調變奈米金粒之分佈於摻鋁氧化鋅膜層中以提升其光電特性之研究

Enhancement of optoelectronic properties by regulating the distribution of Au nano-particles in Al-doped ZnO layer

王渝睿

還原奈米金粒 ； 摻鋁氧化鋅 ； 射頻磁控濺鍍 ； Reductive Au-nano particles ； Aluminum-doped Zinc Oxide (AZO) ； RF-magnetron sputtering

義守大學電子工程學系學位論文

2016年

碩士

林彥勝

繁體中文

本研究主要藉由低成本之化學還原法還原出奈米金粒子，並將其置入於摻鋁氧化鋅薄膜中，藉由調變不同熱處理製程參數，除有效去除奈米金粒子周邊的有機物質外亦藉由重整整體薄膜的緻密性，更進一步提升整體AZO薄膜的光電特性。研究中首先藉由調變不同溫度與持溫時間之熱處理，除去奈米金周邊有機物質外並提升整體膜層品質及奈米金分布，最後再處以不同轉速之旋轉塗佈來更改善奈米金粒子的分布，以提升奈米金粒對整體AZO薄膜的光電特性。製程後藉由掃描式顯微鏡(SEM)、X光繞射儀(XRD)和原子力顯微鏡(AFM)來分析奈米金粒分布、結構與薄膜的特性，再藉由霍爾載子量測(Hall-effect measurement)系統及紫外光/可見光光譜儀(UV-VIS-NIR Spectrophotometer)來量測薄膜的光電特性。研究結果顯示，經700℃、20分鐘的熱燒結處理，可較有效去除奈米金粒子周邊的有機物質，再藉由500℃、10分鐘之熱處理後，整體薄膜品質獲得提升。再導入以500rmp、30秒的旋轉塗佈後，由於奈米金粒子的分布呈現較均勻狀態，最後可使電阻降低至3.77×10-2、穿透率於可見光範圍內可提升為85.63%，且得到最佳光電效益值為4.50×10-5Ω-1。

In this study, the lower cost Au-nano particles(Au-NPs) has been obtained by chemical reduction and inserted the Al-doped Zinc Oxide (AZO) layer to enhance the optoelectronic properties. At first the improved AZO thin film had been treated as seed layer, and then the Au-NPs were dropped on the etched surface of seed layer, the proper treatment as thermal and spin had been done before the deposition of AZO capping layer, and then the AZO/Au-NPs/AZO thin film was finished. The scanning electron microscopy (SEM), X-ray diffraction (XRD) and atomic force microscope (AFM) were used to analysis the structure and distribution of Au nano particles, and the crystalline intensity of AZO thin film. The optoelectronic properties were measured by Hall-effect measurement and UV-VIS-NIR Spectrophotometer system. The result shown the optimum optoelectronic properties of AZO/Au-NPs/AZO thin film was measured after 700℃、20min thermal sintering, 500rpm spin speed and 500℃、10min thermal annealing. The resistance reduces to 3.77×10-2Ω-cm, the average transmittance in visible increases to 85.63%, and the optimum figure of merit is 4.50×10-5Ω-1.

