熱氧化退火法製備氧化銅半導體奈米線及其性質之研究; Synthesis, characterization, and properties of CuO nanowires by thermal oxidation annealing

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题名:	熱氧化退火法製備氧化銅半導體奈米線及其性質之研究;Synthesis, characterization, and properties of CuO nanowires by thermal oxidation annealing
作者:	陳銘鋒;Ming-feng Chen
贡献者:	化學工程與材料工程研究所
关键词:	氧化銅;奈米線;熱氧化退火法;CuO;cupric oxide;nanowire;thermal oxidation annealing
日期:	2009-07-22
上传时间:	2009-09-21 12:31:24 (UTC+8)
出版者:	國立中央大學圖書館
摘要:	本研究中結合電鍍銅製程與熱氧化退火法成功在（001）矽基材上製備出大面積氧化銅奈米線陣列。並且針對氧化銅奈米線的晶體結構、成長動力學、光學能隙、電性以及表面潤濕行為做進一步的研究。由經熱氧化退火後之電鍍銅膜試片，可發現大面積且準直的奈米線生成於矽晶基材上。以TEM、SAED及HRTEM鑑定分析所生成之奈米線，經鑑定可發現所有的奈米線皆為單晶且具單斜之晶體結構，且其並不具固定之成長方向。利用EDS針對奈米線作元素分析後可證實所製備之奈米線為純氧化銅奈米線。為進一步探討以熱氧化退火反應之反應動力學，本實驗設計於不同退火溫度及時間下進行氧化銅奈米線之生成反應。經一系列系統性的實驗後發現，氧化銅奈米線長度與退火時間呈拋物線之關係，此結果顯示氧化銅奈米線生成為一擴散控制的反應機制，且經測量氧化銅奈米線於不同溫度下之生成速率，並藉由阿瑞尼士方程式可推導得氧化銅奈米線生成反應之活化能為174.2 kJ/mol。在本研究中亦提出氧化銅奈米線的可能生成機制是由於氧化層之應力釋放結合銅原子在奈米線中經缺陷擴散所共同作用下之結果。以PL光譜測量分析後顯示，本實驗以熱氧化退火法所製備之氧化銅奈米線能隙約為 1.79 eV。此外，由氧化銅奈米線電性量測結果發現溫度對氧化銅電性表現之影響十分顯著，且隨著溫度升高而電阻下降的趨勢，符合一般半導體材料之特性。而針對氧化銅奈米線試片表面性質做水滴接觸角量測實驗，發現其呈現異常變化現象。對剛製備完成之氧化銅奈米線試片其會隨著時間由親水性漸漸轉變為疏水性，且經水潤濕過後的氧化銅奈米線試片，其與水滴之接觸角會顯著提高。 We report here the study of synthesis and characterization of large-area vertically-aligned CuO nanowires by direct air oxidation of electrodeposited Cu film onto silicon substrate. The crystal structures, formation kinetics, band-gap energy, electrical property, and surface wetting behaviors of the CuO nanowires produced have been investigated. After thermal oxidation of the electrodeposited Cu films on Si simples, high-density vertically-aligned nanowires were found to form on the surface of the oxidized samples. From TEM, SAED, and HRTEM analyses, all the nanowires synthesized were single crystalline with a monoclinic structure and their axial orientations were random. The quantitative EDS analysis demonstrated that those nanowires produced were CuO nanowires. By measuring the length of CuO nanowires with different annealing temperature, the length of CuO nanowires were found to increase parabolically with time. The result clearly indicates that the growth of the CuO nanowires is diffusion-controlled. The activation energy for the formation of CuO nanowires was readily derived from an Arrhenius plot to be about 174.2 kJ/mol. The possible mechanisms for the growth of CuO nanowires are discussed in the context of the stress relaxation from the oxidation layer and the Cu diffusion diffusing along the defects in nanowires. From the photoluminescense measurements, the band-gap energy of synthesized CuO nanowires was found to be about 1.79 eV. The resistance of CuO nanowires was measured to decrease with increasing temperature, which showed the characteristic behavior of semiconducting material. In addition, the surface-wetting properties of the CuO nanowires produced were evaluated by water contact angle measurements. The abnormal changes of the wetting behaviors from hydrophilic to hydrophobic were observed.
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