CN116741871A - 一种扩硼SE结构的N型TOPCon电池制作方法 - Google Patents
一种扩硼SE结构的N型TOPCon电池制作方法 Download PDFInfo
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Abstract
本申请提供一种扩硼SE结构的N型TOPCon电池制作方法,采用硼扩散轻掺杂在硅片正面形成轻掺高方阻区,酸洗去除硅片背面氧化层,硅片背面碱抛光,背面生长隧穿氧化层,沉积掺杂磷多晶硅或者本征多晶硅层,对硅片正面进行图形化的选择性的激光掺杂形成重掺接触区,而后进行高温晶化退火工艺或者高温磷扩散工艺,在高温过程中激光掺杂导致的晶格缺陷得到修复,之后经过湿法清洗去除绕镀多晶硅和正背面氧化层,完成硅片正反面的钝化层和减反层工艺,印刷金属浆料烧结形成SE结构的N型TOPCon电池。
Description
技术领域
本发明涉及光伏领域,具体地,涉及一种扩硼SE结构的N型TOPCon电池制作方法。
背景技术
现有的新型太阳能电池主要以PERC电池为主流,但是随着技术发展的需要,越来越多的电池类型受到产业界的关注。TOPCon电池技术(Tunnel Oxide PassivatedContact,隧穿氧化层钝化接触)电池在电池背面制备有一层超薄的隧穿氧化层和一层高掺杂的多晶硅层,二者共同形成了钝化接触结构,为硅片的背面提供了良好的表面钝化,是由德国由科学家于2013年提出的,该电池技术的关键在于,采用化学湿法氧化和高浓度HNO3进行氧化,首先在电池背面生长一层1.4nm的隧穿氧化层 SiOx,然后沉积磷掺杂的n+-poly-Si薄膜,经过高温退火后,能够有效地降低背面复合电流密度。相较于其他传统的太阳能电池,TOPCon太阳能电池可以明显提高太阳能电池的光电转换效率,目前国内TOPCon太阳能电池市场已经占有一定的市场份额,许多光伏企业已经可以进行自主地研发和量产。
目前TOPCon电池技术中SE(选择性发射极;selective emitter)技术一直被认为能进一步有效提升光电转换效率,但由于工艺实现难度高,传统的“扩散-激光推进”的方式无法达到SE的目的,主要原因在于硼在硅里的固溶度非常低,扩散系数低,且Topcon采用的银铝浆烧结需要更深硼扩散结来防止出现铝穿刺的现象,所以目前没有简单成熟的工艺进行扩硼SE,Topcon-SE电池的提效降本成为亟待解决的关键问题。
表1常规的N型Topcon电池技术和目前主流的Topcon SE技术路线
相比常规N型Topcon电池技术路线,主流N型Topcon SE电池技术路线,增加了激光掺杂,清洗和高温氧化步骤,即使后续的清洗可以去除,也增加了2道工序。N型Topcon 电池技术中,为了增加金属电极与硼发射极的接触性,特意使用了银铝浆(银浆中掺杂了一定含量的铝),利用形成的铝钉刺的深度(深度一般0.6-1μm,极个别甚至>1μm以上) 来增加铝硅合金降低接触接触电阻,为了确保硼发射极不被铝钉刺穿,从而导致漏电和高的金属复合,硼发射极的结深一般都做到0.8μm及以上,因为硼的掺杂难度较大,就导致常规Topcon电池的扩散工艺在3.5-4.5小时,氧化推进温度达到1000度以上,设备故障率较高且能耗相当高。
相比高温气相扩散的掺杂,激光掺杂能够图形化地选择性瞬间将硼原子掺入硅,结深能够控制在1.5μm及以上,既可以降低接触电阻也可以降低金属复合。主流的N型Topcon SE技术路线先做一次硼扩轻掺,然后激光掺杂,之后经过清洗(或可去除),进入高温炉管氧化,这一步高温氧化有以下3个作用:1、进一步降低浅扩区的表面浓度,降低复合;2、高温修复激光掺杂导致的内部晶格损伤;3、在激光掺杂区形成一层较厚的氧化层,防止在背面碱抛光步骤时,激光掺杂区被碱腐蚀。后续工序和常规N型Topcon电池流程相同。
