利用RF 磁控濺鍍，在室溫下沉積氧化鋅鎵(ZnO/Ga；97/3 wt%；簡稱GZO)
薄膜於玻璃基板 (Corning 1737 Glass)，形成用途廣泛的透明導電膜，應用田
口實驗規劃及變異數分析，觀察不同濺鍍參數(濺鍍功率、製程壓力、氬氧比
例、濺鍍時間) 對GZO 透明導電膜的影響。經灰關聯分析，顯示電阻率由
9.23×10-3 為降低至5.77×10-3 Ω-cm，可見光穿透率由79.42 提昇至82.95 %。於
GZO 薄膜添加ZnO 中介層，其電阻率由5.77×10-3 降低到2.38×10-3Ω‧cm，但
是對可見光穿透率影響不大。接下來研究方向可以利用低溫電漿之特性，在室
溫下沉積透明導電膜於高分子基板，應用於可撓性光電元件。

Gallium-doped zinc oxide films have been grown on glass substrates with
and without ZnO buffer layers by r.f. magnetron sputtering at room temperature. In
this approach, the grey relational Taguchi method analysis is adopted to solve the
coating process with multiple deposition qualities. Optimal coating parameters can
then be determined by the gray relational grade as the performance index. The
GZO coating parameters (r.f. power, sputtering pressure, O2/(Ar+O2) flow-rate
ratios, and deposition time) are optimized by taking into account the multiple
performance characteristics (structural, morphological, deposition rate, electrical
resistivity, and optical transmittance). The results indicate that with grey relational
Taguchi method the electrical resistivity of GZO films is reduced from 9.23×10-3 to
5.77×10-3 Ω-cm and optical transmittance increases from 79.42 to 82.95 %,
respectively. The ZnO buffer layer can reduce the electrical resistivity of GZO
films from 5.77×10-3 to 2.38×10-3 Ω-cm. It can be anticipated that the room
temperature deposition enables these films deposition onto polymeric substrates for
flexible optoelectronic devices.

中文摘要 i
英文摘要 ii
致謝 iii
目錄 iv
表目錄 vii
圖目錄 viii
第一章 緒論 1
1.1 前言與研究背景 1
1.2 研究動機 2
1.3 研究目的 3
第二章 實驗相關理論與文獻回顧 4
2.1 氧化鋅薄膜 4
2.1.1 氧化鋅薄膜晶體結構 4
2.1.2 氧化鋅薄膜電學性質 5
2.1.3 氧化鋅薄膜光學性質 5
2.1.4 氧化鋅薄膜製備方法 6
2.2 射頻濺鍍 7
2.3 磁控濺鍍 8
2.4 薄膜成長理論 9
2.5 田口式實驗規劃法 11
2.5.1 因子的種類 12
2.5.2 數據分析 13
2.6 灰關聯分析 16
第三章 實驗方法與步驟 18
3.1 實驗流程 18
3.2 實驗規劃 18
3.3 實驗材料 20
3.3.1 靶材 20
3.3.2 基板 20
3.3.3 工作氣體 20
3.4 實驗設備 21
3.5 實驗步驟 23
3.5.1 基板前處理 23
3.5.2 薄膜濺鍍步驟 24
3.6 鍍層分析及量測 24
3.6.1 膜厚量測 24
3.6.2 薄膜電性量測 25
3.6.3 薄膜結構分析 26
3.6.4 薄膜表面分析 26
3.6.5 薄膜光穿透率分析 27
第四章 結果與討論 28
4.1 薄膜沉積速率 28
4.1.1 射頻功率對薄膜沉積速率之影響 30
4.1.2 製程壓力對薄膜沉積速率之影響 31
4.1.3 氬氧比例對薄膜沉積速率之影響 31
4.2 薄膜電性分析 31
4.2.1 射頻功率對薄膜電阻率之影響 33
4.2.2 製程壓力對薄膜電阻率之影響 35
4.2.3 氬氧比例對薄膜電阻率之影響 37
4.2.4 鍍膜時間對薄膜電阻率之影響 39
4.3 薄膜光學性質分析 41
4.3.1 射頻功率對薄膜光穿透率之影響 43
4.3.2 製程壓力對薄膜光穿透率之影響 44
4.3.3 氬氧比例對薄膜光穿透率之影響 44
4.3.4 鍍膜時間對薄膜光穿透率之影響 44
4.4 灰關聯分析與應證實驗 44
4.4.1 灰關聯分析 45
4.4.2 應證實驗 48
4.5 中介層對GZO的影響 51
第五章 結論 54
參考文獻 55

1. L. Davis, "Properties of Transparent Conducting Oxides Deposited at Room
Temperature", Thin Solid Films, 236(1993).
