橢偏儀在位表征電化學(xué)沉積的系統(tǒng)搭建（十八）- Pb薄膜沉積實(shí)驗(yàn)

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橢偏儀在位表征電化學(xué)沉積的系統(tǒng)搭建（十八）- Pb薄膜沉積實(shí)驗(yàn)

3.2.6.3 Pb薄膜沉積實(shí)驗(yàn)

通過(guò)前面實(shí)驗(yàn)與分析知溶液及溶液濃度對(duì)橢偏儀基底測(cè)試影響可忽略，故用該電解池進(jìn)行了Pb的沉積實(shí)驗(yàn)趾诗。采用三電極體系（工作電極：Au/Si蜡感；對(duì)電極：Pt絲；參比電極：Ag/AgCl）恃泪。溶液為1M的醋酸鈉及1M的醋酸鈉與5mM或10mM的醋酸鉛郑兴。為探究沉積條件，需對(duì)工作電極進(jìn)行CV掃描悟泵，掃描速率為5mV/s杈笔，掃描電勢(shì)窗口為-1.2V—0.5V，從開(kāi)路電壓（OCP）開(kāi)始負(fù)向掃描糕非。通過(guò)恒壓電沉積得到Pb薄膜同時(shí)進(jìn)行400nm到800nm波段的橢偏監(jiān)測(cè)蒙具。實(shí)驗(yàn)中電極的放置如圖3-10所示，Au/Si電極為工作電極置于觀察窗口朽肥；Pt絲對(duì)電極置于工作電極上方（不阻擋光路）禁筏；將置于魯金毛細(xì)管中的Ag/AgCl參比電極zui大限度接近Au/Si表面。將該在位監(jiān)測(cè)沉積電解池置于橢偏儀的監(jiān)測(cè)臺(tái)衡招，調(diào)節(jié)好準(zhǔn)直后開(kāi)始沉積和橢偏監(jiān)測(cè)篱昔。

圖3-10CV掃描及在位監(jiān)測(cè)Pb沉積實(shí)物圖

圖3-11是對(duì)Au/Si基底在醋酸鈉和醋酸鉛中進(jìn)行的CV掃描對(duì)比圖。其中Arccell曲線為1M醋酸鈉和10mM醋酸鉛中的CV掃描曲線始腾；blank control曲線為1M醋酸鈉中的CV掃描曲線州刽；H cell曲線為前期在標(biāo)準(zhǔn)H型電解池中加1M醋酸鈉和10mM醋酸鉛中的CV掃描曲線。對(duì)比Arc cell和H cell兩條曲線可以看到浪箭，所得到的CV曲線正常穗椅，裝置可用。該體系下Pb的沉積峰位和溶出峰位大致相同奶栖，電流密度與H型電解池所測(cè)得的數(shù)據(jù)相比減小匹表，且在-0.28V左右附近的吸附峰消失。電流密度減小的原因可能有兩點(diǎn)宣鄙，一是電極的有效面積比實(shí)際面積信鄱啤；二是工作電極和對(duì)電極不對(duì)稱冻晤。對(duì)比Arc cell和blank control兩條曲線可知苇羡，在只有1M醋酸鈉的電解液中電流密度相對(duì)于有醋酸鉛的可忽略不計(jì)。

圖3-11不同電解池掃描速度5mV/s的CV圖

根據(jù)CV掃描結(jié)果鼻弧，對(duì)Pb薄膜沉積的電壓進(jìn)行選取设江，為了使得沉積時(shí)間更長(zhǎng)，使得更有利于橢偏儀測(cè)試温数，所以選了沉積峰位附近的電壓绣硝，及-0.57V進(jìn)行Pb薄膜沉積。

圖3-12是進(jìn)行電壓沉積過(guò)程的電流-時(shí)間圖撑刺，在不同電解液條件下鹉胖，沉積電壓都是-0.57V。其中藍(lán)色表示1M醋酸鈉溶液够傍，橙色是以1M醋酸鈉加5mM醋酸鉛溶液甫菠，紅色是1M醋酸鈉加10mM醋酸鉛溶液。從圖中可以看到?jīng)]有醋酸鉛存在時(shí)電流基本為零冕屯，而10mM醋酸鉛的沉積電流比5mM醋酸鉛的沉積電流大寂诱。理論上沉積電流越大，沉積速度也快安聘，相同時(shí)間沉薄膜的厚度越厚痰洒。所以由電流時(shí)間圖知只有醋酸鈉存在時(shí)沒(méi)有沉積瓢棒，加入5mM醋酸鉛時(shí)有沉積但是沉積量比10mM醋酸鉛要小。

圖3-12沉積電流時(shí)間圖

圖3-13是沉積結(jié)果實(shí)物圖丘喻，a圖是在1M醋酸鈉為電解液沉積后得到的圖脯宿，可以看到?jīng)]有沉積物；b圖是在1M醋酸鈉加5mM醋酸鉛為電解液溶液的沉積樣品泉粉，有灰黑色的明顯沉積物连霉，沉積不均勻；c圖是在1M醋酸鈉加10mM醋酸鉛為電解液溶液沉積結(jié)果嗡靡，有灰黑色的明顯沉積物跺撼，沉積不均勻。對(duì)比b和c可知讨彼，可以明顯看到電解液為10mM醋酸鉛沉積物顏色加深歉井，說(shuō)明其比5mM沉積量更多，這和i-t圖所顯示的結(jié)果相對(duì)應(yīng)点骑。

圖3-13不同電解液沉積結(jié)果圖酣难，(a)1M醋酸鈉電解液；(b)1M醋酸鈉加5mM醋酸鉛黑滴；(c)1M醋酸鈉加10mM醋酸鉛

在不同的沉積條件下同時(shí)進(jìn)行了橢偏儀的監(jiān)測(cè)憨募。圖3-14為不同條件下的橢偏結(jié)構(gòu)模型，其中Au/Si基底上測(cè)得的數(shù)據(jù)袁辈，其物理模型如圖3-14(a)所示菜谣；在池體中加入去離子水后的數(shù)據(jù)，其物理模型如圖3-14(b)所示晚缩；1M醋酸鈉溶液和5/10mM醋酸鉛溶液的數(shù)據(jù)尾膊，其物理模型如圖3-14(c)所示；1M醋酸鈉溶液的數(shù)據(jù)荞彼，其物理模型如圖3-14(d)所示冈敛。

圖3-14不同條件下的物理模型圖:(a)Au/Si基底；(b)池體中加入去離子水鸣皂；(c)池體中加入1M醋酸鈉和10mM醋酸鉛抓谴；(d)池體中加入1M醋酸鈉

圖3-15是不同條件下進(jìn)行橢偏儀測(cè)量得到的橢偏參數(shù)Psi和Delta各自對(duì)比圖。從圖中可知寞缝，Psi和Delta的值大致的變化趨勢(shì)一致癌压，但是在位監(jiān)測(cè)下有鉛薄膜沉積的兩組數(shù)據(jù)全程擾動(dòng)較大，曲線上有許多的小峰荆陆，這是由于鉛薄膜的沉積帶來(lái)影響滩届。

圖3-15不同條件下(a)Psi和(b)Delta對(duì)比

實(shí)驗(yàn)說(shuō)明該池體在位沉積鉛薄膜橢偏儀測(cè)試得到的數(shù)據(jù)極具不穩(wěn)定性，波動(dòng)較大被啼，且溶液濃度對(duì)橢偏數(shù)據(jù)的影響不明顯帜消，這和之前不同濃度測(cè)試的測(cè)試結(jié)果一致棠枉。

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