磁控濺鍍製備鋯、鈦共摻氧化鋅薄膜之結構與光電特性分析

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朱智誠(Chih-Cheng Chu) 查詢紙本館藏

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材料科學與工程研究所

論文名稱

磁控濺鍍製備鋯、鈦共摻氧化鋅薄膜之結構與光電特性分析
(On the structure and optoelectronic properties of Zr, Ti co-doped ZnO thin films prepared by magnetron sputtering)

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摘要(中)

本研究在玻璃基材上，以磁控濺鍍系統，固定氧化鋅靶在RF 功率為150 W，鈦靶在DC功率分別為10、20和30W，鋯靶在RF 功率分別為0、25、50、60、75 和100 W下濺鍍2小時，可製備出不同鈦含量的摻鈦氧化鋅(Ti doped zinc oxides, TZO)薄膜、不同鋯含量的摻鋯氧化鋅(Zr doped zinc oxides, ZZO)薄膜以及不同鋯含量的鋯、鈦共摻氧化鋅(Zr, Ti co-doped zinc oxides, ZTZO)薄膜。經由感應耦合電漿質譜儀(inductively coupled plasma mass spectrometry; ICP-MS)分析結果顯示：鍍膜中鈦原子百分比則隨著直流濺鍍功率的增加而遞增(0.71~1.12 at.%)；而鍍膜中鋯原子百分比則隨著射頻濺鍍功率的增加而遞增(1.61~6.12 at.%)。薄膜之化學狀態經由X光光電子能譜儀(X-ray photoelectron spectrometer; XPS)分析得知，位於458.8(Ti 2p3/2) eV，為TiO2狀態之正四價鈦。位於182.2 (Zr 3d5/2)與184.5 (Zr 3d3/2) eV束縛能則屬於ZrO2正四價鋯之峰值。晶體結構方面使用XRD分析可得知ZZO、TZO和ZTZO透明導電薄膜都可改善純氧化鋅(002)峰值強度。由場發射式掃瞄式電子顯微鏡(Field Emission Scanning Electron Microscope；FE-SEM)觀察結果顯示：濺鍍所得氧化鋅薄膜皆為柱狀晶，其膜厚均約為350 nm。隨著摻雜量增加，薄膜柱狀晶直徑會有下降的現象。由原子力顯微鏡(Atomic force microscopy; AFM)分析可了解摻鈦氧化鋅薄膜與鋯共摻雜後，因晶粒細化而使得Ra與Rmax下降，導致薄膜表面更平滑。由場發射鎗穿透式電子顯微鏡(Field Emission Gun Transmission Micro-scope, FEG-TEM)結果顯示：於濺鍍沉積時，薄膜以柱狀晶成長且(002)晶面方向垂直於基板。
紫外光光電子能譜儀(Ultraviolet Photoelectron Spectroscopy, UPS)分析顯示：鋯與鈦金屬能使薄膜功函數有效地提升，但隨著載子濃度的增加功函數隨之下降。薄膜光電性質中以Zr 1.61 at. %及Ti 0.91 at.%之ZTZO薄膜具有4.18×10-3Ω-cm之最低電阻率以及在可見光穿透度為92%，其功函數為5.39 eV。薄膜光電性質中以Zr 3.46 at. %及Ti 0.71 at.%之ZTZO薄膜具有5.54×10-3Ω-cm之次低電阻率以及在可見光穿透度為91%，其功函數為5.51eV。於3.5 wt.%NaCl水溶液中由電化學法分析薄膜腐蝕特性發現：ZTZO薄膜中隨摻鋯量增加，其腐蝕電流密度減小，顯示抗蝕性增強。

摘要(英)