2. E. Shanthi, A. Banerjee, V. Dutta and K.L. Chopra, "Electrical and Optical
Properties of Tin Oxide Films Doped with F and（Sb+F）”, Journal of Applied
Physics, 53, pp.1615-1621(1982).
3. A. E. Rakhshani, Y. Makdisi, H. A. Ramazaniyan, “Electronic and optical
properties of fluorine-doped tin oxide films”, Journal of Applied Physics, 83,
pp.1049-1056(1998).
4. I. Safi, R. P. Howson, “The properties of reactively-sputtered
stoichiometry-controlled and optimum-conductivity transparent indium oxide
films as a function of their titanium, aluminium and zinc content; comparisons
with the use of tin as a dopant”, Thin Solid Films, 343-344 , pp.115-118(1999).
5. T. L. Won, H. L. Chang, “Highly oriented ZnO thin films deposited on Ru/Si
substrates”, Thin Solid Films, 353, pp.12-15(1999).
6. D. J. Yun, S. W. Rhee, “Deposition of Al-doped ZnO thin-films with radio
frequency magnetron sputtering for a source/drain electrode for pentacene
thin-film transistor”, Thin Solid Films, 517, pp.4644–4649(2009).
7. M. S. Jang, M. K. Ryu, M. H. Yoon, S. H. Lee, H. K. Kim, A. Onodera, S.
Kojima, “A study on the Raman spectra of Al-doped and Ga-doped ZnO
ceramics”, Current Applied Physics, 9, pp.651-657(2009).
8. S. M. Park, T. Ikegami, K. Ebihara, P. K. Shin, “Structure and properties of
transparent conductive doped ZnO films by pulsed laser deposition”, Applied
Surface Science, 253, pp.1522–1527(2006).
9. T. Yamada, T. Morizane, T. Arimitsu, A. Miyake, H. Makino, N. Yamamoto, T.
Yamamoto, “Application of low resistivity Ga-doped ZnO films to transparent
electromagnetic interference shielding material”, Thin Solid Films, 517,
pp.1027–1031(2008).
10. D. Paraguay, J. Morales, L. Estrada, E. Andrade, M. Miki-Yoshida, “Influence
of Al, In, Cu, Fe and Sn dopants in the microstructure of zinc oxide thin films
obtained by spray pyrolysis”, Thin Solid Films, 366 , pp.16-27(2000).
11. E. L. Paradis and A. J. Shuskus, “RF Sputtered Epitaxial ZnO Films on
Sapphire for Integrated Optics”, Thin Solid Films, 38, pp.131-141(1976).
12. S. Kim, J. Seo, H. W. Jang, J. Bang, W. Lee, T. Lee, J. M. Myoung, “Effects of
H2 ambient annealing in fully 002-textured ZnO:Ga thin films grown on glass
substrates using RF magnetron co-sputter deposition”, Applied Surface Science,
255, pp.4616–4622(2009).
13. T. S. Moss, “The interpretation of the properties of Indium Antimonide”, Phys.
Soc. London Sect. B, vol. 67, pp.775-782(1954).
14. J. Hu, R. G. Gordon, “Textured aluminium-doped zinc oxide thin films from
atmospheric pressure chemical-vapor deposition”, Journal of Applied Physics,
71(2), pp. 880-890(1992).
15. E. S. Shim, H. S. Kang, J. S. Kang, J. H. Kim, S. Y. Lee, “Effect of The
Variation of Films Thickness on The Structural and Optical Properties of ZnO
Thin Films Deposition on Sapphire Substrate Using PLD ”, Applied Surface
Science, 186, pp.474-476(2002).
16. Z. C. Jin, I. Hamberg, C. G. Grangvist., "Optical Properties of sputter-deposited
ZnO:Al thin films", Journal of Applied Physics, 64, pp.5117-5131(1988).
17. F. Furusaki, J. Takahashi and K. Kodaira, “Preparation of ITO Thin Films by
Sool-Gel Method”, Journal of the Ceramic Society of Japan, 102(2),
pp.200-205(1994).
18. T. Minami, H. Sato, T. Sonoda, H. Nanto, S. Takata, “Influence of substrate and
target temperature on properties of transparent and conductive doped ZnO thin
films prepared by RF magnetron sputtering”, Thin Solid Films, 171,pp.307-311(1989).
19. B. Chapman, “Glow Discharge Processes”, John Wiley and Sons, New York,
pp.106-109(1980).
20. J. Venables, “Nucleation and growth of thin films”, Reports On Progress in
Physics, 47, pp.399-459(1984).
