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研究生： 張晞硯
Chang, Hsi-Yen
論文名稱： 延伸閘極式金屬氧化物酸鹼度感測器之製備與特性研究
Preparation and Characterization of pH Sensors Based on Extended-gate Metal Oxides
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： 119
中文關鍵詞： 延伸式閘極場效電晶體 、二氧化鈦 、氧化鎳 、pH感測
外文關鍵詞： EGFET, TiO2, NiO, pH sensor
相關次數： 點閱：59  下載：1 
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    • 本研究分別以TiO2及NiO感測膜製作延伸式閘極場效電晶體式pH感測器，旨在探討各感測膜之製程條件對薄膜性質之影響，並探討所得元件在pH2-12之pH感測特性。
    首先，以熱氧化法來製備TiO2/Ti感測元件，文中針對酸洗處理及煅燒溫度來探討。實驗結果顯示，元件經酸洗處理後，TiO2表面產生較多裂痕且所得晶粒較小，有利於氫離子吸附。煅燒溫度為500℃時所得元件(AT50f)為pH感測性能最佳，另外，在pH2-12間量測，感測靈敏度為56.20mV/pH，線性度為0.99737。此元件之遲滯壓差為12.1mV；在酸性(pH 2)環境下之時漂值最小約為0.479mV/hr；另外，鈉、鉀離子對元件感測之干擾可忽略。
    其次，以沉澱法製備NiO奈米粒子，經旋轉塗佈置得NiO/FTO感測元件，文中改變基材、煅燒溫度、塗佈次數、前驅鹽濃度、沉澱劑種類及濃度來加以探討。結果顯示，FTO之熱穩定性較ITO佳，因此，以FTO作為基材。沉澱劑分別採用NaOH及NH4OH溶液來進行，結果發現NaOH系統所得NiO薄膜之粒徑較小，且粒子堆疊較為緊密，故所得元件之感測性能較優異；在煅燒溫度為400℃時所得NiO薄膜對pH之感測靈敏度最高。
    以NaOH溶液為沉澱劑時，當塗佈次數增加時，膜厚亦增加，但因膜電阻隨之增加，反而不利電訊傳輸。另外，前驅鹽及沉澱劑濃度改變時，元件之靈敏度並未呈明顯變化。當鎳前驅鹽濃度1M、NaOH濃度2.5M、塗佈次數為10次時，所得元件40-10HF25之感測特性最佳，其感測靈敏度為53.40mV/pH，線性度為0.99887，遲滯壓差為6.3mV，時漂值在酸性(pH 2)緩衝液中最小，約為0.068mV/hr；另外，鈉、鉀離子對元件感測之干擾並不明顯。
    綜上所述，本研究利用兩種材料所得之最佳感測元件，皆具有良好之pH感測效果，且製程成本低、可微型化，在pH量測方面展現出應用上之發展潛力。

    In this work, TiO2/Ti and NiO/FTO pH sensors based on extended-gate field-effect transistors (EGFETs) were fabricated. The influence of process variables on properties of sensing films was investigated. Moreover, the sensing characteristics of devices toward pH were also studied in the pH range from 2 to 12.
    At first, TiO2/Ti films were formed by the thermal oxidation method. The effects of acid-washing and calcination temperature on the pH sensing characteristics of devices were under investigation. The experimental results showed that devices with acid-washing treatment exhibited higher pH sensitivity than those without acid-washing, due to the favorable adsorption of hydrogen ions arising from the formations of more cracks and smaller grains on the TiO2 surface. Besides, the device (denoted as AT50f) obtained at calcination temperature of 500oC demonstrated the best sensing characteristics with a sensitivity of 56.20 mV/pH and a linearity of 0.9974. The drift voltage of hysteresis was estimated as 12.1mV, and the drift rate in pH 2 buffer was about 0.479 mV/hr. Furthermore, the sensing interferences of sodium and potassium ions could be negligible.
    Subsequently, the precipitation technique was employed to prepare NiO nanoparticles following by spin-coating to fabricate NiO/FTO device. The influences of preparation variables including substrate material, calcination temperature, number of coating, concentration of precursor, and nature and concentration of precipitant on the pH sensing characteristics were studied. From experimental results, the FTO was chosen as the substrate material due to its good thermal stability. Two precipitants, NaOH and NH4OH solutions, were used for the synthesis of NiO powders, respectively. It was found that the NiO/FTO device derived from NaOH precipitant exhibited superior sensing performances, owing to the smaller grain size and dense packing of film. Moreover, the maximum sensitivity of device obtained at calcination temperature of 400oC.
    As increasing the number of coating, the thickness of NiO film was increased, resulting in the increase of surface area; however, it caused the decline of the electronic signal because of the increase of film resistance. Besides, the pH sensitivity of the device showed no obvious change with varying the concentrations of precursor and precipitant. Among all studied devices, the device 40-10HF25 demonstrated the best sensing characteristics toward pH, which was fabricated under the following conditions: 1M Ni(NO3)2 precursor with 2.5M NaOH solution and the coating number of 10. This device exhibited a sensitivity of 53.40 mV/pH with a linearity of 0.99887, a hysteresis voltage of 6.3mV, and a drift rate of 0.068 mV/h in acidic buffer (pH2). Besides, the interferences of sodium and potassium ions to the sensing characteristics were insignificant.
    In summary, the proposed devices exhibited fairly good sensing performances toward hydrogen ions. With advantages of low production cost and easy miniaturization, they showed great promising potential in the developments of pH sensing.

