CN108389929A - 一种选择性接触晶体硅异质结太阳能电池及其制备方法 - Google Patents
一种选择性接触晶体硅异质结太阳能电池及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种选择性接触晶体硅异质结太阳能电池及其制备方法,电池结构分为若干层,自上而下为:Ag/ITO/MoOx/SiOy/n‑c‑Si/SiOy/LiFz/Al;制备时:利用硝酸氧化法在硅片前后表面生长一层超薄SiOy层(1.0~1.3nm),然后在硅片正面依次生长MoOx、ITO、Ag,硅片背面依次生长LiFx和Al。本发明分别利用MoOx的高功函数、LiFz的低功函数特性弯曲MoOx/c‑Si和LiFz/c‑Si异质结能带,实现对光生载流子进行选择性分离。
Description
技术领域
本发明属于太阳能电池领域,涉及了一种选择性接触的新型晶体硅异质结太阳能电池结构及其制备方法。
背景技术
在太阳能电池中,高效率的光生载流子(电子-空穴对)的分离、输运和收集对电池整体性能的提高至关重要。目前工业化量产的晶体硅太阳能电池片是通过p型硅片表面的磷扩散获得p-n结,光照产生的载流子在p-n结产生的内建电场作用下被分离,然后分别被硅片表面的前后两个电极收集。传统的晶体硅异质结太阳能电池主要以氢化非晶硅(a-Si:H)为掺杂层,但a-Si:H具有较高的缺陷态密度和较窄的禁带宽度(~1.8eV),即使在太阳能电池中的厚度只有几纳米,也会在紫外光和可见光范围内导致显著的寄生光吸收,而这对光电流的产生没有作用,反而会影响器件的性能。此外,通常制备n型和p型a-Si:H需要使用PECVD并用到易燃易爆的特种气体—硅烷、磷烷和硼烷,使得工艺复杂并且成本较高。因此,选择一种可替代a-Si:H的低风险、易制备并能降低制造成本的材料是非常重要的。
假设能找到这样一种材料或结构,它满足:(1)拥有良好的表面钝化效果;(2)可以高效传输一种载流子。那么就可以把这一结构用于电池的表面,形成即满足钝化要求,又无需开孔即可传输电流的钝化接触。这种通过外加材料或结构来弯曲能带,而非电池吸收层本身掺杂,从而实现对载流子选择性通过的表面接触设计,这就是被称为选择性接触电池(即非掺杂电池),而这一设计与传统的通过扩散得到p-n结电池有本质的不同。MartinGreen在1977年就提出了无需扩散p-n结的金属-绝缘层-半导体(MIS)结构太阳能电池。1985年,Eli Yablonovitch提出了理想的太阳能电池应该是“采用两个异质结来设计”,即将吸收材料置于两个宽带隙材料之间。SunPower的创始人之一Richard Swanson在2004年预测接近理论效率的晶体硅太阳能电池应“在硅和金属之间,放置一层宽带隙材料构成异质结”,这些结构都指向选择性接触电池。
过渡金属氧化物—三氧化钼(MoO3)具有高功函数(~6.9eV)、宽带隙(~3.3eV)、低熔点(~795℃)等特点,并可以在低温下利用真空热蒸镀、化学溶液等低成本的方法制备,作为空穴传输层已经被成功应用于有机光电器件中。由于成本低、制备方法简单,氧化钼作为晶体硅异质结电池的空穴选择性接触材料还是有着很好的商业化应用前景。通过真空热蒸发三氧化钼固相粉末获得的非化学计量比的氧化钼(MoOx,0<x<3)薄膜,在低于导带的位置形成氧空位衍生缺陷带,使得氧化钼薄膜表现出n型的半金属特征。由于在MoOx/c-Si界面只存在微弱的费米能级扎钉效应现象,当MoOx与晶体硅接触时,在p型晶体硅(p-c-Si)表面可以期望形成一个空穴堆积层,而在n型晶体硅(n-c-Si)表面形成空穴反型层,这有利于空穴从晶体硅中输运到外部电极,从而可以降低接触电阻,提高了载流子的收集效率。与HIT电池中高掺杂的非晶硅相比,MoOx存在大量的本征氧空位,利用MoOx取代HIT电池中的p型非晶硅层作为空穴选择性接触层,从而可以避免由于掺杂对电池性能造成的不利影响。同时,与非晶硅或微晶硅相比,MoOx具有较大的带隙宽度,可以减少HIT电池和隧穿氧化层钝化接触电池中存在的寄生吸收损失。
