CN116454141B - 一种应用于晶硅太阳电池的透明导电钝化叠层薄膜及其制备方法 - Google Patents
一种应用于晶硅太阳电池的透明导电钝化叠层薄膜及其制备方法 Download PDFInfo
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- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 51
- 238000002161 passivation Methods 0.000 title claims abstract description 47
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 106
- 239000011787 zinc oxide Substances 0.000 claims abstract description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 40
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims abstract description 25
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- MNTPMEHIQKUBIC-UHFFFAOYSA-N silicon;hydrofluoride Chemical compound F.[Si] MNTPMEHIQKUBIC-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明公开一种应用于晶硅太阳电池的透明导电钝化叠层薄膜及其制备方法,属于晶硅太阳电池钝化材料制备领域,叠层薄膜包括:晶硅衬底、超薄氧化硅层、氧化锌层和氧化铟锡层,其中,所述超薄氧化硅层生长在所述晶硅衬底表面,所述氧化锌层沉积在所述超薄氧化硅层表面,所述氧化铟锡层覆盖在所述氧化锌层表面。本发明的结构保证了钝化膜低的寄生光吸收,从而有利于实现大的短路电流,另一方面由氧化锌层和氧化铟锡层叠层膜来承担电流在电极之间的横向导电功能,从而降低了对晶硅衬底重掺杂层方块电阻的要求,有利于降低载流子的俄歇复合损失,提升太阳电池的开路电压。
Description
技术领域
本发明属于晶硅太阳电池钝化材料制备领域,尤其涉及一种应用于晶硅太阳电池的透明导电钝化叠层薄膜及其制备方法。
背景技术
晶体硅多年来一直主导着光伏市场,这都得益于其高转换效率、长稳定性、材料丰富且无毒、成熟的加工技术。提高转换效率、降低成本是光伏行业发展的主题。由于晶体硅表面存在悬挂键或杂质而容易成为载流子的重复区域,因此减小表面复合损失,即表面钝化,是制备高效率晶硅太阳电池的必要手段。目前,晶硅太阳电池产业界常见的表面钝化材料有氧化硅、氢化氮化硅、氧化铝和本征氢化非晶硅薄膜。然而氧化硅、氢化氮化硅、氧化铝均是介电绝缘材料,因此应用于太阳电池中时,需要光刻或高温烧结的工艺使钝化膜局部开窗,以便金属电极能与硅接触来收集光生电流,增加了工艺的复杂性。另外,金属与晶硅直接接触区域缺少了钝化膜,导致这个区域的载流子复合比较严重,而且金属会在硅中产生深能级,这进一步加剧了金属接触区域的载流子复合。在异质结太阳电池中,一般采用本征氢化非晶硅作为钝化材料,尽管本征氢化非晶硅是一种半导体材料,可以解决上述问题,但由于其禁带宽度仅约1.7eV,容易引起寄生光吸收,导致光生电流的损失。
