臺灣博碩士論文加值系統

在現今整個可再生能源以及綠能產業來說，氫能十分有潛力成為未來的主流，相較於過往生產燃料所產生有害氣體(如，SO2¬、NOx、CO2、PM2.5等……)相比，氫能所產生的副產物為潔淨水，因此，當石油與氫氣生產價格相近時，氫能具有更高的吸引性。但是，氫氣為無色無味，並且具有易燃以及爆炸特性的氣體，即便是在高濃度的環境也無法被人眼以及鼻子所偵測到。此外，對於不同材料與金屬的滲透性也具破壞性。
二氧化鈰(CeO2)已經在許多領域都得到廣泛的研究，如催化劑、燃料電池，氣體感測器、生物醫學等， 並且由於其儲氧能力、Ce3+/Ce4+間的變換，以及其晶格中在大量釋放氧接收氧時仍然保持其螢石晶體結構，受到關注。
本論文中使用了一種簡易的超音波震盪研磨物理方式，研製CeO2奈米粉體，及混和金(Au)奈米粒子後，使用點膠的方式在晶片型(MEMS)氣體感測器上形成氣體感測的材料。之後，再使用晶片型氣體感測器之微加熱器在微量的二氧化硫(SO2)氣氛裡進行的自我硫化製程。最後，完成高靈敏CeO2晶片型氫氣感測器。
SEM分析顯示，未經研磨購置的二氧化鈰粉末範圍大至70μm，經由超音波震盪研磨方法在適當的參數比例下，可將未經研磨二氧化鈰粉末研磨至~50nm，且經由拉曼分析結果顯示出良好的二氧化鈰460cm-1 結晶峰。混和Au奈米粒子和自我硫化製程於TEM分析顯示，Au主要在頂部，而硫(S)是均勻的分佈在感測層。
於氫氣氣體量測分析：純的CeO2奈米粉末在最佳的實驗參數下對10ppm氫氣的氣體響應(Ig/Ia)可以從1.0增加到1.04。混和金(Au)奈米粒子催化後氣體響應增加到1.18。再加入硫化製程後，氣體響應增加到2.76，且低濃度在285ppb時的環境中也還有1.07的響應。此外，實驗結果也發現此研製之高靈敏CeO2晶片型氫氣感測器並不隨著濕度變化而改變，且在15天的日程中還保有2.3倍的氣體響應。

Cerium dioxide has been extensively studied in many fields, such as catalysts, fuel cells,gas sensors,biomedicine …etc,and because of its oxygen storage capacity, the conversion between Ce3+ /Ce4+, and its crystal lattice, it still maintains its fluorite crystal structure when a large amount of oxygen is released to receive oxygen, which has attracted attention.In this paper, a simple physical method of ultrasonic vibration grinding is used to develop CeO2 nanopowder,and after mixing gold(Au) nanoparticle, Dispensing gas sensing materials on MEMS gas sensors.after that, micro-heater is used for a self-sulfuration process in a trace SO2 atmosphere.finally,complete the highly sensitive CeO2 MEMS hydrogen sensor.
SEM analysis shows that the range of purchased cerium oxide powder without grinding is as large as 70μm. The unground cerium oxide powder can be ground to ~50nm through the ultrasonic vibration grinding method under the appropriate parameter ratio. and the result of Raman analysis shows a good crystalline peak of CeO2 at 460cm-1, The TEM analysis of the mixed Au nanoparticle and self-sulfuration process showed that Au is mainly on the top and sulfur (S) is evenly distributed in the sensing layer.
For hydrogen gas measurement, The gas response (Ig/Ia) of pure CeO2 nanopowder to 10ppm hydrogen can be increased from 1.0 to 1.04 under the best experimental parameters,the gas response increased to 1.18 after catalyzed by mixed gold (Au) nanoparticles.after adding the vulcanization process, the gas response increased to 2.76, and there was a 1.07 response in the low concentration environment at 285ppb.the experimental results also found that the high-sensitivity CeO2 MEMS hydrogen sensor developed by this method does not change with humidity changes, and it has a gas response of 2.3 times during the 15day.

中文摘要 i
英文摘要 ii
誌謝 iii
目錄 iv
表目錄 v
圖目錄 vi
第一章 緒論 1
1.1 前言 1
1.2 研究主題與動機 8
1.3 研究目的 9
第二章 基本原理與文獻回顧 10
2.1 奈米材料製備方式 10
2.2 二氧化鈰之特性 10
2.2.1 二氧化鈰之微觀結構 11
2.2.2 二氧化鈰中的缺陷化學 11
2.2.3 二氧化鈰中奈米效應 12
2.3 半導體感測器之感測機制 12
2.4 氫氣之感測機制 13
2.5 中性和帶電的金簇與，H2相互作用 14
2.6 二氧化鈰硫毒化 15
第三章 實驗方法與設備簡介 16
3.1 實驗流程 17
3.2 實驗用品及實驗設備 18
3.2.1 實驗用品 18
3.2.2 實驗設備 19
3.3 實驗步驟 19
3.3.1 二氧化鈰奈米粉末制備 19
3.3.2 感測材料與晶片型氣體感測器整合 20
3.3.3 二氧化鈰晶片型氣體感測器之改善 20
3.3.4 奈米材料表徵 20
3.3.5 感測器表徵 21
3.3.6 氣體量測以及微型加熱器量測 22
3.4 分析設備簡介及原理 23
3.4.1 拉曼光譜儀(Raman spectrometers) 23
3.4.2 掃描式電子顯微鏡(SEM) 23
3.4.3 聚焦離子束顯微鏡(FIB) 24
3.4.4 穿透式電子顯微鏡(TEM) 24
第四章 結果與討論 25
4.1 研磨奈米粉末 25
4.2 退火後之感測材料分析 29
4.3 退火後之氣體感測器分析 32
4.4 氣體量測 44
4.4.1 市售二氧化鈰粉末感測器量測 44
4.4.2 退火過後之純二氧化鈰粉末感測器量測 45
4.4.3 退火過後並進行硫化之純二氧化鈰粉末感測器量測 49
4.4.4 退火過後之金/二氧化鈰之感測器量測 51
4.4.5 硫化過後之金/二氧化鈰之感測器量測與老化過後感測器之比較 54
4.4.6 氣體感測器在不同濃度的氫氣下量測 58
4.4.7 氣體感測器在不同濕度下的響應 60
4.4.8 氣體感測器在長時間的量測 62
第五章 結論與未來展望 64
5.1 結論 64
5.2 未來展望 66
參考文獻 66

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