臺灣博碩士論文加值系統

本論文探討在矽基板上研製新穎金屬氧化物P-I-N異質接面(Pd/n-MOX/i-HfO2/p-CuO /p-Si/Al) 運 用 於二氧化碳氣體之感測。吾人先將P型(100)矽基板上利用射頻濺鍍系統(Sputtering system) 通入氬氣(Ar) 50 %、氧氣(O2) 50 %的混合氣體來濺鍍Cu靶材，並經爐管通氧退火形成氧化銅(CuO)薄膜。再濺鍍成長多晶二氧化鉿( HfO2)薄膜於其上。然後濺鍍上各種不同n型之金屬氧化物(WO3、SnO2、ZnO)作為感測層。吾人利用XRD、AFM及SEM分別用來量測薄膜結晶及觀察表面結構和厚度來探討這些材料的基本特性及做最佳選擇。最後利用熱蒸鍍系統(Thermal evaporation)來成長金屬鈀作為催化電極/接觸電極，並在矽背面成長金屬鋁作為歐姆電極，如此完成整體P-I-N異質接面之製作。
本研究共製作四種不同結構元件來比較其感測特性: (1) 不同感測層(ZnO、SnO2、WO3)， (2) 不同CuO薄膜通氧退火溫度， (3) 有無使用CuO薄膜， (4) 有無添加本質絕緣層材料二氧化鉿(HfO2)。
實驗結果顯示，三種不同感測氧化金屬中(ZnO、SnO2、WO3)，ZnO對二氧化碳的敏感度最佳；CuO薄膜通氧退火中，以600℃表面最粗糙度；使用CuO薄膜可提升感測特性，較沒使用者提升257%的靈敏度；添加本質層HfO2後，靈敏度也大幅提升了487%。
本研究發展出之PIN二氧化碳感測器相較於以往文獻發表者有較佳的特性。如在150℃，濃度3000ppm下，其靈敏度為1248%，反應時間為98秒，相較於已發表者Pt/BaTiO3-CuO-Ag/Pt之靈敏度(8%)及反應時間(10min)特性有明顯的提升。

The Pd/MOx/HfO2/CuO p-i-n heterojunctions on Si substrate were developed for methane gas (CO2) sensing applications. Firstly, the CuO layer was deposited on the Si by sputtering Cu target with the mixed gas including argon (Ar) 50%, oxygen (O2) 50% and annealed in oxygen ambient. Then sequentially sputtering growth of HfO2 film and various metal oxide such as WO3、SnO2、ZnO for intrinsic and sensing element ,respectively. The sensing elements were analyzed using XRD、AFM and SEM, respectively for crystallinity, surface roughness and morphology. Finally, Pd and Al metal were deposited thermally on the top and Si bottom as the catalyst/electrode and contact, respectively.
In this work , we compare the CO2 gas sensor performances through the following studies :(1) use of various metal oxides such as WO3、SnO2、ZnO as sensing element, (2) with different CuO annealing temperature, (3) with and without the CuO film, and (4) with and without addition of the intrinsic layer HfO2.
Experimental results show that the ZnO has the best sensitivity to carbon dioxide, the optimized annealing temperature for CuO film is 600 ℃, and use of CuO film can promote 257% in sensitivity. Besides, addition of the intrinsic HfO2 layer improves the sensitivity 487%.
The sensor developed in this study under 150 oC and 3000ppm ambient can attain the best performance of 1248% and 98 sec for sensitivity and response time, respectively. The performances are better than that of 8% and 10min for the reported Pt/BaTiO3-CuO-Ag/Pt M-MOx-M structure under same conditions.

