CN114628538A - N型掺氧型微晶作为窗口层的异质结光伏电池的制备方法 - Google Patents
N型掺氧型微晶作为窗口层的异质结光伏电池的制备方法 Download PDFInfo
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Abstract
本发明公开了N型掺氧型微晶作为窗口层的异质结光伏电池的制备方法,所述方法包括如下步骤:硅片预清洗;PSG氧化层沉积及高温处理;去除表面的PSG/USG氧化层,用碱液去损伤和制绒,并清洗;PECVD镀膜制备表面钝化膜层和掺杂膜层;PVD磁控溅射制备透明导电膜;表面形成金属栅线。本发明保留N型电极前置的技术特点,改造N型非晶硅掺杂层为含氧型N型微晶,通过提升能带带隙导致光学吸收的降低、调节窗口层的光学折射率优化减反效果,短路电流有较大提升,可以匹配传统直拉单晶HIT电池片,传统上成本较低的铸锭单晶方式也可以导入异质结的规模量产,对持续降本非常有利,同时现有的多晶炉可以经简单改造,形成有效产能,减少设备的投资浪费。
Description
技术领域
本发明涉及太阳能电池技术领域,尤其涉及N型掺氧型微晶作为窗口层的异质结光伏电池的制备方法。
背景技术
现有的异质结光伏电池技术是在单晶硅片的正反表面沉积本征型非晶硅,然后在入光面镀P型掺杂非晶硅膜层,背面镀N型掺杂非晶硅膜层。最后双面ITO镀膜及银浆印刷形成金属栅线电极。由于P型非晶硅膜层的电导和透光性较差,2006年Sanyo采用了N型掺杂面朝前的技术方案,并递交相关专利。以上异质结电池片技术采用N型掺杂单晶硅片,且对硅片的单晶品质要求极高,要求本征少子寿命至少3毫秒以上。HIT异质结技术对少子寿命的要求高于PERC或TopCon技术,其中N面朝前的HIT对单晶品质和少子寿命的要求还要高于P面朝前的HIT电池。对硅片品质的严苛要求导致了硅片成本居高不下,难以形成HIT针对PERC的完全技术更替或升级。
采用HIT量产技术的方案对硅片品质要求太高,难以普及推广。如果采用较低品质单晶硅片或铸锭单晶,载流子的平均自由程较短,难以及时从两端电极导出形成最大化光电流,表现为短路电流或填充因子较低。就算窗口层采用能带带隙较宽的N型非晶硅,异质结(HIT)电池技术仍然表现为短路电流相对PERC或TopCon技术较低。同时采用N型电极前置的设计,如果采用品质较低的铸锭单晶或多晶硅片,电池的短路电流和电池片的有效少子寿命强烈相关,同时显著低于普通运用直拉法单晶制作的HIT电池。对发电端电站用户而言,这将带来系统配置和组件匹配的额外困难。
铸锭单晶硅片采用传统多晶炉铸造,在炉子底部铺上品质较高的单晶籽晶,引导多晶料的有序晶向生长。相对于传统的多晶生长技术,片内单一单晶的占比较高,体少子寿命明显高于传统多晶(<100微秒),但是仍然低于主流的直拉法生长得到的CZ单晶硅片(>2毫秒),总体性能在两者之间。传统上铸锭单晶硅片不适于高转化效率的电池技术,例如异质结(HIT/HJT/HDT)和TopCon技术。
发明内容
针对上述问题,本发明提供了保留N型电极前置(向光面)的技术特点,改造N型非晶硅掺杂层为含氧型N型微晶,由于通过提升能带带隙导致光学吸收的降低、调节窗口层的光学折射率优化减反效果,以铸锭单晶硅片制作的HIT电池短路电流有较大提升,可以匹配传统直拉单晶HIT电池片的N型掺氧型微晶作为窗口层的异质结光伏电池的制备方法。
为解决上述技术问题,本发明所采用的技术方案是:N型掺氧型微晶作为窗口层的异质结光伏电池的制备方法,所述方法包括如下步骤:
硅片预清洗;
PSG氧化层沉积及高温处理;
去除表面的PSG/USG氧化层,用碱液去损伤和制绒,并清洗;
PECVD镀膜制备表面钝化膜层和掺杂膜层;
PVD磁控溅射制备透明导电膜;
表面形成金属栅线。
进一步的,所述硅片预清洗采用槽式溶液清洁,除去表面的有机污染和大型颗粒。
进一步的,所述PSG氧化层沉积及高温处理为硅片干燥后,导入PSG高温扩散炉,载体是石英舟或SiC舟,处理温度在700-1000摄氏度之间,PSG钝化工艺需要首先形成一层PSG氧化层,PSG氧化层包括部分USG薄膜,总厚度在20埃-600埃之间,形成PSG膜层之后,施加一个高温退火和磷扩散的过程,包括升温、恒温和降温段,整体高温扩散炉的工艺时间在0.5小时-5小时之间。