Transparent conductive Zr, Ti codoped ZnO (ZTZO) films were prepared on glass substrate by three-target magnetron sputtering system in this work. The glass substrate was heated to 200°C, and the working pressure in the chamber was at 5 × 10-2 Torr. In the process of sputtering, the pure Ti target was bombarded by direct current varying in the power at 10, 20 and 30, the pure ZnO target were bombarded by radio frequency power fixed at 150 W and the pure Zr target were bombarded by radio frequency varying in the power at 0, 25, 50, 60, 75 and 100W, After sputtering for 120 minutes, the thickness of the films varying in Zr-contents was measured to be about 350 nm. The composition of ZTZO thin film was analyzed with inductively coupled plasma-mass spectrometer (ICP-MS) to show that the Zr-content increases with increasing the Zr power in the order: 0 at.% (0 W) < 1.61 at.% (25 W) < 2.76 at.% (50 W) < 3.46 at.% (60 W) < 3.82 at.% (75 W) < 6.12 at.% (100 W), and the Zr-content increases with increasing the Zr power in the order: 0 at.%(0 W) < 0.71 at.%(10 W) < 0.91 at.% (20 W) < 1.22 at.%(30 W). Through examination by X-ray photoelectron spectroscopy (XPS), the ZTZO films revealed TiO2 with binding energy of tetravalent Ti(IV) at 458.8 eV for Ti 2p3/2; ZrO2 with binding energy of tetravalent Zr(IV) at 182.2 and 184.5 eV for Zr 3d5/2 and 3d3/2, respectively. Analysis of X-ray diffraction (XRD) indicated that all the films belong to wurtzite structure textured on (002). The surface morphology and cross section of the films were examined by using field emission scanning electron microscope (FE-SEM). Through examination by atomic force microscopy (AFM), the films displayed their average surface roughness (Ra) decreased with increasing the Zr-dopant.
The carrier concentration of the films, determined by Hall effect analyzer, increased but the carrier mobility decreased with increasing the Zr-dopants so that the lowest resistivity was found at 5.54 × 10-3 Ω-cm for the ZTZO doped with 0.71 at.% Ti and 3.46 at.% Zr. Average optical transmittance of the films was analyzed higher than 90±5% by UV-vis spectra. Estimating by electrochemical measurements in 3.5 wt. % NaCl, the ZTZO films depicted their corrosion current density decreased with increasing the Zr-dopants. Therefore, ZTZOs with higher Zr-dopants were more resistant to corrosion. The features be found with the Zirconium content increase the corrosion current density is smaller, and enhanced corrosion resistance phenomenon.

關鍵字(中)

★ 摻雜氧化鋅
★ 磁控濺鍍
★ 功函數
★ 光學性質
★ 電阻率
★ 電化學特性

關鍵字(英)

★ Doped Zinc Oxide thin film
★ magnetron sputtering
★ work function
★ Optical property
★ electoral property
★ electrochemistry

