橢偏儀在位表征電化學(xué)沉積的系統(tǒng)搭建（八）- 溶液的影響和固液界面的影響

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橢偏儀在位表征電化學(xué)沉積的系統(tǒng)搭建（八）- 溶液的影響和固液界面的影響

4橢偏儀在位監(jiān)測電化學(xué)沉積的挑戰(zhàn)

橢偏儀在位監(jiān)測電化學(xué)沉積的挑戰(zhàn)主要分為：溶液的影響和固液界面的影響后雷，以及裝置的設(shè)計。

4.1溶液

溶液對實(shí)現(xiàn)橢偏儀在位監(jiān)測電化學(xué)沉積薄膜主要會帶來兩方面的影響吠各，第1種是溶液的擾動臀突，比如在開放的溶液體系贾漏，溶液表面的擾動可能會對光產(chǎn)生多種散射機(jī)制候学，從而給測試帶來困難。另外是溶液中濃度變化所帶來的影響纵散。當(dāng)光波場頻率很大且溶液的濃度不太大時盒齿，光學(xué)常數(shù)折射率及消光系數(shù)有如下關(guān)系式：

由朗伯定律與光強(qiáng)度的定義得吸收系數(shù)β與消光系數(shù)k的關(guān)系為：

又由比爾定律知，當(dāng)溶液濃度足夠小以至于分子間相互作用能被忽略時困食，溶液吸收系數(shù)β與溶液的濃度C成正比，即β=αC硕盹，α是與濃度無關(guān)由吸收物質(zhì)分子的特性決定的常數(shù)。因此可以得到溶液濃度與其折射率之間的關(guān)系式為：

由以上推導(dǎo)可知光學(xué)常數(shù)n瘩例、k值和溶液濃度之間的關(guān)系如式(1-11)所示啊胶，而橢偏儀測量得到的參數(shù)ψ和Δ是光學(xué)常數(shù)n、k的函數(shù)垛贤，這意味著溶液直接影響著測試結(jié)果焰坪，不同濃度溶液帶來的影響不同。所以后續(xù)研究過程中溶液以及溶液濃度對測試結(jié)果的影響都是具有挑戰(zhàn)性的聘惦。

4.2固液界面

橢偏儀在位監(jiān)測薄膜沉積過程中涉及多個界面某饰，有空氣/觀察窗口界面、觀察窗口/溶液界面、溶液/沉積薄膜的固液界面和薄膜/基底界面黔漂。每一個界面都會增加測試與分析的難度，如何把復(fù)雜的體系簡化成為可模擬的光學(xué)模型是十分具有挑戰(zhàn)性的炬守。

如圖1-15所示牧嫉，金屬電極和電解液接觸面存在電壓差，電子的分布會隨其改變减途。通常情況下對于金屬-電解質(zhì)界面處的電荷分布如圖1-15所示的簡單方案外酣藻，主要取決于：1.固體的電子性質(zhì)鳍置；2.水分子和水合陽離子的吸附臊恋；3.陰離子的化學(xué)吸附(表面過量)；4.被應(yīng)用的外部控制的電位墓捻。

圖1-15 電極與電解液界面電壓及電子示意圖

在沉積過程中抖仅，薄膜生長經(jīng)歷納米尺度階段，而納米尺度的材料具有共同的電荷存儲和轉(zhuǎn)移能力砖第，在簡單的模型中，半導(dǎo)體梧兼、金屬納米粒子和分子都可以作為給體、受體或電子橋羽杰，如圖1-16所示渡紫。如等離子體金屬納米粒子存在局部表面等離子體共振(LSPR)現(xiàn)象，它包括電子密度的耦合共振振蕩和一個逐漸消失的電磁場(統(tǒng)稱為等離子體激元)考赛，這些激元在粒子表面附近被特定波長的入射光激發(fā)惕澎。LSPR導(dǎo)致了特征消光(吸收加散射)波段，可能跨越紫外颜骤、可見和近紅外部分的能譜唧喉。

圖1-16 金屬納米粒子在半導(dǎo)體點(diǎn)和分子橋之間的電子轉(zhuǎn)移的圖示

因此在電化學(xué)沉積過程可能也會存在襯底與沉積物質(zhì)的電荷轉(zhuǎn)移現(xiàn)象。這些界面效應(yīng)將會給橢偏測試數(shù)據(jù)的分析與提取增加難度忍抽。

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