臺灣博碩士論文加值系統

本論文討論複合材料應用於二氧化碳氣體感測器的研製。複合材料一直是受矚目的研究，本研究使用氧化鋅與二氧化錫製作奈米複合結構。先以濺鍍法或滴塗法於矽基板上成長氧化鋅種晶層，再以水熱合成法於種晶層上成長氧化鋅奈米柱狀結構。接著進行二次水熱法於氧化鋅奈米柱上成長二氧化錫奈米粒子，最後再以退火去除中間產物得到氧化鋅-二氧化錫複合堆疊結構。
　　吾人透過調整不同水熱法化學溶液濃度、不同種晶層製備方式來研究奈米複合材料排列及分佈情況。複合感測層與矽基板形成PN二極體，以蒸鍍法於感測層表面與矽基板背面鍍上鋁電極作為金屬接觸，完成Al/ZnO-SnO2/Si/Al之二極體感測元件。
　　實驗結果發現，以滴塗法種晶層所成長的氧化鋅奈米柱具有花狀放射排列。此元件在二氧化碳濃度為2500 ppm時的靈敏度為250%，是平面型PN接面元件的3倍。而結合氧化鋅奈米花與二氧化錫奈米粒子的元件之靈敏度更是提升到356%。反應時間及回復時間分別為12秒及32秒，因此複合奈米材料能大幅改善二氧化碳氣體感測器的效能。對於應用於室內空氣品質管理與溫室氣體偵測均有相當大的助益。

In this thesis, we investigated the nanocomposite material applying to carbon dioxide (CO2) gas sensor. Composite materials have always been popular research topics. We utilized the zinc oxide(ZnO) and tin oxide (SnO2) to form the nanocomposite. Firstly, we used sputtering or dip coating method to deposit zinc oxide as a seed layer on the p-Si substrate. ZnO nanorods structure was grown on the seed layer by hydrothermal method. Next, the SnO2 particles was synthesized on the top of ZnO nanorods by changing the chemical solution. Finally, an annealing step is used to remove the residual intermediate for obtaining the ZnO-SnO2 nanocomposite.
The morphology and distribution of the nanocomposite has been characterized by adjusting the mixing concentration of the hydrothermal solution. Different fabrication methods of the seed layer have also been analyzed. PN junctions are formed by the p-type Si substrate and the nanocomposite (sensing layer). The aluminum (Al) electrodes were deposited on the top and the bottom of the pn junctions to complete the Al/ZnO-SnO2/Si/Al sensing devices.
Based on the experimental results, the ZnO nanorods grown on the seed layer of dip coating method have radially flower-like distribution. The device with this structure has a sensitivity of 250% under 2500 ppm CO2. It is 3 times of the planar device without nanostructure. Beside, combining the ZnO flower-like nanorods and the SnO2 particles, the device with nanocomposite has a sensitivity raised to 353%. The response and recovery times are 12 s and 32 s, respectively. Therefore, the nanocomposite can substantially enhance the performance of the CO2 sensor. It can promote the applications to the indoor air quality management and the greenhouse gas detection.

