臺灣博碩士論文加值系統

本研究以磁控濺鍍法在玻璃基板與PET基板上，利用氧化鋅掺鋁(AZO)之陶瓷靶材沉積透明導電薄膜，此實驗探討基板溫度與工作壓力對於AZO薄膜的結構及性質之影響，另一方面探討銀奈米線(AgNWs)對於AZO薄膜的可撓性之影響。AZO薄膜方面，在固定膜厚下實驗結果顯示在不同濺鍍條件下薄膜皆呈現(002)的優選方向，當功率50W、工作壓力5 mtorr及氬氣流量15 sccm的條件下，對基板加熱至200℃之AZO薄膜，晶粒大小隨著溫度提高，逐漸變小且緻密，原因為基板溫度使鋁原子容易活化進入氧化鋅結構，測得穿透率85.23%及電阻率4.72×10-4 Ω‧cm；當在功率50W、基板溫度200℃及氬氣流量15 sccm的條件下，工作壓力在1 mtorr時之AZO薄膜，晶粒大小隨著壓力降低，逐漸變小且緻密，原因為粒子自由路徑提高，測得穿透率85.42%及電阻率1.14×10-4 Ω‧cm。AZO/AgNws薄膜方面，測得電阻率1.14×10-4 Ω‧cm，AFM平均粗糙度9.85 nm，可撓性測試1000次後，電阻率由1.14×10-4 Ω‧cm提升至3.46×10-3 Ω‧cm。

In this study, a transparent conductive film was deposited on a glass substrate and a PET substrate by magnetron sputtering. The effects of substrate temperature and working pressure on the structure and properties of AZO thin films investigated by using a zinc oxide doped aluminum (AZO) ceramic target. On the other hand, the effect of AgNWs on the flexibility of AZO films investigated. For AZO film, the experimental results indicate that the films show the best direction of (002) under different sputtering conditions. At the power of 50W, the working pressure of 5mtorr, the argon flow rate of 15 sccm and the substrate of heated to 200℃, the grain size of AZO film decreases with the temperature and becomes dense because Al atoms easily activated into the zine oxide structure by high substrate temperature. The penetration rate of 85.23% and the resistivity of 4.72 × 10-4 Ω‧cm. The particle size decreases with the decreased of pressure, and becomes small and compact because of the freedom of particles. When the working pressure is 1 mtorr, the grain size decreases with the decreased pressure. The reason is form the improved partical free path. A penetration rate of 85.42% and a resistivity of 1.14× 10-4 Ω‧cm. For AZO/AgNws film, the resistivity and AFM average roughness respectively of 1.14 × 10-4 Ω‧cm and 9.85 nm. The resistivity after the flexible test of 1000 times is degraded to 1.73×10-3 Ω‧cm.

中文摘要 I
ABSTRACT II
第一章緒論 1
1.1前言 1
第二章文獻回顧與理論基礎 5
2.1透明導電薄膜 5
2.1.1透明導電薄膜概論 5
2.1.2透明導電膜製備 8
2.1.3氧化鋅特性 9
2.1.4氧化鋅摻鋁(Zno:Al)晶格結構 9
2.1.5 氧化鋅摻鋁(Zno:Al)薄膜之電學性質 10
2.1.6氧化鋅摻鋁(Zno:Al)薄膜之光學性質 10
2.2濺鍍原理 13
2.2.1電漿的定義 13
2.2.2電漿的成分 13
2.2.3電漿的產生 14
2.2.4反應性濺鍍(Reactive Sputtering) 14
