CN111668340B - 一种Cd3Cl2O2薄膜及其制备方法和薄膜太阳能电池 - Google Patents
一种Cd3Cl2O2薄膜及其制备方法和薄膜太阳能电池 Download PDFInfo
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Abstract
本发明是一种Cd3Cl2O2薄膜及其制备方法和薄膜太阳能电池,其特征是,Cd3Cl2O2薄膜的制备方法采用喷雾热解法,以制备得到的Cd3Cl2O2薄膜作为电子传输层,薄膜太阳能电池有正结构和倒结构两种结构,其优点是:采用喷雾热解方法制备出的Cd3Cl2O2薄膜均匀平整、透光率高、导电率高,制备方法的步骤简单,成本低廉,产率高且性质稳定;将Cd3Cl2O2薄膜作为薄膜太阳能电池的电子传输层可以有效提高太阳能电池的器件性能,降低太阳能电池的生产成本,具有较高的工业化应用价值。
Description
技术领域
本发明属于光电材料及薄膜太阳能电池技术领域,具体涉及一种Cd3Cl2O2薄膜及其制备方法和薄膜太阳能电池。
背景技术
随着全球经济的发展,能源消耗越来越多,石油、煤炭、天然气等不可再生能源越来越少,能源问题日益严峻。太阳作为一种可再生能源,用之不尽取之不竭,而且绿色环保,所以太阳能电池的发展具有重要意义。薄膜太阳能电池近几年也得到了飞速发展,比如碲化镉薄膜太阳能电池、钙钛矿薄膜太阳能电池、硒化锑薄膜太阳能电池、硫化锑薄膜太阳能电池等。虽然薄膜太阳能电池的效率得到了快速的提高,但是相比于产业化的晶体硅太阳能电池来说还有一定的差距,需要进一步对其效率进行优化。
在薄膜太阳能电池的结构中,电子传输层是重要的组成部分之一,电子传输层的选材质量不但会影响载流子的提取和输运,而且对于光吸收层的生长也会产生较大影响。目前常用的电子传输层有氧化锌、二氧化钛、二氧化锡、硫化镉等,这些材料存在的问题是:制备方法复杂;薄膜的均匀程度和平整程度不足,透光率低;成本相对较高,不适宜大面积生产;光电性能较差。
发明内容
针对现有技术存在的不足,为使薄膜太阳能电池的效率得到了快速的提高,本发明的目的是提供一种科学合理,制备流程简单、实用,适于工业化生产,成本低,性能稳定且能够适宜大面积生产的Cd3Cl2O2薄膜制备方法;并提供所述方法直接获得的Cd3Cl2O2薄膜;还提供性价比高的薄膜太阳能电池。
实现本发明的目的之一采用的技术方案是:一种Cd3Cl2O2薄膜制备方法,其特征是:它包括:将氯化镉溶于去离子水中,配制成浓度为0.1~10mg/mL氯化镉水溶液;将基底放在加热台上加热,加热台的温度为100~500℃;采用超声喷雾设备在基底上喷涂氯化镉水溶液,喷涂速率为0.5~2mL/min,喷涂时间为5~40min,喷涂距离为10~15cm,喷涂后形成厚度为20~200nm的Cd3Cl2O2薄膜半成品,再将厚度为20~200nm的Cd3Cl2O2薄膜半成品经温度为200~500℃,退火时间为10~30min退火处理,得到Cd3Cl2O2薄膜。
实现本发明的目的之二是,经所述方法制备获得的Cd3Cl2O2薄膜。
实现本发明的目的之三采用两种技术方案,其一是,一种具有Cd3Cl2O2薄膜的正结构薄膜太阳能电池,其特征是,包括:透明导电薄膜、Cd3Cl2O2薄膜、吸光层、空穴传输层和金属电极层依次相接触。其二是,一种具有Cd3Cl2O2薄膜的倒结构薄膜太阳能电池,其特征是,包括:不锈钢衬底、金属电极层、空穴传输层、吸光层、Cd3Cl2O2薄膜、透明导电薄膜和金属栅线电极依次相接触。
所述的透明导电薄膜是掺硼、铝和镓的氧化锌薄膜、掺氟二氧化锡薄膜和氧化铟锡薄膜中至少一种,膜厚为20~200nm。
所述的一种具有Cd3Cl2O2薄膜的薄膜太阳能电池,其特征是,所述的吸光层是碲化镉薄膜、钙钛矿薄膜、硒化锑薄膜或硫化锑薄膜中的一种,厚度为200~1500nm。