进一步的,所述去除表面的PSG/USG氧化层,铸锭单晶硅片经过氢氟酸或BOE溶液处理,用碱液去损伤和制绒,形成粗糙化的陷光结构,再经历RCA清洁,最后HF溶液去表面氧化层,去离子水清洁及表面干燥去水。
进一步的,所述PECVD镀膜制备表面钝化膜层和掺杂膜层为在硅片背面依次镀背面本征型非晶硅层、P型掺杂非晶硅层,硅片正面依次镀正面本征型非晶硅层、N型掺杂非晶硅层,本征型非晶硅层的工艺气体包含硅烷、氢气、CO2和CH4的全部或几种组合,制备P型掺杂非晶硅层的工艺气体包含SiH4、H2、CO2、乙硼烷、TMB的全部或几种组合,制备P型掺杂非晶硅层的工艺气体包含SiH4、H2、CO2、CH4、乙硼烷、TMB的全部或几种组合,制备N型掺杂非晶硅层的工艺气体包含SiH4、H2和磷烷。
进一步的,所述N型掺杂非晶硅层为含氧型微晶膜层,含氧型微晶膜层包含三个阶段工艺:(1)首先是高H2/SiH4比例的非含氧型孵育层,促进微晶态的形成;(2)含氧型微晶层,含氧型微晶μc-SiOx:H(N)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(N)在制绒面上的厚度为40-200埃,优选地为60-120埃;(3)非含氧型的接触层,降低和TCO膜层之间的接触电阻。
进一步的,所述PVD磁控溅射制备透明导电膜,透明导电膜包含氧化锡、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,掺杂材料至少含有氧化锡、氧化钛、氧化锌或氧化镓的,按重量占比0-10%。
进一步的,所述表面形成金属栅线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,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。
由上述对本发明结构的描述可知,和现有技术相比,本发明具有如下优点:
1、本发明经过钝化处理的铸锭单晶的有效体少子寿命接近2毫秒,针对铸锭单晶和异质结电池技术相结合的方式,电性较为稳定,同时短路电流和采用高品质单晶硅片的HIT电池较接近,有利于电站设计匹配和相互置换。电池结构优化,可以适应异质结电池技术的量产需求,发电效率显著优于现在主流的单晶PERC量产水平。
2、本发明保留N型电极前置(向光面)的技术特点,改造N型非晶硅掺杂层为含氧型N型微晶,由于通过提升能带带隙导致光学吸收的降低、调节窗口层的光学折射率优化减反效果,以铸锭单晶硅片制作的HIT电池短路电流有较大提升,可以匹配传统直拉单晶HIT电池片,传统上成本较低的铸锭单晶方式也可以导入异质结的规模量产,对异质结的持续降本非常有利,同时现有的多晶炉可以经简单改造,形成有效产能,减少设备的投资浪费。
附图说明
构成本申请的一部分的附图用来提供对本发明的进一步理解,本发明的示意性实施例及其说明用于解释本发明,并不构成对本发明的不当限定。在附图中:
图1为本发明N型掺氧型微晶作为窗口层的异质结光伏电池的制备方法的流程图;
图2为本发明形成金属栅线之前的异质结光伏电池结构截面图;
图3为本发明形成金属栅线之后的N型导电掺氧型微晶作为窗口层的异质结光伏电池截面图
图4为本发明N型掺杂层的改善对电池片光电流的影响图;
图5为本发明N型掺杂层(窗口层)非晶硅baseline方案和含氧型微晶的电性对比图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
铸锭单晶硅片采用传统多晶炉铸造,在炉子底部铺上品质较高的单晶籽晶,引导多晶料的有序晶向生长。相对于传统的多晶生长技术,片内单一单晶的占比较高,体少子寿命明显高于传统多晶(<100微秒),但是仍然低于主流的直拉法生长得到的CZ单晶硅片(>2毫秒),总体性能在两者之间。传统上铸锭单晶硅片不适于高转化效率的电池技术,例如异质结(HIT/HJT/HDT)和TopCon技术。如果采用所述发明,铸锭单晶的体少子寿命典型值接近2毫秒,经过本发明所述的电池结构优化,可以适应异质结电池技术的量产需求,发电效率显著优于现在主流的单晶PERC量产水平。
铸锭单晶晶锭经过金刚线或砂浆切割,形成厚度为130-250微米的硅片。虽然铸锭单晶的单晶比例较高,但是电池内部仍有较大比例的多晶晶界和晶格缺陷。参见图1的所述发明的工艺流程,在导入异质结生产工艺之前,需要经过2步预处理以达到最佳的晶界(grain boundary)钝化效果。
