臺灣博碩士論文加值系統

本論文主要利用化學氣相沉積(MOCVD)方式，在鍍於石英晶片上之金電極表面沉積二氧化銥，以此製作QCM質量式感測器，針對酸類及胺類氣體進行感測，發現有不錯的感測靈敏度，其偵測濃度可達數個ppm。
當我們將IrO2置於高真空環境下，以不同還原溫度(450 oC~600 oC)及還原時間(30分鐘~90分鐘)，可使IrO2 部份去氧還原，利用XRD、XPS、拉曼光譜、SEM進行還原前後的表面分析。並結合模擬計算探討其吸附與脫附機制。
由XPS分析來看，二氧化銥還原前表面組成為IrO2 / IrO3 / Ir(OH)x，感測1000ppm丙酸所得訊號為160Hz、可逆性73%；在450 oC進行還原，表面組成不變，丙酸訊號仍為160Hz，但可逆性為88%；還原溫度提高至550 oC，則表面還原成Ir/IrO2，丙酸訊號提高為270Hz，可逆性達98%。即其靈敏度比還原高，且可逆性更佳。
當還原溫度再提高至600 oC時，丙酸訊號提高至320Hz，但可逆性降低至32%。為了改善可逆程度，我們預先在金電極上濺鍍ㄧ層Ti薄膜，並在相同的熱還原處裡條件下將IrO2脫氧，發現可逆性可大幅提升至80%。

Nanostructured IrO2 crystals are grown on a gold-coated quartz substrate by metal organic chemical vapor deposition (MOCVD). The resultant quartz crystal microbalance (QCM) sensor shows a good gas sensitivity towards carboxylic acid and amine vapors at the ppm level.
When the oxide is heated at 450oC~600oC in high vacuum, the IrO2 is partially reduced by thermal decomposition. The composition and the morphology of the sample surface before and after reduction are investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and scanning electron microscopy (SEM). Molecular simulation is also used to explain the mechanism of adsorption and desorption.
From XPS analysis, we find that the sample surface composition is IrO2/IrO3/Ir(OH)x before reduction. Upon exposure to 1000 ppm of propanic acid vapors, the QCM frequency shift is found to be 160 Hz with 73% reversibility when desorbed; After a reduction at 450oC, the surface composition and the QCM frequency shift remain the same, while the reversibility becomes 88%; When the reduction is carried out at 550 oC, the surface is reduced to become Ir/IrO2, and the Ir/IrO2 sensor shows a higher gas sensitivity (~270 Hz) and better reversibility (~98%) as compared to the IrO2/IrO3/Ir(OH)x sensor.
When reduction temperature is further increased to 600oC, the sensor shows an even higher sensitivity (~320Hz) but lower reversibility (~32%). However, if a thin Ti layer onto the Au electrode before growing the IrO2 crystals, followed by the 600oC reduction treatment, then the reversibility of the sensor can be improved to about 80%.

中文摘要...I
英文摘要..III
致謝..... V
目錄..... VII
圖目錄... XI
表目錄... XVI
第一章 緒論...... 1
1.1 氣體感測器簡介....... 1
1.2 半導體金屬氧化物感測材料...... 2
1.3 氣體感測器的種類..... 2
1.4 研究動機.............4
第二章 文獻回顧.........6
2.1 IrO2晶體之結構....... 6
2.2 IrO2晶體導電性....... 7
2.3 IrO2晶體成長......... 8
2.4 IrO2之場發射(Field Emission)特性....... 10
2.5 IrO2對氣體感測之應用.......... 11
2.6 石英晶體微量天平（Quartz Crystal Microbalance).. 12
2.6.1石英震盪器之壓電性（Piezoelectricity）....... 12
2.6.2 QCM偵測之理論模式建立..... 14
2.7 金屬對金屬氧化物性質的影響.... 16
2.8 金屬氧化物的還原脫氧...........18
2.8.1 脫氧位置探討..........................................18
2.8.2 IrO2脫氧還原之反應機制....................................20
2.8.3分子吸附於金屬氧化物表面之反應機制......................... 22
2.9 拉曼光譜法介紹......................................... 22
2.9.1 拉曼光譜法與紅外線光譜法的差異................................ 22
2.9.2 脫氧還原前/後的拉曼光譜....................................... 23
第三章 實驗方法及步驟.......25
3.1實驗藥品.......25
3.2 儀器設備......25
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IrO2 / D-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
3.8 參數定義........................................................... 37
第四章 結果與討論.....39
4.0 實驗目的...............................................39
4.1 X-ray分析..........................................................39
4.1.1還原溫度之影響.............................................. 39
4.1.2還原時間之影響................................................... 43
4.2 SEM分析....................................................... 46
4.2.1 還原溫度之影響.......................................... 46
4.2.2 還原時間之影響............................................ 46
4.3 拉曼光譜分析.................................................49
4.3.1還原溫度之影響............................................ 49
4.3.2還原時間之影響.............................................54
4.4 XPS分析................................................................59
4.4.1 還原溫度之影響............................................... 59
4.4.2 還原時間之影響............................................... 65
4.4.2 XPS縱深分析.....................................................69
4.5 氣體感測........................................................71
4.5.1 IrO2對丙酸之氣體感測.......................................72
4.5.1.1 IrO2還原時間的影響.................................. 72
4.5.1.2 IrO2還原溫度的影響..................................74
4.5.1.3 IrO2還原溫度與還原時間的相互關係....................76
4.5.1.4 IrO2/Ti、d-IrO2/Ti 電極製備...................................78
4.5.1.4.1 SEM表面型態分析...................................... 78
4.5.1.4.2 X-ray分析......................................... 81
4.5.1.4.3 Raman光譜分析........................................... 82
4.5.1.4.4 XPS分析........................................ 83
4.5.1.4.5 IrO2/Au、IrO2/Ti/Au在還原後之氣體感測....87
4.5.1.5 IrO2還原前後丙酸感測再現性................................89
4.5.1.6 濃度極限..............................................91
4.5.1.7 以模擬計算探討丙酸分子在脫氧晶格內的吸附行為......93
4.5.2 IrO2對己胺之氣體感測................................95
4.5.2.1 IrO2還原時間的影響.............................95
4.5.2.2 IrO2還原溫度的影響................................97
4.5.2.3 IrO2/Au、IrO2/Ti/Au在還原後之氣體感測............99
第五章 結 論............................................... 101
第六章 參考文獻..................................................... 104

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