所述的一种具有Cd3Cl2O2薄膜的薄膜太阳能电池,其特征是,所述的空穴传输层是氧化镍薄膜、氧化铜薄膜、氧化钼薄膜或P3HT薄膜中至少一种,厚度为50~200nm。
所述的一种具有Cd3Cl2O2薄膜的薄膜太阳能电池,其特征是,所述的金属电极层是金、银、铜或铝薄片,厚度为50~500nm。
所述的一种具有Cd3Cl2O2薄膜的薄膜太阳能电池,其特征是,所述的金属电极层和金属栅线电极为金、银、铜或铝薄片,厚度为50~500nm。
本发明的一种Cd3Cl2O2薄膜制备方法采用喷雾热解法,以制备得到的Cd3Cl2O2薄膜作为电子传输层,采用喷雾热解方法制备出的Cd3Cl2O2薄膜均匀平整、透光率高、导电率高,制备方法的步骤简单,成本低廉,产率高且性质稳定;薄膜太阳能电池有正结构和倒结构两种结构,由于将Cd3Cl2O2薄膜作为薄膜太阳能电池的电子传输层,能够增加电池的性价比,电池质量好,使用寿命长。
附图说明
图1是正结构太阳能电池的结构示意图;
图中:1玻璃基底;2透明导电膜;3Cd3Cl2O2电子传输层;4吸光层;5空穴传输层;6金属电极层。
图2是倒结构太阳能电池的结构示意图;
图中:7不锈钢衬底;6金属电极层;5空穴传输层;4吸光层;3Cd3Cl2O2电子传输层;2透明导电膜;8金属栅线电极。
图3是Cd3Cl2O2薄膜的XRD图谱;
图4是具有Cd3Cl2O2薄膜的薄膜太阳能电池在100mW cm-2的模拟太阳光照射下测量J-V 曲线图。
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,以下结合实施例及附图,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用以解释本发明,并不用于限定本发明。此外,下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
本发明一种Cd3Cl2O2薄膜制备方法,采用喷雾热解法制备Cd3Cl2O2薄膜的具体步骤包括:
步骤S1:将氯化镉溶于去离子水中,搅拌30min,配置成氯化镉水溶液;
步骤S2:将干净的基底放在加热台上,通过超声喷雾设备,以0.5~2mL/min的进液速率喷涂5~40min,形成均匀平整的Cd3Cl2O2薄膜;
步骤S3:喷涂结束后,对薄膜进行10~30min退火,其中步骤S1中氯化镉溶液的浓度为0.1~10mg/mL,步骤S2中加热台温度为100~500℃,喷嘴距衬底的距离为10~15cm,Cd3Cl2O2薄膜的厚度为20~200nm,退火温度为200~500℃。
如图3所示,薄膜衍射峰与JCPDS 84-2209标准卡片对应良好,喷涂氯化镉水溶液得到了结晶良好的Cd3Cl2O2薄膜。
参照图1和图2,本发明一种具有Cd3Cl2O2薄膜的薄膜太阳能电池分为正结构和倒结构两种结构。图1为正结构电池,正结构电池由玻璃基底1、透明导电薄膜2、Cd3Cl2O2薄膜3,吸光层4、空穴传输层5、金属电极层6依次相接触组成。图2为倒结构电池,倒结构电池由不锈钢衬底7、金属电极层6、空穴传输层5、吸光层4、Cd3Cl2O2电子传输层3、透明导电薄膜2和金属栅线电极8依次相接触组成。
所述的透明导电薄膜2为掺硼、铝和镓的氧化锌薄膜、掺氟二氧化锡薄膜和氧化铟锡薄膜中至少一种,膜厚为20~200nm。
所述吸光层4为碲化镉薄膜、钙钛矿薄膜、硒化锑薄膜或硫化锑薄膜中的一种,厚度是 200~1500nm。
所述的空穴传输层5为氧化镍薄膜,氧化铜薄膜、氧化钼薄膜或P3HT薄膜中至少一种,厚度为50~200nm。
所述的金属电极层6和金属栅线电极8是金、银、铜或铝,厚度是50~500nm。
参照图1,本发明一种具有Cd3Cl2O2薄膜的薄膜太阳能电池的正结构电池制备方法,包括以下步骤:
步骤S1:以透明导电玻璃为衬底;
步骤S2:使用喷雾热解法喷涂氯化镉水溶液,制备Cd3Cl2O2薄膜作为电子传输层;
步骤S3:制备太阳能电池吸光层;
步骤S4:采用旋涂方法或者高真空热蒸发法制备空穴传输层;
步骤S5:蒸镀金属电极层作为背电极。
参照图2,本发明一种具有Cd3Cl2O2薄膜的薄膜太阳能电池的倒结构电池制备方法,包括以下步骤:
步骤S1:以不锈钢为衬底;
步骤S2:采用磁控溅射或者高真空热蒸发方法制备金属电极层;
步骤S3:采用旋涂方法或者高真空热蒸发法制备空穴传输层;
步骤S4:制备太阳能电池吸光层;
步骤S5:使用喷雾热解法喷涂氯化镉水溶液,制备Cd3Cl2O2薄膜作为电子传输层;
步骤S6:采用磁控溅射法或者电子束蒸发法制备透明导电膜;
步骤S7:用丝网印刷的方法制备金属栅线电极。
实施例1:实施例1的正结构薄膜太阳能电池制备过程为:
(1)将ITO导电玻璃用洗洁精和去离子水洗涤15min,以便除去油脂和有机物,然后依次用去离子水、丙酮、乙醇超声洗涤10min,氮气吹干待用;
(2)将干净的ITO导电玻璃放在400℃加热台上,使用喷雾热解法喷涂2mg/mL氯化镉水溶液,喷嘴距基底距离为15cm,以2mL/min的速度喷涂10min制备150nm厚的Cd3Cl2O2薄膜,最后在400℃退火20min;
(3)在Cd3Cl2O2薄膜上使用快速热蒸发法在510℃蒸发60s制备500nm厚的Sb2Se3薄膜;
(4)在Sb2Se3薄膜上使用旋涂法制备80~100nm厚的P3HT薄膜,之后在120℃退火10min;
(5)将样品放入蒸发设备中,采用金蒸发源,当真空度小于1×10-3Pa时开始蒸发,沉积速度为1nm/s,蒸发沉积80nm厚的金电极作为金属电极层。获得硒化锑薄膜太阳能电池,并对其进行标准太阳光下电流-电压测试。
实施例2:实施例2的正结构薄膜太阳能电池制备过程为:
(1)将ITO导电玻璃用洗洁精和去离子水洗涤15min,以便除去油脂和有机物,然后依次用去离子水、丙酮、乙醇超声洗涤10min,氮气吹干待用;
(2)将干净的ITO导电玻璃放在400℃加热台上,使用喷雾热解法喷涂2mg/mL氯化镉水溶液,喷嘴距基底距离为15cm,以2mL/min的速度喷涂10min制备150nm厚的Cd3Cl2O2薄膜,最后在400℃退火20min;
(3)取90μl 0.1mmol/mL的溴化铅溶于N,N-二甲基甲酰胺的溶液在2000r.p.m.、30s 的条件下旋涂在Cd3Cl2O2电子传输层上,其后置于80℃平板加热台下退火60min,取90μl 0.07mmol/mL的溴化铯溶于无水甲醇的溶液在2000r.p.m.、30s的条件下旋涂在溴化铅上,生成500nm厚的CsPbBr3吸光层;
(4)在CsPbBr3薄膜上使用旋涂法制备150nm厚的P3HT薄膜,之后在120℃退火10min;
(5)将样品放入蒸发设备中,采用金蒸发源,当真空度小于1×10-3Pa时开始蒸发,沉积速度为1nm/s,蒸发沉积80nm厚的金电极作为金属电极层。获得钙钛矿太阳能电池,并对其进行标准太阳光下电流-电压测试。
实施例3:实施例3的倒结构薄膜太阳能电池制备过程为:
(1)不锈钢衬底进行抛光,使用电子清洗液清洗后,放入酒精超声10min,再放入丙酮超声10min,然后放入烘箱烘干;
(2)将样品放入磁控溅射设备,首先采用银靶,溅射功率为100W,气压保持在0.1Pa,制备厚度为100nm的银电极层。然后采用氧化镍靶,溅射功率为150W,气压保持在5Pa,制备厚度为200nm的NiO薄膜作为空穴传输层;
(3)在NiO薄膜上使用近空间升华法在580℃蒸发制备500nm厚的碲化镉薄膜,后用氯化镉蒸气处理在空气环境中390℃,退火30min;
