CN112349802B - 一种铸锭单晶或多晶非晶硅异质结太阳电池的制作方法 - Google Patents
一种铸锭单晶或多晶非晶硅异质结太阳电池的制作方法 Download PDFInfo
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Abstract
本发明涉及一种以铸锭单晶或多晶为衬底的非晶硅异质结太阳电池片的制作方法,它包括以下步骤:1)将铸锭单晶(或多晶)硅片进行单面抛光制绒;2)在制绒面上形成第一钝化层;3)在第一钝化层上形成本征多晶硅层;4)硅片两面进行磷扩散处理;5)去除扩散层;6)在去除扩散层后的一面形成第二钝化层;7)在硅片两面沉积透明导电膜层;8)在硅片的正反面上形成金属电极。本发明中用薄氧化层叠加多晶掺磷层取代传统的非晶硅本征层和掺磷层,用多晶硅薄膜取代非晶硅薄膜,降低材料的吸光系数,同时提高背电场的导电性,有利于提高电池的短路电流和填充因子。
Description
技术领域
本发明属于太阳电池领域,具体涉及一种以铸锭单晶或多晶为衬底的非晶硅异质结太阳电池片的制作方法。
背景技术
近年来,太阳能作为取之不尽,用之不竭的清洁能源,越来越受各国的青睐。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、类单晶硅片和多晶硅片。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,采用以铸锭单晶或多晶为衬底太阳能硅片来取代传统单晶硅片,有利降低生产生产,提高企业竞争力。
铸锭单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,类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。
然而铸锭单晶,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,按照常规异质结太阳电池的制备方法,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。
因此,为了解决上述存在的技术问题,需要寻找一种适合铸锭单晶或多晶类硅片有效钝化方式,来减少硅片体内和表面的缺陷密度,减少载流子的复合,提升钝化水平和载流子的传输水平,使得类单晶硅片能按照传统的高效电池片制作流程进行,获得高效的电池转换效率。
发明内容
本发明的目的在于提供一种铸锭单晶或多晶非晶硅异质结太阳电池的制作方法。其能够解决现有技术中,太阳电池开路电压低,转换效率不高,产品没有竞争力等问题。
本发明的目的通过如下技术方案实现:
一种铸锭单晶或多晶非晶硅异质结太阳电池的制作方法,它包括以下步骤:
1)将铸锭单晶(或多晶)硅片进行单面抛光、制绒,织构化表面纹理;
此步骤将铸锭单晶(或多晶)片单面进行抛光、制绒,织构化表面纹理,而另一面保持原有的硅片切割的机械损伤层状态;
2)在铸锭单晶(或多晶)硅片的制绒面上,通过氧化形成以氧化硅为主要成分的第一钝化层;
3)在所述第一钝化层上形成本征多晶硅层;
4)将铸锭单晶(或多晶)硅片的两面进行磷扩散处理;其中,第一钝化层上的本征多晶硅层,在磷扩散处理过程中形成N型多晶硅层;
5)去除所述N型多晶硅层的铸锭单晶(或多晶)硅片的另一面的PSG层及磷在体硅中的扩散层;即将铸锭单晶或多晶硅片最初未钝化的一面(即保持原有的硅片切割的机械损伤层状态的一面)所形成的PSG层及磷在体硅中的扩散层除去。
6)在去除所述扩散层后的一面形成第二钝化层,并在所述第二钝化层上形成P型非晶硅或者微晶层;
所述第二钝化层实质上包含本征的非晶硅、或者掺杂剂浓度比所述p型非晶硅层低的非晶硅。
7)在经步骤6)后的铸锭单晶(或多晶)硅片两面沉积透明导电膜层;
8)在经步骤7)后的铸锭单晶(或多晶)硅片的正反面上形成金属电极,铸锭单晶或多晶非晶硅异质结太阳电池制作完成。
