CN109216505A - 具备多晶硅钝化膜的晶体硅太阳电池的制备方法 - Google Patents
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明的具备多晶硅钝化膜的晶体硅太阳电池的制备方法包括:在硅片表面形成纳米绒面结构;在硅片前表面形成发射极;采用一步法湿法刻蚀去除磷硅玻璃并抛光硅片背面;在抛光后的硅片背面,先采用LPCVD沉积SiO,在硅片背面形成SiO2钝化层,再在SiO2钝化层上采用LPCVD沉积PolySi钝化层;采用PECVD设备,在硅片发射极和PolySi钝化层上沉积SiNx钝化层。
Description
技术领域
本发明涉及晶体硅太阳电池制备,具体涉及一种具备多晶硅钝化膜的晶体硅太阳电池的制备方法。
背景技术
P型多晶硅电池由于生产工艺成熟、制造成本低,在目前及今后相当长的一段时间内仍占据绝大部分市场份额。随着国务院颁发的关于光伏产业新建产能单晶电池效率大于20%,多晶电池效率大于18%的若干指导意见,选择易于兼容现有规模生产线,且易于控制生产成本的方案,快速更新核心技术是大势所趋。P型晶体硅太阳能电池要想继续保持竞争力、获得更大的发展与应用,必须进一步提高转换效率,同时降低生产成本。
目前,在P型多晶硅太阳电池的生产工艺中,如何在前表面获得好的绒面结构,以提升减反射效果是制备高效多晶硅电池首要任务,常用的工艺方法包括机械刻槽法、激光刻蚀法、反应离子刻蚀法(RIE)、化学腐蚀法(即金属辅助湿法腐蚀等。其中,机械刻槽法可以得到较低的表面反射率,但是该方法造成硅片表面的机械损伤比较严重,而且其成品率相对较低,故而在工业生产中使用较少。激光刻蚀法是用激光制作不同的刻槽花样,条纹状和倒金字塔形状的表面都已经被制作出来,其反射率可以低至8.3%,但是由其制得的电池的效率都比较低,不能有效地用于生产。RIE法可以利用不同的模版来进行刻蚀,刻蚀一般是干法刻蚀,可以在硅片表面形成所谓的“黑硅”结构,其反射率可以低至4%,但是由于设备昂贵,生产成本较高,因此在工业生产中使用较少。而化学腐蚀法具有工艺简单、廉价优质和现有工艺好兼容等特点,成为了现有工业中使用最多的方法。
与此同时,PERC结构和PERC双面结构技术着眼于电池的背面,利用钝化大大降低了背面的复合速度,同时增加背面入光,该技术近年来在P型晶体硅电池中逐步得到大规模应用,使多晶和单晶电池的效率分别提升0.5%和1%以上。但是高效晶体硅背钝化电池工艺路线依然面临以下几个方面的问题:
1)如何在多晶硅表面提升陷光作用的同时保证优异的表面状态,进而在PECVD设备中实现硅前表面的有效钝化;
2)在电池背面形成优良的表面钝化效果;
3)电池背面形成有效的电极欧姆接触,降低电池的接触电阻。
目前,在已经公开的黑硅材料制作技术中,采用湿法金属催化化学刻蚀法制备黑硅的专利,如CN 102051618 A、CN 102768951 A等都是通过一步法(酸或碱)来实现纳米绒面扩孔来控制表面状态,反应速度快,反应过程不易控制。而CN 104393114 A则是在微米绒面的基础上制备纳米绒面,再进行表面改善刻蚀。有可能存在微纳米结构不均匀,降低后续工艺的钝化效果。对于高效晶硅电池,随着体性能的不断提升,对前表面的复合速度要求更高。
氧化铝氮化硅多层钝化薄膜结构在p型晶体硅应用方面,兼具化学钝化和场钝化效应,有效降低了p型硅片背表面的复合速度,改善了氧化铝薄膜在现有工艺中的稳定性。然而,AlO沉积过程中昂贵的TMA消耗面临当前光伏产品降本增效的挑战。