21. J. Thornton, “Influence of apparatus geometry and deposition conditions on the
structure and topography of thick sputtered coatings”, Journal of Vacuum
Science Technology, 11(4), pp.666-670(1974).
22. J. R. Phillip, “Taguchi Techniques For Quality Engineering”, McGraw-Hill,
pp.18-33(1989).
23. 張偉哲、溫坤禮、張廷政，灰關聯模型方法與應用，高立圖書有限公司，
pp13-26.
24. S. Flickyngerova, K. Shtereva, V. Stenova, D. Hasko, I. Novotny, V. Tvarozek,
P. Sutta, E. Vavrinsky, “Structural and optical properties of sputtered ZnO thin
films”, Applied Surface Science, 254, pp.3643–3647(2008).
25. J. H. Lee, J. T. Song, “Dependence of the electrical and optical properties on
the bias voltage for ZnO:Al films deposited by r.f. magnetron sputtering”, Thin
Solid Films, 516, pp.1377-1381(2008).
26. Y. S. Rim, S. M. Kim, H. W. Choi, S. J. Park, K. H. Kim, “Preparation of
Al-doped ZnO thin film deposited at room temperature”, Colloids and Surfaces
A: Physicochem. Eng. Aspects, 313–314, pp.461-464(2008).
27. Y. C. Lin, M. Z. Chen, C. C. Kuo, W. T. Yen, “Electrical and optical properties
of ZnO:Al film prepared on polyethersulfone substrate by RF magnetron
sputtering”, Colloids and Surfaces A-Physicochemical And Engineering
Aspects, 337, pp.52–56(2009).
28. X. Yua, J. Ma, F. Ji, Y. Wang, X. Zhang, C. Cheng, H. Ma, “Preparation and
properties of ZnO:Ga films prepared by r.f. magnetron sputtering at low
temperature”, Applied Surface Science, 239, pp.222-226(2005).
29. B. Houng, C. S. Hsi, B. Y. Hou, S. L. Fu, “Effect of process parameters on the
growth and properties of impurity-doped zinc oxide transparent conducting
thin films by RF magnetron sputtering”, Vacuum, 83, pp. 534-539(2009).
30. J. Jeong, H. K. Kim, J. Y. Lee, J. H. Lee, H. D. Bae, Y. H. Tak, “Characteristics
of ITO electrode grown by linear facing target sputtering with ladder type
magnetic arrangement for organic light emitting diodes”, Thin Solid Films, 517,
pp.4043–4046(2009).
31. E. Fortunato, A. Goncalves, V. Assuncao, A. Marques, H. Aguas, L. Pereira, I.
Ferreira, R. Martins, “Growth of ZnO:Ga thin films at room temperature on
polymeric substrates: thickness dependence”, Thin Solid Films, 442,
pp.121-126(2003).
32. Q. B. Ma, Z. Z. Ye, H. P. He, J. R. Wang, L. P. Zhu, B. H. Zhao, “Preparation
and characterization of transparent conductive ZnO:Ga films by DC reactive
magnetron sputtering”, materials characterization, 59, pp.124-128(2008).
33. Q. B. Ma, Z. Z. Ye, H. P. He, L. P. Zhu, B. H. Zhao, “Effects of deposition
pressure on the properties of transparent conductive ZnO:Ga films prepared by
DC reactive”, Materials Science in Semiconductor Processing, 10,
pp.167-172(2007).
34. B. D. Ahna, S. H. Oha, C. H. Lee, G. H. Kim, H. J. Kim, S. Y. Lee, “Influence
of thermal annealing ambient on Ga-doped ZnO thin films”, Journal of Crystal
Growth, 309, pp.128–133(2007).
35. X. Yua, J. Ma, F. Ji, Y. Wang, C. Cheng, H. Ma, “Thickness dependence of
properties of ZnO:Ga films deposited by rf magnetron sputtering”, Applied
Surface Science, 245, pp.310-315(2005).
36. C. Lee, A. Park, Y. Cho, M. Park, W. I. Lee, H. W. Kim, “Influence of ZnO
buffer layer thickness on the electrical and optical properties of indium zinc
oxide thin films deposited on PET substrates”, Ceramics International, 34,
pp.1093-1096(2008).
37. J. Y. Tseng, M. Y. Yang, C. Y. Wang, P. C. Li, W. C. Yu, Y. F. Hsu, S. F. Wang,
“Deposition of low-resistivity gallium-doped zinc oxide films by
low-temperature radio-frequency magnetron sputtering”,
doi:10.1016/j.tsf.2009.02.061.