步骤3)中本征多晶硅层通过PECVD(等离子增强化学气相沉积)或LPCVD(低压化学气相沉积)形成,优选地用LPCVD沉积;即多晶硅沉积所用的设备可以用PECVD(等离子增强化学气相沉积)、LPCVD(低压化学气相沉积),优选地用LPCVD沉积;
步骤4)进行磷扩散处理时,在高温扩散过程中通入气体POCl3、O2以及N2,在退火过程中通入O2和N2;其中,扩散温度控制为700-1100℃之间,炉管的压力扩散时控制为50-300mbar之间、扩散时间控制在5-30min。
步骤4)将硅片进行双面磷扩散处理,磷扩散一方面是对多晶硅进行N型掺杂,另一方面磷原子从非多晶面渗透到体硅中进行磷扩散吸杂。
步骤5)中扩散层的去除厚度为10-20um。步骤5)中去除另一面的PSG层及磷在体硅中的扩散层,一般去除扩散层的厚度为10-20um,优选地15um左右。
步骤6)中第二钝化层通过PECVD、Hot wire CVD或LPCVD形成。即所述第二钝化层薄膜的形成,沉积方式可以用PECVD、Hot wire CVD(热丝化学气相沉积)、LPCVD等CVD设备,优选地用PECVD设备。优选地用PECVD设备沉积第二钝化层薄膜,工艺气体包含硅烷、氢气的全部或组合;
步骤7)中对铸锭单晶(或多晶)硅片两面沉积透明导电膜层时,N型多晶硅层上形成的透明导电膜比第二钝化层上的P型非晶硅或微晶层上的透明导电膜薄薄5-20%。
步骤7)中沉积的透明导电膜层为含一种或多种不同金属掺杂的氧化铟膜层或氧化锌膜层。如所述透明导电膜层可以是含一种或多种不同金属掺杂(如锡、钨、钛等)的氧化铟膜层,如ITO、IWO、ITiO等;或者含一种或多种不同金属掺杂(如铝、铟、镓等)的氧化锌膜层,如AZO、GZO、IZO等。优选地用ITO(即含锡掺杂的氧化铟膜层)。
步骤8)中采用印刷银浆或电镀铜的方式形成金属电极。所述金属电极可以是栅线电极,即栅线电极的形成,可以是印刷银浆,也可以是电镀铜方式;
本发明所述步骤2)在硅片制绒面上形成以氧化硅为主要成分的第一钝化层、步骤3)形成本征多晶硅层以及步骤4)进行磷扩散处理,这些工艺的组合实质上用薄氧化层叠加多晶掺磷层取代传统的非晶硅本征层和掺磷层,形成了异质结电池的背电场;
与此同时,多晶硅在磷扩散时,铸造单晶硅片另一面因没钝化层和多晶硅层覆盖,磷原子更容易通过原始硅片的表面扩散至体硅内,特别是铸造单晶(或多晶)存在晶界、位错缺陷等,磷扩散的速度更快,与金属杂质结合,达到PSG辅助吸杂钝化的作用。
在上述技术方案中,构造异质结背电场与PSG辅助钝化同步进行,有利于简化流程,缩短工艺时间。
较之现有技术而言,本发明的优点在于:
1.本发明中用薄氧化层叠加多晶掺磷层取代传统的非晶硅本征层和掺磷层,用多晶硅薄膜取代非晶硅薄膜,降低材料的吸光系数,同时提高背电场的导电性,有利于提高电池的短路电流和填充因子。
2.铸造单晶硅片在形成背电场的过程中,即多晶硅在磷扩散的过程中,同时处理体硅电池片中的金属杂质和位错缺陷等,达到PSG辅助钝化和工艺沉积同步进行的目的。
3.铸造单晶硅片在退火过程中有利于将体硅中晶粒位错进行重整,减少晶格缺陷。
4.部分工艺采用了LPCVD的设备取代传统的工艺中PECVD设备,降低流程中设备的使用成本,提高产品的竞争优势。
附图说明
图1是铸造单晶硅为衬底的非晶硅异质结太阳电池的常规制备流程示意图。
图2是本发明的铸造单晶硅为衬底的非晶硅异质结太阳电池的制备流程示意图。
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:
为了使本发明的目的、技术方案和优点更加清楚明白,以下结合具体实施例,并参照附图1、2,对本发明作进一步说明。
本发明提供一种铸造单晶硅为衬底的非晶硅异质结太阳电池制备方法,包括以下步骤:
S1、将铸造单晶(或多晶)硅片进行湿化学清洗,清洗溶液可以是碱液也可以是酸液,优选地所述清洗溶液用HF等酸液,HF酸质量百分比为1%-8%,去离子水质量百分比为92%-99%,硅片在HF酸溶液中的处理时间为1-6分钟,处理温度为20℃-30℃;
