本實驗於四吋晶圓上成長銅氧化物/金/氧化鋅三元複合材料，並使用此材料進行6種氣體的感測、四吋晶圓級形貌與感測均勻度分析、以及戶外場域的實際測試。
首先以曝光與電子束沉積技術，將302個電極圖案印刷於四吋矽晶圓。以水熱法成長氧化鋅柱於四吋晶圓並退火，再以光還原法依序修飾金與銅氧化物於氧化鋅。形成銅氧化物/金/氧化鋅三元複合材料。
由掃描式電子顯微鏡(SEM)觀察形貌。氧化鋅柱直徑約70 nm，長約1.7 um。銅氧化物呈現球狀並出現在氧化鋅柱頂端與側面，直徑約200 nm。且材料在四吋晶圓各處的形貌大致均勻。
使用此材料進行氣體感測，發現材料對300 ppb二氧化氮有44%響應。對300 ppb臭氧有74%響應。在1 ppm二氧化氮/臭氧內，響應與濃度有高度線性關係(R2>0.98)。而對1 ppm甲醛、2 ppm二氧化硫、2 ppm氨氣、5 ppm一氧化氮的響應分別為-11%、-1.35%、-6.5%、13.3%，皆非常的低。
使用儀科中心的晶圓級感測晶粒批量點測系統，進行302顆銅氧化物/金/氧化鋅晶粒的氣體感測均勻度分析。發現在空氣氣氛的電阻平均為4 MΩ而標準差為6.6 MΩ。在200 ppb二氧化氮，響應平均183%而標準差148%。此結果雖不算均勻，但可以挑選性質相近的晶粒進行分級與使用。
將三元複合材料感測晶片安裝至手機操控可攜式感測器，與智慧型手機一同放入防水之空氣盒子。並部屬到環保署新北永和空氣品質監測站，進行場域測試。並進行人工神經網路(ANN)模型的建構與測試。使用為期兩周的資料建構模型，並套入後續一個月的資料進行濃度分析 。ANN分析之臭氧值與環保署臭氧值比較結果，R2為0.31。ANN分析之二氧化氮值與環保署二氧化氮值比較結果，R2為0.245。
同時也分析二氧化氮與臭氧的組合濃度，依不同組合倍率共嘗試6組。每組與環保署值比較R2，皆大於單一氣體結果。最好的結果R2顯示0.395，為1倍二氧化氮加1倍臭氧的組合濃度。此倍率與實驗室測得臭氧與二氧化氮靈敏度比值1.27相似。並且此R2已接近商用產品，顯示三元複合材料應用於環境氣體感測領域有極高潛力。