有学者尝试在晶硅表面通过原子层沉积掺杂氧化锌并覆盖氧化铝作为钝化材料,并且当氧化锌厚度达到75nm时,可以同时充当透明导电和减小反射损失的功能层。在这种方案中,氧化铝作为覆盖层,对钝化起到关键的作用,然而由于其是绝缘材料,因此用于太阳电池中时,需要额外的后续步骤来去除氧化铝,使电极与氧化锌相接触,这增加了工艺的复杂性。而且在工业生产中,丝网印刷完电极后需要200℃以上的热处理,此时氧化锌由于缺少了氧化铝覆盖层,导致钝化性能和其光电性能都会受到严重的影响。因此目前在晶硅太阳电池中,具有实用性的,同时具有优越钝化、透明导电和减反功能的材料还未研发成功。
发明内容
为解决上述技术问题,本发明提出了一种应用于晶硅太阳电池的透明导电钝化叠层薄膜及其制备方法,工艺步骤简单,可以实现晶硅太阳电池实现全面积优越钝化,即电极接触区域也可实现钝化,同时充当透明导电功能层和减反层。
为实现上述目的,本发明提供了一种应用于晶硅太阳电池的透明导电钝化叠层薄膜,包括:晶硅衬底、超薄氧化硅层、氧化锌层和氧化铟锡层,其中,所述超薄氧化硅层生长在所述晶硅衬底表面,所述氧化锌层沉积在所述超薄氧化硅层表面,所述氧化铟锡层覆盖在所述氧化锌层表面。
本发明制备的应用于晶硅太阳电池的透明导电钝化叠层薄膜兼具表面钝化、透明导电和干涉减反功能。
优选地,所述超薄氧化硅层的厚度为0-2nm,载流子容易以隧穿方式通过超薄氧化硅层。
优选地,所述氧化锌层的厚度为5-50nm,氧化锌为掺杂氧化锌,掺杂元素为铝、硼、镓和铟中的一种或几种。
优选地,所述氧化铟锡层的厚度为10-75nm,与氧化锌层叠加后的方块电阻小于100Ω/□,并且具有优异的干涉减反效果,在制绒硅片上,可见光波段的反射率小于5%,薄膜吸收率小于1%。
一种所述应用于晶硅太阳电池的透明导电钝化叠层薄膜的制备方法,包括以下步骤:在晶硅衬底表面生长一层0-2nm的超薄氧化硅层,再通过原子层沉积方式将氧化锌层沉积在超薄氧化硅层表面,接着在氧化锌层表面沉积一层氧化铟锡层,最后再经过200-500℃退火。
进一步地,晶硅衬底表面生长超薄氧化硅层之前,经过抛光或制绒处理,具体方法:将晶硅放入丙酮溶液中进行清洗,然后在高浓度的碱溶液中进行抛光处理,得到抛光硅片,在此基础上进一步在低浓度的碱溶液中腐蚀制备金字塔绒面,得到制绒硅片,然后在盐酸和过氧化氢混合溶液(体积比为1:1)中去除金属离子,得到洁净的硅表面。高浓度的碱溶液是浓度为10%(质量分数)的氢氧化钠溶液;低浓度的碱溶液是浓度为2%(质量分数)的氢氧化钠溶液。
优选地,采用溶液法、臭氧氧化或热氧化法在上述方法处理后的硅表面生长超薄氧化硅层;采用溶液法时,溶液可以是盐酸和过氧化氢混合溶液,也可以是硝酸溶液。
优选地,分别以二乙基锌和超纯水为前驱体制备氧化锌,并通过调控氧化锌和掺杂源的循环比例,实现不同比例的掺杂氧化锌。
优选地,采用诸如磁控溅射的物理气相沉积方式沉积氧化铟锡层。
优选地,退火氛围为空气、氮气或氮氢混合气体,退火时间为5-30min。退火处理后可以激活超薄氧化硅/氧化锌/氧化铟锡叠层膜的钝化性能,氧化铟锡在退火过程中主要起保护层的作用,阻碍氧化锌中氢原子的溢出,从而实现优异的钝化性能。
与现有技术相比,本发明具有如下优点和技术效果:
第一:本发明提出的原子层沉积氧化锌/氧化铟锡叠层钝化结构在较低温度退火后就能实现优异的钝化效果,有利于节约热成本。
第二:氧化锌层和氧化铟锡层组成的叠层薄膜具有透明导电作用。这一方面保证了钝化膜低的寄生光吸收,从而有利于实现大的短路电流,另一方面由氧化锌层和氧化铟锡层叠层膜来承担电流在电极之间的横向导电功能,从而降低了对晶硅衬底重掺杂层方块电阻的要求,有利于降低载流子的俄歇复合损失,提升太阳电池的开路电压。
第三:本发明提出的钝化叠层薄膜结构可以在晶硅太阳电池中承担干涉减反层的功能。
第四:本发明提出的钝化叠层薄膜结构制备工艺简单,无需额外的工艺去除覆盖层或进行局域开窗。另外本发明中,可以采用较薄的氧化锌层厚度,从而减少原子层沉积的工艺时间,有利于提高生产时的产率。
