CN106531845B - 化学水浴制备太阳能电池吸收层CuInS2薄膜的方法 - Google Patents
化学水浴制备太阳能电池吸收层CuInS2薄膜的方法 Download PDFInfo
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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Abstract
本发明涉及一种化学水浴制备太阳能电池吸收层CuInS2薄膜的方法。采用的技术方案是:对衬底表面进行清洗,利用化学水浴沉积法,将衬底浸泡于硫化铟沉积液中,沉积5‑60min后得到硫化铟薄膜;利用化学水浴沉积法,将沉积有硫化铟薄膜的钼衬底浸泡于氧化亚铜沉积液中继续沉积一层氧化亚铜薄膜,沉积5‑60min后获得的In2S3/Cu2O前驱体;将获得的前驱体,置于硫气氛下进行退火制得所述的太阳能电池吸收层CIS薄膜。本发明提出了一种利用低成本、制备过程简单、成本低廉、制备周期短的化学水浴合成法制备新型Mo/In2S3/Cu2O前驱体,经过分步热处理得到吸收层薄膜。
Description
技术领域
本发明涉及太阳能电池材料与器件技术领域,具体涉及一种化学水浴制备太阳能电池吸收层CuInS2薄膜的方法。
背景技术
随着社会经济的快速发展,人们对化石能源的需求日益增长,传统化石能源所面临的困境越来越严峻。加之过度的化石能源的使用会对环境造成污染。因此,为了发展环境友好型经济跟解决能源危机问题,寻找一种新型的替代性能源显得尤为重要。太阳能是一种储量丰富、清洁无污染的可再生能源。而将该能源直接转化成电能的有效方式是光伏发电,即太阳能电池。
发展至今,太阳能电池种类繁多,其中铜铟镓硒系列薄膜太阳能电池具有效率高、成本低廉、稳定性好、无毒等优点,所以被看作是一类具有最有很大发展潜力的薄膜太阳能电池。而铜铟镓硒系列太阳能电池中的吸收层材料主要包括:铜铟镓硒(Cu(In,Ga)Se2)、铜铟镓硫(Cu(In,Ga)S2)、铜铟硒(CuInSe2)、铜镓硒(CuGaSe2)铜铟硫(CuInS2)、铜镓硫(CuGaS2)等薄膜。其中铜铟硫(CuInS2,CIS)作为一种直接带隙半导体,其具有与太阳光谱较为匹配的带隙宽度(1.50eV),吸收系数(105cm-1)较大,原料便宜等优点,具有很好的产业化发展前景。目前基于磁控溅射制备CIS薄膜为吸收层,取得了超过12.5%效率的太阳能电池;进一步通过使用Ga部分替代CIS中的In已经取得了21.7%的太阳能电池转换效率; 基于CIS为吸收层,通过使用Al部分替代In获得了16.9%的电池转换效率。因此这种新型的无机薄膜太阳能电池有着巨大的应用前景和商机。
当前制备CIS太阳能电池吸收层材料的方法有很多,大致可分为真空法和非真空法两大类。其中真空法主要包括磁控溅射、热蒸发法等方法,这类方法所需设备比较昂贵,生产成本较高;而非真空法可分为电沉积、溶胶凝胶法、化学水浴沉积法及纳米颗粒法等,这类方法具有制备过程简单、制备成本廉价、易于大规模生产等多种优点,得到了更多关注和研究。其中化学水浴沉积法具有过程简单、成本低等特点,有利于实现大规模化生产。经对现有技术文献专利检索发现,吸收层CIS薄膜非真空法制备方面的专利有很多,例如利用硼氢化钠还原铜盐和铟盐制备Cu-In合金纳米颗粒,进而将其溶解在有机溶剂中制备成Cu-In合金墨水,涂覆在Si片,Mo片或者玻璃等衬底上制备成前驱体薄膜。而后,在含有H2S/Ar混合气氛中烧结成为表面呈纳米棒阵列的CuInS2薄膜(申请号201110362766.0)。整个实验过程周期长,涉及有机化学药品,步骤较多,操作难度大。因此本专利专注于此问题,采用操作简单、制备周期短,安全无毒的方法制备出前驱薄膜,再通过在硫气氛中热进行处理,获得均匀大面积、高质量的CIS薄膜。
