臺灣博碩士論文加值系統

本研究目的是利用溶膠凝膠法及濺鍍技術來製備ZnO:Al(AZO)薄膜。
熱處理溫度會影響薄膜的結晶性質，隨著溫度的升高，繞射峰的強度
逐漸增加，XRD結果顯示繞射峰都是朝著(002)的方向，其結晶性可
以被改善。本研究並以可撓式塑膠軟板當基板，使用PES、PET塑膠
基板，利用SIV-3040在室溫下濺鍍ITO在PET和PES塑膠基板上，
其平均電阻濺鍍PET上是4.28×101 (Ω/□)；PES的電阻是5.39×101
(Ω/□)，待AZO材料製程成熟後，也可以此方式成膜在塑膠基板上。
以RF-Sputter濺鍍系統製備AZO薄膜，濺鍍法在通入(N2/Ar)氣
體比例5/5時，會變為p-type；而低於或高於這個比例則會形成
n-type。而通入(N2O/Ar)氣體比例4/6時，會變為p type;而低於會成為n type。本實驗以功率60瓦，N2O/Ar:2/8這情況下，測得電阻值21.5Ω.cm，載子濃度:9.68 1016cm-3。明顯的看出本實驗在電阻值較文獻低。

The goal of this study is to use sol-gel method and sputter technique to prepare ZnO：Al (AZO) thin films.The thermal treatment affected the crystallinility of the AZO films,XRD results showed that (002)-oriented polycrystal films are deposited on glass substrates and the crystalline quality can be improved.This study used flexible PET and PES plastic as substrates. ITO thin films were deposited on PES and PET plastic,and they have been prepared by SIV-3040.Their average resistivity on PES is 5.39×101 (Ω/□) and average resistivity on PET is 4.28×101 (Ω/□) .
The ratio of N2 and Ar gas flows was maintained at 5/5sccm,the samples
sputtered with>50vol%N2 or <50vol%N2 show n-type;50vol%N2 show
p-type. The ratio of N2O and Ar gas flows was maintained at4/6,the
samples sputter with >40 vol%N2O show p-type;< 40 vol% N2O show
n-type.
This study used power:60w and N2O/Ar:2/8 this condition，we
measured it resistivity was 21.5Ω.cm and carrier concentration:
9.68×1016cm-3. Obviously,our study’s resistivity is
lower than reference.

目錄
指導教授推薦書
口試委員審定書
授權書 iii
致謝 iv
中文摘要 v
英文摘要 vi
目錄 vii

第一章序論 1
1-1導論 1
1-2 透明導電膜的分類 4
1-3 研究動機 8
第二章 文獻回顧 9
2-1 ITO 透明導電膜之特性 9
2-2 ZnO透明導電膜之特性 11
2-3 AZO 薄膜之電學性質 13
2-4 AZO 薄膜之光學性質 15
2-5 溶膠凝膠法基本原理 18
2-5.1 Sol-gel法塗佈 20
2-5.2 溶膠凝膠法與濺鍍方式製備AZO薄膜的比較 22
2-6 濺鍍原理 23
2-6.1基本原理 23
2-6.2 RF磁控濺鍍法 (RF-Magnetron Sputtering eposition ) 25
2-7 SIV3040製備ITO薄膜 28
2-8霍爾效應 31
第三章 實驗部份 34
3-1實驗藥品、儀器與材料 34
3-1.1藥品 34
3-1.2 實驗設備與儀器 35
3-2 AZO浸鍍實驗流程 36
3-3 溶膠凝膠法製備AZO前驅液 37
3-3.1 AZO透明導電薄膜的製備 38
3-4 ITO和AZO薄膜沉積製程 39
3-4.1基板前處理 39
3-4.2沉積ITO膜於PET、PES基板 39
3-4.3 沉積AZO膜於玻璃基板 40
3-5 薄膜品質分析 40
3-5.1 膜厚量測 40
3-5.2 可見光穿透量測 40
3-5.3 四點探針 41
3-5.4 X光繞射儀(XRD) 42
3-5.5 霍爾效應分析儀 43
第四章 結果與討論 44
4-1 AZO溶凝膠之組成分析 44
4-1.1 AZO溶凝膠之組成分析 44
4-2 AZO電阻之量測與分析 46
4-3 熱處理溫度對AZO薄膜之性質影響 47
4-4 利用SIV3040沉積ITO薄膜於PES和PET基板上 47
4-5利用RF sputter鍍製AZO薄膜 49
4-5.1改變通入N2氣體的量對AZO薄膜的影響 49
4-5.2 改變通入N2O氣體的量對AZO薄膜的影響 50
第五章 結論 66
第六章 未來展望 68
參考文獻 69



