CN111864013A - 一种单晶硅基倒金字塔绒面的干湿混合制备方法 - Google Patents
一种单晶硅基倒金字塔绒面的干湿混合制备方法 Download PDFInfo
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Abstract
一种单晶硅基倒金字塔绒面的干湿混合制备方法,该方法为先在硅片表面制备一层金属薄膜,然后,通过高温退火使得金属薄膜收缩成金属纳米颗粒,接着,在金属纳米颗粒的化学刻蚀与酸扩孔修饰辅助下在硅片表面制备纳米孔状结构,再接着,使用王水去除硅片表面的金属纳米颗粒,最后,通过碱溶液的各向异性刻蚀作用,在硅片表面制备结构相对均匀、密度较好的倒金字塔结构。该方法能够提高硅片表面纳米粒子分布的均匀性,使得采用金属辅助化学刻蚀方法制备的倒金字塔绒面结构的均匀性、密度更好,尺寸更可控,最终,提高大面积硅倒金字塔绒面的光电性能。
Description
技术领域
本发明涉及太阳能电池技术领域,特别是一种单晶硅基倒金字塔绒面的干湿混合制备方法。
背景技术
太阳电池绒面的陷光能力对于短路电流,短波光谱响应以及最终电池效率的提升具有重大意义。目前,商业太阳电池的前表面绒面采用随机正金字塔结构,其陷光性能有待进一步提高;硅倒金字塔阵列由于其相对于传统正金字塔更加优异的陷光性能而增加了电池的光吸收特别是短波段吸收,同时由于其低的表面增加率不会带来严重的表面复合,从而使得提高电池短路电流进而实现高的转换效率成为可能。
自20世纪80年代以来,利用湿化学蚀刻技术对硅表面进行纹理化和减少反射的简单而实用的方法因其成本低、与大规模生产的兼容性以及蚀刻后缺少残余损伤层而特别受关注。
目前,有一种采用金属辅助化学蚀刻(MACE)与碱各向异性刻蚀相结合的方法被用于制备硅倒金字塔陷光结构;在MACE过程中,金、银或铂的纳米颗粒催化化学氧化剂(通常是H2O2)产生电子-空穴对,这些化学氧化剂被注入半导体的价带,这导致了硅的溶解和微粒附近蚀刻的微孔和纳米孔的形成;金属微粒和纳米颗粒的大小和形状对于控制硅表面的形貌和反射特性至关重要;金属微粒和纳米颗粒的大小和形状受到所用的金属微粒合成方法参数的影响,包括催化剂合成、反应时间和退火温度;金属微粒和纳米颗粒通常是通过化学方法制备的,例如用氢氟酸/硝酸盐溶液或银镜反应制备,此方法获得的金属颗粒是相当不规则的,这将直接导致最终制备的倒金字塔结构开口尺寸不可控、密度差、均匀性不够好。
发明内容
本发明所要解决的技术问题是针对现有技术的不足,提供一种能够提高硅片表面银纳米粒子分布的均匀性、使得采用金属辅助化学刻蚀方法制备的倒金字塔绒面结构的均匀性、密度更好,尺寸更可控,最终提高大面积硅倒金字塔绒面的光电性能的单晶硅基倒金字塔绒面的干湿混合制备方法。
本发明所要解决的技术问题是通过以下的技术方案来实现的。本发明是一种单晶硅基倒金字塔绒面的干湿混合制备方法,该方法为先在硅片表面制备一层金属薄膜,然后,通过高温退火使得金属薄膜收缩成金属纳米颗粒,接着,采用金属辅助化学刻蚀与酸扩孔修饰在硅片表面制备纳米孔状结构,再接着,使用王水去除硅片表面的金属纳米颗粒,最后,通过碱溶液的各向异性刻蚀作用,在硅片表面制备结构相对均匀、密度较好的倒金字塔结构。
本发明所要解决的技术问题还可以通过以下的技术方案来进一步实现,对于以上所述的单晶硅基倒金字塔绒面的干湿混合制备方法,该方法的具体步骤如下:
(1)将原硅片进行RCA标准工艺清洗;
(2)干法制备金属薄膜:在硅片表面制备一层15nm的金属薄膜;
(3)对硅片进行高温退火,使金属薄膜形成金属纳米颗粒:将覆盖有金属薄膜的硅片在大气氛围600℃下保持60min,随后自然降温至室温,使金属薄膜在高温作用下收缩成金属纳米颗粒;
(4)纳米孔制备:将退火后的硅片置于HF与H2O2 混合溶液中,室温下反应9min;
(5)去离子水冲洗:将步骤(4)的硅片放入王水中浸泡10min,洗去硅表面的金属纳米颗粒,再使用去离子水冲洗5min;
(6)将硅片放入在HNO3、H2O与HF的混合溶液中,在7℃条件下,反应2min进行酸扩孔,接着再采用去离子水冲洗5min后制备出纳米孔状结构;
(7)倒金字塔结构制备:将带有纳米多孔的硅片放进60℃的NaOH水溶液中反应20s,利用碱对单晶硅的各向异性刻蚀,制备得到倒金字塔结构。
本发明所要解决的技术问题还可以通过以下的技术方案来进一步实现,对于以上所述的单晶硅基倒金字塔绒面的干湿混合制备方法,该方法采用的硅片为p型100面切割的、尺寸为156×156 mm2、太阳能级的Cz硅片,硅片厚度为190±10μm、电阻率为2 Ωcm。
本发明所要解决的技术问题还可以通过以下的技术方案来进一步实现,对于以上所述的单晶硅基倒金字塔绒面的干湿混合制备方法,步骤(2)中,采用磁控溅射方法,溅射电流20mA,溅射时间60s,在硅片表面制备一层15nm的金属薄膜。
本发明所要解决的技术问题还可以通过以下的技术方案来进一步实现,对于以上所述的单晶硅基倒金字塔绒面的干湿混合制备方法,步骤(2)中,采热蒸发方法在硅片表面制备一层15nm的金属薄膜。
本发明所要解决的技术问题还可以通过以下的技术方案来进一步实现,对于以上所述的单晶硅基倒金字塔绒面的干湿混合制备方法,金属薄膜为金薄膜、银薄膜或铂金薄膜。
本发明所要解决的技术问题还可以通过以下的技术方案来进一步实现,对于以上所述的单晶硅基倒金字塔绒面的干湿混合制备方法,步骤(4)中,HF与H2O2混合溶液中,HF与H2O2的摩尔浓度比为4:1。
本发明所要解决的技术问题还可以通过以下的技术方案来进一步实现,对于以上所述的单晶硅基倒金字塔绒面的干湿混合制备方法,步骤(6)中,HNO3、H2O与HF的混合溶液中,HNO3、H2O与HF的体积比为4:2:1。
本发明所要解决的技术问题还可以通过以下的技术方案来进一步实现,对于以上所述的单晶硅基倒金字塔绒面的干湿混合制备方法,步骤(7)中,NaOH水溶液中NaOH的重量百分率为2wt%。
与现有技术相比,本发明通过干法—磁控溅射方法制备金属薄膜,并在高温下退火使得金属薄膜收缩成尺寸大小更加均一、分布更加均匀的金属纳米颗粒;在此基础上,制备纳米孔状结构,并在碱的各向异性刻蚀作用下制备尺寸大小相对更加均一、分布相对更加均匀、密度更好的倒金字塔结构;最终,使得这种全新的干湿混合方法制备的倒金字塔绒面结构陷光性能记进一步提升,为高效太阳电池的发展注入了新的活力。该方法能够提高硅片表面纳米粒子分布的均匀性,使得采用金属辅助化学刻蚀方法制备的倒金字塔绒面结构的均匀性、密度更好,尺寸更可控,最终,提高大面积硅倒金字塔绒面的光电性能。
附图说明
图1:
(a)为磁控溅射法制备的15nm金薄膜在600℃下退火60min后的扫描电镜(SEM)图;
(b)为金纳米粒子在金属辅助化学刻蚀以及酸扩孔后形成的纳米孔状结构SEM图;
