CN109037042A - 一种基于水性纳米墨水制备铜锌锡硫薄膜的方法 - Google Patents
一种基于水性纳米墨水制备铜锌锡硫薄膜的方法 Download PDFInfo
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Abstract
本发明涉及一种基于水性纳米墨水制备铜锌锡硫薄膜的方法，其包括如下步骤：(1)衬底的清洗；(2)前驱体溶液的制备；(3)Cu2ZnSnS4纳米墨水的制备；(4)Cu2ZnSnS4预制薄膜的制备，在惰性气氛下烘干并退火处理，制备结晶性较好的Cu2ZnSnS4薄膜。本发明所提供的微波法一步制备水性Cu2ZnSnS4纳米墨水具有低成本，环保，工艺简单且稳定性好的优点，并可以解决制备纳米颗粒后再制备纳米墨水易团聚的问题。本发明通过涂覆法将纳米墨水制备成薄膜，无需在硫化气氛退火，只需在惰性气氛退火处理即可得到高质量的Cu2ZnSnS4薄膜。
Description
技术领域
本发明涉及涉及光电功能材料领域，具体地说，涉及一种基于水性纳米墨水制备铜锌锡硫薄膜的方法。
背景技术
随着时代的进步，经济社会的高速发展，现代社会对于能源的需求越来越高。目前使用的传统化石能源造成了严重的环境污染且化石能源日益匮乏，这些因素迫使人们寻找可再生清洁能源。太阳能取之不尽用之不竭，是人类最理想的可替代能源。通过光伏发电技术将太阳能转换为电能，可以更好地位人类服务。
太阳太阳电池是光伏发电的核心部件，经过多年的发展，太阳电池的研究已取得了许多丰硕成果。然而，目前太阳电池依然面临造价成本高的问题。因此，寻找一种低成本且环保的太阳电池材料和其制备方法迫在眉睫。目前，太阳电池材料Cu(Ga,In)(S,Se)2(CIGS)薄膜太阳电池受到广泛关注，其最高转化效率已经达到22.3％(PhotovoltaicSpecialista Conference,2016:1287-1291)。但是，由于其中掺杂的In和Ga为稀缺元素，价格高昂，且Se是有毒的，易造成污染等问题，极大限制了其应用。Cu2ZnSnS4(CZTS)作为CIGS的同类材料，其带隙约为1.48eV，十分接近理想太阳电池吸收层的带隙1.5eV，且具有高的吸收系数(>104cm-1)。同时，Cu2ZnSnS4太阳电池理论效率可高达32.4％，并且Cu、Zn、Sn、S元素在地壳中含量都较高，无毒害。因此CZTS是一种非常理想的太阳电池材料。用一部分Cd取代Cu2ZnSnS4中的S的Cu2(Zn,Cd)SnS4(CZCTS)电池效率可达到9.24％(Advanced EnergyMaterials,2015,5)。综上所述，这种新型Cu2ZnSnS4(CZTS)太阳电池有广阔的应用前景和巨大的商业利用价值。
目前，墨水法制备Cu2ZnSnS4薄膜可以大大降低制备成本，解决磁控溅射法和热蒸发法的高成本问题。目前，采用常规的纳米墨水法制备薄膜，首先制备出Cu2ZnSnS4纳米颗粒，然后将其配制成墨水的方法，再采用旋涂法将其制成薄膜，最后在硫化气氛下退火处理制备出Cu2ZnSnS4薄膜。但这种方法存在几个问题，首先制备出的水性纳米颗粒通过清洗后再分散容易团聚，在清洗过程中将纳米颗粒表面附着的表面活性剂去除从而无法达到良好分散的效果。因此，直接采用这种纳米墨水制备出的薄膜存在大量的裂纹。另外，需要硫化退火，在退火过程中易产生硫化氢气体，污染环境。而采用油性体系制备的纳米颗粒具有较好的分散性，但是所使用的溶剂大多不环保。
发明内容
为解决上述技术问题，本发明提供一种基于水性纳米墨水制备铜锌锡硫薄膜的方法，该方法无需真空设备，降低生产成本，制备周期短，适合工业化大规模生产，制备Cu2ZnSnS4纳米墨水分散性好，工艺稳定性好，易操作，而且制备的Cu2ZnSnS4薄膜的均匀性和致密性大大提高。
为实现上述目的，本发明采用如下技术方案：
一种基于水性纳米墨水制备铜锌锡硫薄膜的方法，包括以下步骤：
(1)衬底的清洗：依次采用去污粉水、去离子水、丙酮-乙醇混合液、去离子水超声清洗衬底；
(2)前驱体溶液的制备：将二价铜盐、二价锌盐、二价锡盐及含硫化合物依次溶解到有机溶剂中，添加比例按照摩尔比Cu/(Zn+Sn)＝0.8-1.2，Sn/Zn＝0.8-1.2，S/(Cu+Zn+Sn)＝1-5；待完全溶解后加入8-20g/L的表面活性剂，制得前驱体溶液；
