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研究生： 楊政憲
Yang, Cheng-Hsien
論文名稱： 以溶膠凝膠法製備二氧化鈦酸鹼度感測器之研究
Preparation of Titania Based pH Sensors by Sol-gel Technique
指導教授： 陳慧英
Chen, Huey-Ing
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2013
畢業學年度： 101
語文別： 中文
論文頁數： 120
中文關鍵詞： 二氧化鈦 、溶膠凝膠 、延伸式閘極場效電晶體 、酸鹼度感測器
外文關鍵詞： titania, sol-gel, EGFET, pH sensor
相關次數： 點閱：73  下載：1 
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    • 本研究係以異丙醇氧化鈦為前驅鹽， 聚乙烯吡咯烷酮(polyvinylpyrrolidone, PVP)為黏結劑，利用溶膠凝膠法製備二氧化鈦薄膜 (titania thin film, TTF)，探討製備變因對薄膜特性之影響；並以延伸式閘極場效電晶體為基礎，將溶膠以旋轉塗佈方式製備出TTF/FTO pH感測器。針對實驗操作變因：溶膠組成、塗佈轉速、塗佈次數及煅燒溫度等因素加以探討，並探討不同變因所得元件之pH感測特性。此外，以最佳感測元件進行操作溫度、遲滯、時漂及金屬離子干擾等特性之分析。
    實驗結果顯示，Ti/PVP比例對TTF表面形態影響甚鉅，當Ti/PVP比例大於5時，TTF呈網狀結構；反之呈顆粒結構。塗佈轉速增加時，TTF膜厚隨之減小，膜電阻亦減小。當製備條件為PVP濃度為3 wt%、鈦前驅鹽濃度為35 wt%、反應溫度為25.1oC、塗佈轉速為3000 rpm、塗佈次數為一次及煅燒溫度為700oC時，所得元件(P3Ti35T70)之pH感測性能最佳，靈敏度達到54.01 mV/pH，線性度達到0.9968。
    進一步探討此元件之感測溫度係數及長時間之穩定性，結果發現，隨著感測溫度增加，感測靈敏度大致呈線性增加，溫度係數估算為0.8978。另外，遲滯位移電位為6.4 mV；元件經5~12小時測試，在pH 2、7、12中之時漂值分別為10.3 mV/h、0.57 mV/h、2.83 mV/h，顯示薄膜在中性溶液中具良好之長期穩定性。此外，在pH 7緩衝溶液中添加鈉及鉀離子，結果發現，量測之閘極電壓並無顯著變化，顯示此元件對氫離子感測有極佳之選擇性。

    In this work, titania thin films (TTFs) were prepared from tetra-isopropoxide with polyvinylpyrrolidone (PVP) via the sol-gel route. The effects of preparation conditions on properties of films were investigated. Furthermore, TTF/FTO pH sensors based on the extended gate-field-effect transistor (EGFET) were fabricated by spin-coating. The influence of experimental conditions including sol composition, spin speed, number of spinning, and calcination temperature on pH sensing characteristics of the resulting devices were investigated. In addition, sensitivities of the best device were measured at different temperatures. The hysteresis, drift, and metal ion interference were also studied.
    From the experimental results, it showed the surface morphologies of TTFs were strongly affected by the Ti/PVP ratio. As the ratio was greater than 5, the TTF showed a net structure; otherwise it showed a particulate structure. With increasing the spin speed, the thickness of TTF was decreased, resulting in the decrease of the electric resistance of TTF. The result found that the best device (denoted as P3Ti35T70 device) was fabricated at the optimal conditions: 3 wt% PVP, 35 wt% Ti, reaction temperature of 25.1oC, spin speed of 3000 rpm, spin number of 1, and calcination temperature of 700oC. The P3Ti35T70 device showed a high sensitivity of 51.41mV/pH with a linearity of 0.9986 at 298.1K in the pH range from 2 to 12.
    To further investigate the sensing temperature coefficient and long-term stability, it found that the sensitivity was increased with linearly increasing the sensing temperature. The temperature coefficient in the sensitivity of the device was estimated as 0.8978. Besides, the voltage drift of the hysteresis was about 6.4 mV with a loop path of pH 7→4→7→10→7, and the drift rate at pH 2, 7 and 10 were 10.28, 0.57 and 2.83mV/h, respectively. This revealed that the TTF exhibited a good long-term stability in the neutral solution. Moreover, the additions of sodium and potassium ions in the pH 7 buffer resulted in negligible effects of sensing, which indicated the studied device exhibited high selectivity toward hydrogen ions.

    中文摘要 I 英文摘要 II 誌 謝 IV 總目錄 V 表目錄 VIII 圖目錄 X 第一章 緒論 1 1.1 前言 1 1.2 延伸式閘極場效電晶體pH感測器 1 1.3 二氧化鈦特性及其pH感測器 3 1.3.1 二氧化鈦性質 3 1.3.2 二氧化鈦感測薄膜之製備 3 1.3.3 二氧化鈦pH感測之應用 4 1.4 研究動機 4 第二章 原理 10 2.1 溶膠凝膠法 10 2.2 兩性氧化物之等電點 11 2.3 延伸式閘極離子感測場效電晶體 12 2.4表面吸附座鍵結模式 14 第三章 實驗 18 3.1 藥品與材料 18 3.1.1 藥品 18 3.1.2 材料 18 3.2 實驗設備與分析儀器 19 3.2.1 實驗設備 19 3.2.2 分析儀器 19 3.3 實驗步驟 20 3.3.1 TiO2/FTO元件之製備 20 3.3.2 pH感測實驗 22 3.3.3 儀器分析方法及條件 23 第四章 二氧化鈦薄膜之製備及其pH感測特性之探討 29 4.1 溶膠組成對薄膜及其感測特性之影響 29 4.1.1 PVP濃度之影響 29 4.1.1.1 PVP濃度對薄膜特性之影響 29 4.1.1.2 PVP濃度對pH感測特性之影響 32 4.1.2鈦前驅鹽濃度之影響 33 4.1.2.1鈦前驅鹽濃度對薄膜特性之影響 33 4.1.2.2鈦前驅鹽濃度對TiO2膜pH感測特性之影響 35 4.2 薄膜製備變因對TiO2膜之特性及感測之影響 35 4.2.1 塗佈轉速之影響 35 4.2.1.1 塗佈轉速對薄膜特性之影響 36 4.2.1.2 塗佈轉速對氫離子感測特性之影響 36 4.2.2 塗佈次數之影響 37 4.2.2.1 塗佈次數對薄膜特性之影響 37 4.2.2.2 塗佈次數對氫離子感測特性之影響 38 4.2.3煅燒溫度對薄膜特性之影響 38 4.2.3.1 煅燒溫度對薄膜特性之影響 38 4.2.3.2 煅燒溫度對氫離子感測特性之影響 40 4.2.4 最佳條件對氫離子感測特性之影響 40 4.3 TTF元件氫離子感測特性之分析 40 4.3.1 二氧化鈦之等電點 41 4.3.2操作溫度對元件感測特性之影響 41 4.3.3 遲滯、時漂及鈉離子干擾 42 第五章 結論與建議 110 5.1 結論 110 5.2 建議 112 參考文獻 113

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