CN108793196A - 银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜及其制备方法和应用 - Google Patents

银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜及其制备方法和应用 Download PDF

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CN108793196A
CN108793196A CN201810170285.1A CN201810170285A CN108793196A CN 108793196 A CN108793196 A CN 108793196A CN 201810170285 A CN201810170285 A CN 201810170285A CN 108793196 A CN108793196 A CN 108793196A
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徐伟
甘营
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Abstract

本发明属于纳米结构功能薄膜技术领域，具体为银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜及其制备方法和应用。本发明提出银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜的制备方法，以硫氰酸亚铜薄膜为前体，依次用硝酸银水溶液和三氯化铈水溶液浸泡处理获得。这种掺杂薄膜有多种用途，其中一个应用是作为表面增强拉曼谱的基底，能检测极微量有机分子，检测极限浓度达到10‑10摩尔/升。

Description

银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜及其制备方法和 应用
技术领域
本发明属于纳米功能薄膜技术领域，具体涉及银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜及其制备方法和应用。
背景技术
硫氰酸亚铜（CuSCN）是一种重要的络合物半导体。发明人前期曾发现氰酸亚铜（CuSCN）薄膜可用做电存储薄膜，还可以与氢氧化钠溶液反应形成氧化亚铜纳米线薄膜。硫氰酸亚铜能够转化成氧化亚铜这一事例表明，硫氰酸亚铜还有更广阔的空间来实现多种类型的功能化改造。[（1） Y-W. Dong, X. Ji, W. Xu, J-Q. Tang, P. Guo. ResistiveSwitching and Memory Effect Based on CuSCN Complex Layer Created ThroughInterface Reactions. Electrochem. Solid-State Lett. 2009, 12(3): H54;（2）X.Ji, Y-W. Dong, Z-Q. Huo, and W. Xu, Resistive Switching Memory Based on CuSCNFilms Fabricated by Solution-Dipping Method. Electrochem. Solid-State Lett.2009, 12(9): H344；（3）X.X Xiao, P. Xia, X. Ji, W. Xu. In situ synthesis andcharacterization of Cu2O nanowire networks from CuSCN films. Materials Letters2014, 128: 271-274]。
掺杂是材料改性的一种有效的手段，作为一种络合物半导体，化学掺杂比较简单，成本低，也更容易打开一个新的空间。基于这样一种简单的考虑，我们最近尝试用硝酸银溶液来处理硫氰酸亚铜薄膜，并成功实现银掺杂。
本发明提出用多种化合物来共掺杂络合物薄膜，并证明有极优异的效果和性能，这种策略能够为功能材料的修饰和改性开辟一个新的方向。
发明内容
本发明的目的在于提出一种银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜及其制备方法和应用。
本发明提出的这种银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜，通过简单的化学掺杂来实现。
本发明提出的银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜的制备方法，以硫氰酸亚铜薄膜为前体，通过与银盐水溶液和铈盐水溶液反应，制备银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜；具体流程为，将沉积在固态基底上的硫氰酸亚铜薄膜浸入银盐水溶液中，反应一段时间，再浸入铈盐水溶液中，继续反应一段时间，从而形成银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜。
本发明中，所述硫氰酸亚铜薄膜由铜膜和可溶性硫氰酸盐（比如：硫氰酸钠或者硫氰酸铵）水溶液反应制备获得。
本发明中，所述银盐水溶液的浓度为0.001~0.05摩尔/升。硫氰酸亚铜薄膜与银盐水溶液的反应时间为5~30分钟。
本发明中，所述铈盐水溶液的浓度为0.001~0.02摩尔/升。硫氰酸亚铜薄膜与铈盐水溶液的反应时间为1~10分钟。
本发明中，所述银盐可采用硝酸银，硝酸银水溶液的浓度为0.001~0.05摩尔/升；硫氰酸亚铜薄膜与硝酸银水溶液的反应时间为5~30分钟。
本发明中，所述铈盐可采用三氯化铈，三氯化铈水溶液的浓度为0.001~0.02摩尔/升；硫氰酸亚铜薄膜与三氯化铈水溶液的反应时间为1~10分钟。