综合而言,本发明提出的应用于晶硅太阳电池的透明导电钝化叠层薄膜同时兼具钝化、透明导电和干涉减反功能层,制备工艺简单,有利于实现高效、低成本的晶硅太阳电池。
附图说明
构成本申请的一部分的附图用来提供对本申请的进一步理解,本申请的示意性实施例及其说明用于解释本申请,并不构成对本申请的不当限定。在附图中:
图1为本发明应用于晶硅太阳电池的透明导电钝化叠层薄膜的结构示意图,其中1-晶硅衬底,2-超薄氧化硅层,3-氧化锌层,4-氧化铟锡层;
图2为本发明实施例1的制备工艺流程图。
具体实施方式
现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值,以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明,否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料,但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入,用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时,以本说明书的内容为准。
在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见得的。本发明说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等,均为开放性的用语,即意指包含但不限于。
本发明应用于晶硅太阳电池的透明导电钝化叠层薄膜的结构示意图见图1,其中1-晶硅衬底,2-超薄氧化硅层,3-氧化锌层,4-氧化铟锡层。其中,所述超薄氧化硅层2生长在所述晶硅衬底1表面,所述氧化锌层3沉积在所述超薄氧化硅层2表面,所述氧化铟锡层4覆盖在所述氧化锌层3表面。
本发明实施例中的常温指的是25±2℃。
本发明实施例中的高纯氮气指的是纯度大于99.999%的氮气;高纯水是指25℃时电导率小于0.1μS/cm和残余含盐量小于0.3mg/L,并去除了非电介质的微量细菌、微生物、微粒等杂质的水,均通过购买得到。
实施例1
本实施例提供了一种应用于晶硅太阳电池的透明导电钝化叠层薄膜的制备方法,制备工艺流程示意图见图2,为铝掺杂氧化锌透明导电薄膜,具体方法如下:
步骤1,准备工业级晶向为(100),电阻率在4~7Ω·cm,厚度为300±10μm的N型CZ双抛硅片作为基底,用丙酮溶液去除掉N型晶硅基底表面的有机物质。
步骤2,用丙酮溶液对步骤1得到的N型晶硅硅片,进行标准RCA清洗,得到预处理后的N型CZ双抛硅片;
步骤3,将步骤2所得到的硅片进行氢氟酸处理后放到紫外臭氧清洗仪中,在空气常温下臭氧氧化1h 30min,形成厚度1.5nm的超薄氧化硅层;
步骤4,(1)将步骤3中所得到的硅片放入到原子层沉积设备中,将沉积腔室抽真空,沉积温度为150℃,压强为0.1torr,气体压强为0.4MPa,向腔室内通入二乙基锌前驱体,前驱体加热到35℃,吹扫45ms,用高纯氮气吹40s,腔室内通入水作为氧源,把水作为前驱体加热到35℃,吹扫40ms,再用高纯氮气吹扫40s清洗腔室,形成一次ZnO沉积,继续按上述ZnO沉积方式循环10次的ZnO沉积以形成ZnO层。
(2)向腔室中通入三甲基铝前驱体吹扫40ms,前驱体加热到40℃,吹扫40ms,用高纯氮气吹40s,腔室内通入高纯水作为氧源,把高纯水作为前驱体加热到40℃,吹扫40ms,再用高纯氮气吹扫40s清洗腔室,形成一次Al沉积(完成一次Al掺杂ZnO沉积)。
(3)按照步骤(2)中Al掺杂ZnO沉积的方式循环20次Al掺杂ZnO,最终形成厚度为20nm的Al掺杂ZnO,Al和Zn的循环比为1:10(Al和Zn的循环比指的是原子层沉积工艺中含Al元素的循环工艺与含Zn元素的循环工艺之比)。
