臺灣博碩士論文加值系統

本論文採用溶膠-凝膠法搭配旋轉塗佈技術，在玻璃基板上成功製備出摻0~4 at.% 鎵(GZO)、摻0~1 at.%鈦(TZO)與共同摻入0.0 ~1.0 at.%鈦和2 at.%鎵之氧化鋅(Ti, Ga co-doped zinc oxides， TGZO)透明氧化物薄膜，進而研究薄膜之微結構與光電特性。薄膜的表面與橫斷面形貌藉由SEM觀察，結果顯示:純氧化鋅薄膜隨著摻鎵、摻鈦及共摻都皆有晶粒細化現象。晶體結構由XRD分析得知:薄膜皆為六方晶系纖維鋅礦結構，以C軸優選方向，可依Scherrer公式估計其晶粒大小，與SEM觀察印證。鈦、鎵共摻薄膜之晶粒，隨摻鈦量由0增加至1 at.%，其尺寸由16減小至13nm，稍有細化現象。Raman分析佐證出氧化鋅薄膜摻雜造成晶粒細化現象。AFM分析顯示:鈦、鎵共摻薄膜中摻鈦濃度由0增至1.0% 會降低其表面粗糙度。XPS分析鎵、鈦共摻薄膜，顯示所摻雜的鎵之化學狀態為Ga2O3(Ga3+)；而及所摻雜的鈦則為TiO2(Ti4+)。薄膜光學性質經UV-Vis光譜儀進行分析，結果得知: 摻鎵薄膜平均透光率約82%、摻鈦者為89%，共摻者約88%；薄膜之電阻率則用四點探針量測、載子濃度和載子移動率則由霍爾分析儀鑑定，結果顯示: 氧化鋅摻2 at.%鎵之有一最低電阻率(約13 Ω cm)、摻0.5 at.%鈦之薄膜有一最低電阻率(約59 Ω cm)，共摻2 at.%鎵與1 at.% 鈦薄膜則其透光率增高至91%而電阻率則降至7.35 Ω cm。

Transparent conductive zinc oxide (ZnO) thin films singly doped with 0.0~4.0 at.% Ga (GZO), 0.0~4.0 at.% Ti (TZO) and co-doped 2 at.% Ga with 0.25, 0.50, 0.75 and 1.00 at.% Ti were prepared on glass substrates by sol-gel method by means of spin-coating. The microstructure, optical, and electrical properties of GZO, TZO and TGZO films were investigated. Through examination by scanning electron microscope (SEM), we found that the surface and cross-sectional morphology indicated grain refinement in the doped films in comparison with the pure ZnO. Analysis of X-ray diffraction (XRD) revealed all the films belonged to wurtzite structure preferred along c-axis and their grain size estimated by Scherrer’s formula was consistent with that observed by SEM. Avereage grain size in TGZO decreased form 16 to 13 nm with increasing Ti-dopant from 0 to 1 at.%. This grain refinement was confirmed with the Raman spectra. Measurement by atomic force microscope indicated that TGZO decreased the surface roughnss with increasing Ti-content from 0 to 1.0 at.%. X-ray photoelectron spectroscopy (XPS) spectra of the TGZO films showed that the binding energy located at 1118.5 eV responsible for Ga3+and that located at 458.7 eV responsible for Ti4+. The electrical properties such as resistivity, carrier concentration, and Hall mobility were detected by four-point probe and Hall measurements. Optical transmittance measured by UV-Vis spectrophotometer indicated 82% for GZO, 89% for TZO and 88% for TGZO. The resistivity was measured at 13 Ω cm for GZO doped with 2 at.%Ga, at 59 Ω cm for TZO doped with 0.5 at.%Ti, at 7.35 Ω cm for T1.00G2.0ZO co-doped 2 at.% Ga with 1 at.% Ti.

