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研究生:林逸欣
研究生(外文):I-Hsin Lin
論文名稱:以電化學沉積法製備含多層硒化鎘-鍗化鎘薄膜之奈米複合材料
論文名稱(外文):Preparation of Nanocomposites Containing Multiple-Layer CdSe-CdTe Thin Films with Electrodeposition
指導教授:呂世源
指導教授(外文):Shin-Yuan Lu
學位類別:碩士
校院名稱:國立清華大學
系所名稱:化學工程學系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:83
中文關鍵詞:硒化鎘鍗化鎘
外文關鍵詞:CdSeCdTe
相關次數:
  • 被引用被引用:3
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摘 要
製備半導體奈米複合材料的方式有許多,其中包含化學氣相沉積法、化學溶膠法、逆微胞法及電化學法等製備方式。其中以電化學法製備半導體奈米複合材料之優點在於此法具有: 可於低溫下進行反應、基質形狀不受限制、易於控制複合材料之厚度與型態及製程較經濟等優點。故以電化學法製備奈米複合材料之研究為近年來的主流之一
本論文內容為以電化學方式製備半導體/高分子複合材料,其中基質(substrate)為覆於雲母(mica)片上之金膜,高分子母體為導電高分子聚吡咯(polypyrrole),半導體奈米材料為由硒化鎘(CdSe)、鍗化鎘(CdTe)所組成之多層薄膜(multiple-layer thin films)。
半導體/高分子複合材料之光學性質、表面形態、組成與組成分佈分別以紫外光/可見光分光光度計、光放光光譜儀、原子力顯微鏡、掃描式顯微鏡及化學分析電子光譜儀檢測。
當半導體/高分子複合材料中半導體薄膜與高分子基材界面間之電子電洞結合效率提昇時,將有助於強化複合材料之光放光性質。本論文當中嘗試討論CdSe/PPy、CdSe-CdTe/PPy、CdSe-CdTe-CdSe/PPy半導體/高分子複合材料中,半導體薄膜厚度之改變及薄膜層數之不同對於半導體/高分子複合材料光學性質之影響。由研究結果得知,CdSe-CdTe/PPy半導體/高分子複合材料具有較佳之光放光性質,其中其光放光強度又可由改變半導體薄膜之厚度而做調整。
Abstract
There are a variety of processes for preparation of semiconductor nano-co- mposites, such as chemical vapor deposition (CVD), chemical colloid, reverse micellar, and electrodeposition. Among them, electrochemical techniques provide several advantages, including low temperature processing, arbitrary substra- te shapes, controllable film thickness and morphology, and potential low produ- ction cost. Consequently, preparation of semiconductor nano-composites with the electrochemical technique has become increasingly popular nowadays.
In this thesis, semiconductor/polymer nano-composites were prepared with the electrodeposition process. The substrate is a gold film deposited on fre- shly cleaved mica and subjected to prolonged annealing at 250℃ forming an epitaxial, polycrystalline substrate. The polymer matrix is polypyrrole (PPy) and the semiconductor multiple-layer is alternating CdSe and CdTe thin films.
The optical properties, surface morphology, composition and composition distribution of the resulting semiconductor/polymer nano-composites were characterized by UV/Vis, PL, AFM, SEM, and ESCA, respectively.
In this thesis, CdSe/PPy, CdSe-CdTe/PPy, and CdSe-CdTe-CdSe/PPy semiconductor/polymer nanocomposites have been produced with the electrodeposition process. The combination of electron-conducting semiconductors with hole-conducting polymers into a single composite provides effective charge tra- nsport and allows the expansion of the recombination zone over the composite layer, which may enhance the luminescent properties of the composite. The luminescent properties of the semiconductor/polymer nano-composites can be tuned by using CdSe/CdTe thin films of different thickness, or of different combi- nations. Compared with CdSe/PPy and CdSe-CdTe-CdSe/PPy nano-composites, the nano-composite structure of CdSe-CdTe/PPy was found to possess enhanced luminescent property, which is promising for optoelectronic applications.