浅掺区因为更低的表面浓度,更浅的结,可以降低表面复合,提高短波响应,提升开路电压和短路电流;激光掺杂区因为更深的结,可以得到更低的金属复合和更低的接触电阻,既可以提升开路电压,也能够平衡浅扩区因为高方阻带来的FF损失。
发明内容
本发明提供的方法,只需要增加一道激光掺杂,不需要额外投入高温氧化设备,即可在常规N型Topcon电池技术路线的基础上形成SE结构。
具体地,一种扩硼SE结构的N型TOPCon电池制作方法,提供N型硅片,采用硼扩散轻掺杂在硅片正面形成轻掺高方阻区,酸洗去除硅片背面氧化层,硅片背面碱抛光后,生长隧穿氧化层,沉积掺磷多晶硅层,对硅片正面进行图形化的选择性的激光掺杂形成重掺接触区,而后进行高温晶化退火工艺,同时对激光导致的晶格缺陷进行修复,或者沉积本征多晶硅,正面采用激光掺杂形成重掺杂接触区,然后经高温磷扩散形成掺杂多晶硅;酸洗去除硅片正面氧化层或者绕扩PSG层,碱洗去除硅片正面绕镀多晶硅层,酸洗去除硅片正面的BSG和硅片背面的PSG层,以及沉积正反面的钝化减反层,印刷金属浆料烧结形成SE结构的N型TOPCon电池。
进一步地,所述N型硅片作为衬底材料,通过清洗制绒使硅片表面产生金字塔状表面结构。
进一步地,所述硼扩轻掺杂高方阻区扩散方阻控制在150-250ohm/口,峰值浓度为5-20E+18cm-3,结深0.3-0.8μm。
进一步地,激光波长为355~1064nm,激光功率为20~1000W,可以是脉冲激光,也可以是连续激光,扫描速度为5~70m/s,光斑尺寸为50~150μm。
进一步地,激光掺杂区的峰值浓度:3-15E+18cm-3,结深>1μm,方阻控制在50-130ohm/ 口。
进一步地,经激光掺杂后,激光掺杂区的反射率上升≤1%,绒面金字塔结构几乎不受损伤。
进一步地,钝化后激光掺杂区相比非激光掺杂区的电性能,反向饱和电流密度J0上升的幅度≤20fA/cm2,Voc的下降幅度≤20mV。
进一步地,激光掺杂区接触电阻≤1.5mohm*cm2,金属接触J0≤400fA/cm2。
进一步地,可以采用先沉积形成掺磷多晶硅,再激光掺杂,最后高温晶化退火的方式;也可以采用沉积先形成本征多晶硅,再激光掺杂,最后高温磷扩散形成掺杂多晶硅;沉积多晶硅可以采用LPCVD或者PECVD等方式。
进一步地,在激光掺杂后增加简单清洗工序,降低掺杂过程中的污染可能性。
进一步地,激光掺杂工序在高温晶化退火工艺或者高温磷扩散之后进行。本发明申请与背景技术相比,具有的有益的效果是:
1、只需要增加一道激光掺杂,简化工艺流程,不需要额外投入高温氧化设备,即可形成SE结构,降低了投资成本。
2、硼扩散工艺只需要调整一次即可,不需要在硼扩散工艺中匹配高温氧化工艺,工艺时长和控制难度大大降低,大幅度缩减热制程的时间,可显著节约能耗;高温晶化退火工艺或者高温磷扩散形成掺杂多晶硅,同时对激光掺杂产生的晶格缺陷进行修复,激光掺杂区的损伤依旧能够得到很好的控制。
3、将激光掺杂工序放在背面抛光之后,避免了传统流程激光作用后金字塔塔尖有破坏,在抛光过程中对金字塔塔尖腐蚀造成漏电的风险;同时利用硼扩散的较厚硼硅玻璃,可以大幅度降低激光损伤,提高电池电性能的稳定性。
4、选择性发射极SE结构能够有效提升开路电压,短路电流,降低接触电阻和金属复合,提升转换效率。
附图说明
为了更清楚地说明本申请实施例或相关技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本申请的实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据提供的附图获得其他的附图。
