臺灣博碩士論文加值系統

一氧化氮與血液中的血紅素很容易結合，形成亞硝基血素，當吸入之濃度過高，會慢慢的抑鬱中樞神經，所以試圖發展奈米錫鎢氧化薄膜來偵測空氣中低濃度一氧化氮之含量，此外，人體所呼出氣體中NO的量增加，可作為肺炎或氣喘之警訊。
價格昂貴、偵測費時、且笨重的氣體感測器如今已經不敷使用，所以撇去過去的厚膜與薄膜感測器，近幾年製備奈米薄膜氣體感測器已經廣泛被討論到。
本研究利用奈米技術的發展使得氣體感測器不僅偵測快、體積小、耗能低，分別利用四氯化錫及六氯化鎢當作前驅物，以溶膠-凝膠法製備出二氧化錫及三氧化鎢之凝膠作為氣體感測器的感測材料，使用可以在高溫及惡劣環境生存且機械性質穩定的二氧化錫做為基本材料，並且摻雜對於氮氧化物(NOx)具有高度靈敏度的WO3，並且嘗試摻雜能提升氧化能力之CuO，比較其間之差異，同時利用液晶模板的方式來輔助電泳方式製備薄膜，並調整膠體溶液之表面電位到pH值為10，以電泳的方式讓材料在已經鍍有梳狀電極之氧化鋁板上形成薄膜，經過一小時不同溫度的鍛燒後，可得到奈米錫鎢氧化薄膜，經過XRD、SEM、ESCA來鑑定成分並觀察結晶及化學結構以及表面型態，再分別探討不同條件下所製備出的氣體感測器。
實驗結果發現二氧化錫與三氧化鎢對於一氧化氮均有感測能力，但是並不具有選擇性，是以無法判斷ㄧ氧化氮或二氧化氮；經過實驗後，發現薄膜中添加微量的硫酸銅，有助於提高感測器的選擇性。在莫耳濃度比為Sn ：W ： Cu = 1：1：0.0125% 時，操作溫度在200 ℃時可以偵測0.1 ~ 25ppm範圍之ㄧ氧化氮，並且在相同的操作條件下，對於二氧化氮並不具有感測效果，因此本研究發展出ㄧ選擇性高之一氧化氮感測器。

NO is easy to combine with hemoglobin of blood and become nitro-hemoglobin. When exposed in high NO concentration environment for a long period of time, our central nerve will be inhibited, so the objective of this work is to invent nanocrystalline tin-tungsten oxide thin film to detect the NO concentration in atmosphere. Also, an increasing of NO concentration exhaled from human can be an indication of important symptom of pneumonia or asthma.
Expensive, long detecting time and heavy sensors are no longer used in recent years. Instead of thick film and thin film sensor technologies, nanocrystalline thin film gas sensors are widely considered in these few year because of its fast detect, small size and low energy consumption.
In this research, SnCl4 and WCl6 were utilized as precursor to synthesis SnO2 and WO3 sol for sensing materials of gas sensor by sol-gel method. Tin oxide was used as the based material because of its high mechanism properties, stable in high temperature and bad environment. Doped WO3 ,which has high sensitivity to NOx, and doped CuO ,which can enhance ability of oxidization, were both utilized to compare the relationship between these few condition. Electrophoresis method was adopted to make sensing films with the help of liquid crystal template method and adjusted surface potential of sol solution to pH=10. After calcination one hour at several different temperatures, a high surface area nanocrystalline tin-tungsten oxide thin film with interdigitate electrode by electrophroesis was produced. XRD, SEM and ESCA were utilized to define the different parameters of its crystal and chemical structure, its surface morphology and component.
It is observed that both tin oxide and tungsten oxide have sensing ability to nitric oxide but didn’t have any selectivity to distinguish between NO and NO2 ；By adding a hint of copper sulphate, the selectivity of sensor was enhanced, when molar concentration of mixed solution is Sn : W : Cu = 1 : 1 : 0.0125%, NO sensor can detect NO from 0.1 ~ 25 ppm at operating temperature 200 ℃, at the same operating temperature, however it didn’t work when it contacted to NO2. Consequently, a highly selective nanocrytalline copper doped NO sensor was developed in this study.

中文摘要 Ⅰ
英文摘要 Ⅲ
誌謝 Ⅴ
目錄 Ⅵ
圖目錄 Ⅷ
表目錄 ⅩⅠ
第一章 前言 1
第二章 文獻回顧 3
2.1 NO之簡介 3
2.2 金屬氧化物半導體氣體感測器 4
2.3 二氧化錫及三氧化鎢之結構與特性 6
2.4 奈米錫鎢氧化薄膜之製備方式 9
2.4.1 溶膠-凝膠法 9
2.4.2 液晶模板機制 11
2.4.3 電泳 12
2.4.4 摻雜( Dopping ) 14
2.5 金屬氧化物氣體感測器之原理(導電機制) 16
2.6 半導體氧化物薄膜之氣體偵測性及應用 20
第三章 實驗方法與步驟 22
3.1 藥品資料表 22
3.2 實驗設備 23
3.3 實驗架構圖 24
3.4 感測材料的製備方式 25
3.5 氧化鋁板的清洗方法 28
3.6 鍍膜方式 29
3.6.1 浸鍍法 ( Dip Coating ) 29
3.6.2 電泳( Electrophoresis ) 30
3.7 氣體系統 31
3.8 感測系統 32
第四章 結果與討論 34
4.1 金屬氧化物薄膜 34
4.1.1 XRD 分析 34
4.1.2 SEM 分析 37
4.1.3 ESCA 分析 41
4.2 氣體感測結果與討論 43
4.2.1 界面活性劑之影響 43
4.2.2 操作溫度對感測之影響 44
4.2.3 靈敏度( Sensitivity ) 44
4.2.4 選擇性( Selectivity ) 47
第五章 結論 53
第六章 未來發展 54
參考文獻 55
圖目錄