发明内容
本发明的目的在于提供一种具备多晶硅钝化膜的晶体硅太阳电池的制备方法,采用PolySi薄膜进行钝化,有效降低了p型硅片背面复合速度,且成本低。
为了达到上述的目的,本发明提供一种具备多晶硅钝化膜的晶体硅太阳电池的制备方法,包括:在硅片表面形成纳米绒面结构;在硅片前表面形成发射极;采用一步法湿法刻蚀去除磷硅玻璃并抛光硅片背面;在抛光后的硅片背面,先采用LPCVD沉积SiO,在硅片背面形成SiO2钝化层,再在SiO2钝化层上采用LPCVD沉积PolySi钝化层;采用PECVD设备,在硅片发射极和PolySi钝化层上沉积SiNx钝化层。
上述具备多晶硅钝化膜的晶体硅太阳电池的制备方法中,所述SiO2钝化层的厚度为1~3nm,所述PolySi钝化层的厚度为30~200nm。
上述具备多晶硅钝化膜的晶体硅太阳电池的制备方法中,所述在硅片表面形成纳米绒面结构包括:将硅片放入金属盐溶液中坠饰金属颗粒;将坠饰金属颗粒的硅片放入HF/H2O2氧化性溶液中进行纳米绒面结构制备;对具备纳米结构绒面的硅片进行金属颗粒去除处理;将去除金属颗粒的硅片放入第一氢氧化钾溶液中改善纳米绒面结构;再将硅片放入第二氢氧化钾溶液中进行纳米绒面结构修正;其中,第二氢氧化钾溶液的浓度比第一氢氧化钾溶液的浓度低,第一氢氧化钾溶液具备各向同性腐蚀特性,第二氢氧化钾溶液具备各向异性腐蚀特性。
上述具备多晶硅钝化膜的晶体硅太阳电池的制备方法中,所述第一氢氧化钾溶液的浓度为0.5~2wt%,在20~50℃下改善纳米绒面结构;所述第二氢氧化钾溶液的浓度为0.05~0.1wt%的低浓度氢氧化钾溶液在20~50℃进行纳米绒面结构修正。
上述具备多晶硅钝化膜的晶体硅太阳电池的制备方法中,所述金属盐溶液为0.003-0.05mol/L的硝酸银或硝酸铜溶液,在附加超声波的水浴中进行坠饰金属颗粒,超声频率为20~40kHz,超声功率为0.2~0.5W/cm2。
上述具备多晶硅钝化膜的晶体硅太阳电池的制备方法中,发射极上的SiNx钝化层的厚度为75~85nm;PolySi钝化层上的SiNx钝化层的厚度为50~100nm。
上述具备多晶硅钝化膜的晶体硅太阳电池的制备方法中,在硅片表面形成纳米绒面结构之前还包括:将硅片放入NaOH和NaClO的混合碱溶液中清洗,去除表面损伤层、切割线痕,完成双面抛光。
上述具备多晶硅钝化膜的晶体硅太阳电池的制备方法中,所述NaOH和NaClO的混合碱溶液,NaOH与NaClO的体积比为3:1~1:1。
上述具备多晶硅钝化膜的晶体硅太阳电池的制备方法中,所述在硅片前表面形成发射极为:将硅片放入高温炉中进行POCl3单面沉积扩散,在硅片前表面形成发射极。
与现有技术相比,本发明的有益技术效果是:
1、本发明的具备多晶硅钝化膜的晶体硅太阳电池的制备方法,采用PolySi薄膜有效代替AlO薄膜,避免高成本的TMA的消耗,且能够形成有效的背面钝化,降低背面复合电流密度;
2、本发明的具备多晶硅钝化膜的晶体硅太阳电池的制备方法,采用具备浓度梯度的两步碱溶液对绒面进行扩孔修饰,反应速度可控,应用不同浓度碱溶液具备的各向异性刻蚀差异,可以有效改善黑硅纳米结构的深度,并且避免黑洞残留,在有效降低硅表面态的同时保证优异的陷光特性;且高浓度削峰特性还可以提升工艺时间;
3、本发明的具备多晶硅钝化膜的晶体硅太阳电池的制备方法,在附加超声波的水浴中进行坠饰金属颗粒,可以有效控制金属颗粒的尺寸和密度,从而达到对纳米绒面结构的优化(纳米孔洞的开孔大小和密度);