本说明书附图所绘示的结构、比例、大小等,均仅用以配合说明书所揭示的内容,以供熟悉此技术的人士了解与阅读,并非用以限定本申请可实施的限定条件,故不具技术上的实质意义,任何结构的修饰、比例关系的改变或大小的调整,在不影响本申请所能产生的功效及所能达成的目的下,均应仍落在本申请所揭示的技术内容得能涵盖的范围内。
图1为本申请一种扩硼SE结构的N型TOPCon电池示意图;
图2为本申请一种扩硼SE结构的N型TOPCon电池制备流程图;
图3为本申请实施例扩硼SE-TOPcon电池激光掺杂后的表面SEM图(8000X);
图4为本申请实施例扩硼SE-TOPcon电池与常规TOPcon电池的扩硼ECV曲线对比图;
图5为本申请实施例扩硼SE-TOPcon电池与常规TOPcon电池的接触电阻对比图。
附图标记:1、硅基体;2、硼扩散轻掺区;3、隧穿氧化层;4、掺磷多晶硅;5、激光掺杂区;6、钝化层;7、正面钝化减反层;8、背面钝化减反层。
具体实施方式
下面将结合本申请实施例中的附图,对本申请中的实施例进行清楚、完整地描述,显然,所描述的实施例仅仅是本申请一部分实施例,而不是全部的实施例。基于本申请中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本申请保护的范围。
附图1为本申请一种扩硼SE结构的N型TOPCon电池示意图,N型硅基体1;硼扩散轻掺区2;隧穿氧化层3;掺磷多晶硅层4;激光掺杂区5,掺杂深度深于硼扩散轻掺区2;钝化层6,钝化材料通常为氧化铝、氧化硅;正面钝化减反层7,背面钝化减反层8,钝化减反层通常为氮化硅、氮氧化硅或碳氧化硅等太阳能电池常用的单层或者复合薄膜介质层。
附图2为本申请的扩硼SE结构的N型TOPCon电池制作方法流程示意图,在N型硅片上通过清洗制绒使硅片表面产生金字塔状表面结构,采用硼扩轻掺杂在硅片正面形成轻掺高方阻区,酸洗去除硅片背面氧化层,硅片背面碱抛光后,生长隧穿氧化层,沉积掺磷多晶硅层或者沉积本征多晶硅,对硅片正面进行图形化的选择性的激光掺杂形成重掺接触区,进行高温晶化退火工艺或者高温磷扩散形成掺杂多晶硅,同时对激光掺杂形成的晶格缺陷进行修复,酸洗去除硅片正面绕扩PSG层,碱洗去除硅片正面绕镀多晶硅层,酸洗去除硅片正面的BSG和背面的PSG层,以及镀膜形成正面的钝化层和减反层以及背面的钝化保护层,印刷金属浆料烧结形成SE结构的N型TOPCon电池。
下面用具体实施例说明本申请,并不代表是对本发明申请的限制。
一种扩硼SE结构的N型TOPCon电池制作方法,包括以下步骤:
1)对N型硅片进行清洗以及绒面的制作,使用清洗液为双氧水,盐酸,去离子水;制绒液包括氢氧化钠以及添加剂的混合液,其中碱制绒氢氧化钠的质量浓度为2-10%,温度控制在70-85℃;
2)将清洗制绒后的硅片放在石英晶舟内进入低压扩散炉内,进行硼扩轻掺杂,硼扩散轻掺杂在硅片正面形成轻掺高方阻区区,硼扩轻掺杂高方阻区扩散方阻控制在150-250ohm /口,峰值浓度为5-20E+18cm-3,结深0.3-0.8μm;具体包括将扩散炉升温至扩散温度900℃以上并稳定后,恒压通入氮气、氧气,在硅片表面制作一层薄层氧化硅;温度保持在扩散温度900℃,通入氮气、氧气和硼源对硅片表面进行沉积,将硼原子均匀分布在硅片表面,扩散时间为15-30min,升温至950℃以上推结和氧化,通入氮气稳压恒温推结45-60min形成生成浅结硼轻掺杂区;而后降温出炉;
3)湿法制程单面去除背面的BSG,将硅片置于2-40%的碱性溶液进行电池背面抛光;
4)对硅片背面进行隧穿氧化层生长,隧穿氧化层可以通过热氧化、PECVD笑气或者臭氧氧化实现;
5)采用LPCVD/PECVD的方式在硅片背面生长磷掺杂n型多晶硅薄膜层;
