CN108292691A - 一种局部背接触太阳能电池的制备方法 - Google Patents
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Abstract
一种局部背接触太阳能电池的制备方法，包括如下步骤：去除硅片表面损伤层并进行双面抛光、制绒、形成PN结、刻蚀和去杂质玻璃、背面沉积钝化膜、正面沉积钝化减反射层、背面局部开口、丝网印刷正背面金属浆料、烧结；其中，制绒步骤采用金属催化腐蚀法，其绒面结构为纳米级绒面结构。将去除硅片表面损伤层和双面抛光结合成一步工序来实现，简化了工艺流程，降低了成本。
Description
本发明涉及一种局部背接触太阳能电池的制备方法，属于太阳能电池技术领域。
常规的化石燃料日益消耗殆尽，在现有的可持续能源中，太阳能无疑是一种最清洁、最普遍和最有潜力的替代能源。太阳能发电装置又称为太阳能电池或光伏电池，可以将太阳能直接转换成电能，其发电原理是基于半导体PN结的光生伏特效应。
随着科技的发展，出现了局部接触背钝化(PERC)太阳能电池，这是新开发出来的一种高效太阳能电池，得到了业界的广泛关注。其核心是在硅片的背光面用氧化铝或者氧化硅薄膜(5～100纳米)覆盖，以起到钝化表面，提高长波响应的作用，从而提升电池的转换效率。但是，氧化铝或者氧化硅不导电，因此需要对该薄膜局部开口，以便于铝金属与硅片背表面接触，收集电流。另外，铝金属(通常是铝浆)，在高温烧结过程中，会破坏氧化铝或者氧化硅的钝化作用，因此通常要在氧化铝或者氧化硅薄膜上再覆盖氮化硅薄膜，起到保护作用。
现有的局部背接触太阳能电池的制备方法主要包括如下步骤：去除硅片表面损伤层、制绒、扩散、背抛光、刻蚀和去杂质玻璃、背面沉积氧化铝或氧化硅薄膜、沉积氮化硅保护膜、正面沉积氮化硅减反射层、背面局部开口、丝网印刷正背面金属浆料、烧结，即可得到太阳能电池。
然而，上述制备方法存在如下问题：(1)由于工艺步骤较多，导致其成本较高，需要进一步降低成本；(2)得到的局部背接触太阳能电池的光电转换效率仍然较低，有进一步提升的空间。
发明内容
本发明的发明目的是提供一种局部背接触太阳能电池的制备方法。
为达到上述发明目的，本发明采用的技术方案是：一种局部背接触太阳能电池的制备方法，包括如下步骤：去除硅片表面损伤层并进行双面抛光、制绒、形成PN结、刻蚀和去杂质玻璃、背面沉积钝化膜、正面沉积
钝化减反射层、背面局部开口、丝网印刷正背面金属浆料、烧结；
其中，所述制绒步骤采用金属催化腐蚀法，其绒面结构为纳米级绒面结构。
上文中，所述制绒步骤采用金属催化腐蚀法，金属催化化学腐蚀法是现有技术。
所述纳米级绒面结构的表面反射率在12～20％之间。
本发明将去除硅片表面损伤层和双面抛光结合成一步工序来实现，不仅达到了去除硅片表面损伤层的目的，同时还形成了背钝化的抛光面，从而节省了现有技术中在扩散步骤之后需要进行背抛光的步骤，简化了工艺流程，降低了成本。同时抛光后再形成纳米级绒面能使PN结更平整，降低结区复合，提高开路电压，还有利于金属接触，在提高开压的同时提升FF。
优选的，所述所述去除硅片表面损伤层并进行双面抛光步骤采用酸液或碱液进行，时间为2～20min，
所述酸液为HNO3与HF的混合液，或H2CrO4与HF的混合液；温度为5～45℃；
在HNO3与HF的混合液中，HNO3(69％)/HF(49％)或H2CrO4(60％)/HF(49％)体积比大于4:1；
所述碱液为NaOH溶液、KOH溶液或四甲基氢氧化铵溶液；温度为5～95℃；上述碱液的体积浓度大于1％。
上文中，所述HNO3(69％)/HF(49％)是指体积浓度为69％的HNO3和体积浓度为49％的HF；
所述H2CrO4(60％)/HF(49％)是指体积浓度为60％的H2CrO4和体积浓度为49％的HF。
所述四甲基氢氧化铵溶液也称为TMAH溶液。
优选的，所述去除硅片表面损伤层并进行双面抛光步骤的处理时间为2～10min。
上述技术方案中，所述制绒步骤如下：先将硅片放入含有金属离子的溶液中浸泡，使硅片表面涂覆一层金属纳米颗粒；
然后用化学腐蚀液腐蚀硅片表面，形成纳米级绒面；所述化学腐蚀液为含有氧化剂的氢氟酸溶液。该方法即为两步金属催化刻蚀法。
上述技术方案中，所述含有金属离子的溶液为含有氢氟酸的金属盐溶液。
上述技术方案中，所述制绒步骤如下：将硅片放入含有氧化剂以及金属盐的氢氟酸溶液中，在硅片表面形成纳米级绒面。该方法即为一步金属催化刻蚀法。
所述金属离子可从现有技术的金属离子中选用，比如金、银、铜、镍中的一种或几种；所述氧化剂可以是H2O2、HNO3或H2CrO4。
上述技术方案中，所述溶液中金属离子的浓度大于6E-5mol/L。