1. “Highly transparent and infrared reflective AZO/Ag/AZO multilayer
   連結：
2. filmprepared on PET substrate by RF magnetron sputtering,”
   連結：
3. Vacuum 106, pp. 1-4, 2014.
   連結：
4. Figure of Merit for Transparent Conducting Nanotube Films,”
   連結：
5. [10] X.-D. Z. Gregory J. Exarhos, “Discovery-based design of transparent
   連結：
6. 科技大學, 2008.
   連結：
7. [13] Matt Law, Lori E. Greene, Justin C. Johnson, Richard Saykally and
   連結：
8. “Preparation of transparent conducting ZnO:Al films on polymer
   連結：
9. “Growth of transparent conducting nanocrystalline Al doped ZnO
   連結：
10. thin films by pulsed laser deposition,” Journal of Crystal Growth,
    連結：
11. Kubokawa, “Photocatalytic hydrogenation of propyne with water on
    連結：
12. Kim, “Annealing effect of ZnO/Au/ZnO transparent conductive
    連結：
13. 電特性之研究,＂ 義守大學, 2014.
    連結：
14. [29] H. W. X. L. a. B. S. Xin Huang, “One-step, size-controlled synthesis
    連結：
15. of gold nanoparticles at room temperature using plant tannin,” Green
    連結：
16. 電特性之研究,＂ 義守大學, 2004.
    連結：
17. microfabricated disposable,” Biosensors and Bioelectronics January,
    連結：
18. [35] J. D. Verhoeven, Fundamentals of physical metallurgy, 美國: Wiley,
    連結：
19. size-controlled synthesis of gold nanoparticles at room temperature
    連結：
20. [37] E. H. Putley, The Hall effect and semi-conductor physics, New York:
    連結：
21. Dover Publications, 1968.
    連結：
22. [1] D. Kim, "The influence of Au thickness on the structural, optical and electrical properties of ZnO/Au/ZnO multilayer films," Optics Communications vol. 285, p. 1212–1214, 2012.
23. [2] H.M. Lee, Y.J. Lee, I.S. Kim, M.S. Kang, S.B. Heo, Y.S. Kim, Daeil Kim, “Annealing effect of ZnO/Au/ZnO transparent conductive films,” Vacuum 86, pp. 1494-1498, 2012.
24. [3] Dagang Miao, Shouxiang Jiang, Songmin Shang, Zhuoming Chen, “Highly transparent and infrared reflective AZO/Ag/AZO multilayer filmprepared on PET substrate by RF magnetron sputtering,” Vacuum 106, pp. 1-4, 2014.
25. [4] 吳金寶, “AZO 透明導電薄膜技術近況發展與應用,＂ 材料世界網,工研院材化所, 2008.
26. [5] 黃宏欣, “光電平面顯示器導論-透明導電膜,＂ 正修科技大學電機工程學系, 2009.
27. [6] 王慶鈞, “透明導電薄膜之應用概論,＂ 機械工業雜誌, 編號338, pp. 5-6, 2011.
28. [7] 楊明輝, 透明導電膜, 2012.
29. [8] Á. Pekker, K. Kamarás, N. M. Nemes and M. Garcia-Hernandez, “A Figure of Merit for Transparent Conducting Nanotube Films,” 1204-K10-41.R2 , pp. 1-5, 2009.
30. [9] 吳品諺, “摻氟氧化錫透明導電膜之特性分析,＂ 國立台北科技大學, 2005.
31. [10] X.-D. Z. Gregory J. Exarhos, “Discovery-based design of transparent conducting oxide films,” Thin Solid Films,Vol.515, pp. 7025-7052, 2007.
32. [11] 何建志, “摻雜鋁之p-type 氧化鋅薄膜特性分析,＂ 國立台北科技大學, 2008.
33. [12] Su-Shia Lin, Jow-Lay Huang, “The effect of thickness on the properties of heavily Al-doped ZnO films by simultaneous rf and dc magnetron sputtering,” Ceramics International,Vol.30, pp. 497-501, 2004.
34. [13] Matt Law, Lori E. Greene, Justin C. Johnson, Richard Saykally and Peidong Yang, “Nanowire dye-sensitized solar cells,” nature materials, pp. 455-459, 2005.
35. [14] D.H Zhang, T.L Yang, J Mac, Q.P Wang, R.W Gao, H.L Ma, “Preparation of transparent conducting ZnO:Al films on polymer substrates by r. f. magnetron sputtering,” Applied Surface Science,Vol.158, pp. 43-48, 2000.