6)对硅片正面进行图形化的选择性的激光掺杂形成重掺接触区,将硼扩轻掺杂后硅片表面的BSG中富含的B原子推进至N型硅基体中,激光波长为355~1064nm,激光功率为20~1000W,可以是脉冲激光,也可以是连续激光,扫描速度为5~70m/s,光斑尺寸为50~150μm;激光掺杂后,激光掺杂区的峰值浓度:3-15E+18cm-3,结深>1μm,典型地,结深控制在1.5-2.5μm,方阻控制在50-130ohm/口;经激光掺杂后,激光掺杂区的反射率上升≤1%,绒面金字塔结构几乎不受损伤,参见附图3-本申请实施例电池激光掺杂后的表面SEM图(8000X),从图中可以明显的看到金字塔塔尖构型保持完好;
7)对硅片进行清洗,如果清洁度可以保证,可以省略;
8)进行高温晶化退火工艺,退火温度为850-950℃,时间为20-50min,多晶硅晶化的同时可以有效修复激光掺杂导致的晶格损伤;
9)酸洗去除硅片正面氧化层或者绕扩PSG层,碱洗去除硅片正面绕镀多晶硅层,酸洗去除硅片正面的BSG和背面的PSG层;
10)沉积硅片正反面的钝化层和减反层,印刷金属浆料烧结形成SE结构的N型TOPCon 电池;钝化后激光掺杂区相比非激光掺杂区的电性能,反向饱和电流密度J0上升的幅度≤20fA/cm2,Voc的下降幅度≤20mV;激光掺杂区接触电阻≤1.5mohm*cm2,金属接触 J0≤400fA/cm2;电池转换效率提升≥0.2%,开路电压提升≥5mV。
表2常规的N型Topcon电池技术和本申请的Topcon SE技术路线
本发明申请提供的扩硼SE结构的N型TOPCon电池制作方法技术路线,硅片制绒后,进行一次低表面浓度,浅结的硼轻掺扩散工艺,以确保在开路电压和短路电流上的优势,之后进行背面酸洗去氧化层,背面碱抛光,生长隧穿氧化层生长,掺磷多晶硅沉积,完成上述步骤后再进行激光掺杂。因为背面碱抛光的腐蚀程度较深,本发明利用硼轻掺扩散的 BSG层和伴生的薄氧化层作为阻挡层,在背面碱抛光前不去除BSG层和伴生的薄氧化层,避免在背面碱抛光工艺中被腐蚀。将激光掺杂放置在掺磷多晶硅沉积后,避免了常规N型 TOPCon电池必须在激光掺杂后在表面再生长一层氧化层来避免激光掺杂区被碱腐蚀,也就是说将激光掺杂置后的工艺,可省去激光掺杂区表面生长氧化层的步骤,避免过多的热消耗和工艺耗时。
另外多晶硅沉积对洁净度的要求非常高,因此激光掺杂也需放置在掺杂多晶硅层沉积之后。激光掺杂后,就进行高温晶化退火,这一步的温度较高(850-950℃),且时间较长,可以修复激光掺杂导致的晶格损伤。
酸洗去除正面高温晶化退火过程中的氧化层或者高温磷扩散产生的绕扩PSG(磷硅玻璃)、碱洗去除正面绕镀多晶硅,此时去除正面绕镀多晶硅的碱浓度较低,激光掺杂区域在激光掺杂时也形成了一定厚度的氧化层,这个氧化层厚度足够抵挡此处的碱腐蚀。
最后就是酸洗去除正面的BSG(硼硅玻璃),背面的PSG(磷硅玻璃),完成背面氧化铝生长和正反面钝化减反射层沉积,最后完成印刷金属浆料烧结,增加光/电注入可以进一步提升电性能。
表3本发明实施例与对比例电性能比较
本发明申请实施例取一组与常规TOPcon电池一组进行电性能测试,得到二者对比值,从表3的对比结果来看开路电压和短路电流均有明显提升,开路电压提升显著,能达到721mV以上,本发明的新型N型TOPcon电池扩硼SE结构,有更优的最终电性能表现;具体表现参见附图4-本申请一种扩硼SE结构的N型TOPCon电池的扩硼ECV曲线图,在激光掺杂后,激光掺杂区的峰值浓度今略微降低至3-15E+18cm-3,但是推进结深明显增加至>1μm,深结能够与银铝浆烧结后的铝钉刺充分地接触,形成较好的铝硅接触,显著降低接触电阻;参见附图5,本申请的SE硼扩技术,能将常规硼扩散的接触电阻值从约1.77mohm*cm2降低至0.83mohm*cm2,从而提升由接触改善带来的电池电性能参数。