目錄
中文摘要 I
英文摘要 III
致謝 V
表目錄 VIII
圖目錄 IX
第一章 導論 1
1-1前言 1
1-2氣體感測器 1
1-3二氧化碳氣體特性 2
1-4 高介電係數(High K)絕緣薄膜之特性及應用 3
1-5 各種金屬氧化物(ZnO、SnO2、WO3、CuO)的特性 4
1-6 論文架構 5
第二章 理論基礎 6
2-1 元件基礎理論 6
2-2 感測器工作原理 8
2-3 濺鍍理論 9
2-3-1 濺設現象 9
2-3-2 輝光放電[17] 10
2-3-3沉積現象 11
2-4 CuO 濺鍍系統含氧量差異 12
第三章 實驗與量測機台及製程步驟 13
3-1 成長系統 13
3-1-1 射頻磁控濺鍍系統(Ratio-Frequency Sputtering System) 13
3-1-1-1 射頻濺射 14
3-1-1-2 反射性濺鍍 15
3-1-1-3 磁控濺鍍理 15
3-1-2 退火系統(Annealing System) 17
3-1-3 真空蒸著系統(Thermal Vacuum Evaporation System) 18
3-2 薄膜分析量測儀器 19
3-2-1 場發射掃瞄式電子顯微鏡(FE-SEM) 19
3-2-2 原子力顯微鏡(Atomic Force Microscope, AFM) 19
3-2-3 X光繞射儀(X-ray Diffractometer, XRD) 20
3-2-4 膜厚量測儀(α-Step) 21
3-2-5 氣體感測量測系統 21
3-2-6 HP4145B半導體參數分析儀 22
3-3 製程步驟與成長參數 22
3-3-1 矽基板的預處理 22
3-3-2 使用濺鍍系統成長金屬層 23
3-3-3 使用爐管通氧熱退火CuOx 23
3-3-4 使用濺鍍系統成長本質絕緣層 24
3-3-5 使用濺鍍系統成長金屬氧化層 24
3-3-6 使用熱蒸鍍系統成長電極 24
3-3-7 量測實驗 25
第四章 結果與討論 26
4-1 元件製作與特性量測 26
4-2 CO2對不同感測層的影響 26
4-3 CuO通氧退火溫度對感測元件的影響 29
4-4 感測層搭配CuO薄膜對感測元件的影響 30
4-4-1 CuO薄膜對SnO2感測層之影響 31
4-4-2 CuO薄膜對ZnO感測層之影響 32
4-4-3 CuO薄膜對WO3感測層之影響 33
4-5針對ZnO/CuO材料做氣體選擇比 34
4-6 本質絕緣層材料對感測元件之影響 35
第五章 結論與未來展望 37
5-1 結論 37
5-2 未來展望 38
※參考文獻 39

[1]“減少二氧化碳排放由日常生活著行政院國家科學委員會.
[2]蔡嬪嬪，曾明漢，“氣體感測器之簡介、應用及市場，材料與社會，第68期 1992.
[3]蔡嬪嬪，曾明漢，“氣體感測器之簡介、應用及市場， 材料與社會，第150期1999.
[4]HS Zhou,T Yamada,K Asai,I Honma ,H Uchida and T Katsube,NO gas sensor based on surface photovoltage system fabricated by self-ordered hexagonal mesoporous silicate film,Japanese Journal Of Applied Physics,vol 40,2001.
[5]T Suzuki,K Kunihara,M Kobayashi,S Tabata,K Higakiand H Ohnishi ,A micromachined gas sensor based on a catalytic thick film/SnO2 thin film bilayer and thin film heater - Part 1: CH4 sensingSensors And Actuators B-Chemical,vol 109, 2005.
[6]L Liao,Z Zhang,B Yan,Z Zheng,Q L Bao,T Wu,C M Li,X Shen,J X Zhang,H Gong,J C Li and T Yu,Physical behaviour of BaTiO3–CuO thin-film under carbon dioxide atmospheres,Nanotechnology 20 (2009) 085203 (6pp).
[7]Jaime Herran,Gemma Garcia Mandayo,Enrique Castano,Physical behaviour of BaTiO3–CuO thin-film under carbon dioxide atmospheres,Sensors and Actuators B 127 (2007).
[8]維基百科，氧化鋅， https://zh.wikipedia.org/wiki/%E6%B0%A7%E5%8C%96%E9%8B%85
[9]You-Pin Gong, Ai-Dong Li, Xu Qian, Chao Zhao and Di Wu,Interfacial structure and electrical properties of ultrathin HfO2 dielectric films on Si substrates by surface sol–gel method, J. Phys. D: Appl. Phys. 42 (2009).