(3)Cu2ZnSnS4纳米墨水的制备：表面活性剂未完全溶解之前，将得到的前驱体溶液放入到微波反应器中，采用微波法制备Cu2ZnSnS4纳米墨水，微波功率为50-1000W，微波时间1-30min；
(4)Cu2ZnSnS4预制薄膜的制备：将所制备的Cu2ZnSnS4纳米墨水均匀的涂敷到衬底上，将衬底放置到真空退火炉中；在氮气或氩气气氛中，5-20℃/min升温速率升温至300-500℃下烘干并退火处理20-120min，然后随炉冷却至室温。
进一步的技术方案，所述的步骤(1)中，衬底为钠钙玻璃、康宁玻璃中一种。
进一步的技术方案，所述的步骤(2)中，二价铜盐为氯化铜、乙酸铜或硝酸铜；
二价锡盐为氯化亚锡；二价锌盐为氯化锌、乙酸锌或硝酸锌；
含硫化合物为硫脲、硫代乙酰胺、L-半胱氨酸中的一种或两种组合；
有机溶剂为乙二醇、正丙醇、丙三醇、乙二醇甲醚中的一种或两种组合；
表面活性剂为聚乙烯吡咯烷酮(PVP)。
本发明原理：利用微波加热反应速度快且加热均一的特点，快速制备出高质量的Cu2ZnSnS4纳米墨水；同时利用纳米墨水预先成相的特点，不需要再硫化气氛下退火处理，可以直接在较为环保的惰性气氛下退火处理制备光电性能优异的Cu2ZnSnS4薄膜。
有益效果
1、本发明采用的原材料都是环境相容性的，不会对环境造成破坏，避免使用难以降解或者对环境污染的化学药品或试剂。
2、本发明退火处理时不需要硫化处理，极大地提高了纳米颗粒的分散性，从而提高了薄膜的致密性和均匀性，同时避免了退火处理过程中产生的硫化氢气体污染节能环保。
3、本发明将纳米颗粒的制备与纳米墨水配制两个过程融合为一个步骤，原前驱体溶液中的表面活性剂吸附在纳米颗粒表面有益于抑制纳米颗粒团聚，达到纳米墨水稳定分散的效果，工艺步骤更为简单，工艺可控制性高，生产出的纳米薄膜性质稳定且均匀，有良好的光电转化效率，有效解决制备纳米颗粒后再制备纳米墨水易团聚的现象，提高了纳米墨水的分散性，提高了薄膜的均匀性。
4、本发明所采用的墨水法属于非真空法，避免了采用真空设备昂贵的问题，而且这种方法适合大规模生产，具有广阔的应用前景。
附图说明
图1为对比例中所制备的Cu2ZnSnS4薄膜的扫描电子显微镜(SEM)图片；
图2为实施例1中所制备的Cu2ZnSnS4薄膜的扫描电子显微镜(SEM)图片；
图3为实施例1中所制备的Cu2ZnSnS4薄膜的X射线衍射(XRD)图谱；
图4为实施例1中所制备的Cu2ZnSnS4薄膜的拉曼(Raman)光谱。
具体实施方式
下面结合实施例对本发明作进一步描述，但不应以此限制本发明的保护范围。
对比例和实施例中的衬底依次采用去污粉水、去离子水、丙酮-乙醇混合液、去离子水超声清洗，备用。
对比例
一种Cu2ZnSnS4薄膜的制备方法，包括以下步骤：
称取0.001mol乙酸锌、0.001mol氯化亚锡、0.0018mol硝酸铜和0.009mol硫代乙酰胺和0.64g PVP依次溶于50mL的乙二醇中，配制成前驱体溶液。采用微波法将前驱体溶液微波加热，微波功率为400W，微波时间10min制备得到Cu2ZnSnS4纳米颗粒，然后采用去离子水和无水乙醇清洗所得到Cu2ZnSnS4纳米颗粒。将清洗后的纳米颗粒按照100mg/mL分散在无水乙醇中，在超声中分散30min得到Cu2ZnSnS4纳米墨水。再将纳米墨水涂敷至玻璃衬底上，放置到真空退火炉中。在氮气气氛下，按照10℃/min升温至400℃，保温60min，然后随炉冷却至室温。图1为所得到薄膜的SEM图片，薄膜表面明显存在大量的裂纹。
实施例1
一种基于水性纳米墨水制备铜锌锡硫薄膜的方法，包括以下步骤：
(1)称取0.001mol乙酸锌、0.001mol氯化亚锡、0.0018mol硝酸铜和0.009mol硫代乙酰胺依次溶于50mL的乙二醇中，待其完全溶解之后加入0.64g PVP配制成前驱体溶液。
(2)采用微波法将前驱体溶液微波加热，微波功率为400W，微波时间10min制备得到Cu2ZnSnS4纳米颗墨水。
(3)将纳米墨水涂敷至玻璃衬底上，放置到真空退火炉中。在氮气气氛下，按照10℃/min升温至400℃，保温60min，然后随炉冷却至室温。