S2、将S1清洗后的铸锭单晶(或多晶)硅片单面抛光、制绒,织构化表面纹理;制绒所用的碱性溶液为氢氧化钾、制绒添加剂与水的混合液,其中氢氧化钾的质量分数为1%-5%,制绒添加剂的质量分数为0.5%-3%。制绒时间为8-12分钟,制绒温度为75℃-85℃;
所述制绒添加剂一般为碱性,主要成分是水、IPA(异丙醇)、NaOH(氢氧化钠)、弱酸盐以及若干表面活性剂组成。典型配方如下:以质量比计为:氢氧化钠0.1%~3%,异丙醇2%~10%,添加剂0.01%~2%,其余为水;其中添加剂的配方以质量比计为:葡萄糖、葡萄糖酸钠或葡萄糖酸钾0.001%~3%,聚氧乙烯醚100ppb~8000ppb,乳酸钠或柠檬酸钠0.001%~2%,丙二醇0.001%~2%,硅酸钠0.01%~6%,碳酸钠或碳酸氢钠0.001%~2%,其余为水;
常用的制绒方式是将硅片放入槽式溶液中,双面都会制绒,织构化表面纹理,然而要实现单面制绒的方式,可以用水上漂方式进行,即硅片的下面进入溶液中,上面露出溶液,在传动的过程中,只对硅片的下方进行抛光、制绒与清洗;也可以在硅片的一面镀氮化硅等保护层,然后进行常规槽式抛光、制绒,这样有保护层的一面在溶液不会被抛光,出绒,从而实现单面制绒,最后再将保护层氮化硅一起腐蚀清洗干净;
优选地,本实施例中采用氮化硅保护另一面方式进行,即在硅片的一面镀氮化硅保护层,另一面裸露,采用槽式制绒清洗方式,镀有氮化硅保护层的一面在溶液能够阻挡溶液的刻蚀,使得硅表面不会被抛光和出绒,最后再将保护层氮化硅过1%-10%的HF酸和纯水清洗干净;
所述的氮化硅膜层可以用LPCVD、PECVD等设备进行镀膜,优选地用PECVD镀膜,所通气体为氮气、硅烷、氨气、氢气中的全部或几种组合,温度控制在200-500℃,射频功率密度控制0.1-0.5w/cm2,沉积时间为30-150s,膜厚控制在
所述的氮化硅膜层要求能够忍耐碱性溶液的腐蚀,膜层性质为富氮类型,氮硅比大于3:4;
S3、在铸锭单晶(或多晶)片的制绒面上,形成以氧化硅为主要成分的第一钝化层;氧化硅的形成方式可以通臭氧氧化法、硝酸氧化法以及LPCVD(低压化学气相沉积)高温氧化法,优选地,用LPCVD高温氧化法,所通气体可以为O2或者O2、N2的混合气体。温度控制在500-700℃,沉淀的时间控制为2-15min,膜厚控制在
上述第一钝化层上形成本征多晶硅层,本征多晶硅层的形成可以通过PECVD、LPCVD设备镀膜,优选地用LPCVD设备沉积,所通气体可以为硅烷、氢气、氮气的全部或几种组合,温度控制在500-700℃,膜厚控制在沉淀的时间控制为3min-15min。
S4、在S3已形成本征多晶硅层的铸锭单晶(或多晶)片的两面进行磷扩散处理,在高温扩散过程中通入POCl3、O2、N2等气体,在退火过程中可以通入O2和N2。扩散温度范围为700-1100℃之间,炉管的压力扩散时为50-300mbar之间、扩散时间控制在5-30min;
通过三氯氧磷扩散后再进行退火处理,退火可以是高温退火的方式进行,也可以是微波退火方式进行,优选地用高温退火方式进行,退火过程可以包含了升温、恒温、降温过程的全部或者几个组合,退火温度可以为600-1100℃之间,退火气压为100-500mbar之间,退火时间控制在60-180min;
所述第一钝化层上的本征多晶硅层,在磷扩散的过程中形成N型多晶硅层,另一面因没钝化层和多晶硅层覆盖,将在硅片表面形成PSG层,且磷原子将通过原始硅片的表面扩散至体硅内,形成磷扩散层,特别是铸造单晶(或多晶)因位错缺陷等,磷扩散的速度更快,与金属杂质结合,达到PSG辅助钝化的作用;
S5、去除所述N型多晶硅层的铸锭单晶(或多晶)片的另一面的PSG(磷酸玻璃)层及磷在体硅中的扩散层。一般PSG层采用氢氟酸浸泡清洗方式进行,磷扩散层采用碱腐蚀抛光的方式进行,为了使得实施更加方便,可以采用水上漂方式进行分步腐蚀,水上漂即硅片的下面(即形成PSG层及磷扩散层的一面)进入溶液中,上面露出溶液,在硅片在机台滚轮传动的过程中,只对硅片的下方进行清洗、抛光或制绒;
