。PVD采用的靶材也可以是纯氧化铟，然后在工艺其中总导入H2或水蒸气，形成掺杂的In2O3:H薄膜。P型掺杂层前置的电池设计需要较薄的宽带隙P型窗口层以降低光学吸收和加强正面钝化效果。相应地，需要高功函数(WF)TCO作为接触层来降低接触电阻。征对以氧化铟为主体的TCO材料，可以通过调节有效掺杂来调节TCO材料的费米面位置(或功函数)。降低有效掺杂，在降低P面接触电阻的同时可以降低TCO材料的红外吸收，有利于提升FF和Isc,从而提高转化效率
H、金属栅线集成，采用丝网印刷的方式，转移金属栅线图形到电池片表面。与异质结工艺配合的金属浆料是低温银浆，退火温度在170-220摄氏度之间，优选地在180-200摄氏度范围。所形成的电池片表面形成一系列平行金属细栅线，宽度在20-70微米，高度在3-40微米。为了形成和焊带的有效电接触，还有一系列垂直于细栅线的主栅线和一定数目的焊盘。电池和组件的设计还可以采用无主栅方式(SMART WIRE技术)，表面只有一系列平行金属细栅线。
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 | 2526 | 0.737 |
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 | 9.743 | 0.74193 | 81.44 | 23.36 |
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。
Claims (9)
1.一种铸造单晶或多晶类硅片的磷氢退火预处理方法，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.高温氢气退火：将经步骤C一次除杂处理后的硅片置于高纯氢气氛中进行高温退火处理。
2.根据权利要求1所述的一种铸造单晶或多晶类硅片的磷氢退火预处理方法，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磷氢退火预处理方法，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磷氢退火预处理方法，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磷氢退火预处理方法，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磷氢退火预处理方法，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磷氢退火预处理方法，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。
8.根据权利要求7所述的一种铸造单晶或多晶类硅片的磷氢退火预处理方法，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。
9.根据权利要求1-8任意一项所述的一种铸造单晶或多晶类硅片的磷氢退火预处理方法，其特征在于：所述步骤D高温氢气退火的具体方法为，将经步骤C一次除杂处理后的硅片置于高纯氢气氛中进行高温退火处理，氢气纯度为99.999％，退火温度范围为1100℃-1350℃，退火气体流量为200sccm-100sccm，退火压力为100mbar-400mbar，退火时间为30min-120min。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113644157A (zh) * | 2021-08-10 | 2021-11-12 | 浙江大学 | 一种高效铸造类单晶硅双面太阳电池结构及其制备方法 |
| CN113937184A (zh) * | 2021-09-26 | 2022-01-14 | 福建新峰二维材料科技有限公司 | 一种采用钝化前氢处理技术的异质结太阳电池的制造方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101331615A (zh) * | 2005-10-14 | 2008-12-24 | 荷兰能源建设基金中心 | 制造n型多晶硅太阳能电池的方法 |
| US20090093081A1 (en) * | 2007-10-08 | 2009-04-09 | Csi Cells Co., Ltd | Process of phosphorus diffusion for manufacturing solar cell |
| CN103165730A (zh) * | 2011-12-09 | 2013-06-19 | 浚鑫科技股份有限公司 | 一种太阳能电池的钝化及制作方法 |
| CN109980043A (zh) * | 2019-02-27 | 2019-07-05 | 镇江仁德新能源科技有限公司 | 一种湿法黑硅片的高效量产制备方法 |
-
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- 2021-02-07 CN CN202110177455.0A patent/CN113161447B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101331615A (zh) * | 2005-10-14 | 2008-12-24 | 荷兰能源建设基金中心 | 制造n型多晶硅太阳能电池的方法 |
| US20090093081A1 (en) * | 2007-10-08 | 2009-04-09 | Csi Cells Co., Ltd | Process of phosphorus diffusion for manufacturing solar cell |
| CN103165730A (zh) * | 2011-12-09 | 2013-06-19 | 浚鑫科技股份有限公司 | 一种太阳能电池的钝化及制作方法 |
| CN109980043A (zh) * | 2019-02-27 | 2019-07-05 | 镇江仁德新能源科技有限公司 | 一种湿法黑硅片的高效量产制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| 邹子英等: "高温氢气退火提高硅片质量的研究" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113644157A (zh) * | 2021-08-10 | 2021-11-12 | 浙江大学 | 一种高效铸造类单晶硅双面太阳电池结构及其制备方法 |
| CN113937184A (zh) * | 2021-09-26 | 2022-01-14 | 福建新峰二维材料科技有限公司 | 一种采用钝化前氢处理技术的异质结太阳电池的制造方法 |
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