步骤5,将步骤4中所得到的硅片放入到磁控溅射设备中,将沉积腔室抽真空,沉积温度为常温,压强为8×10-5Pa,通入气体为氩气,气体流量40SCCM,气体压强0.3Pa,氧化铟锡为磁控溅射的靶材。对步骤4中所得到的硅片进行50W 30min的射频溅射,形成70nm的氧化铟锡层。
步骤6,磁控溅射沉积过后,对步骤5得到的硅片进行200℃,15min的空气退火,得到应用于晶硅太阳电池的透明导电钝化叠层薄膜。钝化后的硅片隐含开路电压(iVOC)达到690mV,叠层薄膜在晶硅衬底上的方块电阻为45Ω/□,在制绒硅片上,可见光波段的反射率小于5%,薄膜吸收率小于1%。
实施例2(与实施例1比,臭氧氧化时间缩短)
超薄氧化硅层采用臭氧氧化工艺生长,具体工艺为:硅片进行氢氟酸处理后放到紫外臭氧清洗仪中,在空气常温下臭氧氧化30min,氧化硅厚度为0.5nm,其余制备方法及结构同实施例1,得到钝化后的硅片隐含开路电压(iVOC)为687mV,叠层薄膜在晶硅衬底上的方块电阻为47Ω/□,在制绒硅片上,在可见光波段的反射率小于5%,薄膜吸收率小于1%。
实施例3(与实施例1比,氧化层工艺不同)
超薄氧化硅层采用热氧氧化工艺生长,具体工艺为:将硅片进行氢氟酸处理后晶硅放入到箱式退火炉中进行300℃45min的热氧氧化,超薄氧化硅厚度为2nm,其余制备方法及结构同实施例1,得到钝化后的硅片隐含开路电压(iVOC)达到680mV,叠层薄膜在晶硅衬底上的方块电阻为43Ω/□,在制绒硅片上,在可见光波段的反射率小于5%,薄膜吸收率小于1%。
实施例4(与实施例1比,氧化层工艺不同)
超薄氧化硅采用湿氧氧化工艺生长,具体工艺为:硅片晶硅氢氟酸处理后放入超纯水:盐酸:过氧化氢=5:1:1的溶液中进行湿氧氧化10min,形成1.6nm的超薄氧化硅。其余制备方法及结构同实施例1,得到钝化后的硅片隐含开路电压(iVoc)达到684mV,叠层薄膜的方块电阻为40Ω/□,在制绒硅片上,在可见光波段的反射率小于5%,薄膜吸收率小于1%。
实施例5(与实施例1比,未沉积超薄氧化硅层)
制备方法同实施例1,不同之处仅在于未沉积超薄氧化硅,即氧化硅层厚度为0nm。硅片进行200℃,15min的空气退火,钝化后的硅片隐含开路电压(iVOC)达到674mV。叠层薄膜的方块电阻为47Ω/□,在制绒硅片上,在可见光波段的反射率小于5%,薄膜吸收率小于1%。
实施例6
超薄氧化硅采用湿氧氧化工艺生长,具体工艺为:硅片晶硅氢氟酸处理后放入超纯水:盐酸:过氧化氢=5:1:1的溶液中进行湿氧氧化10min,形成1.6nm的超薄氧化硅。原子层沉积(ALD)氧化锌薄膜20nm,Al和Zn的循环比为1:15。其余制备方法及结构同实施例1,得到钝化后的硅片隐含开路电压(iVoc)达到687mV,叠层薄膜的方块电阻为36Ω/□,在制绒硅片上,在可见光波段的反射率小于5%,薄膜吸收率小于1%。
实施例7
超薄氧化硅采用湿氧氧化工艺生长,具体工艺为:硅片晶硅氢氟酸处理后放入超纯水:盐酸:过氧化氢=5:1:1的溶液中进行湿氧氧化10min,形成1.6nm的超薄氧化硅。原子层沉积(ALD)氧化锌薄膜20nm(制备方法同实施例1,不同之处在于改变锌源和掺杂源的比例),Al和Zn的循环比为1:25。得到钝化后的硅片隐含开路电压(iVoc)达到680mV,叠层薄膜的方块电阻为39Ω/□,在可见光波段的反射率小于5%,薄膜吸收率小于1%。
实施例8
制备方法同实例1,不同之处在于改变退火氛围,硅片进行400℃,15min的氮氢气体退火,得到钝化后的硅片隐含开路电压(iVoc)达到686mV,在制绒硅片上,叠层薄膜在可见光波段的反射率小于5%,薄膜吸收率小于1%。