N型掺氧型微晶作为窗口层的异质结光伏电池的制备方法,所述方法包括如下步骤:
S01、硅片预清洗;采用槽式溶液清洁,除去表面的有机污染和大型颗粒。
S02、PSG氧化层沉积及高温处理;硅片干燥后,导入PSG高温扩散炉,载体是石英舟或SiC舟,处理温度在700-1000摄氏度之间,PSG钝化工艺需要首先形成一层PSG氧化层,PSG氧化层包括部分USG薄膜,总厚度在20埃-600埃之间,形成PSG膜层之后,施加一个高温退火和磷扩散的过程,包括升温、恒温和降温段,整体高温扩散炉的工艺时间在0.5小时-5小时之间。
S03、去除表面的PSG/USG氧化层,用碱液去损伤和制绒,并清洗;铸锭单晶硅片经过氢氟酸或BOE溶液处理,用碱液去损伤和制绒,形成粗糙化的陷光结构,再经历RCA清洁,最后HF溶液去表面氧化层,去离子水清洁及表面干燥去水。
S04、PECVD镀膜制备表面钝化膜层和掺杂膜层;PECVD设备电源采用13.56MHz、26MHz或40MHz,优选地采用13.56MHz,如图2所示,在硅片10背面依次镀背面本征型非晶硅层25、P型掺杂非晶硅层26,硅片10正面依次镀正面本征型非晶硅层21、N型掺杂非晶硅层22,本征型非晶硅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P型掺杂非晶硅层的工艺气体包含SiH4、H2、CO2、CH4、乙硼烷(B2H6)、TMB的全部或几种组合,制备N型掺杂非晶硅层的工艺气体包含SiH4、H2和磷烷(PH3);所述N型掺杂非晶硅层为含氧型微晶膜层,含氧型微晶膜层包含三个阶段工艺:(1)首先是高H2/SiH4比例的非含氧型孵育层,促进微晶态的形成;(2)含氧型微晶层,含氧型微晶μc-SiOx:H(N)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(N)在制绒面上的厚度为40-200埃,优选地为60-120埃;(3)非含氧型的接触层,降低和TCO膜层之间的接触电阻。
S05、PVD磁控溅射制备透明导电膜;如图2中的31和35,透明导电膜包含氧化锡、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,掺杂材料至少含有氧化锡、氧化钛、氧化锌或氧化镓的,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。如图4所示,比较baselineN型非晶和含氧型N型掺杂的微晶方案,由于含氧型微晶的带隙较宽,膜层的光学吸收随膜厚增长较慢。含氧型微晶的光学折射率有序地为2.5~2.6,介于TCO(1.8)和晶硅(3.5)之间,随着膜厚的增加,表面反射损失反而降低,和N型非晶硅的表现完全不同。综合效果而言,根据光学模拟结果(图4下图),采用8nm厚度的含氧型微晶(制绒面上厚度)比4纳米厚度的传统非晶提升光电流大约1%。对膜厚的低敏感性同时带来工艺上的稳定性。
S06、表面形成金属栅线;如图3所示,在PVD工艺之后施加金属栅线,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150-220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,如图3中的41和45,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(SMARTWIRE技术),表面只有一系列平行金属细栅线。
实施例1
P面和硅片接触的本征型氢化非晶硅(a-SiC:H)层,可以被掺氧(O)或掺碳(C)的本征型非晶硅代替。氧掺杂或碳掺杂可以提升本征型非晶硅的能带带隙,有利于钝化。氧掺杂的通用气体是CO2,碳掺杂的通用气体是CH4。
实施例2
在本发明中采用的金属栅线,除了低温退火银浆的丝网印刷方案之外,还可以采用铜电镀的方式形成。在铜电镀工艺形成金属栅线之后,表面采用含银或锡的表面覆盖层,减少铜的氧化,保证可焊接性。
本发明经过钝化处理的铸锭单晶的有效体少子寿命接近2毫秒,针对铸锭单晶和异质结电池技术相结合的方式,电性较为稳定,同时短路电流和采用高品质单晶硅片的HIT电池较接近,有利于电站设计匹配和相互置换。电池结构优化,可以适应异质结电池技术的量产需求,发电效率显著优于现在主流的单晶PERC量产水平。