4、本发明的具备多晶硅钝化膜的晶体硅太阳电池的制备方法,双面抛光可优化硅片表面,提升金属盐溶液坠饰的均匀性。
附图说明
本发明的具备多晶硅钝化膜的晶体硅太阳电池的制备方法由以下的实施例及附图给出。
图1所示为本发明的具备多晶硅钝化膜的晶体硅太阳电池的结构示意图。
具体实施方式
以下将结合图1对本发明的具备多晶硅钝化膜的晶体硅太阳电池的制备方法作进一步的详细描述。
本发明的具备多晶硅钝化膜的晶体硅太阳电池的制备方法包括以下步骤:
1)对硅片进行双面抛光;
将硅片放入NaOH和NaClO的混合碱溶液中清洗,去除表面损伤层、切割线痕,完成双面抛光;
所述NaOH和NaClO的混合碱溶液,NaOH与NaClO的体积比为3:1~1:1;
该步骤兼具清洗和抛光工艺,节省了前清工艺环节,提升产能;
2)将抛光后的硅片放入金属盐溶液中坠饰金属颗粒;
较佳地,所述金属盐溶液为0.003-0.05mol/L的硝酸银或硝酸铜溶液,在附加超声波的水浴中进行坠饰金属颗粒,超声频率为20~40kHz,超声功率为0.2~0.5W/cm2;通过引入超声控制,可以有效控制银颗粒(或铜颗粒)的尺寸和密度,从而达到对纳米绒面结构的优化(纳米孔洞的开孔大小和密度);
双面抛光可优化硅片表面,提升步骤2)中金属盐溶液坠饰的均匀性;
3)将坠饰金属颗粒的硅片放入HF/H2O2氧化性溶液中进行纳米绒面结构制备;
4)对具备纳米结构绒面的硅片进行金属颗粒去除处理;
5)将去除金属颗粒的硅片放入第一氢氧化钾溶液中改善纳米绒面结构;
较佳地,采用浓度为0.5~2wt%的氢氧化钾溶液在20~50℃改善纳米绒面结构;
本发明采用浓度为0.5~2wt%的氢氧化钾溶液进行第一次削峰和扩孔,修饰黑硅绒面;室温条件下,适度的反应速度提升了修正工艺窗口时间(60~240s),而较高的碱溶液浓度具备更好的各向同性腐蚀特性,能够首先有效修正纳米孔洞的深度(或纳米柱的高度);基于步骤5)高浓度削峰特性,还可以提升步骤3)的工艺时间,从而改善纳米孔的深度及均匀性,为最终均匀适度的微纳米绒面提供基础;
6)再将硅片放入第二氢氧化钾溶液中进行纳米绒面结构修正;
第二氢氧化钾溶液与第一氢氧化钾溶液具有不同浓度,第二氢氧化钾溶液的浓度比第一氢氧化钾溶液的浓度低;
步骤6)后在硅片表面形成“黑硅”结构;
较佳地,采用浓度为0.05~0.1wt%的低浓度氢氧化钾溶液在20~50℃进行纳米绒面结构修正,从而对黑硅绒面结构进行微调;低浓度的氢氧化钾溶液体现优异的各向异性腐蚀特性,能够择优去除多孔硅残留,降低界面态对后续光生电流复合的影响;
本发明利用步骤5)和步骤6)采用两步碱法碱扩孔制备微纳米陷光绒面,反应速度可控,应用不同浓度碱溶液具备的各向异性刻蚀差异,可以有效改善黑硅纳米结构的深度,并且避免黑洞残留,在有效降低硅表面态的同时保证优异的陷光特性;
还需要说明的是,步骤6)采用低浓度碱溶液充分发挥碱溶液各向异性择优腐蚀的特性,达到修正微纳绒面的倾角和界面态的目的,以利于前表面扩散制结和表面钝化;如果持续使用高浓度碱溶液(例如步骤5)中的浓度范围)进行修正,很容易造成陷光的大幅损失而导致太阳电池的光学损失;而碱溶液浓度过低,有可能影响残留多孔硅的有效去除,进而影响太阳电池的光电输出特性及其稳定性;
另外,步骤5)、步骤6)的碱溶液的室温下扩孔工艺的开发,也有效降低了酸溶液的消耗量;
7)将纳米绒面结构修正后的硅片放入高温炉中进行POCl3单面沉积扩散,形成发射极;
