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研究生： 陳佳吟
Chen, Chia-Ying
論文名稱： 氧化銦鋅薄膜感測含氯VOCs之研究
Sensing of Cl-containing VOCs with Indium-zinc-oxide Thin Films
指導教授： 王鴻博
Wang, Hong-Paul
學位類別： 碩士
Master
系所名稱： 工學院 - 環境工程學系
Department of Environmental Engineering
論文出版年： 2005
畢業學年度： 93
語文別： 英文
論文頁數： 113
中文關鍵詞： XANES 、含氯VOCs 、氣體感測器 、半導體薄膜 、氧化銦鋅 、濺鍍 、EXAFS
外文關鍵詞： semiconductor thin films, gas sensors, Cl-containing VOCs, XANES, EXAFS, sputtering, indium-zinc oxide
相關次數： 點閱：115  下載：24 
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    • 　　含氯揮發性有機物(Cl-VOCs)大多具毒性及可能具致癌性，也是管制之溫室氣體，因此發展一套即時、連續而且利於攜帶之感測設備，可以預警環境中可能存在Cl-VOCs之危害性。雖然各類感測器已被廣泛研發及應用，但針對Cl-VOCs之感測器相對未被重視，而且感測材料與Cl-VOCs間複雜的感測機制仍未完全了解，因此，本研究之主要目的包括：(1)合成氧化銦鋅(IZO)薄膜；(2)IZO薄膜感測Cl-VOCs (CCl4、CHCl3、CH2Cl2)及ethanol之靈敏度及再現性；(3)感測CCl4時鋅之即時精細結構分析；(4)設計整合即時感測及礦化去除之個人化系統。
    　　實驗結果顯示，濺鍍產生之IZO薄膜含銦量1～3%，厚度介於400～645 nm間，X射線繞射分析顯示薄膜呈現ZnO(002)之擇優取向趨勢。IZO薄膜之組成(In/Zn=0.028~0.062)及表面吸附面積影響CCl4感測度(sensitivity)，感測時間(response time)皆低於2分鐘，而其中In/Zn = 0.056薄膜對350 ppm CCl4之感測度高達20。感測溫度低於623 K之感測度較低，而且感測時間較長。IZO於濺鍍合成中基版加熱處理，可增加其結晶性及導電度，但因接觸面積降低，反而不利於感測度。IZO薄膜對CHCl3及CH2Cl2之感測度類似CCl4，但感測度依含氯量之減少而減少。另外，IZO薄膜對250~1000 ppm乙醇之感測電阻之變化與Cl-VOCs相反，顯示IZO也可同時應用於Cl-VOCs (電阻增加)及C2H5OH (電阻降低)之感測。即時X射線吸收近邊緣結構(X-ray absorption near edge structural, XANES)光譜顯示IZO薄膜中鋅之主要物種為奈米ZnO(>80%)及ZnO原子簇(<11%)，並於623 K通入350 ppm CCl4後發現少量ZnCO3(7%)。X射線吸收光譜之延伸區微細結構(Extended X-ray absorption fine structural, EXAFS)光譜顯示IZO薄膜中鋅之Zn-O鍵距為1.972 Å，提高溫度至623 K， Zn-O鍵距增加0.022Å，通入350 ppm CCl4後Zn-O鍵距微幅減少至1.978 Å，並於停止通入CCl4氣體後恢復至1.991 Å。依據上述實驗數據也初步設計一套整合Cl-VOCs感測及礦化方法，成為一種可以在可能具Cl-VOCs存在風險之場所之個人防護器具。

