低維金屬氧化物奈米結構之表面修飾在光電與光觸媒特性之研究

Studies on Low-dimensional Metal Oxide Nanostructures and Their Surface Modification on Optoelectric and Photocatalystic Properties

潘科穎(Ko-Ying Pan)

指導教授 ： 施漢章 ； 吳志明

國立清華大學/工學院/材料科學工程學系/博士(2014年)

摘要

本論文之研究中，包含：(一) 二氧化錫/氧化鋅核殼奈米線之合成與光電特性研究，和氧化銦及氧化銦錫奈米結構之合成與其光電特性應用之研究；(二) 二氧化矽/銀之奈米核殼顆粒之合成與其表面電漿子共振引發之光觸媒催化反應研究和奈米銀鑲嵌於二氧化矽複合結構之合成，及其退火與抗菌應用之研究。
在二氧化錫/氧化鋅之核殼奈米線之合成過程中，採用熱蒸鍍法在氧化鋁基板上製造出密集之二氧化錫奈米線。接著以原子層沉積法(atomic layer deposition, ALD)，奈米級氧化鋅附合於二氧化錫奈米線上，以獲得二氧化錫/氧化鋅核殼結構奈米線。材料分析可以確認其成分與結構，電性量測及紫外光分析，顯示本材料具備優秀的紫外光探測能力。
在氧化銦及氧化銦錫奈米結構合成，採用熱蒸鍍法在氧化矽基板上，不同的製程參數，分別沉積出氧化銦奈米棒、奈米塔及氧化銦錫奈米棒。材料分析證明其成分與結構，且更進一步做電性測試及陰極激發光譜儀(Catho- doluminescence, CL) 之分析，發現其可應用於有機發光二極體之元件。
在二氧化矽/銀之奈米核殼顆粒製作過程，先利用Stöber法製作出奈米級二氧化矽球，接著以種子成長法來合成二氧化矽/銀之奈米核殼結構粒子，並用葡萄糖當還原劑來控制奈米銀之幾何形狀。紫外光-可見光吸收光譜特性檢測發現：紅位移現象與特徵吸收峰的寬度皆與銀顆粒尺寸成正比的關係，且當粒子結構外型呈橢圓形時，雙特徵吸收峰的現象，隨即產生。這特殊的表面電漿子共振吸收的現象也與其後之光分解效率試驗相互呼應，共振程度愈高者其效率也愈佳。
在奈米級銀鑲嵌於二氧化矽複合型材料結構之合成、退火及抗菌應用之研究中，先採用溶凝膠法(Sol-gel method)製作二氧化矽奈米顆粒，其後再做退火熱處理。經由化學穩定性及抗菌測試對一系列的產物中，可證明其可有效用於抗菌相關之產業。

關鍵字

二氧化錫/氧化鋅核殼奈米線 ； 氧化銦及氧化銦錫奈米結構 ； 氧化矽/銀之奈米核殼顆粒 ； 表面電漿子 ； 光觸媒 ； 奈米銀鑲嵌於二氧化矽複合結構 ； 退火 ； 抗菌 ； 陰極激發光譜儀

並列摘要

There are two major parts in this thesis, including Part I: the fabrications, materials characteristics and optoelectronic applications of nanostructures of core-shell SnO2-ZnO, tin-doped indium oxide, and Part II: the syntheses, materials features and optoelectronic applications of nanoparticles of core-shelled silica-silver and silver-embedded aluminum/silica.
In the Part I, as for core-shell SnO2-ZnO nanowires, in advance, tin dioxide nanowires were synthesized by thermal evaporation. Then, depositions of ZnO nanolayer on SnO2 nanowires have been successfully synthesized by atomic layer deposition (ALD). These results demonstrated that the SnO2-ZnO core-shell nanowires have potential application as UV photodetectors with high photon-sensing properties.
In terms of nanostructures of tin-doped indium oxide, indium oxide (In2O3) nanorods, nanotowers and tin-doped (Sn:In=1:100) indium oxide (ITO) nanorods have been successfully fabricated by thermal evaporation, respectively. Judging from cathodeluminescence (CL) spectra of these three nanoproducts, it is clear that tin-doped (Sn:In=1:100) indium oxide (ITO) nanorods cause a blue shift. No doubt that ITO nanorods obtains the most effective performance among these three nanoproducts, and this also means doping elements in original nanomaterials would be the best way to enhance physical properties. Additionally, this study would be beneficial to the applications of In2O3 nanorods, nanotowers and ITO nanorods in optoelectronic nanodevices, especially in organic light-emitting diode (OLED).
In the Part II, as for core-shelled silica-silver nanoparticles, abundant core-shelled silica-silver nanospheres with uniform diameter and morphology were successfully synthesized by Stöber and seed-mediated method, in sequence. Moreover, by the different additions of glucose as the reducing agent, the silver nanoparticles were deposited on silica spheres by redox reaction, and the dimensions of samples were well controlled. The surface plasmon resonance absorption band shifted toward infra-red region and became broader gradually during the dimensions of silver nanoparticles were increased in the growth range. Meanwhile, this intriguing result shows that two absorption characteristics peaks are observed in the spectra while the morphologies of nanoparticles are becoming oval-shaped. The amazing data imply that using core-shelled silica-silver nanospheres efficiently enhances the degradation of the organic pollutants under solar energy, which means the core-shelled silica-silver nanospheres is not only a cost-effective route but an energy-saving way to our planet.
In terms of silver-embedded aluminum/silica nanoparticles, in order to improve the time-consumption issue of the above method, substantial silver-embedded aluminum/silica nanospheres with uniform diameter and morphology were successfully synthesized by a modified sol-gel technique, a one-spot method. The chemical durable examinations and antibacterial tests of each sample were also carried out for the confirmation of usages in practical. As a result of above analyses, the silver-embedded aluminum/silica nanospheres are eligible for fabricating antibacterial utensils.

並列關鍵字

core-shell SnO2-ZnO nanowire ； Tin-doped indium oxide nanostructure ； core-shelled silica-silver nanoparticle ； surface plasmon resonance ； Photocatalyst ； Silver-embedded aluminum/silica nanoparticles ； Annealing ； Antibacterial ； Cathodeluminescence

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