(c)为纳米孔状结构在碱可向异性刻蚀作用下形成的倒金字塔结构SEM图;
(d)为现有文献报道的在HF (0.2 M) /AgNO3 (3 × 10−5 M)水溶液中 ,25 °C条件下2min硅片表面沉积的银粒子SEM图;
(e)为图d中的银粒子在银粒子辅助刻蚀以及酸扩孔后形成的纳米孔状结构SEM图;
(f)图e中纳米孔在碱各向异性刻蚀作用下形成的倒金字塔结构图;
图2为本发明与原始硅片、全湿法制备的倒金字塔结构在400-1100nm波段的反射率对比图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面将结合本发明附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,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,都属于本发明保护的范围。
参照图1-2,一种单晶硅基倒金字塔绒面的干湿混合制备方法,通过磁控溅射方法在硅片表面制备一层金薄膜,随后,通过高温退火使得金薄膜收缩成纳米金颗粒;接着,在金辅助化学刻蚀与酸扩孔修饰下在硅片表面制备纳米孔状结构;然后,使用王水去除硅片表面的金纳米粒子;最后,通过碱溶液的各向异性刻蚀作用,在硅片表面制备结构相对均匀、密度较好的倒金字塔结构。
具体实施方案如下:采用p型(100)面切割的、尺寸为156×156 mm2、太阳能级的Cz硅片,硅片厚度190±10μm,电阻率为2Ωcm;
太阳能级的Cz硅片是指采用Cz法制作的太阳能级硅片,Cz法指的是直拉单晶制造法;
制备过程如下:
(1)将原硅片进行RCA标准工艺清洗;
(2)干法制备金属薄膜,采用磁控溅射方法,溅射电流20mA,溅射时间60s,在硅片表面制备一层15nm的金薄膜;
(3)高温退火形成纳米颗粒,将覆盖有金属薄膜的硅片在大气氛围600℃下保持60min,随后自然降温至室温,金属薄膜将会在高温作用下收缩成纳米金属粒子;
(4)纳米孔制备,将退火后的硅片置于HF与H2O2 混合溶液中,室温下反应9min;其中,HF与H2O2的摩尔浓度比为4:1;
(5)去离子水冲洗5min后将上一步的硅片放入王水中10min,洗去硅表面的金纳米粒子并使用去离子水冲洗5min;
(6)然后在HNO3:H2O:HF的混合溶液中,温度在7℃条件下,反应2min进行酸扩孔,去离子水冲洗5min后最终制备出纳米孔状结构;其中,HNO3、H2O、HF的体积比为4:2:1;
(7)倒金字塔结构制备,将带有纳米多孔的硅片放进60℃的NaOH水溶液中反应20s,NaOH水溶液中NaOH的重量百分率为2wt%,利用碱对单晶硅的各向异性刻蚀,制备得到倒金字塔结构。
在步骤(2)中,采用磁控溅射镀膜仪制备一层15nm的金薄膜,也可以采用热蒸发方法制备,膜层厚度不变。
在步骤(2)中,采用磁控溅射镀膜仪制备一层15nm的金薄膜,也可以采用银、铂金属代替金,膜层厚度不变。
由图1可以看出,采用磁控溅射方法沉积的金属粒子相较于AgNO3/HF /H2O2溶液中沉积的金属粒子大小和形状更加均一,分布更加均匀,最终导致制备的倒金字塔密度、均匀性更好;
从图2中可以看出,干湿混合方法制备的倒金字塔结构反射率在450-1100nm波段均低于全湿法制备的倒金字塔结构,展现出了更好的陷光性能。
本申请的发明点在于:
1.本申请的单晶硅基倒金字塔绒面制备方法由干法—磁控溅射法制备金属薄膜和湿法—金属辅助化学刻蚀和碱各向异性刻蚀相结合。
2.采用磁控溅射方法制备一层15nm的金薄膜,溅射电流为20mA,溅射时间60s。
3.采用磁控溅射方法制备一层15nm的金薄膜,并在600℃下,空气氛围中退火60min,之后自然降温至室温。
4.采用将硅片置于王水中10min溶解并去除金属辅助化学刻蚀后硅片表面残余的金纳米粒子。
Claims (9)
1.一种单晶硅基倒金字塔绒面的干湿混合制备方法,其特征在于:该方法为先在硅片表面制备一层金属薄膜,然后,通过高温退火使得金属薄膜收缩成金属纳米颗粒,接着,采用金属辅助化学刻蚀与酸扩孔修饰在硅片表面制备纳米孔状结构,再接着,使用王水去除硅片表面的金属纳米颗粒,最后,通过碱溶液的各向异性刻蚀作用,在硅片表面制备结构相对均匀、密度较好的倒金字塔结构。
2.根据权利要求1所述的单晶硅基倒金字塔绒面的干湿混合制备方法,其特征在于:该方法的具体步骤如下:
(1)将原硅片进行RCA标准工艺清洗;
(2)干法制备金属薄膜:在硅片表面制备一层15nm的金属薄膜;
(3)对硅片进行高温退火,使金属薄膜形成金属纳米颗粒:将覆盖有金属薄膜的硅片在大气氛围600℃下保持60min,随后自然降温至室温,使金属薄膜在高温作用下收缩成金属纳米颗粒;
(4)纳米孔制备:将退火后的硅片置于HF与H2O2 混合溶液中,室温下反应9min;
(5)去离子水冲洗:将步骤(4)的硅片放入王水中浸泡10min,洗去硅表面的金属纳米颗粒,再使用去离子水冲洗5min;
(6)将硅片放入在HNO3、H2O与HF的混合溶液中,在7℃条件下,反应2min进行酸扩孔,接着再采用去离子水冲洗5min后制备出纳米孔状结构;
(7)倒金字塔结构制备:将带有纳米多孔的硅片放进60℃的NaOH水溶液中反应20s,利用碱对单晶硅的各向异性刻蚀,制备得到倒金字塔结构。
3.根据权利要求2所述的单晶硅基倒金字塔绒面的干湿混合制备方法,其特征在于:该方法采用的硅片为p型100面切割的、尺寸为156×156 mm2、太阳能级的Cz硅片,硅片厚度为190±10μm、电阻率为2 Ωcm。
4.根据权利要求2所述的单晶硅基倒金字塔绒面的干湿混合制备方法,其特征在于:步骤(2)中,采用磁控溅射方法,溅射电流20mA,溅射时间60s,在硅片表面制备一层15nm的金属薄膜。
5.根据权利要求2所述的单晶硅基倒金字塔绒面的干湿混合制备方法,其特征在于:步骤(2)中,采热蒸发方法在硅片表面制备一层15nm的金属薄膜。
6.根据权利要求1-5任意一项所述的单晶硅基倒金字塔绒面的干湿混合制备方法,其特征在于:金属薄膜为金薄膜、银薄膜或铂金薄膜。
7.根据权利要求2所述的单晶硅基倒金字塔绒面的干湿混合制备方法,其特征在于:步骤(4)中,HF与H2O2混合溶液中,HF与H2O2的摩尔浓度比为4:1。
8.根据权利要求2所述的单晶硅基倒金字塔绒面的干湿混合制备方法,其特征在于:步骤(6)中,HNO3、H2O与HF的混合溶液中,HNO3、H2O与HF的体积比为4:2:1。
9.根据权利要求2所述的单晶硅基倒金字塔绒面的干湿混合制备方法,其特征在于:步骤(7)中,NaOH水溶液中NaOH的重量百分率为2wt%。
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