    　Cl-containing volatile organic compounds (Cl-VOCs) are toxic and carcinogenic. Real-time detecting of Cl-VOCs is of increasing importance. Thin films have been widely used in sensing of toxic gases. However, reaction mechanism on the thin films during sensing of Cl-VOCs is still lacking in the literature. Thus, the main objectives of this work were (1) Synthesis of novel IZO (indium-zinc-oxide) thin films, (2) Determination of sensitivity, response time, and reproducibility of the IZO thin films with Cl-VOCs (such as CCl4, CHCl3, and CH2Cl2) as well as ethanol, (3) Speciation studies of Zn in the IZO thin films, and (4) Conceptual design of an IZO thin film based sensor for sensing of Cl-VOCs.
    　The IZO (a promising transparent conducting oxide (TCO)) thin films synthesized in a RF magnetron sputtering system were used in sensing of toxic Cl-containing VOCs (such as chlorinated mathanes) in the present work. The IZO thin films having thickness of 400-645 nm (determined by α-step) contain 1-3% indium. X-ray diffraction patterns of the IZO films illustrate a preferred c-axis orientation of ZnO (002).
    　The sensing experiments were conducted with in-situ measurements of thin film resistance. At the sensing temperature of 623 K, the IZO thin films posses a high sensitivity, low response time and good reproducibility. An effective sensitivity (RCCl4/Rair > 20) and low response time (< 2 min) of the thin film with In/Zn = 0.056 was observed. The IZO thin films synthesized at the substrate temperature of 300 K during sputtering have a desired sensing characteristic for CCl4. The IZO thin films have a high sensitivity for Cl-rich chlorinated methanes. In addition, ethanol can also be detected with the IZO thin films during sensing of ethanol was observed, the IZO thin films can detect simultaneously both Cl-VOCs (RCCl4/Rair > 10) and ethanol (Rair/RC2H5OH > 10). To further understand speciation of zinc in the IZO thin films, in-situ XANES (X-ray absorption near edge structural) and EXAFS (Extended X-ray absorption fine structural) spectra of zinc were measured during sensing of 350 ppm CCl4. The main zinc species in the IZO thin films were nano (80-90%) and cluster (< 11%) ZnO. During sensing of CCl4, a small amount (7%) of ZnCO3 in the thin films was found. Zinc in the IZO thin films at 300 K possessed a Zn-O bond distance of 1.972 Å with a CN (coordination number) of 3.2. The bond distance was decreased slightly of 0.022 Å during sensing of 350 ppm CCl4 at 623 K, and restored as CCl4 was absent. Based on experimental data for sensing of Cl-VOCs, a simple, inexpensive, miniaturized and portable device has been designed.

    中文摘要.....................................................................Ⅰ ABSTRACT.....................................................................Ⅱ 致謝.........................................................................Ⅲ CONTENT......................................................................IV LIST OF TABLES...............................................................VI LIST OF FIGURES.............................................................VII CHAPTER 1 INTRODUCTION........................................................1 CHAPTER 2 LITERATURE SURVEY ...................................................3 2.1 Toxic Cl-Containing Organic Matters.......................................3 2.2 The Transparent Conducing Oxide Thin-Films................................4 2.2.1 Basic Properties of TCO Thin Films......................................6 2.2.2 Indium-Zinc Oxide Thin Films............................................9 2.3 Gas Sensors..............................................................13 2.3.1 Semiconducting Transparent Thin-Film Gas Sensors.......................15 2.3.2 Metal-oxide-semiconductor (MOS) Sensing Mechanisms.....................15 2.3.3. Factors Affect the Sensing Behaviors..................................20 2.3.4 Chlorinated Methanes Detected with TCO Thin Films......................21 2.4 Sputtering...............................................................26 2.4.1 The Sputtering Systems.................................................26 2.4.2 DC Glow Discharge Sputtering...........................................27 2.4.3 RF Magnetron Sputtering................................................32 2.4.4 Reactive Sputtering....................................................32 2.4.5 Nucleation and Formation of Thin Films.................................32 CHAPTER 3 EXPERIMENTAL METHODS...............................................35 3.1 The Experimental Design ..................................................35 3.2 Preparations of Thin Films...............................................37 3.2.1 Sputtering.............................................................37 3.2.2 Thin Films.............................................................37 3.3 Characterization of the Thin Films.......................................39 3.3.1 Film Thickness Measurements............................................39 3.3.2 Rutherford Backscattering Spectrometry.................................39 3.3.3 X-Ray Diffraction Spectroscopy (XRD)...................................39 3.3.4 Surface Morphology Measurements........................................39 3.3.5 Electricity Properties.................................................39 3.4 Sensitivity Measurements.................................................40 3.5 In-situ X-ray Absorption Spectroscopy (XAS)..............................42 CHAPTER 4 RESULTS AND DISCUSSION.............................................46 4.1 Sensing of CCl4 with IZO Thin Films......................................46 4.2 Synthesis of IZO Thin Films for Sensing of CCl4..........................57 4.3 Sensing of Chlorinated Methanes and Ethanol with IZO Thin Films..........66 4.4 In-situ EXAFS Studies of Zinc in the IZO Thin Films During Sensing of CCl4.........................................................................76 4.5 A Preliminary Design of Personal Real-Time Cl-VOCs Sensing System Combined with Mineralization..........................................................83 CHAPTER 5 CONCLUSIONS AND SUGGESTIONS........................................86 REFERENCES...................................................................88 APPENDIXES...................................................................95

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