本論文探討多重奈米結構異質接面(ZnSnO3/ZnO/P-Si)與(Zn2SnO4/ZnO/P-Si) 之二氧化碳(CO2)氣體感測器。首先以氫氧化鉀、異丙醇及去離子水混合之濕蝕刻溶液，將P型(100)矽基板上蝕刻出矽金字塔陣列。透過射頻濺鍍系統(RF Sputtering System)沉積ZnO種晶層，再以水熱合成法於種晶層上合成氧化鋅奈米柱結構。
於具有氧化鋅奈米柱的矽金字塔陣列上，分別以化學溶液腐蝕法與二次水熱合成法形成奈米異質接面結構。前者在氧化鋅奈米柱表面直接腐蝕形成ZnSnO3層，完成ZnSnO3/ZnO結構。後者先在表面合成ZnSn(OH)6 (ZHS)，再經由退火轉變成Zn2SnO4微米立方，完成Zn2SnO4/ZnO結構。兩種異質接面再分別蒸鍍金屬鋁(Al)作為金屬接觸電極完成Al/ZnSnO3/ZnO/P-Si/Al以及Al/Zn2SnO4/ZnO/P-Si/Al之元件製作。
利用XRD、EDS、SEM分別對材料進行分析及觀察奈米結構，藉以探討ZnSnO3/ZnO與Zn2SnO4/ZnO奈米異質接面結構的特性及最佳製程選擇。透過電性量測分析，研究矽金字塔奈米陣列結構以及異質接面對二氧化碳氣體感測之影響。矽金字塔奈米結構可有效增加感測氣體接觸之比表面積。而異質接面則使得元件能障上升進而降低漏電流，並且增強對CO2的吸附反應。實驗結果發現，結合兩者可大幅提升元件對二氧化碳氣體的靈敏度。
在2500 ppm二氧化碳環境下，ZnSnO3/ZnO/P-Si的金字塔陣列對氣體之靈敏度為365%，是無蝕刻平面型薄膜元件ZnO/P-Si的4倍。而Zn2SnO4/ZnO/P-Si的金字塔陣列更提高到398%。含有鋅與錫的複合奈米材料能大幅改善二氧化碳氣體感測器的效能，對於應用在室內空氣品質監控與溫室氣體偵測皆具相當大的助益。

In this thesis, we develop the heterojunction with nanostructures for CO2 gas sensing applications. Silicon nano-pyramid arrays are formed by etching the P(100) Si substrate with the mixture of potassium hydroxide (KOH), isopropyl alcohol (IPA) and DI water. Zinc oxide (ZnO) film is deposited on the Si nano-pyramid arrays as the seed layer by RF sputtering system. ZnO nanorods are grown on the seed layer by using hydrothermal method.
Corrosion process and second-time hydrothermal method are proceeded individually to form the heterojunction on the nano-pyramid arrays with ZnO nanorods. The corrosion process corrodes the ZnO nanorods to produce ZnSnO3 on ZnO surface directly. While the second-time hydrothermal method synthesizes ZnSn(OH)6 (ZHS) at first and then ZHS is transformed into Zn2SnO4 microcubes after an annealing process. The heterojunctions are evaporated with aluminum on top and bottom of the devices to complete the Al/ZnSnO3/ZnO/P-Si/Al and Al/Zn2SnO4 /ZnO/P-Si/Al structures.
The nanostructures are examined with XRD, EDS and SEM for crystallinity and surface morphology. Electrical analyses of the devices are studied for investigating the influence of Si nano-pyramid arrays and heterojunctions. Nano-pyramid arrays can increase the CO2 absorption area effectively and heterojunctions can raise the potential barrier height thus reducing leakage current. Heterojunctions can also enhance the adsorption reaction to the target gas. The experimental results show that the sensing ability of the devices increase effectively by combining these two methods.
ZnSnO3/ZnO/P-Si with nano-pyramid arrays has a sensitivity of 365% under the condition of 2500 ppm CO2 concentration. It is 4 times of the planar device ZnO film/P-Si without etching process. Furthermore, sensitivity of Zn2SnO4/ZnO/P-Si with nano-pyramid arrays increases to 398%. Therefore, the nanocomposite with Zinc and Tin can substantially enhance the performance of the CO2 sensors. It can promote the applications to the indoor air quality management and the greenhouse gas detection.