致謝 ii
摘要 iii
Abstract iv
第一章: 概論 1
1-1前言 : 1
1-2氣體感測器 : 1
1-3二氧化碳介紹 2
1-4奈米結構簡介 : 3
1-5材料介紹： 3
1-5-1氧化鋅(ZnO) : 3
1-5-2二氧化錫(SnO2): 4
1-6論文架構 4
第二章 理論基礎 6
2-1感測器的工作原理： 6
2-2二氧化碳的吸附機制： 7
2-3元件基礎理論: 8
2-4 複合材料的理論應用於氣體感測器之上 10
2-5水熱法的原理 11
2-5-1 氧化鋅奈米柱的成長機制 11
2-5-2 二氧化錫奈米粒子的成長機制 12
2-5-3 氧化鋅上成長二氧化錫粒子的方法 13
2-6 溶液滴塗法 14
2-7 濺鍍理論 14
2-7-1濺射現象 14
2-7-2輝光放電 15
2-7-3沉積現象 15
第三章 實驗步驟與量測儀器 17
3-1 成長系統 17
3-1-1 射頻濺鍍系統(Ratio Sputtering System) 17
3-1-2 真空熱蒸鍍系統(Thermal Vacuum Evaporation System) 18
3-2 薄膜分析量測儀器 19
3-2-1 掃描式電子顯微鏡(FE-SEM) 19
3-2-2氣體感測量測系統 20
3-2-5 KEITHLEY 2400半導體參數分析儀 20
3-2-4 Bede D1 HR-XRD單晶薄膜繞射儀 20
3-3 製程步驟與成長參數 21
3-3-1 矽基板清洗流程 21
3-3-2使用濺鍍系統成長金屬氧化層 21
3-3-3 氧化鋅奈米柱水熱成長流程 21
3-3-4 二氧化錫粒子水熱成長流程 22
3-3-5 滴塗法成長氧化鋅種子層： 23
3-3-6 ZnO/ SnO2 複合材料的成長方式 : 23
3-3-7 退火系統: 24
3-3-8 使用熱蒸著系統成長電極： 24
3-3-9 量測實驗： 24
3-4 元件結構: 25
第四章 結果與討論 26
4-1不同氧化層對元件的影響（單層薄膜） 26
4-1-1 電流特性分析 26
4-1-2 氣敏特性 27
4-2 氧化鋅奈米柱 28
4-2-１ 不同的莫爾濃度成長的氧化鋅奈米柱 28
4-2-2 : 不同莫爾濃度比對於氣敏特性的影響 28
4-2-3 滴塗法種子層成長氧化鋅奈米柱 29
4-3 成長二氧化錫粒子 30
4-2-1 在二氧化錫種子層上成長二氧化錫粒子 30
4-2-2 不同種子層成長二氧化錫的比較 31
4-4 氧化鋅-二氧化錫結構 31
4-3-1 有無二氧化錫種子層對ZnO/ SnO2奈米結構的影響 32
4-3-2 滴塗法氧化鋅奈米柱應用在ZnO/ SnO2奈米結構上 33
第五章　總結 34
5-1 實驗結果歸納： 35
5-2 未來展望 36
參考文獻 36
附表 44
表1-1 氣體對人體危害之指標濃度 44
表1-2 SnO2 的XRD峰值表 45
表4-1氧化鋅薄膜二極體以及二氧化錫薄膜二極體對於CO22500ppm下的氣體靈敏度比較表 45
表4-2 水熱莫爾濃度對於氧化鋅/矽氣體感測器之比較表 46
表4-3 水熱二氧化錫(SnO2)的實驗相關表格 46
表4-4 本實驗所有元件的靈敏度統整 46
表4-5 與其他論文的比較 47
附圖 48
圖1-1 氧化鋅的晶體結構 48
圖1-2 二氧化錫的結構圖 48
圖2-1 氧空缺在金屬氧化物中的示意圖 49
圖2-2 氣體吸附於晶粒表面產生空乏區的示意圖 49
圖2-3 CO2吸附在PN接面上時能障的變化 50
圖2-4 SnO2-ZnO的能障 50
圖2-5 氧化鋅奈米柱的成長機制 51
圖2-6 O.Lupan團隊以水熱法成長的SnO2結晶 51
圖2-7表面濺射原理示意圖 52
圖2-8輝光放電示意圖 52
圖2-9薄膜沉積步驟 53
圖3-1 射頻濺鍍系統之簡易模型 54
圖3-2 量測系統 54
圖3-3 水熱法成長氧化鋅的裝置 55
圖3-4 水熱法成長二氧化錫時條配PH值的示意圖 55
圖4-1 常溫下ZnO/Si結構跟SnO2/Si之IV曲線比較圖 56
圖4-2 氧化鋅薄膜(100nm)在100~250℃之間電流對氣體濃度的變化響應圖 57
圖4-3 (左)氧化鋅薄膜於150℃、100ppm下的響應曲線、(右)電壓與靈敏度的關係圖(-5v之絕對值電流) 57
圖4-3 二氧化錫薄膜(100nm)在100~250℃之間電流對氣體濃度的變化響應圖 58
圖4-4 (左) 二氧化錫薄膜於150℃、100ppm下的響應曲線、(右)二氧化錫薄膜之電壓與靈敏度的關係圖 58
圖4-5 二氧化錫/矽 接面與 氧化鋅/矽 接面之能帶示意圖 59
圖4-6 二氧化錫/矽 接面與 氧化鋅/矽 溫度與靈敏度的關係(2500ppm下) 59
圖4-7 莫爾濃度(0.05M)成長的氧化鋅奈米柱 60
圖4-8 莫爾濃度(0.07M)成長的氧化鋅奈米柱 61
圖4-9 莫爾濃度(0.1M)成長的氧化鋅奈米柱 62
圖4-10 氧化鋅奈米柱(莫爾濃度比=0.05M)在100~250℃之間電流對氣體濃度 63