摘 要 i
Abstract iii
誌 謝 iv
目 錄 v
表目錄 x
圖目錄 x
一、緒 論 1
1-1 前言 1
1-2 研究動機、目的與目標 2
二、基礎理論與文獻回顧 5
2-1 氧化鋅簡介 5
2-2 氧化鋅之異質元素摻雜 6
2-3 溶膠凝膠法製備氧化鋅文獻回顧 7
2-4 摻鎵氧化鋅薄膜之文獻回顧 10
2-5 摻鈦氧化鋅薄膜之文獻回顧 12
2-6 溶膠-凝膠法 13
2-7各項以溶膠凝膠法製備薄膜方法 17
三、研究方法 21
3-1 實驗規劃 21
3-2 實驗藥品、裝置 22
3-2-1 實驗藥品 22
3-2-2 實驗裝置 22
3-3 實驗步驟 22
3-3-1 試片清洗 22
3-3-2 前驅物合成及薄膜製備 23
3-4分析儀器與分析方法 24
3-4-1 前驅物溶液之pH值分析 24
3-4-2 氧化鋅前驅物溶膠材料熱分析 25
3-4-3 低掠角X-ray繞射分析儀 25
3-4-4 拉曼光譜分析儀 26
3-4-5薄膜表面形貌觀察 26
3-4-6 薄膜表面粗糙度之原子力顯微鏡分析 26
3-4-7 薄膜紫外-可見光穿透率分析 27
3-4-8 薄膜表面電阻之四點探針測量 27
3-4-9 薄膜載子濃度及載子移動率之霍爾量測 28
3-4-10 薄膜之化學狀態分析 29
3-4-11 穿透式電子顯微鏡結構分析 29
3-4-12 電化學實驗 30
3-4-13 薄膜光電化學分析 30
四、結果 31
4-1 溶膠凝膠法製備氧化鋅薄膜之關鍵參數選定 31
4-1-1 溶膠pH控制 31
4-1-2溶膠凝膠旋塗膜之熱重分析 31
4-2 GZO、TZO、TGZO薄膜結構與成分分析 31
4-2-1 XRD 分析 31
4-2-1-1 GZO 薄膜 31
4-2-1-2 TZO 薄膜 33
4-2-1-3 TGZO薄膜 34
4-2-2 FE-SEM分析 35
4-2-2-1 GZO薄膜 35
4-2-2-2 TZO薄膜 35
4-2-2-3 TGZO薄膜 36
4-2-3 Raman光譜分析 36
4-2-4 薄膜表面粗糙度分析 37
4-2-5 薄膜化學元素鍵結能分析 37
4-2-5-1 GZO薄膜 37
4-2-5-2 TGZO薄膜 38
4-2-6 TEM 分析 39
4-3 GZO、TZO、TGZO薄膜性質分析 40
4-3-1 UV-Vis 透光性分析 40
4-3-1-1 GZO薄膜 40
4-3-1-2 TZO薄膜 40
4-3-1-3 TGZO薄膜 41
4-3-2薄膜能隙估算 41
4-3-2-1 GZO薄膜 41
4-3-2-2 TZO薄膜 42
4-3-2-3 TGZO薄膜 43
4-3-3 薄膜電性量測 43
4-3-3-1 GZO薄膜 43
4-3-3-2 TZO薄膜 44
4-3-3-3 TGZO薄膜 44
4-4 TGZO薄膜腐蝕與光觸媒分析 45
4-4-1 TGZO薄膜腐蝕分析 45
4-4-1-1 線性極化法 45
4-4-1-2 Tafel極化法 46
4-4-1-3交流阻抗頻譜分析 46
4-4-2 光觸媒分析 47
五、討論 48
5-1溶膠凝膠法之pH值與塗佈薄膜之熱處理溫度選定 48
5-1-1 pH值選定 48
5-1-2探討溶凝膠之熱分析(TGA)的影響 48
5-2 摻雜不同金屬元素對透明導電膜的影響 49
5-2-1薄膜結構與組成 49
5-2-2薄膜光性與電性分析 51
5-3鈦(0~1 at.%)、鎵(2 at.%)共摻雜(TGZO)薄膜討論 54
5-3-1薄膜結構與組成 54
5-3-2薄膜光學性質與電性質 57
5-3-3 薄膜電化學實驗 59
六、結論 61
七、未來展望 63
參考文獻 64

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