发明内容
本发明的目的是提出一种低成本化学水浴制备化合物薄膜太阳能电池吸收层CuInS2 (CIS)薄膜的方法。此方法先利用化学水浴沉积制备出In2S3/Cu2O前驱体,并经过硫(S)气氛中热处理获得CIS薄膜的方法,该方法具有合成工艺简单、制备设备简单、可大面积均匀制备、成膜致密、薄膜成分以及厚度易控等优点,适用于大规模的工业生产。
为实现本发明的目的所采用的技术方案是:
步骤一:对衬底表面进行清洗,利用化学水浴沉积法,将衬底浸泡于硫化铟(In2S3)沉积液中,沉积5-60min后得到硫化铟薄膜;
步骤二:利用化学水浴沉积法,将沉积有硫化铟薄膜的钼(Mo)衬底浸泡于氧化亚铜(Cu2O)沉积液中继续沉积一层氧化亚铜(Cu2O)薄膜,沉积5-60min后获得的In2S3/Cu2O前驱体;
步骤三:将获得的In2S3/Cu2O前驱体,置于硫(S)气氛下在密闭或者流通的管式炉内进行退火制得本发明所述的太阳能电池吸收层CIS薄膜。
本发明步骤一所述的In2S3沉积液是指:先分别配置浓度分别为37.5mM的氯化铟溶液,1.58mM硫代乙酰胺溶液,然后取20mL配好的氯化铟溶液、10mL配好的硫代乙酰胺溶液、0.092mL盐酸(36%-38%)和0.515mL的冰醋酸(>95.5%)混合搅匀得到沉积液。
本发明步骤一中所述的衬底为镀钼薄膜的钠钙玻璃、石英玻璃中的一种。
本发明步骤二中所述的氧化亚铜的沉积液,是指:先分别配置浓度分别为0.5M的硫酸铜,0.5M的抗坏血酸钠,0.5M二水合柠檬酸三钠,(25%-28%)的氨水溶液,分别取13mL的硫酸铜、7mL抗坏血酸钠、13 mL二水合柠檬酸三钠、0.7 mL氨水并加入26.3mL去离子水混合搅匀即可。
本发明步骤二中所述的沉积,是指将沉积液倒入插有生长硫化铟薄膜的Mo玻璃中,在80℃恒温水浴下沉积5-60min。
本发明步骤三中所述的硫(S)气氛下进行退火,是指将In2S3/Cu2O前驱薄膜与固态硫源或硫化氢气体置于密闭空间退火,或者是将In2S3/Cu2O前驱体薄膜处于流动的硫蒸汽或者硫化氢气体中退火;
当上述步骤中的退火采用固态硫时,保持固态硫源温度450~600℃,热处理时间20~60 min。
当上述步骤中的退火采用流动的硫蒸汽时,保持固态硫源温度250~600℃,热处理时间20~60 min。
上述技术方案中所涉及到的化学试剂均采购于国药集团化学试剂公司,硫粉采购于Aladdin Chemistry co.ltd,衬底所涉及到的镀钼玻璃和钠钙玻璃分别采购于生阳新材料科技(宁波)有限公司和洛阳龙耀玻璃有限公司。
本发明的原理是:
1)使用化学水浴沉积的方法在Mo衬底上沉积出硫化铟和氧化亚铜叠层的前驱体薄膜。
2)将上述前驱体薄膜在硫气氛下退火,得到相应的吸收层CIS薄膜。
本发明具有以下突出有益效果:本发明提出了一种利用低成本、制备过程简单的化学水浴合成法制备新型Mo/In2S3/Cu2O前驱体,经过分步热处理得到吸收层薄膜。根据前面相关专利报道,其他非真空方法制备CIS薄膜材料的前驱薄膜,操作复杂,大都需要长时间的制备,降低生产效率。因此本专利采用了公认的制备方法简单的化学水浴方法成功合成CIS吸收层薄膜。具体有益如下几点:
1)专利检索发现,本专利首次利用低成本的化学水浴沉积法利用新型的Mo/In2S3/Cu2O前驱体制备出CIS薄膜;
2)用化学水浴法制备CIS薄膜有文献报道有两个大的方面的益处:其一,在于薄膜成分可以很容易的通过控制叠层厚度来实现;其二,在于化学水浴可以做到大面积的沉积,并且制得的薄膜具有较高的平整度跟致密性,适合工业化大规模制备要求;