优选的，所述纳米级绒面的尺寸为100～900nm。
上述技术方案中，所述制绒和形成PN结步骤之间，还有绒面微结构修正刻蚀步骤，具体如下：将带有绒面的硅片放入化学腐蚀液中进行微结构修正刻蚀；
所述化学腐蚀液选自以下溶液中的一种：NaOH溶液、KOH溶液、四甲基氢氧化铵溶液、酸性氧化剂与HF酸的混合溶液。
上述利用化学腐蚀溶液对硅片表面进行微结构修正刻蚀，即利用碱液(NaOH溶液、KOH溶液、四甲基氢氧化铵溶液或混合酸(HF和HNO3))对上述制得的纳米绒面的微结构(线状或深孔状)进行腐蚀修正，碱液主要是对上述线状或深孔状微结构进行各向异性腐蚀，这种各向异性腐蚀会沿着原来的线状或深孔状微结构优先进行，刻蚀结果就会使原来的线状或深孔状微结构被修正成带有棱角的纳米金字塔或纳米椎体或纳米坑状结构，而混合酸(HF和HNO3)主要是对上述线状或深孔状微结构进行各向同性腐蚀，这种各向同性腐蚀会沿着原来的线状或深孔状微结构优先进行，刻蚀结果就会使原来的线状或深孔状微结构被修正成孔径较大，深度较浅的纳米孔状结构，通过该步的修正刻蚀最终制得较优的纳米绒面。
上述技术方案中，在所述绒面微结构修正刻蚀步骤之前或之后，还有去除金属颗粒步骤，具体如下：分别用酸液、去离子水清洗硅片，去除金属颗粒。
本发明的制备方法可用于金刚线切割硅片制作的太阳能电池。
由于上述技术方案运用，本发明与现有技术相比具有下列优点：
1、本发明开发了一种新的局部背接触太阳能电池的制备方法，在去除硅片表面损伤层的同时将硅片进行双面抛光，即将去除硅片表面损伤层和双面抛光结合成一步工序来实现，不仅达到了去除硅片表面损伤层的目的，同时还形成了背钝化的抛光面，从而节省了现有技术中在扩散步骤之后需要进行背抛光的步骤，简化了工艺流程，节约了生产时间，提高了效率，降低了成本；可以在不增加电池每瓦制造成本的情况下大批量生产多晶硅PERC电池；
2、本发明先采用化学腐蚀进行双面抛光，然后形成纳米级绒面，使扩散后形成的PN结更平整，降低结区复合，提高开路电压，还有利于金属接触，在提高开压的同时提升FF，实验证明，与现有技术相比，本发明制得的多晶硅PERC电池的电池效率提升0.47％左右，取得了意想不到的技术效果；
3、本发明的前表面采用了纳米绒面结构，降低前表面的反射率增加短波的吸收，再结合背面钝化膜工艺，实现了增加全波段光吸收的目的，大幅提高了多晶硅电池的效率。
下面结合实施例对本发明进一步描述。
实施例一：
一种多晶硅PERC太阳能电池的制备方法，由如下步骤组成：
首先，采用质量浓度为2％的KOH溶液将多晶硅片去除表面损伤层和双面抛光，温度为70℃，时间为6min；
紧接，着将抛光后的硅片进行金属催化腐蚀制备纳米绒面，纳米绒面大小为300～500nm，反射率为17％；所述制绒步骤如下：将硅片放入含有金属离子的化学腐蚀液中，在硅片表面形成纳米级绒面；所述化学腐蚀液是含有银离子的H2O2和氢氟酸混合溶液，其中金属离子的浓度大于6E-5mol/L；H2O2浓度为0.5mol/l，HF浓度为10mol/L；
然后，将制绒后的硅片放入扩散炉内进行扩散，扩散温度为800℃～840
℃，运行时间为60～90min，方块电阻为60～120Ω/sq；
再然后，将扩散后硅片进行背面、边缘刻蚀并去除表面PSG层；
其次，将刻蚀后硅片背面ALD沉淀Al2O3钝化层并做退火处理，
随后再在Al2O3钝化层上PECVD沉积SiNx薄膜；
再其次，在硅片的前表面PECVD沉积氮化硅减反射薄膜；
随后，利用激光对背面局域开口；
最后，丝网印刷制备电极并形成欧姆接触。
对比例一
采用与实施例相同的原料制备局部背接触太阳能电池，其制备方法主要包括如下步骤：去除硅片表面损伤层、制绒、扩散、背抛光、刻蚀和去杂质玻璃、背面沉积氧化铝或氧化硅薄膜、沉积氮化硅保护膜、正面沉积氮化硅减反射层、背面局部开口、丝网印刷正背面金属浆料、烧结，即可得到太阳能电池。
将上述实施例和对比例的太阳能电池进行测试，结果如下：
| Uoc(mV) | Jsc(mA/cm<sup>2</sup>) | FF(％) | EFF | |
| 常规多晶电池 | 633.3 | 36.02 | 78.46 | 17.90％ |
| 对比例一 | 641.4 | 36.80 | 77.82 | 18.37％ |
| 实施例一 | 644.2 | 37.22 | 78.58 | 18.84％ |
由上表可见，与对比例相比，本发明制得的多晶硅PERC电池的电池效率提升0.47％左右，取得了意想不到的技术效果；且在提高开压的同时提升了填充因子FF，说明本发明在扩散后形成的PN结更平整，有利于金属接触。
Claims (9)
