臺灣博碩士論文加值系統

本論文主要利用化學氣相沉積方式合成氧化銥/氧化釕奈米桿為感測材料在石英感測晶片上的金電極進行沉積，用XRD與FESEM分析氧化銥/氧化釕的薄膜表面結構。其次以QCM 質量式感測器針對有機揮發化合物(VOC)氣體進行感測，且深入探討薄膜型態對氣體感測的影響。
合成氧化銥/氧化釕方面，主要探討基板溫度、沉積時間對薄膜型態的影響，結果顯示基板溫度為薄膜型態形成的關鍵，氧化銥在350~400oC下形成葉片狀奈米桿薄膜，450oC 下形成葉片狀+螺旋狀薄膜型態，至高溫500oC型態轉變為四方形柱狀奈米桿。合成氧化釕奈米桿薄膜方面，無法在金上形成奈米桿，以薄膜型態結構為主。
在QCM感測方面，RuO2活性強，對氣體吸附不可逆，感測價值低。而在IrO2奈米桿薄膜對烷類、醇類、芳香族類、酸類、胺類的氣體感測中，以對胺類和酸類的靈敏度最高，我們發現：
(1) IrO2奈米桿對酸類有較佳的感測特性，為可逆性吸附，t80快，吸附訊號也大。以IrO2感測1000ppm 丙酸為例， t80為194秒， △f= 170Hz。
(2) IrO2奈米桿沉積時間越長，膜越厚，感測靈敏度增加。以基板溫度350oC而言，在不同沉積時間20min、30min、40min、50min、60min下，沉積60min的薄膜吸附訊號較20-40min的訊號大四倍。
(3) IrO2奈米桿可偵測至1ppm以下的丙酸濃度，隨濃度提高(1~1000ppm)，感測靈敏度增加，濃度曲線隨基板溫度、沉積時間增加而升高。
(4)基板溫度的提高，薄膜型態改變，以350oC下沉積的葉片狀型態薄膜感測靈敏度薄膜最佳。

In this thesis we investigated the metal organic chemical vapor deposition (MOCVD) deposition of ruthenium oxide and iridium oxide onto the gold electrode on the piezoelectric quartz crystal for gas sensor applications. The surface structure and morphology of RuO2 and IrO2 layers were studied with X-ray diffraction (XRD) and field emission scanning electron microscope (FESEM), and the gas sensing of volatile organic compond (VOC) were carried out with the quartz crystal microbalance (QCM) technique.
For the deposition, the effects of substrate temperature and the deposition time on the oxides structure were investigated. We found that IrO2 exhibit wedge-shape nanorods with the substrate temperature in the 350-400 oC range, some of the wedges enfold into a spiral square tube at the substrate temperature of 450oC, and the square obelisk nanorods are observed at 500 oC. However, within the same temperature range, RuO2 were found only in the form of continuous film, with no nanorods.
For QCM gas sensing, we found that RuO2 interacts with most VOC irreversibly, has less values as a gas sensor. IrO2, however, shows reversible behavior in the adsorption of aromatics and acids. The sensing of organic acids is of high sensitivity and fast response. For example, in sensing of 1000ppm propionic acid vapor, the IrO2 sensor shows a frequency shift of 170Hz, and t80 of 194 seconds. A good response signal can be detected with 1ppm propionic acid vapor; the detection limit is in the ppb range.
The sensitivity goes up with the amount of IrO2 deposited. With the deposition time of 60 minutes, the QCM signal is four-fold larger than that of 20-40 minutes deposition. The sensitivity is also found to be the largest for the wedge-shape IrO2 deposited at 350 oC.

中文摘要 ……………I
英文摘要 ……………..III
誌謝 ……………..VI
目錄 ……………..V
圖目錄 ……………..XIII
表目錄 ……………..XIV
第一章緒論 1
1.1 奈米科技的簡介 1
1.2 感測器之原理與簡介 2
1.3 研究動機 6
第二章文獻回顧 7
2.1 RuO2與IrO2晶體結構 7
2.2 RuO2與IrO2晶體導電性 9
2.3 RuO2與IrO2晶體成長 10
2.4 RuO2與IrO2之場發射(Field Emission)特性 15
2.5 RuO2與IrO2對氣體感測之應用 17
2.5.1 IrO2的氣體感測應用 17
2.5.2 RuO2的氣體感測應用 17
2.5.2.1氧氣在RuO2的化學吸附 19
2.6 石英晶體微量天平 21
2.6.1 石英震盪器之壓電性（Piezoelectricity） 21
2.6.2 QCM偵測之理論模式建立 22
第三章實驗方法與步驟 24
3.1 實驗藥品 24
3.1.1 前驅物 25
3.2 儀器設備 26
3.2.1 化學氣相沉積設備 27
3.3 實驗流程 29
3.4石英震盪晶體處理 30
3.5以MOCVD法製備RuO2與IrO2薄膜步驟 31
3.6結構分析與性質量測儀器 33
3.7 QCM(Quartz Crystal Membrane)裝置 35
第四章結果與討論 37
4.1氧化銥奈米桿實驗結果與討論 37
4.1.1基板溫度之影響 38
4.1.2沉積時間之影響 43
4.2氧化釕奈米桿實驗結果與討論 46
4.2.1基板溫度之影響 47
4.3氧化銥/氧化釕結構分析總結 50
4.4氧化銥與氧化釕奈米桿的氣體感測 55
4.4.1氧化銥奈米桿薄膜的氣體感測 55
4.4.1.1氧化銥感測器的吸附應答時間 60
4.4.1.2氧化銥奈米桿薄膜對酸類之感測 61
4.4.1.3氧化銥奈米感測薄膜對丙酸之重現性 65
4.4.1.4氧化銥奈米桿薄膜對胺類之感測 66
4.4.1.5濃度效應 69
4.4.1.6膜厚效應 71
4.4.1.7薄膜型態對氣體感測之影響 74
4.4.2氧化釕奈米桿薄膜的氣體感測 78
4.4.2.1氧化釕薄膜的可逆性 82
4.4.2.2氧化釕薄膜感測器的吸附應答時間 85
4.4.2.3氧化釕薄膜對酸類之感測 86
4.4.2.4氧化釕薄膜對胺類之感測 87
4.4.2.5濃度效應 88
4.4.2.6薄膜型態對氣體感測之影響 89
第五章結論 92
參考文獻 95

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