椭偏仪在位表征电化学沉积的系统搭建（八）- 溶液的影响和固液界面的影响

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椭偏仪在位表征电化学沉积的系统搭建（八）- 溶液的影响和固液界面的影响

4椭偏仪在位监测电化学沉积的挑战

椭偏仪在位监测电化学沉积的挑战主要分为：溶液的影响和固液界面的影响，以及装置的设计。

4.1溶液

溶液对实现椭偏仪在位监测电化学沉积薄膜主要会带来两方面的影响，第1种是溶液的扰动，比如在开放的溶液体系，溶液表面的扰动可能会对光产生多种散射机制，从而给测试带来困难。另外是溶液中浓度变化所带来的影响。当光波场频率很大且溶液的浓度不太大时，光学常数折射率及消光系数有如下关系式：

由朗伯定律与光强度的定义得吸收系数β与消光系数k的关系为：

又由比尔定律知，当溶液浓度足够小以至于分子间相互作用能被忽略时，溶液吸收系数β与溶液的浓度C成正比，即β=αC，α是与浓度无关由吸收物质分子的特性决定的常数。因此可以得到溶液浓度与其折射率之间的关系式为：

由以上推导可知光学常数n、k值和溶液浓度之间的关系如式(1-11)所示，而椭偏仪测量得到的参数ψ和Δ是光学常数n、k的函数，这意味着溶液直接影响着测试结果，不同浓度溶液带来的影响不同。所以后续研究过程中溶液以及溶液浓度对测试结果的影响都是具有挑战性的。

4.2固液界面

椭偏仪在位监测薄膜沉积过程中涉及多个界面，有空气/观察窗口界面、观察窗口/溶液界面、溶液/沉积薄膜的固液界面和薄膜/基底界面。每一个界面都会增加测试与分析的难度，如何把复杂的体系简化成为可模拟的光学模型是十分具有挑战性的。

如图1-15所示，金属电极和电解液接触面存在电压差，电子的分布会随其改变。通常情况下对于金属-电解质界面处的电荷分布如图1-15所示的简单方案外，主要取决于：1.固体的电子性质；2.水分子和水合阳离子的吸附；3.阴离子的化学吸附(表面过量)；4.被应用的外部控制的电位。

图1-15 电极与电解液界面电压及电子示意图

在沉积过程中，薄膜生长经历纳米尺度阶段，而纳米尺度的材料具有共同的电荷存储和转移能力，在简单的模型中，半导体、金属纳米粒子和分子都可以作为给体、受体或电子桥，如图1-16所示。如等离子体金属纳米粒子存在局部表面等离子体共振(LSPR)现象，它包括电子密度的耦合共振振荡和一个逐渐消失的电磁场(统称为等离子体激元)，这些激元在粒子表面附近被特定波长的入射光激发。LSPR导致了特征消光(吸收加散射)波段，可能跨越紫外、可见和近红外部分的能谱。

图1-16 金属纳米粒子在半导体点和分子桥之间的电子转移的图示

因此在电化学沉积过程可能也会存在衬底与沉积物质的电荷转移现象。这些界面效应将会给椭偏测试数据的分析与提取增加难度。

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