本发明还提出具体的制备步骤，如下：
将硫氰酸亚铜薄膜浸入硝酸银水溶液中，反应一段时间，再浸入铈盐水溶液中继续反应一段时间，自然晾干，即得银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜。
扫描电子显微镜（SEM）分析显示这种复合薄膜的主要形貌特征为纳米结构。
本发明提出的银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜的应用，即用做表面增强拉曼谱（SERS）的检测基底，能够用于检测极微量的有机分子，有极高的灵敏度，例如对于罗丹明6G分子（R6G）极限检测浓度能达到1×10-10摩尔/升。可用于分子科学研究、污染物检测、食品中微量物质检测以及生物医药和环境卫生等领域。
本发明提出的银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜，由于存在多组元的相互作用，在某些功能方面会进一步相互加强，在光电功能材料和吸附材料领域还有广泛的应用价值。
附图说明
图1银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜的SEM图像。
图2银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜的高分辨SEM图像。
图3 银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜用做SERS基底。罗丹明6G水溶液的浓度为10-9 摩尔/升。图中，上面一条拉曼曲线采用银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜基底；下面一条曲线采用的基底只用银盐掺杂。说明银盐和铈盐共掺杂的增强效果要明显优于银盐单独掺杂的效果。
图4银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜用做SERS基底。罗丹明6G水溶液的浓度为10-10 摩尔/升。
具体实施方式
下面通过实施例进一步描述本发明提出的银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜及其制备方法和应用。
实施例1（薄膜制备）
将硫氰酸亚铜薄膜浸入浓度为0.025摩尔/升的硝酸银水溶液中，浸泡15分钟后，取出，再浸入浓度为0.01摩尔/升的三氯化铈水溶液中，浸泡5分钟，然后取出晾干或者热风吹干。即得银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜。
图1和图2是硫氰酸亚铜复合薄膜的SEM图像。
实施例2
配制浓度为10-9摩尔/升的罗丹明6G水溶液，将银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜浸入其中，浸泡2小时，取出晾干。然后用于表面增强拉曼检测。
图3显示银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜具有极高的拉曼增强效果。作为对比，银盐单独掺杂的硫氰酸亚铜复合薄膜基底的增强效果相对较弱。
实施例3
配制浓度为10-10摩尔/升的罗丹明6G水溶液，将银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜浸入其中，浸泡24小时，取出晾干。然后用于表面增强拉曼检测。
图4显示银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜基底仍然能检测出罗丹明6G的特征峰。作为对比，银盐单独掺杂的硫氰酸亚铜复合薄膜基底检测不出罗丹明6G。
结论：
银盐单独掺杂的硫氰酸亚铜复合薄膜基底的最低检测极限浓度为10-9摩尔/升；
银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜基底的最低检测极限浓度为10-10摩尔/升。
本发明证明，银盐和铈盐共掺杂可提高一个数量级的灵敏度。

Claims (5)

1.一种银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜的制备方法，其特征在于，以硫氰酸亚铜薄膜为前体，通过与硝酸银水溶液和铈盐水溶液反应，制备银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜；具体流程为：将沉积在固态基底上的硫氰酸亚铜薄膜浸入硝酸银水溶液中，反应一段时间，再浸入铈盐水溶液中，继续反应一段时间，从而形成银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜；其中：
所述银盐水溶液的浓度为0.001~0.05摩尔/升；硫氰酸亚铜薄膜与银盐水溶液的反应时间为5~30分钟；
所述铈盐水溶液的浓度为0.001~0.02摩尔/升；硫氰酸亚铜薄膜与铈盐水溶液的反应时间为1~10分钟。
2.根据权利要求1所述的银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜的制备方法，其特征在于，所述银盐采用硝酸银。
3.根据权利要求1所述的银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜的制备方法，其特征在于，所述铈盐采用三氯化铈。
4.由权利要求1-3之一所述的制备方法得到的银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜。
5.一种权利要求4所述的银盐和铈盐共掺杂的硫氰酸亚铜复合薄膜作为表面增强拉曼谱的检测基底的应用，用于检测极微量的有机分子。
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