[10]施仁斌、黃啟翔，“電化學沉積法製備氧化銅、氧化亞銅與硫化銅薄膜及其特性研究，中華民國九十九。
[11]Rideout VLA Review Of Theory, Technology And Applications Of Metal-Semiconductor RectifiersThin Solid Films ,vol 48, 1978.
[12]S. M. Sze,Physics of semiconductor devicesch5, wiley, New York, 1980.
[13]Neamen,Semiconductor physics and devicech9, p336, McGraw-Hill, 1992.
[14]J.Herran,G.Ga Mandayo,I.Ayerdi,E.Castano,Influence of silver as an additive on BaTiO3–CuO thin film for CO2 monitoring,Sensors and Actuators B 129 (2008) 386–390.
[15]賴耿陽，“IC 製程之濺射技術，復漢出版社 1997年。
[16]莊達人，“VLSI製造技術，高立圖書股份有限公司，1995年。
[17]王福貞，聞立時，“表面沉積技術，機械工業出版社。
[18]G. BEENSH-MARCHWICKA, L. KROL-STEPNIEWSKA AND M. SLABY,EFFECT OF THE OXYGEN PRESSURE DURING SPUTTERING ON THE PROPERTIES OF THIN CuOx FILMS,Thin Solid Films, 88 (1982).
[19]F.Shionki and A. Itoh,Mechanism of rf reactive sputtering, J.Appl. Phys.,vol.46,p.3381,1975.
[20]Steckl AJ, LI JP,Epitaxial Growth Of Beta-SiC On Si By RTCVD With C3H8 And SiH4, IEEE Transactions On Electron Devices ,vol 39, 1992.
[21]Bedair Sm,Mcdermott Bt,Reid Kg,Neudeck Pg,Cooper Ja,Melloch Mr,Extremely Low-Leakage GaAs P-I-N Junctions And Memory Capacitors Grown By Atomic Layer Epitaxy,IEEE Electron Device Letters,vol.11,1990.
[22]S. M. Sze, Semiconductor sensors, John Wiley ＆ Sons, New York, chap.8, pp. 383- (1994).
[23]Y. Nakamura ,H. Yoshioka ,M. Miyayama , Selective Co Gas Sensing Mechanism With Cuo/Zno Heterocontact , Journal Of The Electrochemical Society ,vol.137,1990.
[24]鄭紹良、陳銘鋒，“熱氧化退火法製備氧化銅半導體奈米線及其性質之研究，國立中央大學，中華民國九十八年。
[25]Yoshinobu Nakamura, Honxia Zhuang, Akira Kishimoto, Osamu Okada and Hiroaki Yanagida,Enhanced CO and CO2 Gas Sensitivity of the CuO/ZnO Heterocontact Made by Quenched CuO Ceramics,J. Electrochem. Soc. 1998, Volume 145, Issue 2, Pages 632-638.
[26]J. Robertson,High dielectric constant oxides,Eur. Phys.J. Appl. Phys. 28, 265–291 (2004).
[27]方炎坤、王厚入，“新型高性能3D奈米柱狀結構PIN二極體甲烷(CH4)感測器研製＂，國立成功大學，中華民國一百零一年。
[28]Hung-Hsien Li,Chi-En Yang, Chi-Chung Kei,Chung-Yi Su,Wei-Syuan Dai,Jung-Kuei Tseng,Po-Yu Yang,Jung-Chuan Chou,Huang-Chung Cheng,Coaxial-structured ZnO/silicon nanowires extended-gate field-effect transistor as pH sensor,Thin Solid Films,TSF-30669,No of Pages 4.
[29]Elidia Maria Guerra,Glaucio Ribeiro Silva,Marcelo Mulato,Extended gate field effect transistor using V2O5 xerogel sensing membrane by solegel method,Solid State Sciences 11 (2009) 456e460.
[30]陳建瑞，季彥良，“AgIn5S8 延伸式閘極離子感測場效電晶體之研究 ＂，國立清華大學，中華民國九十七年。
[31]Zheng Jiao,Feng Chen,Run Su,Xingjiu Huang,Wei Liu and Jinhuai Liu,Study on the Characteristics of Ag Doped CuO-BaTiO3 CO2 Sensors,Sensors 2002, 2.