論文目次

目錄
摘要 i
Abstract ii
目錄 iv
表目錄 viii
圖目錄 ix
第一章緒論 1
1-1 前言 1
1-2研究動機 2
1-3 研究目的 3
1-4研究目標 4
第二章原理與文獻回顧 5
2-1濺鍍沉積理論基礎 5
2-1-1濺射理論[15] 5
2-1-3濺鍍系統[15] 6
2-1-3-1直流式濺鍍 6
2-1-3-2射頻式濺鍍 7
2-1-3-3磁控濺鍍系統 8
2-1-4薄膜沉積原理[15] 8
2-1-4-1孕核（nucleation） 9
2-1-4-2晶粒成長（grain growth） 9
2-1-4-3晶粒聚集（coalescence） 10
2-1-4-4縫道填補（filling of channels） 10
2-1-4-5薄膜成長（film growth） 10
2-1-5鍍層微結構的Thornton模型 10
2-2氧化鋅薄膜性質 12
2-2-1氧化鋅薄膜特性[17][18] 12
2-2-2摻雜氧化鋅之能帶理論[19] 13
2-2-3氧化鋅薄膜晶體結構 14
2-2-4氧化鋅薄膜光學性質 14
2-3 氧化鋅文獻整理 15
2-3-1一元摻雜氧化鋅薄膜 15
2-3-2二元摻雜氧化鋅薄膜 16
第三章實驗方法與儀器設備 17
3-1 實驗規劃 17
3-2 實驗步驟 17
3-2-1 試片清洗 17
3-2-2 磁控濺鍍薄膜製作參數設定 17
3-3 分析儀器 18
3-3-1感應耦合電漿質譜分析儀 18
3-3-2 場發式掃描式電子顯微鏡分析 20
3-3-3低掠角 X光結晶繞射分析 20
3-3-4 原子力顯微鏡分析 21
3-3-5 場發射鎗穿透式電子顯微鏡 21
3-3-6 試片表面化學元素鍵結能分析 22
3-3-7紫外光光電子能譜分析 22
3-3-8 表面電阻量測 23
3-3-9 薄膜載子濃度及霍爾移動率量測 23
3-3-9 UV-Visible 量測穿透率與經由光譜吸收計算能階(Eg) 24
3-4 電化學分析實驗 24
3-4-1 相對電極及參考電極 24
3-4-2電化學試驗環境 24
3-4-3 實驗流程及設置 24
3-4-4 電化學實驗方法 25
3-4-4-1 開路電位(Open circuit potential) 25
3-4-4-2 動態極化(Potentiodynamic polarization scanning) 25
3-4-4-3交流阻抗法(Electrochemical impedance spectroscopy) 25
第四章實驗結果 27
4-1薄膜成分與結構分析 27
4-1-1薄膜成分分析 27
4-1-1-1感應耦合電漿質譜分析儀分析 27
4-1-1-1-1 TZO薄膜 27
4-1-1-1-2 ZZO薄膜 27
4-1-1-1-2 ZTZO薄膜 27
4-1-1-2 X光光電子能譜分析 28
4-1-1-2-1 TZO薄膜 28
4-1-1-2-2 ZZO薄膜 28
4-1-1-2-3 ZTZO薄膜 29
4-1-2表面形貌分析 30
4-1-2-1 場發式掃描式電子顯微鏡分析 30
4-1-2-1-1 TZO薄膜 30
4-1-2-1-2 ZZO薄膜 30
4-1-2-1-3 ZTZO薄膜 31
4-1-2-2 原子力顯微鏡分析 32
4-1-2-2-1 TZO薄膜 32
4-1-2-2-2 ZZO薄膜 32
4-1-2-2-3 ZTZO薄膜 33
4-1-3 晶體結構分析 34
4-1-3-1 低掠角 X光結晶繞射分析 34
4-1-3-1-1 TZO薄膜 34
4-1-3-1-2 ZZO薄膜 34
4-1-3-1-3 ZTZO薄膜 35
4-1-3-2場發射鎗穿透式電子顯微鏡分析 36
4-2薄膜性質與功能分析 37
4-2-1 薄膜電性分析霍爾量測儀 37
4-2-1-1 TZO薄膜 37
4-2-1-2 ZZO薄膜 37
4-2-1-3 ZTZO薄膜 37
4-2-2 薄膜可見光穿透率分析 39
4-2-2-1 TZO薄膜 39
4-2-2-2 ZZO薄膜 39
4-2-2-3 ZTZO薄膜 40
4-2-3 紫外光光電子能譜分析 41
4-2-3-1 TZO薄膜 41
4-2-3-2 ZZO薄膜 42
4-2-3-3 ZTZO薄膜 42
4-3電化學分析 43
4-3-1 腐蝕電位量測 43
4-3-2 塔佛曲線分析 44
4-3-3 交流阻抗分析 44
第五章實驗討論 46
5-1不同元素摻雜對氧化鋅薄膜之影響 46
5-1-1成分與化學組態 46
5-1-2晶體結構特性 46
5-1-3導電特性 47
5-1-4光學特性 48
5-1-5功函數值比較 48
5-2鋯摻雜量對ZTZO薄膜之影響 49
5-2-1成分與化學組態 49
5-2-2晶體結構特性之影響 49
5-2-3導電特性之影響 49
5-2-4光學特性之影響 50
5-2-5功函數值之影響 51
5-2-6電化學特性之影響 51
第六章結論 53
第七章未來展望 55
參考文獻 56

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指導教授

林景崎(Jing-Chie Lin)

審核日期

2013-8-29

推文