臺灣博碩士論文加值系統

一氧化碳是無色無味且毒性可令人致死的危險氣體，在個人安全及工安意識的提高下為一般居家必備之感測器，近年來，一氧化碳感測器朝著更高的輕便性和敏感度發展。網版印刷製程在太陽能光電產業及生醫檢測上受到青睞，因其製程簡易、材料使用少、易大量生產和生產成本低，為競爭力非常高的製程技術；金屬氧化物半導體型氣體感測器具備了耐熱、耐腐蝕、材料成本低、和易於微小化之優點，鋅和錫元素是基礎材料中具代表性的模型電子材料，其氧化物氧化鋅與二氧化錫是一種新穎的寬能帶半導體材料，具有良好的光學、電性和氣體感測特性，在未來的半導體工業相當被重視。本論文使用ZnO和SnO2粉末經球磨研磨製成漿料後以網版印刷的製程於玻璃基板上製作ZnO和SnO2感測膜及量測用之銀電極，並探討感測膜之材料、熱處理溫度、熱處理時間和感測溫度對其一氧化碳感測能力的影響。
在本論文中，製作出奈米粒樣品以自行架設之實驗I-V量測設備即時量測樣品在空氣和一氧化碳環境下的電阻變化並探討其感測度和反應時間，也利用光學顯微鏡(OM)和掃描式電子顯微鏡(SEM)分析感測膜的表面形貌和微結構。
實驗結果發現感測膜在熱處理時隨時間增長會有不同的機制變化，在熱處理初期為樣品排膠形成氣孔的行為，若使用較高的溫度排膠，樣品會得到較佳的一氧化碳感測度，樹脂排除完畢後，熱處理的機制轉變為粉末的燒結。燒結時間持續越久，樣品孔隙融結減少，一氧化碳感測度也隨之下降。ZnO和SnO2製作出的感測膜在操作溫度300 oC會有較佳的一氧化碳感測能力，但隨使用時間增長其感測度衰減的速度也較快，在量測溫度250 oC下，感測度雖較低但經長時間使用後其感測度穩定乃至無衰減。以純ZnO材料組成的感測膜其一氧化碳感測度較純SnO2佳，且雖然隨著SnO2混合比例的增加其一氧化碳感測度會隨之下降，但可有效的減少長時間使用後其感測度的衰減，實驗也顯示了以網版印刷製作的ZnO及SnO2一氧化碳感測器在敏感度及壽命都具有優秀的特性。

Due to the increased awareness of living and industrial safety, carbon monoxide detectors must be geared towards better portability and sensitivity. Metal oxide semiconductor sensors should possess advantages such as heat and corrosion resistance,
low cost materials, and ease of miniaturization. This thesis applied ball milled and powdered ZnO and SnO2 to manufacture into paste, then used the screen printing method deposited ZnO and SnO2 paste film and silver electrode on glass substrate. The influence
on sensing film materials, temperature, time of heat treatment, and temperature of measurement was investigated. The samples were fabricated and measured by setting up self-measurement apparatus. The data was analyzed the changes of resistance under different air and carbon monoxide environments. This is followed by analysis of both
surface topography and microstructure of the sensing film under OM and SEM.
Experiment reveals that samples under different annealing process yield different surface morphology and micro structure while at the beginning of the heat treatment, epoxy evaporates from the sample brought about porous structure. Annealing at higher temperature sample will have more rough surface and better sensitivity in detecting carbon monoxide. After epoxy removed, heat treatment mechanism is then switched to sinter ZnO and SnO2 powders. the longer the samples are sintered, the lower the sensitive.
Sensing films composited with ZnO and SnO2 will have better carbon monoxide sensitivity at 300oC but its sensitivity decays at a faster rate than samples working at 250 oC despite the slightly weaker sensitivity. Sensing films with pure ZnO will have higher sensitivity compared to pure SnO2 one. With the increase of SnO2 proportion, carbon monoxide sensitivities of detectors decreases, however, its life time can be improve significantly.

致謝 ………………………………………………… i
中文摘要 …………………………………………… ii
Abstract ……………………………………………iii
目錄 ………………………………………………… iv
表目錄 ……………………………………………… vi
圖目錄 ……………………………………………… vii
第一章 緒論 ………………………………………… 1
1.1 前言 ……………………………………………… 1
1.2 氣體感測器種類介紹 …………………………… 3
1.2.1 吸附質量型 …………………………………… 3
1.2.2 電化學型 ……………………………………… 3
1.2.3 光吸收型 ……………………………………… 3
1.2.4 觸媒燃燒型 …………………………………… 3
1.3 金屬氧化物半導體型氣體感測器 ……………… 7
第二章 文獻回顧與探討 …………………………… 8
2.1 材料簡介 ………………………………………… 8
2.1.1 氧化鋅材料特性簡介 ………………………… 8
2.1.2 二氧化錫材料特性簡介 ……………………… 8
2.2 半導體材料的導電機制 ………………………… 9
2.3 氧氣吸附機制與溫度對半導體導電性的影響 … 10
2.4 一氧化碳氣體感測機制 ………………………… 12
第三章 實驗方法及步驟 …………………………… 13
3.1 感測元件製作 …………………………………… 13
3.1.1 配置漿料 ……………………………………… 13
3.1.2 網版印刷成膜 ………………………………… 13
3.1.3 熱處理 ………………………………………… 13
3.1.4 電極製作 ……………………………………… 14
3.1.5 實驗樣品編號 ………………………………… 15
3.2 一氧化碳感測能力分析 ………………………… 17
第四章 結果與討論 ………………………………… 21
4.1 粉末粒徑對感測膜表面形貌和一氧化碳感測能力之影響 ……………………………………………………… 21
4.2 熱處理溫度與時間變化對感測膜表面形貌和一氧化碳感測能力影響及熱處理機制的變化 ………………… 24
4.3 SnO2與ZnO 混合比例和長時間使用的壽命測試對感測膜一氧化碳感測能力之影響 ……………………… 40
第五章 結論 ………………………………………… 47
第六章 參考文獻 …………………………………… 48

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