[32]J.Herran,G.Ga Mandayo,E.Castano,Semiconducting BaTiO3-CuO mixed oxide thin films for CO2 detection,Thin Solid Films 517 (2009).
[33]A.M.El-Sayedy,F.M.Ismail and S.M.Yakout,Electrical Conductivity and Sensitive Characteristics of Ag-Added BaTiO3-CuO Mixed Oxide for CO2 Gas Sensing,J. Mater. Sci. Technol., 2011, 27(1).
[34]Gemma Garcia Mandayo,Fernando Gonzalez,Isabel Rivas,Isabel Ayerdi,Jaime Herran,BaTiO3–CuO sputtered thin film for carbon dioxide detection,Sensors and Actuators B 118 (2006).
[35]吳泉毅、楊宗燁、林鴻明，“奈米半導體材料之氣體感測性質。
[36]P.W. Atkins,Physical Chemistry Fifth edition,Oxford,1994.
[37]Y. Nakamura ,H. Yoshioka ,M. Miyayama , Selective Co Gas Sensing Mechanism With Cuo/Zno Heterocontact, Journal Of The Electrochemical Society ,vol.137,1990.
[38]Yoon-Sung Kim, In-Sung Hwang, Sun-Jung Kim, Choong-Yong Lee, Jong-Heun Lee,CuO nanowire gas sensors for air quality control in automotive cabin,Sensors and Actuators B 135 (2008).
[39]Department of Chemistry, The Key Laboratory of Atomic and Molecular Nanoscience, Ministry of Education,High sensitivity of CuO modified SnO2 nanoribbons to H2S at room temperature,Sensors and Actuators B 105 (2005).
[40]Nianqiang Wu1,2,5, Minhua Zhao3, Jian-Guo Zheng2,
[41]Chuanbin Jiang, Ben Myers, Shuoxin Li, Minking Chyu and Scott X Mao,Porous CuO–ZnO nanocomposite for sensing electrode of high-temperature CO solid-state electrochemical sensor,Nanotechnology 16 (2005).
[42]Won Jae Moon, Ji Haeng Yu, Gyeong Man Choi,The CO and H2 gas selectivity of CuO-doped SnO2–ZnO composite gas sensor,Sensors and Actuators B 87 (2002).
[43]N. Barsan, D. Koziej, U. Weimar,Metal oxide-based gas sensor research: How to?,Sensors and Actuators B 121 (2007).
[44]J. Herran,G. GaMandayo,I. Ayerdi,E. Castano,Influence of silver as an additive on BaTiO3–CuO thin film for CO2 monitoring,Sensors and Actuators B 129 (2008).
[45]Tetsuya Kida , Yuji Miyachi , Kengo Shimanoe , Noboru Yamazoe,NASICON thick film-based CO2 sensor prepared by a sol-gel method,Sensors and Actuators B 80 (2001).
[46]TAKAYUKI ITO, HIROYUKI YAMAGUCHI, KATSUYA OKABEt,TAIZO MASUMI,Single-crystal growth and characterizationof Cu2O and CuO,JOURNAL OF MATERIALS SCIENCE 33 (1998).
[47]粘駿楠、鄧熙聖，“銅氧化物結構對其催化和光電化學反應性之影響＂，國立成功大學，中華民國九十五年。
[48]王畯閎、劉正毓，“氧化銦錫添加三氧化鎢薄膜之研究＂，國立中央大學，中華民國九十六年。
[49]Gemma Garcia Mandayo,Jaime Herran,Irene Castro-Hurtado,Enrique Castano,Performance of a CO2 Impedimetric Sensor Prototype for Air Quality Monitoring,Sensors 2011.
[50]J X Wang,X W Sun,Y Yang,H Huang1,Y C Lee1,O K Tan1and L Vayssieres,Hydrothermally grown oriented ZnO nanorod arrays for gas sensing applications,Nanotechnology 17 (2006).
[51]Ulnch Hoefer,Gerd Kuhner,Werner Schweizer,Gerd Sulz, Klaus Steiner,CO and CO2 thin-film SnO, gas sensors on Si substrates,Sensors and Actuators B 22 (1994).