具有低功函数的碱金属氟化物,如氟化锂(LiF,2.86eV)、氟化钾(KF,2.74eV)、氟化铯(CsF,2.67eV)等,作为电子传输层已经被用于有机光电器件中。LiF是最早应用于有机光电器件,LiF与金属铝(Al)形成的接触可以减低Al的功函数,使得LiF与有机材料形成近似欧姆接触,可以增强电子的注入。非化学计量比的LiFz(0<z<1)薄膜作为晶体硅异质结电池的电子选择性接触材料,LiFz与晶体硅形成的接触比与有机材料形成的接触更接近欧姆接触,这样更有利于电子从晶体硅输运到外部电极,但是,这种结构设计目前还未见公开的报道。
发明内容
本发明的目的是提供一种选择性接触的晶体硅异质结太阳能电池,能够提高载流子的收集效率,减少界面复合损失。
本发明的另一目的是提供上述太阳能电池的制备方法。
为此,本发明采用的技术方案是这样的:
一种选择性接触晶体硅异质结太阳能电池,其特征在于:电池结构分为若干层,自上而下为:Ag/ITO/MoOx/SiOy/n-c-Si/SiOy/LiFz/Al,其中Ag为金属银,ITO为掺锡氧化铟透明导电薄膜,MoOx为氧化钼,x=2.3~3.0,SiOy为氧化硅,y=1.5~2.0,n-c-Si为n型单晶硅,LiFz为氟化锂,z=0.8~1.0,Al为金属铝。
其中Ag为指叉状电极。
为实现第二个发明目的,所采用的技术方案是这样的:一种选择性接触晶体硅异质结太阳能电池的制备方法,包括如下步骤:
1)硅片的清洗:把硅片放入浓度为10~15%的KOH溶液中,在80~85℃温度下反应15~20分钟,然后采用RCA标准清洗法对硅片进行表面清洗,清除表面污染杂质,再把硅片放入浓度为3~5%的HF溶液中浸泡2~3分钟;
2)生长超薄SiOy层:利用油浴加热的方式把61-68wt%的HNO3溶液加热到113-121℃,然后把步骤1)清洗好的硅片浸泡在其中,时间为10~20分钟;
3)生长LiFz层和Al电极:将步骤2)所得的硅片放入蒸镀腔,腔体的真空度优于1×10-3Pa,硅片的正面用掩膜板盖住,并用锡箔包裹,首先在硅片的背面蒸镀LiFz层,速率为0.05nm/s,时间为10~30s,随后在LiFz层上面蒸镀Al电极,速率为1nm/s,时间为200~300s;
4)生长MoOx、ITO和Ag电极:将步骤3)所得的硅片放入溅射腔,腔体的本底真空度优于1×10-3Pa,工作气体为氩气,工作气压为0.5Pa,溅射功率为25W,衬底温度为200℃。首先,依次在硅片正面生长10nm厚的MoOx和80nm厚的ITO层。然后,利用掩膜板在ITO上面溅射一层指叉状的Ag电极,厚度为200~500nm。
减少光生载流子在硅片体内和表面的复合对提高载流子的收集效率很重要,因此,MoOx/c-Si和LiFz/c-Si异质结界面钝化是晶体硅异质结太阳能电池设计和优化的关键。在传统的HIT晶体硅异质结设计中,c-Si两侧通过n型和p型的a-Si:H薄膜实现电子和空穴的收集,为了减少载流子的复合,本发明在c-Si和掺杂的a-Si:H薄膜之间各插入一层高质量的本征a-Si:H钝化层以降低降低界面态外。因此,为了降低MoOx/c-Si和LiFz/c-Si异质结界面态密度,减少界面复合损失,在MoOx和LiFz与c-Si之间分别插入一层氧化硅(SiOy)作为钝化层。本发明分别利用MoOx的高功函数、LiFz的低功函数特性弯曲MoOx/c-Si和LiFz/c-Si异质结能带,实现对光生载流子进行选择性分离,而不是利用晶体硅材料的吸收层掺杂形成p-n结内建电场分离光生载流子,从而能够完成发明目的。
附图说明
图1是本发明的选择性接触晶体硅异质结太阳能电池结构示意图。
具体实施方式
如图1所示,本实施例所述太阳能电池结构分为若干层,自上而下为:Ag/ITO/MoOx/SiOy/n-c-Si/SiOy/LiFz/Al,其中Ag为金属银,ITO为掺锡氧化铟透明导电薄膜,MoOx为氧化钼,x=2.3~3.0,SiOy为氧化硅,y=1.5~2.0,n-c-Si为n型单晶硅,LiFz为氟化锂,z=0.8~1.0,Al为金属铝。
制备方法为:首先对单晶硅片进行表面化学处理,去除损伤层和清除表面污染杂质,其次利用硝酸氧化法在硅片前后表面生长一层超薄SiOy层(1.0~1.3nm),然后在硅片正面依次生长MoOx、ITO、Ag,硅片背面依次生长LiFx和Al。
具体步骤如下:
1)硅片的清洗