从上述表征参数也体现出了本发明申请电池制备工艺的简化,能够有效提升电池的各项电性能参数。正面结构使得硼扩散区为轻掺高方阻区,减少浅掺杂区的复合,提高入射光的短波响应,使得Voc、Isc增益明显,同时激光掺杂区为重掺的低方阻区,减少前金属电极的接触电阻,使得短路电流、填充因子都得到较好的改善,从而提高转换效率。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (11)
1.一种扩硼SE结构的N型TOPCon电池制作方法,其特征在于,提供N型硅片,采用硼扩散轻掺杂在硅片正面形成轻掺高方阻区,酸洗去除硅片背面氧化层,硅片背面碱抛光后,生长隧穿氧化层,沉积掺磷多晶硅层,对硅片正面进行图形化的选择性的激光掺杂形成重掺接触区,而后进行高温晶化退火工艺,同时对激光导致的晶格缺陷进行修复;或者沉积本征多晶硅,正面采用激光掺杂形成重掺杂接触区,然后经高温磷扩散,然后酸洗去除硅片正面氧化层或者绕扩PSG层,碱洗去除硅片正面绕镀多晶硅层,酸洗去除硅片正面的BSG和硅片背面的PSG层,以及形成硅片正反面的钝化层和减反层,印刷烧结形成SE结构的N型TOPCon电池。
2.根据权利要求1所述的一种扩硼SE结构的N型TOPCon电池制作方法,其特征在于,所述N型硅片作为衬底材料,通过清洗制绒使硅片表面产生金字塔状表面结构。
3.根据权利要求1所述的一种扩硼SE结构的N型TOPCon电池制作方法,其特征在于,硼扩轻掺杂高方阻区扩散方阻控制在150-250ohm/口,峰值浓度为5-20E+18cm-3,结深0.3-0.8μm。
4.根据权利要求1所述的一种扩硼SE结构的N型TOPCon电池制作方法,其特征在于,激光波长为355~1064nm,激光功率为20~1000W,可以是脉冲激光,也可以是连续激光,扫描速度为5~70m/s,光斑尺寸为50~150μm。
5.根据权利要求1所述的一种扩硼SE结构的N型TOPCon电池制作方法,其特征在于,激光掺杂区的峰值浓度:3-15E+18cm-3,结深>1μm,方阻控制在50-130ohm/口。
6.根据权利要求1所述的一种扩硼SE结构的N型TOPCon电池制作方法,其特征在于,经激光掺杂后,激光掺杂区的反射率上升≤1%,绒面金字塔结构几乎不受损伤。
7.根据权利要求1所述的一种扩硼SE结构的N型TOPCon电池制作方法,其特征在于,钝化后激光掺杂区相比非激光掺杂区的电性能,反向饱和电流密度J0上升的幅度≤20fA/cm2,Voc的下降幅度≤20mV。
8.根据权利要求1所述的一种扩硼SE结构的N型TOPCon电池制作方法,其特征在于,激光掺杂区接触电阻≤1.5mohm*cm2,金属接触J0≤400fA/cm2。
9.根据权利要求1所述的一种扩硼SE结构的N型TOPCon电池制作方法,其特征在于,可以采用先沉积掺磷多晶硅,再激光掺杂,最后高温晶化退火的方式;也可以采用沉积先形成本征多晶硅,再激光掺杂,最后高温磷扩散形成掺杂多晶硅;沉积多晶硅可以采用LPCVD或者PECVD等方式。
10.根据权利要求1所述的一种扩硼SE结构的N型TOPCon电池制作方法,其特征在于,在激光掺杂后增加简单清洗工序,降低掺杂过程中的污染可能性。
11.根据权利要求1所述的一种扩硼SE结构的N型TOPCon电池制作方法,其特征在于,激光掺杂工序在高温晶化退火工艺或者高温磷扩散之后进行。
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CN117352597A (zh) * | 2023-12-05 | 2024-01-05 | 一道新能源科技股份有限公司 | 一种太阳能电池的制备方法、太阳能电池和用电设备 |
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