電鍍法製備準直排列ZnO; 奈米結構陣列及其特性之研究 Fabrication of large-area vertically aligned ZnO nanostructure arrays by electrodeposition and their properties.

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Title:	電鍍法製備準直排列ZnO;奈米結構陣列及其特性之研究 Fabrication of large-area vertically aligned ZnO nanostructure arrays by electrodeposition and their properties.
Authors:	葉秉昀;Ping-Yun Yeh
Contributors:	化學工程與材料工程研究所
Keywords:	大面積;奈米結構;氧化鋅;電鍍法;Zinc Oxide;Electrodeposition;nanostructure;large-area
Date:	2010-07-28
Issue Date:	2010-12-08 13:37:22 (UTC+8)
Publisher:	國立中央大學
Abstract:	本研究首先利用射頻磁控濺鍍系統沉積ZnO:Al透明導電薄膜作為後續電鍍沉積ZnO 奈米柱陣列之導電基材，並對此ZnO:Al導電薄膜經真空熱處理前後之晶體結構、表面形貌、顯微結構與光、電特性等方面進行探討，接著針對不同電鍍沉積ZnO 奈米柱陣列之控制參數，進行有系統的討論分析，找出大面積ZnO 奈米柱陣列之製備最佳製程參數，研究中並首度成功結合奈米球微影技術，在ZnO:Al透明導電薄膜的表面製備出具大面積碗形-蜂巢狀規則有序之ZnO 雙奈米結構。在導電基材之ZnO:Al薄膜方面，由TEM橫截面影像可發現經真空退火熱處理前後的ZnO:Al 薄膜為多晶柱狀結構，擇優成長方向為[0001]。經真空退火後之在X光繞射圖中，其(0002)繞射峰所對應的角度位置，會明顯往高角度偏移，而在光學特性與電性上，除了光學吸收邊有藍位移現象，薄膜的電阻率也從初鍍膜之1.26 Ω-cm下降至3.0 x 10-3 Ω-cm，即結果可用Burstein–Moss現象解釋。以電鍍沉積製備ZnO 奈米柱陣列於ZnO:Al 薄膜上之研究方面，實驗結果顯示在0.5mM的 ZnCl2 濃度和80 ℃沉積溫度，為最佳化的ZnO 奈米柱陣列生成條件，在沉積5 min與10 min ZnO 奈米柱陣列於ZnO:Al 薄膜上，不僅擁有最高光穿透率約為90 %，比平整ZnO:Al薄膜要多3-4 %，此結構也會提升光散射現象，比平整ZnO:Al 薄膜0.64 %高出1-4 %。利用奈米球微影術製作不同大小之奈米球模板，並結合電化學沉積技術製備尺度大小可調變之碗形-蜂巢狀規則有序之ZnO 雙奈米結構，而此種具奈米雙結構之ZnO:Al透明導電薄膜，在400 nm-800 nm波長之光穿透率皆可>80%，其在波長550 nm霧度高達17.69 %，而可見光波長範圍平均霧度也有16.37 %，遠高於ZnO:Al薄膜與ZnO 奈米柱陣列結構薄膜的霧度約10 %。 In this study, ZnO:Al(AZO) transparent conducting oxide thin films were deposited on glass by a RF sputtering system to serve as the substrates for the electrodeposition of ZnO nanorods. The microstructue, surface morphology, and physical properties of the AZO thin films before and after annealing have been investigated. Large-area vertically aligned ZnO nanorod arrays were obtained under controlled electrodeposition conditions. Furthermore, bowl-like ZnO nanorod structures were successfully fabricated on AZO films by using nanosphere lithography combined with the electrodeposition technique. According to the XTEM examinations, it is clearly revealed that the AZO films were polycrystalline and exhibited a wurtzite structure with a strong preferred [0002] orientation. From XRD & UV-VIS analyses, the (0002) peak position was found to shift toward higher angle and the optical transmittance spectra showed blue shift of annealed AZO films and their resistivity decreased from 1.26 Ω-cm to 3.0 x 10-3 Ω-cm. These observed results can be explained by Burstein–Moss effect. In this work, the optimum electrodeposition conditions for the growth of ZnO nanorods were : 0.5 mM ZnCl2, 80 ℃, and 5–10 min. The formation of vertically aligned ZnO nanorod arrays was lead to enhance visible light transmittance and diffuse transmittances to 90 % and 2-5 % which is both higher than that of flat AZO thin films. The size and periodicity of bowl-like ZnO nanorodstructures can be controlled by turning the diameter of nanosphere and the electrodeposition conditions, In the optimum conditions, the transmittance of the ZnO nanorods sample was>80 % in the ranges of 400-800 nm. In addition, The HAZE of the bowl-like ZnO nanorods sample is 17.7 % at 550nm wavelength, and the average HAZE in the ranges of 400-800 nm is 16.4%. These exceed the ZnO nanorod samples(<10 %).
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