- 一种局部背接触太阳能电池的制备方法，其特征在于，包括如下步骤：去除硅片表面损伤层并进行双面抛光、制绒、形成PN结、刻蚀和去杂质玻璃、背面沉积钝化膜、正面沉积钝化减反射层、背面局部开口、丝网印刷正背面金属浆料、烧结；其中，所述制绒步骤采用金属催化腐蚀法，其绒面结构为纳米级绒面结构。
- 根据权利要求1所述的制备方法，其特征在于：所述去除硅片表面损伤层并进行双面抛光步骤采用酸液或碱液进行，时间为2～20min，所述酸液为HNO3与HF的混合液，或H2CrO4与HF的混合液；温度为5～45℃；在HNO3与HF的混合液中，HNO3(69％)/HF(49％)或H2CrO4(60％)/HF(49％)体积比大于4:1；所述碱液为NaOH溶液、KOH溶液或四甲基氢氧化铵溶液；温度为5～95℃；上述碱液的体积浓度大于1％。
- 根据权利要求2所述的制备方法，其特征在于：所述去除硅片表面损伤层并进行双面抛光步骤的处理时间为2～10min。
- 根据权利要求1所述的制备方法，其特征在于，所述制绒步骤如下：先将硅片放入含有金属离子的溶液中浸泡，使硅片表面涂覆一层金属纳米颗粒；然后用化学腐蚀液腐蚀硅片表面，形成纳米级绒面；所述化学腐蚀液为含有氧化剂的氢氟酸溶液。
- 根据权利要求4所述的制备方法，其特征在于，所述含有金属离子的溶液为含有氢氟酸的金属盐溶液。
- 根据权利要求1所述的制备方法，其特征在于，所述制绒步骤如下：将硅片放入含有氧化剂以及金属盐的氢氟酸溶液中，在硅片表面形成纳米级绒面。
- 根据权利要求4或6所述的制备方法，其特征在于，所述溶液中金属离子的浓度大于6E-5mol/L。
- 根据权利要求1所述的制备方法，其特征在于：所述制绒和形成PN 结步骤之间，还有绒面微结构修正刻蚀步骤，具体如下：将带有绒面的硅片放入化学腐蚀液中进行微结构修正刻蚀；所述化学腐蚀液选自以下溶液中的一种：NaOH溶液、KOH溶液、四甲基氢氧化铵溶液、酸性氧化剂与HF酸的混合溶液。
- 根据权利要求8所述的制备方法，其特征在于：在所述绒面微结构修正刻蚀步骤之前或之后，还有去除金属颗粒步骤，具体如下：分别用酸液、去离子水清洗硅片，去除金属颗粒。
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| CN104993019A (zh) | 2015-07-09 | 2015-10-21 | 苏州阿特斯阳光电力科技有限公司 | 一种局部背接触太阳能电池的制备方法 |
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2015
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| CN103283001A (zh) * | 2011-03-08 | 2013-09-04 | 可持续能源联盟有限责任公司 | 蓝光响应增强的高效黑硅光伏器件 |
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| CN102569522A (zh) * | 2012-02-09 | 2012-07-11 | 常州大学 | 一种高效晶体硅太阳电池局部背接触结构的制备方法 |
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| CN115241330A (zh) * | 2022-09-19 | 2022-10-25 | 英利能源发展(天津)有限公司 | 一种氢氟酸刻蚀太阳能电池用半导体硅片装置 |
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| WO2017004958A1 (zh) | 2017-01-12 |
| US20170294545A1 (en) | 2017-10-12 |
| EP3321979B1 (en) | 2021-01-20 |
| TW201703277A (zh) | 2017-01-16 |
| JP6666438B2 (ja) | 2020-03-13 |
| CN104993019A (zh) | 2015-10-21 |
| US9966484B2 (en) | 2018-05-08 |
| JP2018526835A (ja) | 2018-09-13 |
| TWI669830B (zh) | 2019-08-21 |
| EP3321979A4 (en) | 2019-03-20 |
| EP3321979A1 (en) | 2018-05-16 |
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