3)本发明利用化学水浴沉积的方法制备前驱膜,并通过硫化得到吸收层薄膜,具有设备简单,制备成本低廉,可大面积制备沉积,制备周期较短,成分以及薄膜厚度易控等优点。
附图说明
下面结合附图,对本发明作进一步说明。
图1为本发明所述制备吸收层CIS薄膜的XRD图。
图2为本发明所述制备吸收层CIS薄膜的Raman图。
图3为本发明所述制备吸收层CIS薄膜的SEM图。
具体实施方式
为了对本发明有更好的理解,现以实施例的方式对本发明做进一步的说明。实施例1
1、将钼玻璃衬底依次浸入普通洗涤剂、去离子水、乙醇,丙酮溶液中,然后去离子水超声并冲洗干净,氮气吹干备用;
2、先分别配置浓度分别为37.5mM氯化铟,1.58mM硫代乙酰胺,然后取20mL配好的氯化铟溶液、10mL配好的硫代乙酰胺溶液、0.092mL盐酸(36%-38%)和0.515mL的冰醋酸(>95.5%)混合搅匀,将溶液倒入插有衬底的空瓶子中,在80℃恒温水浴中生长15min,得到一定薄膜厚度的硫化铟薄膜,取出后用去离子水冲洗干净,在60℃干燥箱中干燥1h;
3、接着分别配置浓度分别为0.5M的硫酸铜,0.5M抗坏血酸钠,0.5M二水合柠檬酸三钠,(25%-28%)氨水溶液,分别取13mL的硫酸铜、7mL抗坏血酸钠、13 mL二水合柠檬酸三钠、0.7 mL氨水并加入26.3mL去离子水混合搅匀,将溶液倒入插有生长硫化铟薄膜的Mo玻璃中,在80℃恒温水浴生长12min,得到生长了Mo/In2S3/Cu2O前驱体的薄膜,取出后用去离子水冲洗干净,在60℃干燥箱中干燥1h;
4、利用步骤3)得到的Mo/In2S3/Cu2O前驱体薄膜先后在硫气氛中热处理。选择密闭管式炉,使用硫粉作为硫源,将0.02g硫粉与Mo/In2S3/Cu2O前驱体薄膜置于密闭管式炉内,抽背景真空至10-2pa。使硫粉与Mo/In2S3/Cu2O前驱体薄膜同时从室温开始升温,升温速率40℃/min,最终保持在580℃,保温30min,随后缓慢冷却到室温后,得到CIS薄膜。
利用X射线衍射和拉曼光谱对本实施例制备的CIS薄膜进行测试,CIS薄膜的X射线衍射图谱如图2所示,图3为本实施例制备的CIS薄膜的拉曼图谱。从图2和图3可以看出,所述CIS薄膜为单相黄铜矿结构的CIS,具有较强的(112)取向。利用扫描电镜对本实施例制备的CIS薄膜进行观察可以看出,该CIS薄膜致密性好、结晶性强、平整性高。
实施例2
1、将钼玻璃衬底依次浸入普通洗涤剂、去离子水、乙醇,丙酮溶液中,然后去离子水超声并冲洗干净,氮气吹干备用;
2、先分别配置浓度分别为37.5mM氯化铟,1.58mM硫代乙酰胺,然后取20mL配好的氯化铟溶液、10mL配好的硫代乙酰胺溶液、0.092mL盐酸(36%-38%)和0.515mL的冰醋酸(>95.5%)混合搅匀,将溶液倒入插有衬底的空瓶子中,在60℃恒温水浴中生长15min,得到一定薄膜厚度的硫化铟薄膜,取出后用去离子水冲洗干净,在60℃干燥箱中干燥1h;
3、接着分别配置浓度分别为0.5M的硫酸铜,0.5M抗坏血酸钠,0.5M二水合柠檬酸三钠,(25%-28%)氨水溶液,分别取13mL的硫酸铜、7mL抗坏血酸钠、13 mL二水合柠檬酸三钠、0.7 mL氨水并加入26.3mL去离子水混合搅匀,将溶液倒入插有生长硫化铟薄膜的Mo玻璃中,在60℃恒温水浴生长12min,得到生长了Mo/In2S3/Cu2O前驱体的薄膜,取出后用去离子水冲洗干净,在60℃干燥箱中干燥1h。
实施例3
1、将钼玻璃衬底依次浸入普通洗涤剂、去离子水、乙醇,丙酮溶液中,然后去离子水超声并冲洗干净,氮气吹干备用;