实验用的硅片为n型直拉单晶硅片,双面非抛光,厚度190μm,电阻率2~5Ω·cm。首先,把硅片放入浓度为10~15%的KOH溶液中,在80~85℃温度下浸泡15min,以去除硅片表面的损伤层。其次,采用RCA标准清洗法对硅片进行表面清洗,清除表面污染杂质,RCA是一种目前普遍使用的湿式化学清洗法,是1965年由美国新泽西州普林斯顿RCA实验室Kern和Puotinen等人提出的。最后,把硅片放入浓度为3~5%的HF溶液中浸泡3min,去除硅片表面的自然氧化层。
2)硝酸氧化法生长超薄SiOy层
利用油浴加热的方式把重量百分比为61~68的HNO3溶液加热到121~123℃,,然后把经过第一步清洗好的硅片浸泡在其中,时间为10min。利用X射线光电子能谱(XPS)测试分析,可以获得SiOy层的y为2.3~3.0,厚度为1.0~1.3nm。
3)热蒸镀法生长LiFz层和Al电极
把表面已经生长一层超薄SiOy层的硅片放入蒸镀腔,腔体的真空度优于1×10- 3Pa,硅片的正面用掩膜板盖住,并用锡箔包裹,首先在硅片的背面蒸镀LiFz层,速率为0.05~0.1nm/s,时间为20s。利用XPS测试分析,可以获得LiFz层的z为0.8~1.0,厚度为1.2~2.3nm。随后,在LiFz层上面蒸镀金属Al电极,厚度为200~300nm。
4)磁控溅射法生长MoOx、ITO和Ag电极
在背面已经生长的LiFz层和Al电极的硅片放入溅射腔,腔体的本底真空度优于1×10-3Pa,工作气体为氩气,工作气压为0.5Pa,溅射功率为25W,衬底温度为200℃。首先,依次在硅片正面生长10nm厚的MoOx和80nm厚的ITO层,利用XPS测试分析,x为2.3~3.0。然后,利用掩膜板在ITO上面溅射一层指叉状的金属Ag电极,厚度为200~500nm。
5)电池光电性能测试
标准测试条件(AM1.5,100mW/cm2,25℃)下,电池的开路电压为0.43V,短路电流密度为21.8mA/cm2,填充因子为36%,光电转换效率为3.37%。目前制备的新型选择性接触晶体硅异质结太阳能电池—Ag/ITO/MoOx/SiOy/n-c-Si/SiOy/LiFz/Al的效率很低,是因为电池的各部分参数还有待优化,比如晶体硅表面制绒、MoOx、LiFz层的光电性能、SiOy的介电性能等需要进一步优化设计。尽管如此,本发明提出的无需掺杂的晶体硅异质结太阳能电池的设计思路,为找到一种选择一种可替代掺杂a-Si:H的晶体硅异质结电池提供可借鉴的指导意义,因为通常制备n型和p型a-Si:H需要使用易燃易爆有剧毒的气体—硅烷、磷烷和硼烷。
Claims (2)
1.一种选择性接触晶体硅异质结太阳能电池,其特征在于:电池结构分为若干层,自上而下为:Ag/ITO/MoOx/SiOy/n-c-Si/SiOy/LiFz/Al,其中Ag为金属银,ITO为掺锡氧化铟透明导电薄膜,MoOx为氧化钼,x=2.3~3.0,SiOy为氧化硅,y=1.5~2.0,n-c-Si为n型单晶硅,LiFz为氟化锂,z=0.8~1.0,Al为金属铝。
2.一种权利要求1所述太阳能电池的制备方法,包括如下步骤:
1)硅片的清洗:把硅片放入浓度为10~15%的KOH溶液中,在80~85℃温度下反应15~20分钟,然后采用RCA标准清洗法对硅片进行表面清洗,清除表面污染杂质,再把硅片放入浓度为3~5%的HF溶液中浸泡2~3分钟;
2)生长超薄SiOy层:利用油浴加热的方式把61-68wt%的HNO3溶液加热到113-121℃,然后把步骤1)清洗好的硅片浸泡在其中,时间为10~20分钟;
3)生长LiFz层和Al电极:将步骤2)所得的硅片放入蒸镀腔,腔体的真空度优于1×10- 3Pa,硅片的正面用掩膜板盖住,并用锡箔包裹,首先在硅片的背面蒸镀LiFz层,速率为0.05nm/s,时间为10~30s,随后在LiFz层上面蒸镀Al电极,速率为1nm/s,时间为200~300s;
4)生长MoOx、ITO和Ag电极:将步骤3)所得的硅片放入溅射腔,腔体的本底真空度优于1×10-3Pa,工作气体为氩气,工作气压为0.5Pa,溅射功率为25W,衬底温度为200℃。首先,依次在硅片正面生长10nm厚的MoOx和80nm厚的ITO层。然后,利用掩膜板在ITO上面溅射一层指叉状的Ag电极,厚度为200~500nm。
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