    中文摘要……………………………………………………………………I 英文摘要………………………………………………………………III 誌謝……………………………………………………………………………V 總目錄……………………………………………………………………VI 表目錄………………………………………………………………………X 圖目錄……………………………………………………………………XI 符號說明…………………………………………………………………XV 第一章 緒論 1 1.1 前言 1 1.2 場效電晶體型pH感測器之簡介 1 1.3 二氧化鈦感測膜 4 1.3.1 結構與性質 4 1.3.2 薄膜製備 5 1.4 氧化鎳感測膜 6 1.4.1 結構與性質 6 1.4.2 薄膜製備 6 1.5 研究動機 7 第二章 原理 16 2.1 場效電晶體基礎理論 16 2.2 離子感測場效電晶體操作原理 17 2.3 延伸式閘極離子感測場效電晶體操作原理 19 2.4表面吸附座鍵結模型 20 第三章 實驗 24 3.1 藥品及材料 24 3.2 儀器及分析設備 25 3.2.1 設備及裝置 25 3.2.2 分析儀器 25 3.3 實驗方法與步驟 27 3.3.1 元件製備 27 3.3.1.1 感測薄膜製備 27 3.3.1.2 延伸式閘極之封裝 29 3.3.2 pH感測 29 3.3.2.1 參數設定 29 3.3.2.2 pH量測步驟 30 3.3.2.3 感測靈敏度之定義 31 3.3.3分析條件 31 第四章 二氧化鈦pH感測元件之製備與特性探討 36 4.1 熱氧化製程變因探討 36 4.1.1 煅燒溫度之影響 36 4.1.2 酸洗處理之影響 38 4.2 感測元件電性特性之探討 39 4.2.1 pH感測特性之探討 39 4.2.2 遲滯現象之探討 40 4.2.3 時漂效應之探討 41 4.2.4 元件等電點之探討 41 4.2.5 共存陽離子之干擾 42 4.2.6 操作溫度之影響 42 4.3 感測元件之綜合討論 42 第五章 氧化鎳pH感測元件之製備與特性探討 60 5.1 基材之選擇 60 5.2 氧化鎳粒子之製備 61 5.2.1 沉澱反應 61 5.2.2 粒徑大小及表面形態 62 5.3 煅燒溫度之探討 63 5.3.1 熱重分析結果 63 5.3.2 XRD分析結果 64 5.3.3 SEM分析結果 65 5.3.4 FTIR分析結果 65 5.3.5 XPS分析結果 66 5.3.5 BET分析結果 67 5.4 旋轉塗佈次數之影響 69 5.5 沉澱劑濃度變因之影響 70 5.6 感測元件pH感測特性之探討 70 5.6.1 pH感測靈敏度之探討 70 5.6.2 遲滯現象之探討 71 5.6.3 時漂效應之探討 72 5.6.4 最佳感測元件等電點之探討 72 5.6.5 共存陽離子干擾探討 73 5.6.6 操作溫度之影響 73 5.7 感測元件之綜合討論 73 第六章 結論與建議 109 6.1 結論 109 6.2 建議 111 第七章 參考文獻 112

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