總 目 錄
中文摘要………………………………………………………………..Ⅰ
英文摘要………………………………………………………………..Ⅱ
誌謝…………………………………………………………………….Ⅲ
總目錄…………………………………………………………………..Ⅵ
表目錄…………………………………………………………………..Ⅶ
圖目錄…………………………………………………………………..Ⅷ
第一章 緒論……………………………………………………………1
1.1 奈米粒子之簡介…………………………………………...1
1.2 奈米粒子的特性…………………………………………...1
1.3 奈米粒子之製備方法……………………………………...4
1.4 奈米粒子的應用…………………………………………...6
第二章 半導體材料之簡介……………………………………………7
2.1 半導體材料之分類………………………………………...7
2.2 奈米級半導體材料之特性………………………………...8
2.3 奈米級半導體材料之製備方法………………………….12
2.4 奈米級半導體材料之應用……………………………….15
第三章 文獻回顧……………………………………………………..16
3.1 奈米級半導體粒子之製備方法………………………….16
3.2 CdSe與CdTe生成機制與性質………………………….17
3.2.1 CdSe與CdTe生成機制………………………….17
3.2.2 CdSe與CdTe之性質…………………………….19
3.2.3 Cd(Se,Te)、(CdSe)CdTe與(CdTe)CdSe性質…...20
3.3 半導體/高分子複合材料之製備………………………….23
3.4 研究動機……………………………….………………….24
第四章 半導體/高分子複合材料之製備及檢測…………………....25
4.1 實驗藥品………………………………………………….25
4.2 實驗設備與儀器………………………………………….26
4.2.1 製程部分之設備………………………………....26
4.2.2 分析設備…………………………………………26
4.3 半導體/高分子複合材料之製備…………………………..29
4.3.1 電極(MLA/Au)之製備……………………….……32
4.3.2 聚吡咯(PPy)高分子層之製備……………...……32
4.3.3 CdSe之製備……………………………………...32
4.3.4 Cd(Se,Te)之製備………………….……………...32
4.3.5 CdSe-CdTe之製備…………….…………………33
4.3.6 CdSe-CdTe-CdSe之製備………………………...33
第五章 結果與討論…………………………………………………..34
5.1 UV/ Vis 吸收光譜………………...……………………...34
5.1.1 MLA/Au/PPy之製備及檢測………………………34
5.1.2 CdSe半導體生成於MLA/Au/PPy基質上之檢測.36
5.1.3 CdSe/PPy複合材料之檢測……………………....37
5.1.4 Cd(Se,Te)複合型薄膜生成於MLA/Au/PPy基質上之
檢測……………………………………………..39
5.1.5 CdSe-CdTe多層薄膜生成於MLA/Au/PPy基質上之
製備及檢測……………………………………...41
5.1.6 CdSe-CdTe/PPy複合材料之檢測………………..46
5.2 光放光圖譜……………………………………………….47
5.2.1 CdSe薄膜生成於MLA/Au/PPy基質上及CdSe/PPy
複合材料之檢測…………………………………47
5.2.2 Cd(Se,Te)複合型薄膜生成於MLA/Au/PPy基質上之
檢測………………………………………………49
5.2.3 CdSe-CdTe多層薄膜生成於MLA/Au/PPy基質上及CdSe-CdTe/PPy複合材料之檢測……………….51
5.2.4 CdSe-CdTe-CdSe/PPy複合材料之檢測………….55
5.3 化學分析電子光譜……………………………………….58
5.4 掃描式顯微鏡圖………………………………………….61
5.5 原子力顯微鏡圖………………………………………….64
第六章 結論..………………………………………………………….77
參考文獻………………………………………………………………...78
表 目 錄
表1.1 立方體粒子的大小及表面原子比率………………………...……3
表1.2 銅粒子粒徑與表面能量比率…………………………………...…3
表1.3 金屬奈米粒子的熔點及燒結溫度………………………………...3
表1.4 奈米粒子的製備方法……………………………………………...4
表1.5 奈米粒子的應用範圍……………………………………………...6
表2.1 不同半導體複合材料之組成及製備方式……………………….13
表2.2 層狀結構之不同半導體複合材料之組成及製備方式………….14
表4.1 半導體/高分子複合材料之結構圖示及文字表示方式示意圖…31
表5.1 製備CdSe-CdTe多層薄膜之反應時間與對照組之反應時間一覽
表……………………………………………………..…………..41
圖 目 錄
圖1.1 物理法及化學法製備奈米粒子示意圖………………………….5
圖2.1 以分子軌域說明不同粒徑之粒子所對應的能階圖…………….8
圖2.2 半導體之量子結構示意圖……………………………………….9