实施例9
制备方法同实施例1,不同之处在于改变氧化锌厚度,原子层沉积(ALD)氧化锌厚度为10nm,硅片进行200℃,15min的空气退火,得到钝化后的硅片隐含开路电压(iVoc)达到679mV,叠层薄膜的方块电阻为38Ω/□,在可见光波段的反射率小于5%,薄膜吸收率小于1%。
实施例10(作为对比,未进行退火)
制备方法同实施例1,不同之处在于沉积氧化铟锡层后,未进行退火。硅片隐含开路电压(iVOC)达到543mV,叠层薄膜的方块电阻36Ω/□,在制绒硅片上,在可见光波段的反射率小于5%,薄膜吸收率小于1%。显然,不进行退火时,叠层薄膜的钝化性能很差,远低于目前的产业化工艺水平。
实施例11(作为对比,退火温度过高)
制备方法同实施例1,不同之处在于沉积氧化铟锡层后,进行600℃15min氮氢退火。硅片隐含开路电压(iVOC)达到606mV,叠层薄膜的方块电阻大于1000Ω/□。显然,退火温度过高时,将会导致钝化性能变差,方块电阻变高,不能满足实际应用要求。
实施例12(作为对比,未沉积氧化铟锡层)
制备方法同实施例1,不同之处在于未沉积氧化铟锡层。硅片进行200℃,15min的空气退火,钝化后的硅片隐含开路电压(iVOC)仅为631mV,薄膜的方块电阻为130Ω/□。因此,未沉积氧化铟锡层时,薄膜的钝化性能不够优越,薄膜方块电阻过高,难以满足实际应用需求。
实施例13(作为对比,未沉积氧化锌)
制备方法同实施例1,不同之处在于未沉积氧化锌。硅片进行200℃,15min的空气退火,钝化后的硅片隐含开路电压(iVOC)仅为530mV,此时方块电阻为51Ω/□。未沉积氧化锌时,薄膜的钝化性能很差,难以满足实际应用需求。
以上,仅为本申请较佳的具体实施方式,但本申请的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本申请揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本申请的保护范围之内。因此,本申请的保护范围应该以权利要求的保护范围为准。
Claims (5)
1.一种应用于晶硅太阳电池的透明导电钝化叠层薄膜的制备方法,其特征在于,由以下步骤制备:在晶硅衬底表面生长一层0-2 nm的超薄氧化硅层,再采用二乙基锌和超纯水通过原子层沉积方式将氧化锌层沉积在超薄氧化硅层表面,接着通过磁控溅射在氧化锌层表面沉积一层氧化铟锡层,最后再经过200-400 ℃退火,退火氛围为氮气,退火时间为5-30min;
所述应用于晶硅太阳电池的透明导电钝化叠层薄膜由晶硅衬底、超薄氧化硅层、氧化锌层和氧化铟锡层构成,其中,所述超薄氧化硅层生长在所述晶硅衬底表面,所述氧化锌层沉积在所述超薄氧化硅层表面,所述氧化铟锡层覆盖在所述氧化锌层表面;
氧化铟锡层与氧化锌层叠加后的方块电阻小于100 Ω/□。
2.根据权利要求1所述一种应用于晶硅太阳电池的透明导电钝化叠层薄膜的制备方法,其特征在于,所述氧化锌层的厚度为5-50 nm,氧化锌为掺杂氧化锌,掺杂元素为铝、硼、镓和铟中的一种或几种。
3.根据权利要求1所述一种应用于晶硅太阳电池的透明导电钝化叠层薄膜的制备方法,其特征在于,所述氧化铟锡层的厚度为10-75 nm。
4.根据权利要求1所述一种应用于晶硅太阳电池的透明导电钝化叠层薄膜的制备方法,其特征在于,晶硅衬底表面生长超薄氧化硅层之前,经过抛光或制绒处理。
5.根据权利要求1所述一种应用于晶硅太阳电池的透明导电钝化叠层薄膜的制备方法,其特征在于,生长超薄氧化硅层时,采用溶液法、臭氧氧化或热氧化法;采用溶液法时,溶液为盐酸和过氧化氢混合溶液、或者是硝酸溶液。
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