36. [15] Ryoken, Haruki; Sakaguchi, Isao; Ohashi, Naoki; Sekiguchi, Takashi; Hishita, Shunichi; Haneda, Hajime, “Non-equilibrium defects in aluminum-doped zinc oxide thin films grown with a pulsed laser deposition method,” Journal of Materials Research, Vol. 20, pp. 2866-2872, 2005.
37. [16] R.K. Shukla, Anchal Srivastava, Atul Srivastava, K.C. Dubey, “Growth of transparent conducting nanocrystalline Al doped ZnO thin films by pulsed laser deposition,” Journal of Crystal Growth, Vol.294, Issue 2, pp. 427-431, 2006.
38. [17] Masakazu. Anpo, Takahito. Shima, Sukeya. Kodama, Yutaka. Kubokawa, “Photocatalytic hydrogenation of propyne with water on small-particle titania: size quantization effects and reaction intermediates,” J. Phys. Chem, Vol.91, pp. 4305-4310, 1987.
39. [18] 楊明輝, “工業材料,＂ 第 冊第179 卷, pp. 134-144, 1999.
40. [19] D. Kim, “The influence of Au thickness on the structural, optical and electrical properties of ZnO/Au/ZnO multilayer films,” Optics Communications, Vol.285, pp. 1212-1214, 2012.
41. [20] H.M. Lee, Y.J. Lee, I.S. Kim, M.S. Kang, S.B. Heo, Y.S. Kim, Daeil Kim, “Annealing effect of ZnO/Au/ZnO transparent conductive films,” Vacuum 86, pp. 1494-1498, 2012.
42. [21] 杜念魯, “Digitimes,＂ 2012.
43. [22] 林子暘, “以濺鍍沉積法沉積以氮化鋁為緩衝層之氮化銦薄膜特性研究,＂ 國立高雄大學電機系, 2008.
44. [23] 戴 國 良, “離子輔助反應射頻磁控濺鍍紫外光薄膜之研究,＂國 立 中 央 大 學, 2007.
45. [24] 陳宏昌, “以射頻反應新式磁控濺鍍法於藍寶石基板成長鋅摻雜氮化銦材料及其相關特性之研究,＂ 國立台北科技大學,2005.
46. [25] 邱欣慶, “二氧化碳雷射輔助電漿激發式化學,＂ 國 立 中 央大 學, 2000.
47. [26] 張光儀, “添加金、銀於AZO 透明導電薄膜中之研究,＂ 大同大學, 2007.
48. [27] 羅翊瑋, “科學Online 科技部高瞻自然科學教學資源平台,＂國立彰化師範大學, 2011.
49. [28] 陳正偉, “建構奈米金類網狀結構於摻鋁氧化鋅薄膜以提升光電特性之研究,＂ 義守大學, 2014.
50. [29] H. W. X. L. a. B. S. Xin Huang, “One-step, size-controlled synthesis of gold nanoparticles at room temperature using plant tannin,” Green Chemistry, pp. 395-399, 2010.
51. [30] 王志峰, “應用非線性 D-EWMA 控制器,＂ 國立交通大學,2007.
52. [31] 吳則學, “藉由置入奈米銀結構以提升超薄摻鋁氧化鋅膜層光電特性之研究,＂ 義守大學, 2004.
53. [32] Ju-Ho Kim, C.J. Kang, Yong-Sang Kim, “Development of a microfabricated disposable,” Biosensors and Bioelectronics January, 2005.
54. [33] 黃忠仁, “ITO 薄膜之蝕刻速率與表面粗糙度於不同蝕刻液及溫度下之探討,＂ 華梵大學,南台科技大學, 2005.
55. [34] 黃書瑋, “以 SF6/O2/Ar 感應偶合電漿蝕刻碳化矽材料,＂ 中華 大 學, 2007.
56. [35] J. D. Verhoeven, Fundamentals of physical metallurgy, 美國: Wiley, 1975, 2007.
57. [36] Xin Huang, Hao Wu, Xuepin Liao and Bi Shi, “One-step, size-controlled synthesis of gold nanoparticles at room temperature using plant tannin,” pp. 395-399, 2010.
58. [37] E. H. Putley, The Hall effect and semi-conductor physics, New York: Dover Publications, 1968.
59. [38] 羅聖全, “研發奈米科技的基本工具之一電子顯微鏡介紹 – SEM,＂
60. [39] 林智仁, “場發射穿透式電子顯微鏡簡介,＂ 工業材料雜誌,編號 201, pp. 90-98, 2003.
61. [40] 羅聖全, “研發奈米科技的基本工具之一 電子顯微鏡介紹 – TEM,＂ 材料世界網.
62. [41] 陳建淼, “科學Online – 科技部高瞻自然科學教學資源平台,＂
63. [42] 張育唐, “科學Online – 科技部高瞻自然科學教學資源平台, 77
64. [43] 林麗娟, “X 光繞射原理及應用,＂ 工業材料, 編號 86, pp.100-109.
65. [44] 張原逢, “氮化鎵發光二極體濕式蝕刻之技術,＂ 逢甲大學, 2000.
66. [45] 李承臻, “掃描式電子顯微鏡,＂
67. [46] G. Haacke, “New figure of merit for transparent conductors,” Journal of Applied Physics, vol. 47, pp. 4086-4089, 1976.