POCl3单面沉积扩散后,在硅片一表面上形成发射极,该表面称为硅片前表面,而硅片的另一表面就称为硅片背表面或硅片背面;
8)采用一步法湿法刻蚀去除磷硅玻璃并抛光硅片背面;
POCl3单面沉积扩散过程中,在硅片前表面及边缘有磷硅玻璃生成,该磷硅玻璃是不希望生成的物质,需去除;
步骤8)在去除磷硅玻璃的同时对硅片背面具有抛光作用;
9)在抛光后的硅片背面,先采用LPCVD沉积SiO,在硅片背面形成SiO2钝化层,再在SiO2钝化层上采用LPCVD沉积PolySi钝化层;
即本发明采用LPCVD沉积工艺,在硅片背面沉积SiO2/PolySi叠层钝化薄膜;
较佳地,所述SiO2钝化层的厚度为1~3nm,所述PolySi钝化层的厚度为30~200nm;
步骤8)中采用LPCVD法沉积厚度为30~200nm的多晶硅膜作为背面钝化薄膜的设计,能够形成有效的背面钝化,降低背面复合电流密度;PolySi薄膜可以有效代替AlO薄膜,避免高成本的TMA的消耗;
10)采用PECVD设备,在硅片发射极和PolySi钝化层上沉积SiNx钝化层;
步骤7)在硅片前表面形成发射极,步骤9)在硅片背面形成SiO/PolySi叠层钝化薄膜,步骤10)在发射极和PolySi薄膜上形成SiNx薄膜;
较佳地,发射极上的SiNx钝化层的厚度为75~85nm,对常规的85nm进行了扩展;PolySi钝化层上的SiNx钝化层的厚度为50~100nm;
11)在硅片背面的SiNx钝化层上开槽开孔;
可采用激光开槽、化学湿法刻蚀、光刻或类光刻工艺在背钝化层开槽开孔,优选采用激光开槽实现背接触电极结构,这样能够形成增强铝背场;
12)丝网印刷烧结背铝栅线电极、背银电极及正银电极即可。
本发明的具备多晶硅钝化膜的晶体硅太阳电池的制备方法,通过优化的腐蚀溶液在产业化黑硅制绒机中实现易于钝化的微纳米表面状态,同时运用LPCVD沉积SiO2/PolySi的叠层钝化取代TMA的消耗,制备高效且兼具成本优势的多晶硅电池。
现以一具体实施例说明本发明的具备多晶硅钝化膜的晶体硅太阳电池的制备方法。
图1所示为本实施例的具备多晶硅钝化膜的晶体硅太阳电池的结构示意图。
参见图1,本实施例的具备多晶硅钝化膜的晶体硅太阳电池的制备方法采用以下步骤:
1)P型硅片在NaOH/NaClO混合碱溶液中清洗抛光,以去除表面损伤层、切割线痕等;
2)将抛光后的硅片在硝酸银溶液中进行银坠饰;
3)将银坠饰后的硅片放入HF/H2O2混合溶液中进行纳米绒面结构制备;
4)将具备纳米绒面结构的硅片放入双氧水和氨水混合溶液中去除金属阴离子;
5)将去除金属阴离子的硅片在1wt%KOH碱溶液中进行扩孔和削减纳米空洞高度;
6)再将硅片在0.1wt%的KOH碱溶液中进行绒面修饰,去除金属辅助腐蚀步骤4)留下的多孔硅结构;
7)将修饰后的硅片1放入高温炉中进行POCl3单面(前表面)沉积扩散,在硅片前表面形成发射极2;
8)采用湿法刻蚀设备去除硅片表面磷硅玻璃(PSG)并实现硅片背面抛光;
9)采用LPCVD设备,先在抛光后的硅片背面生长2nm SiO2薄膜3,再在SiO2薄膜上沉积170nm PolySi薄膜4;然后采用管式PECVD设备,在PolySi薄膜上沉积150nm左右的SiNx层5,形成SiO2/PolySi/SiNx的叠层钝化;
10)采用管式PECVD设备,沉积85nm氮化硅层6在硅片的发射极上;
11)采用激光或湿法在硅片背面钝化层开槽开孔;
12)丝网印刷烧结背铝栅线、背电极及正电极,测试电池效率,测试得到的数据如表1所示。