硅片在机台滚轮上传动,传动的过程中硅片浸泡面进行了化学反应如抛光或制绒,传动腐蚀可以提高效率。
S6、在去除PSG层及磷扩散层的一面形成第二钝化层,和在所述第二钝化层上形成P型非晶硅或者微晶层。所述第二钝化层实质上包含本征的非晶硅、或者掺杂剂浓度比所述p型非晶硅层低的非晶硅,从而形成有效PN结;
所述本征非晶层或者掺杂剂浓度比所述p型非晶硅层低的非晶硅层一般采用PECVD沉积法,通入硅烷、氢气或者硅烷、氢气及乙硼烷掺杂气体,沉积功率密度为0.005-0.02w/cm2,沉积厚度为5-15nm,沉积时间为30-150s;
所述P型非晶硅层或微晶硅一般采用PECVD沉积法,通入硅烷、氢气及乙硼烷掺杂气体,沉积功率密度为0.005-0.03w/cm2,沉积厚度为3-10nm,沉积时间为50-250s,P型掺杂剂的浓度例如是1×1020atoms/cm3以上;
S7、将S6后的硅片进行透明导电层沉积,透明导电膜层可以是含一种或多种不同金属掺杂(如锡、钨、钛等)的氧化铟膜层,如ITO、IWO、ITiO等;或者含一种或多种不同金属掺杂(如铝、铟、镓等)的氧化锌膜层,如AZO、GZO、IZO等。优选地用ITO(即含锡掺杂的氧化铟膜层),一般ITO层采用PVD(物理气相沉积)的方式沉积,膜层透过率控制在90%-99%之间,方块电阻为10-100欧姆/方块,膜厚为50-120nm;
S8、金属栅线集成,最后在硅片正反面上形成金属栅线,便于后续IV测试。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种铸锭单晶或多晶非晶硅异质结太阳电池的制作方法,其特征在于:它包括以下步骤:
1)将铸锭单晶或多晶硅片进行单面抛光、制绒,织构化表面纹理;
2)在铸锭单晶或多晶硅片的制绒面上,通过氧化形成第一钝化层;
3)在所述第一钝化层上形成本征多晶硅层;
4)将铸锭单晶或多晶硅片的两面进行磷扩散处理;其中,第一钝化层上的本征多晶硅层,在磷扩散处理过程中形成N型多晶硅层;
5)去除带有N型多晶硅层的铸锭单晶或多晶硅片的另一面的PSG层及磷在体硅中的扩散层;
6)在去除所述扩散层后的一面形成第二钝化层,并在所述第二钝化层上形成P型非晶硅或者微晶层;
7)在经步骤6)后的铸锭单晶或多晶硅片两面沉积透明导电膜层;
8)在经步骤7)后的铸锭单晶或多晶硅片的正反面上形成金属电极,即完成铸锭单晶或多晶非晶硅异质结太阳电池的制作。
4.根据权利要求1所述的铸锭单晶或多晶非晶硅异质结太阳电池的制作方法,其特征在于:步骤3)中本征多晶硅层通过PECVD或LPCVD形成。
5.根据权利要求1所述的铸锭单晶或多晶非晶硅异质结太阳电池的制作方法,其特征在于:步骤4)进行磷扩散处理时,在高温扩散过程中通入气体POCl3、O2以及N2,在退火过程中通入O2和N2;其中,扩散温度控制为700-1100℃之间,炉管的压力扩散时控制为50-300mbar之间、扩散时间控制在5-30min。
6.根据权利要求1所述的铸锭单晶或多晶非晶硅异质结太阳电池的制作方法,其特征在于:步骤5)中扩散层的去除厚度为10-20um。
7.根据权利要求1所述的铸锭单晶或多晶非晶硅异质结太阳电池的制作方法,其特征在于:步骤6)中第二钝化层通过PECVD、Hot wire CVD或LPCVD形成。
8.根据权利要求1所述的铸锭单晶或多晶非晶硅异质结太阳电池的制作方法,其特征在于:步骤7)中对铸锭单晶或多晶硅片两面沉积透明导电膜层时,N型多晶硅层上形成的透明导电膜层 比第二钝化层上的P型非晶硅或微晶层上的透明导电膜层 薄5-20%。
9.根据权利要求1所述的铸锭单晶或多晶非晶硅异质结太阳电池的制作方法,其特征在于:步骤7)中沉积的透明导电膜层为含一种或多种不同金属掺杂的氧化铟膜层或氧化锌膜层。
10.根据权利要求1所述的铸锭单晶或多晶非晶硅异质结太阳电池的制作方法,其特征在于:步骤8)中采用印刷银浆或电镀铜的方式形成金属电极。
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