圖2.3 量子薄膜、量子線及量子點之能階密度函數示意圖…………..11
圖2.4 分子中螢光與磷光之形成………………………………………11
圖3.1 磊晶與基質錯位之示意圖……………………………………...18
圖3.2 不同磊晶成長模式……………………………………………...19
圖3.3 以CdSe及CdTe為例,不同組成分佈之複合型粒子與核殼型粒子結構示意圖…………………………………………………...21
圖4.1 紫外光可見光分光光度計之原理示意圖……………………...27
圖4.2 簡單的AFM示意圖……………………………………………..28
圖4.3 簡化之製備半導體/高分子複合材料流程圖…………………..30
圖5.1 當製備PPy薄膜之反應時間為5秒時,PPy薄膜生成於MLA/Au基質上之紫外光可見光圖譜…………………………………...35
圖5.2 CdSe半導體生成於MLA/Au/PPy基質上之紫外光可見光圖….36
圖5.3 CdSe/PPy複合材料之紫外光可見光圖譜……………………...38
圖5.4 CdSe薄膜與Cd(Se,Te)複合型薄膜分別生成於MLA/Au/PPy5s基質上所測得之紫外光可見光圖譜…………………………...40
圖5.5(A)隨著製備CdSe薄膜之反應時間增加時,CdSe奈米粒子分佈之可能情況示意圖………………………………………………...42
圖5.5(B)微觀範圍內,CdSe半導體與CdTe半導體界面處形(CdSe)CdTe核殼型奈米粒子之示意圖…………………………………...…42
圖5.6 依表5.1之方式1製備條件下,CdSe-CdTe多層薄膜與其對照組CdSe薄膜之紫外光可見光圖譜……………………………..44
圖5.7 依表5.1之方式2製備條件下,CdSe-CdTe多層薄膜與其對照組CdSe薄膜之紫外光可見光圖譜…………………………….45
圖5.8 CdSe-CdTe/PPy複合材料之紫外光-可見光圖譜……………...46
圖5.9 CdSe薄膜生成於MLA/Au/PPy基質上,與CdSe薄膜被包覆於PPy高分子層中形成CdSe/PPy複合材料後二者之光放光圖譜比較圖…………………………………………………………...48
圖5.10 Cd(Se,Te)複合型薄膜生成於MLA/Au/PPy5s基質上之光放光強度與CdSe薄膜生成於MLA/Au/PPy5s基質上之光放光強度比較圖………………………………………………………………...50
圖5.11 CdSe-CdTe多層薄膜與CdSe薄膜分別生成於MLA/Au/ PPy基質上之光放光強度比較圖……………………………………...53
圖5.12 CdSe薄膜、CdSe-CdTe多層薄膜分別生成於MLA/Au/PPy基質上以及CdSe-CdTe/PPy複合材料之光放光強度比較圖………54
圖5.13 CdSe、CdTe及PPy材料之相對能階圖……………………….54
圖5.14 CdSe-CdTe/PPy複合材料與CdSe-CdTe-CdSe/PPy複合材料二者光放光強度之比較圖…………………………………………...56
圖5.15 改變CdSe-CdTe- CdSe/PPy複合材料中最外層CdSe薄膜厚度後,其光放光強度改變之情形………………………………….57
圖5.16 結構為MLA/Au/PPy/CdSe-CdTe材料之化學分析電子光譜…..59
圖5.17 在較小能量範圍內,隨著製備CdTe薄膜之反應時間增加,結構為MLA/Au/PPy/CdSe-CdTe之材料經過75小時氧化處理後,其Se原子及SeO2氧化物所對應之訊號強度減弱之情形…….60
圖5.18 結構為MLA/Au之基質之掃描式顯微鏡圖…………………….61
圖5.19 結構為MLA/Au/PPy5s/CdSe15s材料之掃描式顯微鏡圖……...62
圖5.20 結構為MLA/Au/PPy5s/CdSe15s-CdTe10s材料之掃描式顯微鏡圖
…………………………………………………………………...63
圖5.21 片狀雲母之原子力顯微鏡圖…………………………………...65
圖5.22 寡聚體PPy薄膜生成於MLA/Au基質上之原子力顯微鏡圖…..66
圖5.23 結構為MLA/Au/PPy5s/CdSe15s材料之原子力顯微鏡圖……...68
圖5.24 結構為MLA/Au/PPy5s/CdSe15s/PPy20材料之原子力顯微鏡...69
圖5.25 結構為MLA/Au/PPy5s/Cd(Se,Te)30s材料之原子力顯微鏡圖...70
圖5.26 結構為MLA/Au/PPy5s/CdSe60s-CdTe60s材料之原子力顯微鏡圖
…………………………………………………………………...72
圖5.27 結構為MLA/Au/PPy5s/CdSe15s-CdTe5s材料之原子力顯微鏡圖
…………………………………………………………………...73
圖5.28 結構為MLA/Au/PPy5s/CdSe15s-CdTe80s材料之原子力顯微鏡圖
…………………………………………………………………...74
圖5.29 結構為MLA/Au/PPy5s/CdSe15s-CdTe5s/PPy20s材料之原子力顯微鏡圖…………………………………………………………...75
圖5.30 結構為MLA/Au/PPy5s/CdSe15s-CdTe80s/PPy20s材料之原子力顯微鏡圖………………………………………………………...76
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