圖目錄
Fig.2.1 The structure of ZnO 12
Fig.2.2 混摻不同雜質之ZnO 薄膜 14
Fig.2.3 Al摻雜ZnO薄膜的電阻變化圖 15
Fig.2.4 In2O3混摻雜質前後的能階變化(Burstein-Moss shift) 16
Fig.2.5 AZO薄膜隨著摻雜Al濃度增加造成穿透度的改變 17
Fig.2.6 溶膠凝膠製程及產物 19
Fig.2.7 電漿產生器基本結構及離子濺擊效應 24
Fig.2.8濺鍍時所產生原子解離的現象 26
Fig. 2.9 Variation of hole density, resistivity, and mobility as a function of various N2O partial pressure ratios 28
Fig.2.10 SIV-3040 DC sputter apparatus 29
Fig.2.11 XRD analysis of IT0 films on PET substrate 30
Fig.2.12 XRD analysis of IT0 films on PET substrate 31
Fig.2.13 Hall effect measurement 33
Fig.3.1 The flow chart shows the procedure for preparing ZnO:Al films by sol–gel method. 36
Fig.3.2 四點探針法示意圖 42
Fig.4.1 X-Ray diffraction patterns of samples heated at different temperatures, 0.5M. 57
Fig.4.2 X-Ray diffraction patterns of samples heated at different temperatures, 0.8M 58
Fig.4.3 Resistivity of Al-doped ZnO films pre-theated at various
temperatures, 0.5M,Al/Zn=2at%. 59
Fig.4.4 Resistivity of Al-doped ZnO films pre-theated at various
temperatures, 0.8M,Al/Zn=2at% 60
Fig.4.5 Transmittance spectra of Al-doped ZnO films pre-heated at various temperatures,0.5M,Al/Zn=2at%. 61

Fig.4.7 Optical transmission spectra of IT0 films on plastic substrates in the wavelength range of 300-900 nm. 63
Fig.4.8 XRD analysis of IT0 films on PES substrate. 64
Fig.4.9 XRD analysis of IT0 films on PET substrate. 65










表目錄

Table 1.1 The properties of In2O3,SnO2,ZnO 6
Table 1.2 The electrical applications of TCO 7
Table 2.1 Comparison of structural and electrical parameters of
N-doped ZnO films 27
Table 4.1 Resistivity of IT0 films on PET substrates 52
Table 4.2 Resistivity of IT0 films on PES substrates 53
Table 4.3 Comparison of structural and electrical paprameter of N-doped ZnO films 54
Table 4.4 Conditions for the AZO film preparation by sol-gel
method 55
Table 4.5 growth conditions for the p-type ZnO film by Al-N
codoping and the electrical properties of the
corresponding sample. 56