2.2.5射頻濺鍍(RF Sputtering System) 15
2.2.6磁控濺鍍(Magnetron Sputtering) 16
2.3薄膜結構與特性 17
2.3.1薄膜成長機制 17
2.3.2薄膜微結構 21
2.4銀奈米線製備方法 25
2.4.1 模板合成法(template-mediated process) 25
2.4.2 晶種合成法(seed-mediated growth) 26
2.4.3多元醇合成法(polyol process) 28
2.4.4 零維奈米結構之自組裝(self-assembly) 31
2.5銀奈米線透明導電薄膜後製處理技術 32
第三章 實驗方法與步驟 34
3.1實驗材料 34
3.1.1濺鍍靶材 34
3.1.2工作氣體 34
3.1.3基板種類 34
3.1.4銀奈米線材料 35
3.2實驗步驟 36
3.2.1銀奈米線合成 37
3.2.2基板清洗 38
3.2.3鍍膜製程參數 39
3.3實驗設備與原理 41
3.3.1 磁控濺鍍機 (Magnetron reactive sputtering) 41
3.3.2紫外光/可見光(UV-Vis)光譜儀分析 42
3.3.3掃描式電子顯微鏡(SEM) 42
3.3.4四點探針阻抗分析儀(Four point probe) 43
3.3.5原子力顯微鏡(AFM) 44
3.3.6　X光繞射儀(X-Ray Diffractometer, XRD) 45
第四章 實驗分析與討論 47
4.1.AZO薄膜性質 47
4.2AZO薄膜結構分析 50
4.3AZO薄膜表面粗糙度分析 55
4.4AZO薄膜之光學性質量測 58
4.5AZO薄膜之XRD分析 61
4.6　AZO薄膜之電學量測 64
4-7　AZO/AgNWs薄膜結構分析 67
第五章 結論 70
5.1基板溫度對於AZO薄膜性質之影響 70
5.2工作壓力對於AZO薄膜性質之影響 70
5.3銀奈米線對於AZO薄膜性質之影響 70
參考文獻 71
誌謝 76

表目錄
表1-1 常見TCO薄膜製備方法 4
表2-1 常見TCO薄膜製備方法 8
表3-1 AZO薄膜不同基板溫度製程參數表 40
表3-2 AZO薄膜不同工作壓力製程參數表 40
表3-3 AZO/AGNWS薄膜製程參數 41

圖目錄
圖2-1 柏斯坦-摩斯(BURSTEIN- MOSS)效應 12
圖2-2 反應性濺鍍 15
圖2-3 磁控濺鍍示意圖 16
圖2-4 薄膜沉積機制圖 19
圖2-5 薄膜成長流程 20
圖2-6 吸解反應流程 20
圖2-7 MOVCHAN AND DEMCHISHIN之結構模型 21
圖2-8 THORNTON結構模型 23
圖2-9 MESSIER結構區模型 24
圖2-10 晶種合成法之主要合成步驟 27
圖2-11 晶種合成法所合成的奈米銀線 27
圖2-12 多醇合成法製備奈米銀線之流程圖 28
圖2-13 進行多元醇合成法的成核步驟所得到不同形態的成核粒子 30
圖2-14 多元醇合成反應時PVP吸附於特定晶面的示意圖 31
圖2-15 (A)未處理 (B)高溫燒結 (C)成膜後經由漂洗(RINSING)程序 32
圖2-16 (A)機械壓合法TOP VIEW 與(B)CROSS-SECTIONAL VIEW (C)機械壓力對薄膜阻值之變化 33
圖3-1 實驗流程 36
圖3-2 銀奈米線合成 37
圖3-3 基板清洗步驟 38
圖3-4 四點探針示意圖 44
圖3-5 X-射線經晶體繞射 46
圖4-1 AZO薄膜在不同溫度下之沉積速率 49
圖4-2 AZO薄膜在不同工作壓力下沉積速率 49
圖4-3 AZO薄膜在不同溫度下之表面形貌 52
圖4-4 AZO薄膜在不同溫度下之斷面 52
圖4-5 AZO薄膜在不同工作壓力下之表面形貌 53
圖4-6 AZO薄膜在不同工作壓力下之斷面 54
圖4-7 AZO薄膜在不同溫度下之表面粗糙度 56
圖4-8 AZO薄膜在不同工作壓力下之表面粗糙度 57
圖4-9 AZO薄膜在不同溫度下之穿透率 59
圖4-10 AZO薄膜在不同溫度下之能隙 59
圖4-11 AZO薄膜在不同工作壓力下之穿透率 60
圖4-12 AZO薄膜在不同工作壓力下之能隙 60
圖4-13 (a)AZO薄膜在不同溫度下之XRD分析(b)晶粒大小 62
圖4-14 (a)AZO薄膜在不同工作壓力下之XRD分析(b)晶粒大小 63
圖4-15 AZO薄膜在不同溫度下之電阻率 66
圖4-16 AZO薄膜在不同工作壓力下之電阻率 66
圖4-17 AZO/AGNWS低倍下表面形貌 68
圖4-18 AZO/AGNWS高倍下表面形貌 68
圖4-19 AZO/AGNWS薄膜表面粗糙度 69
圖4-20 AZO/AGNWS薄膜可撓性測試 69

1.H. L. Hartnagel, A. L. Dawar, A. K. Jain, and C. Jagadish. Semiconducting Transparent Thin Films. Institute of Physics Publishing, 1995.