对得到的产品进行检测，图1为所制备Cu2ZnSnS4薄膜的SEM图片，与对比例中所制备的薄膜相比，此方法得到的薄膜表面平整且致密。图2为实施例1所制备Cu2ZnSnS4薄膜的XRD图谱，所制备的薄膜具有明显的衍射峰，衍射峰较为尖锐说明具有很好的结晶性，衍射峰对应于锌黄锡矿结构的Cu2ZnSnS4。图3为所制备Cu2ZnSnS4薄膜的Raman光谱，在288cm-1、338cm-1和368cm-1处存在三个Raman峰，也对应于锌黄锡矿结构的Cu2ZnSnS4。
实施例2
一种基于水性纳米墨水制备铜锌锡硫薄膜的方法，包括以下步骤：
(1)称取0.001mol乙酸锌、0.0012mol氯化亚锡、0.00176mol氯化铜和0.0396mol的硫脲溶于50mL正丙醇中，待其完全溶解之后加入0.7g PVP，配制成前驱体溶液。
(2)采用微波法将前驱体溶液微波加热，微波功率为600W，微波时间8min，得到Cu2ZnSnS4纳米墨水。
(3)将纳米墨水涂敷至玻璃衬底上，放置到真空退火炉中。在氩气气氛下，按照20℃/min升温至500℃，保温20min，然后随炉冷却至室温，即可得到较为致密的Cu2ZnSnS4薄膜。
实施例3
一种基于水性纳米墨水制备铜锌锡硫薄膜的方法，包括以下步骤：
(1)称取0.001mol氯化锌、0.0008mol氯化亚锡、0.0018mol氯化铜和0.018mol的L-半胱氨酸溶于50mL的丙三醇中，搅拌均匀使其完全溶解于丙三醇中，加入0.4g PVP配制成前驱体溶液。
(2)采用微波法将前驱体溶液微波加热，微波功率为50W，微波时间30min，得到Cu2ZnSnS4纳米墨水。
(3)将纳米墨水涂敷至玻璃衬底上，放置到真空退火炉中。在氮气气氛下，按照5℃/min升温至300℃，保温120min，然后随炉冷却至室温，即可得到较为致密的Cu2ZnSnS4薄膜。
实施例4
一种基于水性纳米墨水制备铜锌锡硫薄膜的方法，包括以下步骤：
(1)称取0.001mol氯化锌、0.001mol氯化亚锡、0.0024mol乙酸铜和0.0088mol硫脲溶于50mL的乙二醇甲醚中，搅拌均匀使其完全溶解于乙二醇甲醚中，加入1g PVP配制成前驱体溶液。
(2)采用微波法将前驱体溶液微波加热，微波功率为200W，微波时间25min，得到Cu2ZnSnS4纳米墨水。
(3)将纳米墨水涂敷至玻璃衬底上，放置到真空退火炉中。在氩气气氛下，按照15℃/min升温至450℃，保温60min，然后随炉冷却至室温，即可得到较为致密的Cu2ZnSnS4薄膜。
Claims (3)
1.一种基于水性纳米墨水制备铜锌锡硫薄膜的方法，其特征在于：包括以下步骤：
(1)衬底的清洗：依次采用去污粉水、去离子水、丙酮-乙醇混合液、去离子水超声清洗衬底；
(2)前驱体溶液的制备：将二价铜盐、二价锌盐、二价锡盐及含硫化合物依次溶解到有机溶剂中，添加比例按照摩尔比Cu/(Zn+Sn)＝0.8-1.2，Sn/Zn＝0.8-1.2，S/(Cu+Zn+Sn)＝1-5；待完全溶解后加入8-20g/L的表面活性剂，制得前驱体溶液；
(3)Cu2ZnSnS4纳米墨水的制备：表面活性剂未完全溶解之前，将得到的前驱体溶液放入到微波反应器中，采用微波法制备Cu2ZnSnS4纳米墨水，微波功率为50-1000W，微波时间1-30min；
(4)Cu2ZnSnS4预制薄膜的制备：将所制备的Cu2ZnSnS4纳米墨水均匀的涂敷到衬底上，将衬底放置到真空退火炉中；在氮气或氩气气氛中，5-20℃/min升温速率升温至300-500℃下烘干并退火处理20-120min，然后随炉冷却至室温。
2.根据权利要求1所述的基于水性纳米墨水制备铜锌锡硫薄膜的方法，其特征在于：
所述的步骤(1)中，衬底为钠钙玻璃、康宁玻璃中一种。
3.根据权利要求1所述的基于水性纳米墨水制备铜锌锡硫薄膜的方法，其特征在于：
所述的步骤(2)中，二价铜盐为氯化铜、乙酸铜或硝酸铜；
二价锡盐为氯化亚锡；二价锌盐为氯化锌、乙酸锌或硝酸锌；
含硫化合物为硫脲、硫代乙酰胺、L-半胱氨酸中的一种或两种组合；
有机溶剂为乙二醇、正丙醇、丙三醇、乙二醇甲醚中的一种或两种组合；
表面活性剂为聚乙烯吡咯烷酮。
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