[1].趙學禮，2007，中央大學物理研究所碩士論文“非晶矽太陽能電
池之材料成長、元件製作及特性分析”。
[2]. V. M. Gusev, V. V. Zadde, A. P. Landsman, and. V. V. Titov,
Sov.Phys.-Solid State 8, 1363 (1966).
[3]. D. E. Carlson and C. R. Wronski, “Amorphous silicon solar cell”, Appl. Phys. Lett. 28,671(1976).
[4]. Y. Uchida, T. Ichimura, M. Ueno and M. Osawa, J.Phys.
42(1981)C4-265.
[5]. P. H. Fang, L. Ephrath, and W. B. Nowak,“Polycrystalline
silicon films on aluminum sheets for solar cell
application”, Appl. Phys. Lett. 25, 583(1974).
[6]. H. Morisaki, T. Watanabe, M. Iwase, and K. Yazawa,
“ Photoelectrolysis of water with TiO2-covered solar-cell
electrodes”,Appl.Phys.Lett. 29, 338 (1976).
[7].謝振剛，2005，中央大學光電科學研究所碩士論文“氧化鋅鋁透
明導 電膜光、電特性之研究“ 。
[8].H.Sheng,1 N.W. Emanetoglu,1 S. Muthukumar,2 B.V. Yakshinskiy,3 S. Feng,1 and Y.Lu1, J.Electron Mater, Vol.32, p.9, April 1 2003.
[9].Han-Ki Kim, Sang-Heon Han, and Tae-Yeon Seong, Appl.Phys.Lett. Vol.77,p.11 , 11 September 2000.
[10].Han-Ki Kim, Kyoung-Kook Kim, Seong-Ju Park, and Tae-Yeon
Seong , J.Appl.Phys.Vol.94, p.6 ,15 September 2003.
[11].Y.G. Wanga, S.P. Laua,, X.H. Zhangb, H.H. Hngc, H.W. Leea,
S.F. Yua, B.K. Taya ,Journal of Crystal Growth,Vol.259,
p.335–342 ,31 July 2003.
[12].Y.R. Ryu, S. Zhu,1, D.C. Look, J.M. Wrobel, H.M. Jeong, H.W.White , Journal of Crystal Growth, Vol.216 ,
p.330-334 ,21 March2000.
[13].李玉華,”透明導電膜及其應用”,科儀新知,12卷第一
期,(79),94-102.
[14].J.L.Vossen,physics of thin films, Vol.9, p.1-64 ,1997.
[15].H. L. Hartnagel, A.L. Dawar, A. K. Jain and C. Jagadish, Semiconductoer Transparent Thin Films, IOP Publishing Ltd., p.1-4,1995.
[16]. J. J. Shyh and K. L. Mo, Jpn. J. Appl.Phys. 34 (1995) 683.
[17]. J. D. Mackenzie, J. Non-Crystal Solid 48(1982) 1.
[18]. R. Wang, A. Sleight, and R. Gardner, J. Mater. Res., 11,
1659(1996).
[19]. T. Minami, T. Takumu, and S. Takata, “Preparation of transparent and conductive In2O3–ZnO films by radio frequency magnetron sputtering”J. Vac. Sci. Technol.
A, 14,1704 (1996).
[20].曲喜新、楊邦朝、姜節儉、張懷武編撰，“電子薄膜材料”，
北京科學出版社 (1996)。
[21].蔡瑛修，2000，成功大學化學工程所碩士論文〝以感應偶合電
漿輔助磁控溅鍍法於低溫成長ITO膜〞。
[22].古俊能，2001年1月，工業材料雜誌169期，P106。
[23].R. G. Gordon, MRS Bull.,“ Criteria for choosing transparent conductors”, Phys.Rev.B, Aug., 52 (2000).
[24].S.B.Majumder,M.Jain.,“ Investigations on solution
derived aluminium doped zinc oxide thin films”, Materials
Science and Engineering B 103(2003) 16-25.