本发明保留N型电极前置(向光面)的技术特点,改造N型非晶硅掺杂层为含氧型N型微晶,由于通过提升能带带隙导致光学吸收的降低、调节窗口层的光学折射率优化减反效果,以铸锭单晶硅片制作的HIT电池短路电流有较大提升,可以匹配传统直拉单晶HIT电池片,传统上成本较低的铸锭单晶方式也可以导入异质结的规模量产,对异质结的持续降本非常有利,同时现有的多晶炉可以经简单改造,形成有效产能,减少设备的投资浪费。
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 (8)
1.N型掺氧型微晶作为窗口层的异质结光伏电池的制备方法,其特征在于:所述方法包括如下步骤:
硅片预清洗;
PSG氧化层沉积及高温处理;
去除表面的PSG/USG氧化层,用碱液去损伤和制绒,并清洗;
PECVD镀膜制备表面钝化膜层和掺杂膜层;
PVD磁控溅射制备透明导电膜;
表面形成金属栅线。
2.根据权利要求1所述N型掺氧型微晶作为窗口层的异质结光伏电池的制备方法,其特征在于:所述硅片预清洗采用槽式溶液清洁,除去表面的有机污染和大型颗粒。
3.根据权利要求1所述N型掺氧型微晶作为窗口层的异质结光伏电池的制备方法,其特征在于:所述PSG氧化层沉积及高温处理为硅片干燥后,导入PSG高温扩散炉,载体是石英舟或SiC舟,处理温度在700-1000摄氏度之间,PSG钝化工艺需要首先形成一层PSG氧化层,PSG氧化层包括部分USG薄膜,总厚度在20埃-600埃之间,形成PSG膜层之后,施加一个高温退火和磷扩散的过程,包括升温、恒温和降温段,整体高温扩散炉的工艺时间在0.5小时-5小时之间。
4.根据权利要求1所述N型掺氧型微晶作为窗口层的异质结光伏电池的制备方法,其特征在于:所述去除表面的PSG/USG氧化层,铸锭单晶硅片经过氢氟酸或BOE溶液处理,用碱液去损伤和制绒,形成粗糙化的陷光结构,再经历RCA清洁,最后HF溶液去表面氧化层,去离子水清洁及表面干燥去水。
5.根据权利要求1所述N型掺氧型微晶作为窗口层的异质结光伏电池的制备方法,其特征在于:所述PECVD镀膜制备表面钝化膜层和掺杂膜层为在硅片背面依次镀背面本征型非晶硅层、P型掺杂非晶硅层,硅片正面依次镀正面本征型非晶硅层、N型掺杂非晶硅层,本征型非晶硅层的工艺气体包含硅烷、氢气、CO2和CH4的全部或几种组合,制备P型掺杂非晶硅层的工艺气体包含SiH4、H2、CO2、乙硼烷、TMB的全部或几种组合,制备P型掺杂非晶硅层的工艺气体包含SiH4、H2、CO2、CH4、乙硼烷、TMB的全部或几种组合,制备N型掺杂非晶硅层的工艺气体包含SiH4、H2和磷烷。
6.根据权利要求5所述N型掺氧型微晶作为窗口层的异质结光伏电池的制备方法,其特征在于:所述N型掺杂非晶硅层为含氧型微晶膜层,含氧型微晶膜层包含三个阶段工艺:(1)首先是高H2/SiH4比例的非含氧型孵育层,促进微晶态的形成;(2)含氧型微晶层,含氧型微晶μc-SiOx:H(N)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(N)在制绒面上的厚度为40-200埃,优选地为60-120埃;(3)非含氧型的接触层,降低和TCO膜层之间的接触电阻。
7.根据权利要求1所述N型掺氧型微晶作为窗口层的异质结光伏电池的制备方法,其特征在于:所述PVD磁控溅射制备透明导电膜,透明导电膜包含氧化锡、氧化钛、氧化锌或氧化镓掺杂的氧化铟薄膜,其中氧化铟是主体材料,按重量比占比90%以上,掺杂材料至少含有氧化锡、氧化钛、氧化锌或氧化镓的,按重量占比0-10%。
8.根据权利要求1所述N型掺氧型微晶作为窗口层的异质结光伏电池的制备方法,其特征在于:所述表面形成金属栅线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,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。
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2020
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