2、先分别配置浓度分别为37.5mM氯化铟,1.58mM硫代乙酰胺,然后取20mL配好的氯化铟溶液、10mL配好的硫代乙酰胺溶液、0.092mL盐酸(36%-38%)和0.515mL的冰醋酸(>95.5%)混合搅匀,将溶液倒入插有衬底的空瓶子中,在80℃恒温水浴中生长12min,得到一定薄膜厚度的硫化铟薄膜,取出后用去离子水冲洗干净,在60℃干燥箱中干燥1h;
3、接着分别配置浓度分别为0.5M的硫酸铜,0.5M抗坏血酸钠,0.5M二水合柠檬酸三钠,(25%-28%)氨水溶液,分别取13mL的硫酸铜、7mL抗坏血酸钠、13 mL二水合柠檬酸三钠、0.7 mL氨水并加入26.3mL去离子水混合搅匀,将溶液倒入插有生长硫化铟薄膜的Mo玻璃中,在80℃恒温水浴生长12min,得到生长了Mo/In2S3/Cu2O前驱体的薄膜,取出后用去离子水冲洗干净,在60℃干燥箱中干燥1h。
以上所述实施例仅表达了本发明的具体实施方式,是对本发明做了进一步说明,描述较为详细和具体,但并不能因此理解为对本发明专利的限制。应当指出的是,在不脱离本发明构思的前提下,做出若干改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (7)
1.一种化学水浴制备太阳能电池吸收层CuInS2薄膜的方法,其特征在于: 步骤一:对衬底表面进行清洗,利用化学水浴沉积法,将衬底浸泡于硫化铟(In2S3)沉积液中,沉积5-60min后得到硫化铟薄膜; 步骤二:利用化学水浴沉积法,将沉积有硫化铟薄膜的钼(Mo)衬底浸泡于氧化亚铜(Cu2O)沉积液中继续沉积一层氧化亚铜(Cu2O)薄膜,沉积5-60min后获得的In2S3/Cu2O前驱体; 步骤三:将获得的In2S3/Cu2O前驱体,置于硫(S)气氛下在密闭或者流通的管式炉内进行退火制得所述的太阳能电池吸收层CIS薄膜;步骤二中所述的氧化亚铜的沉积液,是指:先分别配置浓度分别为0.5M的硫酸铜,0.5M的抗坏血酸钠,0.5M二水合柠檬酸三钠,25%~28%的氨水溶液,分别取13mL的硫酸铜、7mL抗坏血酸钠、13 mL二水合柠檬酸三钠、0.7 mL氨水并加入26.3mL去离子水混合搅匀即可。
2.根据权利要求1所述的化学水浴制备太阳能电池吸收层CuInS2薄膜的方法,其特征在于步骤一所述的In2S3沉积液是指:先分别配置浓度分别为37.5mM的氯化铟溶液,1.58mM硫代乙酰胺溶液,然后取20mL配好的氯化铟溶液、10mL配好的硫代乙酰胺溶液、0.092mL质量浓度为36%-38%的盐酸和0.515mL质量浓度>95.5%的冰醋酸混合搅匀得到沉积液。
3.根据权利要求1所述的化学水浴制备太阳能电池吸收层CuInS2薄膜的方法,其特征在于步骤一中所述的衬底为镀钼薄膜的钠钙玻璃、石英玻璃中的一种。
4.根据权利要求1所述的化学水浴制备太阳能电池吸收层CuInS2薄膜的方法,其特征在于步骤二中所述的沉积,是指将沉积液倒入插有生长硫化铟薄膜的Mo玻璃中,在80℃恒温水浴下沉积5-60min。
5.根据权利要求1所述的化学水浴制备太阳能电池吸收层CuInS2薄膜的方法,其特征在于步骤三中所述的硫(S)气氛下进行退火,是指将In2S3/Cu2O前驱薄膜与固态硫源或硫化氢气体置于密闭空间退火,或者是将In2S3/Cu2O前驱体薄膜处于流动的硫蒸汽或者硫化氢气体中退火。
6.根据权利要求4所述的化学水浴制备太阳能电池吸收层CuInS2薄膜的方法,其特征在于当退火采用固态硫时,保持固态硫源温度450~600℃,热处理时间20~60 min。
7.根据权利要求4所述的化学水浴制备太阳能电池吸收层CuInS2薄膜的方法,其特征在于当退火采用流动的硫蒸汽时,保持固态硫源温度250~600℃,热处理时间20~60 min。
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