[25].楊明輝，工業材料，“金屬氧化物透明導電材料的基本原理”, 179，134 (1999)。
[26].H. L. Hartnagel, A. L. Dawar, A. K. Jain, C. Jagadish,“Semiconducting Transparent Thin Films”, Institute of
Physics Publishing (1995).
[27]. Z. Jiwei , Z. Liangying , and Y. Xi , “The dielectric properties and optical propagation loss of c- axis oriented ZnO thin films deposited by sol- gel process ”, Ceramics International , 26 , (2000) pp.883- 885.
[28].顧鴻壽，光電液晶平面顯示器技術基礎及應用，新文京出版(2004)。
[29]. A. Kobayashi, O.F. Sankey, J.D. Dow,“Semiempirical tight-binding band structures of wurtzite semiconductors: aluminum nitride, cadmium sulfide, cadmium selenide, zinc sulfide, and zinc oxide”, Phys. Rev. B 28 (1983) 946.
[30]. A. Tsukazaki, A. Ohtomo, T. Onuma, M. Ohtani, T. Makino, M. Sumiya, K. Ohtani ,“Repeated temperature modulation epitaxy for p-type doping and light-emitting diode based on ZnO”, Nat. matters 4 (2005) 42.
[31]. W.Z. Xu, Z.Z. Ye, Y.J. Zeng, L.P. Zhu, B.H. Zhao, L. Jiang, J.G. Lu, H.P.He, S.B. Zhang, “ZnO light-emitting diode grown by plasma-assisted metal organic chemical vapor deposition”,Appl. Phys. Lett. 88 (2006) 173506.
[32]. H. Matsui, H. Saeki, T. Kawai, H. Tabata, B. Mizobuchi,“N doping using N2O and NO sources: From the viewpoint of ZnO”, J. Appl. Phys. 95 (2004) 5882.
[33]. Z.Z. Ye, J.G. Lu, H.H. Chen, Y.Z. Zhang, L.Wang, B.H. Zhao, J.Y. Huang,J.“Preparation and characteristics of p-type ZnO films by DC reactive magnetron sputtering”, Cryst. Growth 253 (2003) 258.
[34]. M. Futsuhara, K. Yoshioka, O. Takai,“Optical properties of zinc oxynitride thin films” Thin Solid Films 317 (1998) 322.
[35]. Y. Nakano, T. Morikawa, T. Ohwaki, Y. Taga, “Deep-level
characterization of N-doped ZnO films prepared by reactive magnetron sputtering”,Appl. Phys. Lett. 87 (2005) 232104.

[36].Jinzhong Wang, Vincent Sallet, François Jomard, Ana M. Botelho do Rego, Elangovan Elamurugu, Rodrigo Martins, Elvira Fortunato,“Influence of the reactive N2 gas flow on the properties of rf-sputtered ZnO thin films”,Thin Solid Films 5 (2007)22953.
[37]. Y.F. Yan,S.B. Zhang,“Control of doping by impurity chemical potentials: Predictions for p-type ZnO”,Phys.Rev.Lett. 86 (2001) 5723.
[38]. F. Zhuge, L.P. Zhu, Z.Z. Ye*, J.G. Lu, B.H. Zhao, J.Y. Huang, L. Wang, Z.H. Zhang, Z.G. Ji,“Effects of growth ambient on electrical properties of Al–N co-doped p-type ZnO films” Thin Solid Films 476 (2005) 272– 275.
[39].TANG Wu , WENG Xiaolong , WU Yutm , and DENG Longiiang,“Study on adhesion and electro-optical properties of IT0
films on flexible PET substrate”,RARE METALS, Vol. 25, Spec. Issue , Dec 2006, p .65
[40].H. Kim, C. M. Gilmore, A. Pique, J. S. Horwitz, H. Mattoussi, H.Murata, Z. H. kafafi and D.B.Chr“Electrical, optical, and structural properties of indium–tin–oxide thin films for organic light-emitting devices”J.Appl.Phys.,86, 6451(2001).
[41].郭俊頡“The study of deposited ITO films on flexible
substrates by RF sputtering technology at room
temperature ”中山大學物理系碩士論文(九十四年)。
[42].連昭榮“Study of the Electronic Properties of InGaAs/GaAs Single QuantumWells”中山大學物理系碩士論文(九十三年)。
[43].姚文醮 “ Transport studies of Two-Dimensional Electron Gas in AlGaN/GaN Quantum Well at Low Temperature and High Magnetic Field ” 中山大學物理系碩士論文(九十二年)。
[44]. D. Bao, H. Gu, A. Kuang,“Sol-gel-derived c-axis oriented ZnO thin films” Thin Solid Films 312 (1998) 37.