表1电池测试数据列表
表1的数据进一步说明本实施例方法制备得到的电池能够获得何种技术效果。双面PERC结构太阳电池大幅降低了传统铝背场的复合作用,明显提升了开路电压。同样关键的因素是,采用具备浓度梯度的碱溶液修正工艺,在保持高陷光效果的同时(Jsc>39.7mA),有效降低了太阳电池前表面复合。本实施例制备的晶体硅太阳电池实现了效率20.6%的突破。
以上对本发明的具体实施例进行了描述。需要理解的是,本发明并不局限于上述特定实施方式,本领域技术人员可以在权利要求的范围内做出各种变形或修改,这并不影响本发明的实质内容。
Claims (9)
1.具备多晶硅钝化膜的晶体硅太阳电池的制备方法,其特征在于,包括:在硅片表面形成纳米绒面结构;在硅片前表面形成发射极;采用一步法湿法刻蚀去除磷硅玻璃并抛光硅片背面;在抛光后的硅片背面,先采用LPCVD沉积SiO2,在硅片背面形成SiO2钝化层,再在SiO2钝化层上采用LPCVD沉积PolySi钝化层;采用PECVD设备,在硅片发射极和PolySi钝化层上沉积SiNx钝化层。
2.如权利要求1所述的具备多晶硅钝化膜的晶体硅太阳电池的制备方法,其特征在于,所述SiO2钝化层的厚度为1~3nm,所述PolySi钝化层的厚度为30~200nm。
3.如权利要求1所述的具备多晶硅钝化膜的晶体硅太阳电池的制备方法,其特征在于,所述在硅片表面形成纳米绒面结构包括:将硅片放入金属盐溶液中坠饰金属颗粒;将坠饰金属颗粒的硅片放入HF/H2O2氧化性溶液中进行纳米绒面结构制备;对具备纳米结构绒面的硅片进行金属颗粒去除处理;将去除金属颗粒的硅片放入第一氢氧化钾溶液中改善纳米绒面结构;再将硅片放入第二氢氧化钾溶液中进行纳米绒面结构修正;其中,第二氢氧化钾溶液的浓度比第一氢氧化钾溶液的浓度低,第一氢氧化钾溶液具备各向同性腐蚀特性,第二氢氧化钾溶液具备各向异性腐蚀特性。
4.如权利要求3所述的具备多晶硅钝化膜的晶体硅太阳电池的制备方法,其特征在于,所述第一氢氧化钾溶液的浓度为0.5~2wt%,在20~50℃下改善纳米绒面结构;所述第二氢氧化钾溶液的浓度为0.05~0.1wt%的低浓度氢氧化钾溶液在20~50℃进行纳米绒面结构修正。
5.如权利要求3所述的具备多晶硅钝化膜的晶体硅太阳电池的制备方法,其特征在于,所述金属盐溶液为0.003-0.05mol/L的硝酸银或硝酸铜溶液,在附加超声波的水浴中进行坠饰金属颗粒,超声频率为20~40kHz,超声功率为0.2~0.5W/cm2。
6.如权利要求1所述的具备多晶硅钝化膜的晶体硅太阳电池的制备方法,其特征在于,发射极上的SiNx钝化层的厚度为75~85nm;PolySi钝化层上的SiNx钝化层的厚度为50~100nm。
7.如权利要求1所述的具备多晶硅钝化膜的晶体硅太阳电池的制备方法,其特征在于,在硅片表面形成纳米绒面结构之前还包括:将硅片放入NaOH和NaClO的混合碱溶液中清洗,去除表面损伤层、切割线痕,完成双面抛光。
8.如权利要求7所述的具备多晶硅钝化膜的晶体硅太阳电池的制备方法,其特征在于,所述NaOH和NaClO的混合碱溶液,NaOH与NaClO的体积比为3:1~1:1。
9.如权利要求1所述的具备多晶硅钝化膜的晶体硅太阳电池的制备方法,其特征在于,所述在硅片前表面形成发射极为:将硅片放入高温炉中进行POCl3单面沉积扩散,在硅片前表面形成发射极。
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