(4)将前置基底放在200℃加热台上,使用喷雾热解法喷涂2mg/mL氯化镉水溶液,喷嘴距基底距离为15cm,以2mL/min的速度喷涂5min制备80nm厚的Cd3Cl2O2薄膜,最后在200℃,退火20min;
(5)将样品放入磁控溅射设备中,采用氧化铟锡靶,溅射功率为40W,气压保持在0.1 Pa,溅射100nm厚的氧化铟锡透明导电薄膜;
(6)使用丝网印刷设备,制备银栅线电极。获得碲化镉薄膜太阳能电池,并对其进行标准太阳光下电流-电压测试。
图4是具有Cd3Cl2O2薄膜的薄膜太阳能电池在100mW cm-2的模拟太阳光照射下测量J-V 曲线图,可以看到具有Cd3Cl2O2薄膜的硒化锑太阳能电池达到3.81%的效率。
本发明的技术方案与现有技术相比,能够取得下列有益效果:
(1)本发明以Cd3Cl2O2薄膜作为电子传输层材料,扩展了太阳能电池中电子传输层材料的应用范围;
(2)采用本发明的方法制备的Cd3Cl2O2薄膜作为薄膜太阳能电池的电子传输层,薄膜均匀平整,透光率高,导电率高,有利于提高太阳能电池效率,电池性价比高,使用寿命长;并且制备步骤简单,成本低廉,产率高且性质稳定,可进行工业化生产,进一步降低了薄膜太阳能电池的成本;
(3)Cd3Cl2O2薄膜为电子传输层的薄膜太阳能电池有较高的光电转换效率;
(4)Cd3Cl2O2薄膜用途广泛,可作为碲化镉薄膜太阳能电池、钙钛矿薄膜太阳能电池、硒化锑薄膜太阳能电池、硫化锑薄膜太阳能电池的电子传输层。
以上所述仅是本发明的优选方式,应当指出的是,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应该视为本发明的保护范围。
Claims (8)
1.一种Cd3Cl2O2薄膜制备方法,其特征是,它包括:将氯化镉溶于去离子水中,配制成浓度为0.1~10mg/mL氯化镉水溶液;将基底放在加热台上加热,加热台的温度为100~500℃;采用超声喷雾设备在基底上喷涂氯化镉水溶液,喷涂速率为0.5~2mL/min,喷涂时间为5~40min,喷涂距离为10~15cm,喷涂后形成厚度为20~200nm的Cd3Cl2O2薄膜半成品,再将厚度为20~200nm的Cd3Cl2O2薄膜半成品经温度为200~500℃,退火时间为10~30min退火处理,得到Cd3Cl2O2薄膜。
2.一种具有Cd3Cl2O2薄膜的薄膜太阳能电池,其特征是,包括:透明导电薄膜、Cd3Cl2O2薄膜、吸光层、空穴传输层和金属电极层依次相接触。
3.一种具有Cd3Cl2O2薄膜的薄膜太阳能电池,其特征是,包括:不锈钢衬底、金属电极层、空穴传输层、吸光层、Cd3Cl2O2薄膜、透明导电薄膜和金属栅线电极依次相接触。
4.根据权利要求2或3所述的一种具有Cd3Cl2O2薄膜的薄膜太阳能电池,其特征是,所述的透明导电薄膜是掺硼、铝和镓的氧化锌薄膜、掺氟二氧化锡薄膜和氧化铟锡薄膜中至少一种,膜厚为20~200nm。
5.根据权利要求2或3所述的一种具有Cd3Cl2O2薄膜的薄膜太阳能电池,其特征是,所述的吸光层是碲化镉薄膜、钙钛矿薄膜、硒化锑薄膜或硫化锑薄膜中的一种,厚度为200~1500nm。
6.根据权利要求2或3所述的一种具有Cd3Cl2O2薄膜的薄膜太阳能电池,其特征是,所述的空穴传输层是氧化镍薄膜、氧化铜薄膜、氧化钼薄膜或P3HT薄膜中至少一种,厚度为50~200nm。
7.根据权利要求2所述的一种具有Cd3Cl2O2薄膜的薄膜太阳能电池,其特征是,所述的金属电极层是金、银、铜或铝薄片,厚度为50~500nm。
8.根据权利要求3所述的一种具有Cd3Cl2O2薄膜的薄膜太阳能电池,其特征是,所述的金属电极层和金属栅线电极为金、银、铜或铝薄片,厚度为50~500nm。
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