論文審定書 i
誌謝 ii
摘要 iii
Abstract v
目錄 vii
表目錄 x
圖目錄 xi
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 4
1-5-1氧化鋅(ZnO) 4
1-5-2氧化鋅錫(ZTO) 5
1-6論文架構 6
第二章、理論基礎 7
2-1感測器工作原理 7
2-2二氧化碳吸附機制 8
2-3元件基礎理論 9
2-4水熱法原理 11
2-4-1氧化鋅奈米結構之生長機制 12
2-4-2 ZnSnO3腐蝕反應機制 13
2-4-3 Zn2SnO4微米立方之生長機制 13
2-5濕式蝕刻理論 14
2-5-1奈米金字塔陣列蝕刻機制與原理 14
2-6濺鍍理論 16
2-6-1濺射現象 16
2-6-2輝光放射 16
2-6-3薄膜沉積現象 17
第三章、實驗步驟與量測儀器 19
3-1原料選用 19
3-2成長系統 21
3-2-1射頻濺鍍系統(RF Sputtering System) 21
3-2-2真空熱蒸鍍系統(Thermal Vacuum Evaporation System) 23
3-3薄膜分析量測儀器 23
3-3-1場發射掃描式電子顯微鏡（Field emission scanning electron microscope, FE-SEM）分析 23
3-3-2能量散佈光譜儀（Energy dispersive spectrometer, EDS）分析 24
3-3-3氣體感測器量測系統 24
3-3-4 KEITHLEY 2400半導體參數分析儀 25
3-3-5 X光繞射（X-ray diffraction, XRD）分析 25
3-4製程步驟與成長參數 26
3-4-1 矽基板清洗流程 26
3-4-2矽奈米金字塔陣列蝕刻 26
3-4-3濺鍍沉積氧化鋅薄膜種晶層 27
3-4-4水熱法生長氧化鋅奈米結構 27
3-4-5氧化鋅錫(ZnSnO3)/氧化鋅(ZnO)奈米結構水熱腐蝕成長流程 28
3-4-6氧化鋅錫(Zn2SnO4)微米立方水熱成長流程 28
3-4-7退火系統 29
3-4-8使用熱蒸鍍系統成長電極 29
3-4-9量測實驗 29
第四章、結果與討論 31
4-1氧化層對元件的影響（異質接面感測層材料對感測元件之影響） 31
4-1-1溫度與靈敏度的關係 32
4-2氧化鋅奈米結構 33
4-2-1不同的莫爾濃度之的氧化鋅奈米結構 33
4-2-2不同莫爾濃度對於氣敏特性的影響 33
4-3氧化鋅錫(ZnSnO3)/氧化鋅(ZnO)奈米結構水熱腐蝕成長 34
4-3-1氧化鋅錫(ZnSnO3)/氧化鋅(ZnO)奈米結構氣敏特性的影響 35
4-4氧化鋅錫(Zn2SnO4)微米立方/氧化鋅(ZnO)奈米結構 35
4-4-1水熱時間對於氣敏特性之影響 35
4-5矽奈米金字塔陣列結構分析 37
4-6矽奈米金字塔陣列結構之感測元件分析 38
4-6-1氧化鋅(ZnO)奈米結構生長於矽奈米金字塔陣列結構 38
4-6-2氧化鋅錫(ZnSnO3)/氧化鋅(ZnO)奈米結構生長於矽奈米金字塔陣列結構 39
4-6-3氧化鋅錫(Zn2SnO4)微米立方/氧化鋅(ZnO)奈米結構長於矽奈米金字塔陣列結構 40
4-7最佳性能元件之氣體動態響應圖 40
第五章、結論與未來展望 42
5-1實驗結果歸納 42
5-2未來展望 43
參考文獻 45

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