In this work, a compact chemiresistive gas sensor is developed by using a CuxO/Au/ZnO ternary nanocomposite. Batch production of nanocomposite sensing chips was realized on a 4-inch Si wafer along with wafer scale characterization. The nanocomposite sensor was used for sensing 6 different gases and deployed for field test.
First, 302 electrode patterns were printed on a 4-inch Si wafer by photolithography and electron beam deposition. ZnO nanorods were grown on this 4-inch wafer via a hydrothermal method. After thermal annealing, gold and copper oxides were sequentially deposited on ZnO nanorods. Consequently, a CuxO/Au/ZnO ternary nanocomposite was formed.
The morphology of the CuxO/Au/ZnO nanocomposite was investigated by a scanning electron microscope. The diameter of the ZnO nanorods was 70 nm and the length was 1.7 um. The copper oxides were spherical and appeared on the top and side of the ZnO nanorods. The diameter of spherical copper oxides was 200 nm. The morphology of CuxO/Au/ZnO on a 4-inch wafer was uniform.
A CuxO/Au/ZnO sensing chip was set in a homemade chamber and activated by a 365 nm UV LED during gas sensing. The sensing results showed responses of 74% at 300 ppb O3 and 44% at 300 ppb NO2. Both showed an excellent linear range from 25 ppb to 1 ppm (R2>0.98). Furthermore, the sensing results also showed responses of 11%, 1.35%, 6.5%, and 13.3% at 1 ppm HCHO, 2 ppm SO2, 2 ppm NH3, and 5 ppm NO, respectively.
Using the wafer level gas sensor probing system from Taiwan Instrument Research Institute (TIRI) to analyze the gas sensing consistency of 302 CuxO/Au/ZnO dies. It was found that the air resistance was 4 MΩ on average and the standard deviation was 6.6 MΩ. The response at 200 ppb NO2 was 183% on average and the standard deviation was 148%.
A CuxO/Au/ZnO sensing chip was installed in a smart phone-operated portable gas sensor. The portable sensor and a smart phone were integrated in a waterproof air box. The box was deployed at an Environmental Protection Agency (EPA) environmental monitoring station in Yonghe, New Taipei City for field test. Data from the first 2 weeks was used for constructing an artificial neural network (ANN) algorithm. The ANN algorithm was responsible for converting the CuxO/Au/ZnO resistance to the gas concentration. The ANN converted gas concentration was compared with the EPA station data. Therefore, a linear coefficient of determination R2 could be calculated.
Eight different combinations of CNO2 + CO3 had been tested including a single component. For one month test, it was found that the R2 was 0.31 for pure O3 and 0.245 for pure NO2. The best one was the combination of 1CNO2 + 1CO3 with an R2 value of 0.395, which ratio was close to the experimental O3 to NO2 sensitivity ratio of 1.27. This R2 value compares well with values of some commercial products. With wafer-scale uniformity and acceptable field test results, the CuxO/Au/ZnO ternary nanocomposite has excellent potential for environmental gas sensing.

摘要---i
Abstract---iii
致謝---vi
總目錄---vii
圖目錄---xi
表目錄---xvi
第一章 序論---1
1.1 研究背景---1
1.2 研究動機---2
第二章 文獻回顧---4
2.1 氣體感測器概述---4
2.1.1 氣體感測器種類---4
2.1.2 氣體感測器效能指標---8
2.2 化學電阻式感測器原理---9
2.2.1 吸附原理---10
2.2.2 脫附原理---12
2.2.3 吸附化學反應式---15
2.3 材料對感測的影響---18
2.3.1 材料結構---18
2.3.2 缺陷---22
2.3.3 修飾物---22
2.3.4 氣體選擇性---25
2.5 氧化鋅概論---26
2.5.1 晶體結構---26
2.5.2 缺陷---28
2.5.3 成長方法---30
2.6 複合材料---32
2.6.1 複合材料優勢---32
2.6.2 合成方法---34
第三章 實驗流程與儀器---36
3.1 實驗架構---36
3.2 材料合成---37
3.2.1 基板製作---37
3.2.2 氧化鋅合成---37
3.2.3 退火---38
3.2.4 奈米粒子修飾---39
3.3 材料分析---40
3.4 實驗室氣體感測---40
3.4.1 封閉式---41
3.4.2 流動式---45
3.5 戶外場域氣體感測---49
3.5.1 手機操控可攜式氣體感測器---49
3.5.2 戶外感測系統架構---52
3.6 感測晶片批量挑選---53
第四章 結果與討論---56
4.1 材料分析---56
4.1.1 表面形貌---56
4.1.2 元素組成---60
4.1.3 晶體結構---62
4.1.4 光致發光性質---63
4.2 氣體感測結果---64
4.2.1 二氧化氮感測---65
4.2.2 臭氧感測---67
4.2.3 甲醛感測---70
4.2.4 氨氣感測---71
4.2.5 二氧化硫感測---72
4.2.6 一氧化氮感測---73
4.2.7 選擇性結果整理---74
4.3 感測晶片批量挑選---75
4.4 戶外場域測試---81
4.4.1 人工神經網路計算---83
第五章 結論---91
第六章 參考文獻---94

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