2.K. L. Chopra, S. Major, and D. K. Pandya, “Transparent Conductors—A Status Review,” Thin Solid Films, Vol. 102, No. 1, 1983, pp. 1-46.
3.楊明輝，“金屬氧化物透明導電材料的基本原理”，工業材料，一百七十九期，134頁。
4.李玉華，“透明導電薄膜及其應用”，科儀新知，第十二卷，第一期，1990，94-102頁。
5.J. H. Shin, D. K. Shin, H. Y. Lee, and J. Y. Lee, “Properties of multilayer gallium and aluminum doped ZnO(GZO/AZO) transparent thin films deposited by pulsed laser deposition process, ” Transactions of Nonferrous Metals Society of China, Vol. 21, 2011, pp. 96-99.
6.D. R. Sahu, S. Y. Lin, and J. L. Huang, “Improved properties of Al-doped ZnO film by electron beam evaporation technique,” Microelectronics Journal, Vol. 38, 2007, pp. 245-250.
7.Z. Zhang, C. Bao, W. Yao, S. MA, L. Zhang, and S. Hou, ”Influence of deposition temperature on the crystallinity of Al-doped ZnO thin films at glass substrates prepared by RF magnetron sputtering method,” Superlattices and Microstructures, Vol. 49, 2011, pp. 644-653.
8.L. N. Li, Y. Zhao, X. L. Chen, J. Sun, and X. D. Chang, ”Effects of Oxygen Flux on the Aluminum Doped Zinc Oxide Thin Films By Direct Current Magnetron Sputtering,” Physics Procedia, Vol. 32, 2012, pp. 687-695.
9.W. T. Yen, Y. C. Lin, and J. H. Ke, “Surface textured ZnO:Al thin films by pulsed DC magnetron sputtering for thin film solar cells applications,” Applied Surface Science, Vol. 257, 2010, pp. 960-968.
10.Y. Y. Chen, J. C. Hsu, P. W. Wang, Y. W. Pai, C. Y. Wu, and Y. H. Lin, “Dependence of resistivity on structure and composition of AZO films fabricated by ion beam co-sputtering deposition,” Applied Surface Science, Vol. 257, 2011, pp.3446-3450.
11.D. K. Kim, and H. B. Kim, “Dependence of the properties of sputter deposited Al-doped ZnO thin films on base pressure,” Journal of Alloys and Compounds, Vol. 522, 2012, pp. 69-73.
12.J. I. Nomoto, T. Hirano, T. Miyata, and T. Minami, “Preparation of Al-doped ZnO transparent electrodes suitable for thin-film solar cell applications by various types of magnetron sputtering depositions,” Thin Solid Films, Vol. 520, 2011, pp.1400-1406.
13.L. N. Li, Y. Zhao, X. L. Chen, Q. Huang, Y. F. Wang, and X. D. Zhang, “Plasma State of Pulse Reactive Magnetron Sputtering ZnO: Al Thin Films,” Physics Procedia, Vol. 32, 2012, pp. 423-429.
14.N. Tsukamoto, N. Oka, and Y. Shidesato, “In-situ analyses on the reactive sputtering process to deposit Al-doped ZnO films using an Al–Zn alloy target,” Thin Solid Films, Vol. 520, 2012, pp. 3751-3754.
15.Y. Xia, P. Wang, S. Shia, M. Zhang, G. He, J. Lv, and Z. Sun, “Deposition and characterization of AZO thin films on flexible glass substrates using DC magnetron sputtering technique,” ScienceDirect, Vol. 43, 2017, pp. 4536-4544.