圖 2.1 二氧化錫之單位晶格圖。大圓為O，小圓為Sn 7
圖 2.2 典型ReO3結構：Re可座落在立方體單位晶胞之 (a)角落位置或 (b) 中心位置 8
圖 2.3 液晶模板機制示意圖 12
圖 2.4 電泳示意圖 13
圖 2.5 添加摻雜物到金屬半導體氧化物後所發生的現象 15
圖 2.6 晶界理論模型示意圖 17
圖 2.7 不同的Debye 會造成半導體晶粒與奈米晶粒之導電度及巨蝻⑩漣幭?18
圖 3.1 實驗架構圖 24
圖 3.2 SnO2製備流程圖 26
圖 3.3 WO3製備流程圖 27
圖 3.4 氧化鋁板基材之清洗步驟 28
圖 3.5 溫度曲線分佈圖 29
圖 3.6 電泳裝置示意圖 30
圖 3.7 氣體測試系統 31
圖 3.8 氣體感測裝置 32
圖 3.9 氣體感測器製備流程圖 33
圖 4.1 SnO2鍛燒於400、500、600、700、800 ℃的XRD繞射光譜 35
圖 4.2 電泳製備薄膜，經過600 ℃鍛燒 (a) WO3 (b) Sn：W：Cu＝ 1：1：0.0125% 36
圖 4.3 鍛燒600 ℃ 各薄膜之SEM 表面型態 (a) SnO2 (b) WO3 (c) Sn：W＝ 1：1 (d) Sn：W：Cu＝ 1：1：0.0125% 38
圖 4.4 浸鍍法製備薄膜，固定鍛燒溫度在600 ℃，Sn：W：Cu=1：1：0.0125% 加入不同濃度(a)0.5 M (b)0.1 M (c)0.05 M (d)0.001 M (e)0.0005 M 的界面活性劑 39
圖 4.5 電泳製備薄膜，固定鍛燒溫度在600 ℃，Sn：W：Cu=1：1：0.0125% 加入不同濃度(a)0.5 M (b)0.1 M (c)0.05 M (d)0.001 M (e)0.0005 M 的界面活性劑 40
圖 4.6 利用浸鍍法與電泳製備Sn：W：Cu = 1：1：0.0125%之ESCA光譜
圖比較(虛線為浸鍍法，實線為電泳) 42
圖 4.7 WO3 (不加CTAB)，鍛燒600 ℃，操作溫度分別為 (a)150 (b)200 (c) 250 ℃製備 44
圖 4.8 電泳，SnO2鍛燒600 ℃，操作溫度200 ℃ 46
圖 4.9 電泳製備WO3 ，鍛燒600 ℃，操作溫度 (a) 150 ℃ (b) 200 ℃ 46
圖 4.10 電泳，莫爾濃度比Sn ：W ＝1 ： 1 鍛燒 600 ℃在操作溫度
(a) 150 ℃ (b) 200 ℃ 46
圖 4.11 電泳，莫爾濃度比Sn ：WO3 ＝1 ： 5鍛燒600 ℃，操作溫度200 ℃ 47
圖 4.12 將電泳製備的(a) SnO2 (b) WO3 薄膜固定操作溫度在200 ℃，並通入NO2 47
圖 4.13 電泳，莫耳濃度比Sn：W：Cu＝1：5：0.1% 鍛燒600 ℃，操作溫度(a)150 (b) 200 ℃ 49
圖 4.14 電泳，莫耳濃度比Sn：W：Cu＝1：5：0.0125%，操作溫度250 ℃鍛燒溫度(a) 400 (b) 500 (c) 600 (d) 700 ℃ 49
圖 4.15 電泳，鍛燒600 ℃，操作溫度250 ℃，莫耳濃度比(a) Sn：W：Cu＝1：1：0.0225% (b) Sn：W：Cu＝1：1：0.0325% 50
圖 4.16 電泳，莫爾濃度比Sn：W：Cu＝1：1：0.0125%，鍛燒600 ℃，操作溫度 (a) 180 (b) 200 ℃ 50
圖 4.17 電泳，莫爾濃度比Sn：W：Cu＝1：1：0.0125%，鍛燒600 ℃，操作溫度(a)200 (b) 250 ℃ 通入NO2 50
圖 4.18 各薄膜靈敏度之比較圖 52

















表目錄

表1-1 恕限值( Threshold Limited Value, TLV ) 2
表2-1 二氧化錫為基底，摻雜或加入觸媒的氣體感測器 4
表2-2 一般氣體感測器的偵測方式與原理 5
表2-3 各類氣體感測器優缺點比較 6
表2-4 二氧化錫做為感測材料之優缺點 18
表3-1 藥品資料表 22
表3-2 溶膠凝膠法之優缺點 25
表4-1 電泳製備薄膜之反應時間與恢復時間 51

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