圖4-11 150℃下，逆偏壓時靈敏度與電壓的關係圖，可以看出靈敏度隨氣體濃度變化而穎明顯的差別(0.05M) 63
圖4-12 氧化鋅奈米柱(莫爾濃度比=0.07M)在100~250℃之間電流對氣體濃度的變化響應圖 64
圖4-13 150℃下，逆偏壓時靈敏度與電壓的關係圖(0.07M) 64
圖4-14 : 氧化鋅奈米柱(莫爾濃度比=0.1M)在100~250℃之間電流對氣體濃度的變化響應圖 65
圖4-15 150℃下，逆偏壓時靈敏度與電壓的關係圖(0.1M) 65
圖4-16 莫爾濃度與靈敏度的關係 66
圖4-17 氧化鋅奈米柱的響應時間(100ppm、0.07M、150℃)以及連續響應 66
圖4-18 以滴塗法滴塗(1ml)的醋酸鋅水溶液形成的種子層 67
圖4-19 以滴塗法滴塗(1ml)的種子層成長的氧化鋅奈米柱 67
圖4-20 以滴塗法滴塗(2ml)的醋酸鋅水溶液形成的種子層 68
圖4-21 以滴塗法滴塗(2ml)的種子層成長的氧化鋅奈米柱 69
圖4-22圖以滴塗法種子層成長氧化鋅奈米柱的機制 70
圖4-23 常溫下，1ml之滴塗法種子層成長之氧化鋅奈米柱之I-V曲線 70
圖4-24 2ml之滴塗法種子層成長之氧化鋅奈米柱(莫爾濃度=0.07M)在100~250℃之間電流對氣體濃度的變化響應圖 71
圖4-25 150℃下，逆偏壓時靈敏度與電壓的關係圖(0.07M) 71
圖4-26 150℃下，100ppm時滴塗法氧化鋅奈米柱的響應曲線 72
圖4-27 以不同種子層成長二氧化錫粒子 72
圖4-28 以0.03g的四氯化錫成長在SnO2種子層二氧化錫微粒子 73
圖4-29 以0.12g的四氯化錫成長在SnO2種子層二氧化錫微粒子 74
圖4-30 以0.03g的四氯化錫成長在ZnO種子層二氧化錫微粒子 75
圖4-31 以0.12g的四氯化錫成長在ZnO種子層二氧化錫微粒子 76
圖4-32 以0.12g的四氯化錫成長在SnO2種子層二氧化錫微粒子之XRD圖 76
圖4-33 以0.03g四氯化錫成長的二氧化錫奈米粒子成長在二氧化錫種子層 之不同二氧化碳濃度下的IV曲線 77
圖4-35 以0.03g四氯化錫成長的二氧化錫奈米粒子成長在二氧化錫種子層上之靈敏度與電壓的關係圖 78
圖4-36 以0.12g四氯化錫成長的二氧化錫奈米粒子成長在二氧化錫種子層之不同二氧化碳濃度下的IV曲線 79
圖4-37 以0.12g四氯化錫成長的二氧化錫奈米粒子成長在二氧化錫種子層上之靈敏度與電壓的關係圖 79
圖4-38 以0.12g四氯化錫成長的二氧化錫奈米粒子成長在ZnO種子層上之不同二氧化碳濃度下的IV曲線 80
圖4-39 (左圖)以0.12g四氯化錫成長的二氧化錫奈米粒子成長在ZnO種子層上之靈敏度與電壓的關係圖 80
圖4-40 堆疊式複合型金屬氧化物之P-N二極體元件之結構 80
圖4-41 堆疊式複合型金屬氧化物之P-N二極體元件結構之能帶 81
圖4-42 以0.12g的四氯化錫成長在ZnO奈米線上之二氧化錫微粒子 82
圖4-43 以0.12g的四氯化錫成長二氧化錫微粒子在ZnO奈米線上側面圖 83
圖4-44 以0.12g的四氯化錫成長二氧化錫微粒子在ZnO奈米線上之不同二氧化碳濃度下的IV曲線 83
圖4-45 150℃下，以0.12g的四氯化錫成長二氧化錫微粒子在ZnO奈米線上之逆偏壓時靈敏度與電壓的關係圖 84
圖4-46 以0.12g的四氯化錫成長二氧化錫微粒子在ZnO奈米線上在150℃下、100ppm下的響應圖 84
圖4-47 (上)以0.12g的四氯化錫成長二氧化錫微粒子在ZnO奈米線上之XRD圖 85
圖4-48 以0.12g的四氯化錫成長二氧化錫微粒子在鍍有SnO2種子層的ZnO奈米線上 86
圖4-49 以0.12g的四氯化錫成長二氧化錫微粒子在鍍有SnO2種子層的ZnO奈米線上之不同二氧化碳濃度下的IV曲線 87
圖4-50 150℃下，以0.12g的四氯化錫成長二氧化錫微粒子在鍍有SnO2種子層的ZnO奈米線上之逆偏壓時靈敏度與電壓的關係圖 87
圖4-51 當二氧化碳通入時ZnO/SnO2接面裸露在外能帶圖 88
圖4-52 當二氧化碳通入時ZnO奈米柱SnO2粒子緊緊覆蓋的能帶圖 88
圖4-53 以0.12g的四氯化錫成長二氧化錫微粒子於滴塗法種子層成長之ZnO奈米線上之元件 89
圖4-54 以0.12g的四氯化錫成長二氧化錫微粒子於滴塗法ZnO種子層成長之ZnO奈米線上之側面圖 90
圖4-55 以0.12g的四氯化錫成長二氧化錫微粒子在滴塗法ZnO種子層成長的ZnO奈米線上之不同二氧化碳濃度下的IV曲線 90
圖4-56 150℃下，以0.12g的四氯化錫成長在滴塗法ZnO種子層成長之ZnO奈米線上附著二氧化錫微粒子之逆偏壓時靈敏度與電壓的關係圖 91
圖4-57 150℃下，以0.12g的四氯化錫成長在滴塗法ZnO種子層成長之ZnO奈米線上附著二氧化錫微粒子之響應圖(電流-秒) 91

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