16.吳金寶，“AZO透明導電薄膜之技術發展與應用，材料世界綱材料最前線，2008。
17.W. D. Callister. Materials Science and Engineering: an Introduction. New York: John Wiley and Sons, 1992.
18.T. Minami, H. Sato, H. Imamoto, and S. Takata, “Substrate temperature dependence of transparent conducting Al-doped ZnO thin films prepared by magnetron sputtering,” Journal of Applied Physics, Vol. 31, 1992, p. 253.
19.B. E. Sernelius, K. F. Berggren, Z. C. Jin, I. Hamberg, and C. G. Granqvist, “Bang gap tailoring of ZnO by means of heavy Al doping,” Physical Review B, Vol. 37, No. 17, 1988, p. 10244.
20.蕭宏，半導體製程技術導論。台灣：全華圖書，2009年。
21.F. Shinoki, and A. Itoh, “Mechanism of RF reactive sputtering,” Journal of Applied Physics, Vol. 46, No. 8, 1975, p. 3381.
22.B. Chapman. Glow Discharge Processes. New York: John Wiley & Sons, 1980.
23.K. Wasa, and S. Hayakawa. Handbook of Sputter Deposition Technology - Principles, Technology and Applications. Noyes, 1992.
24.周安琪譯，薄膜材料。台灣：徐氏基金會，1975。
25.莊達人編著，VLSI製造技術。台灣：高立圖書有限公司，2006。
26.J. Sellers, “Asymmetric bipolar pulsed DC: the enabling technology for reactive PVD,” Surface and Coatings Technology. Vol. 98, 1998, p. 1245.
27.J. A. Thornton, “Influence of Apparatus Geometry and Deposition Conditions on the Structure and Topography of Thick Sputtered Coatings,” Journal of Vacuum Science & Technology, Vol. 11, 1974, pp. 666-670.
28.R. Messier, A. P. Giri and R. A. Roy, “Revised structure zone model for thin film physical structure,” Journal of Vacuum Science and Technology A, Vol. 500, 1984, pp. 500-503.
29.X. J. Xu, G. T. Fei, X. W. Wang, Z. Jin, W. H. Yu, L. D. Zhang, “Synthetic control of large-area, ordered silver nanowires with different diameters,” Materials Letters, Vol. 61, 2007, pp. 19-22.
30.R. L. Zong, J. Zhou, Q. Li, B. Du, B. Li, M. Fu, X. W. Qi, L.T. Li, S. Buddhudu, “Synthesis and Optical Properties of Silver Nanowire Arrays Embedded in Anodic Alumina Membrane,” J. Phys. Chem. B, 2004, pp. 16713-16716.
31.M. H. Huang, A. Choudrey and P. Yang, “Ag nanowire formation within mesoporous silica,” Chem Commun, 2000, pp. 1063–1064.
32.Y.J. Han, J.M. Kim and G.D. Stuchy, “Preparation of Noble Metal Nanowires Using Hexagonal Mesoporous Silica SBA-15,” Chem Mater, Vol. 12, 2000, pp. 2068-2069.
33.A. Goindaraj, B. C. Satishkumar, M. Nath, and C. N. R. Rao, “Metal Nanowires and Intercalated Metal Layers in Single-Walled Carbon Nanotube Bundles,” Chem Mate, 2000, pp. 202-205.
34.N. R. Jana, L. Gearheart, C. J. Murphy, “Wet chemical synthesis of silver nanorods and nanowires of controllable aspect ratio,” Chem Commun, 2001, pp. 617－618.
35.C. J. Murphy, N. R. Jana, “Controlling the Aspect Ratio of Inorganic Nanorods and Nanowires,” Adv Mater, 2002, pp. 80－82.
36.J. Chen, B. Wiley, Y. Xia, Langmuir, “One-Dimensional Nanostructures of Metals:  Large-Scale Synthesis and Some Potential Applications,” American Chemical Society, 2007, pp. 4120－4129.
37.B. J. Wiley, S. H. Im, Z. Y. Li, J. McLellan, A. Siekkinen, Y. Xia, “Maneuvering the surface plasmon resonance of silver nanostructures through shape-controlled synthesis,” J. Phys. Chem. B, Vol. 110, 2006, pp. 15666–15675.