本論文研究主題可分為兩部分，第一部份探討利用聚乙烯吡咯烷酮(PVP)作為保護劑所合成出之銀和金奈米粒子因加熱所造成的結構變化以及奈米粒子與一般常使用的銅、鎳電子金屬基板之間的反應。利用新竹國家同步輻射中心BL-17B1光束線升溫X光繞射儀分析，透過監測X光繞射圖譜中繞射峰變化進行討論。第二部分是利用相同保護劑合成雙金屬奈米粒子，以穿透式電子顯微鏡(TEM)及紫外光可見光吸收光譜儀(UV-vis)分析，探討結構及成份對其特性吸收峰之影響。
第一部份實驗結果顯示，隨著溫度上升，銀(9.6nm)、金(4.2nm)奈米粒子之繞射峰會由寬弱轉為尖銳，主要是由於粒子的粗大化與接合所造成。並且觀察到在金奈米粒子沉積於銅基板上之相轉變主要是由於金與銅具有負的混合焓所導致。奈米粒子沉積物與基板間交互作用會使繞射峰相低角度偏移，主要與熱膨脹及氧化物形成之溫度有關。相較於金奈米粒子，銀奈米粒子沉積物不會與銅及其氧化物形成介金屬化合物，主要是由於銀-銅系統中向分離的特徵所導致。
第二部份實驗結果顯示，以逐步還原法先還原銀再還原金所得之奈米粒子並非核殼結構,而是中空結構奈米粒子，主要的原因是銀原子與金離子之間產生了氧化還原取代反應,且根據推測之成長機制，反應初期先形成中空金殼，而後隨時間增加，原先因氧化還原反應形成之銀離子與剩餘金離子再度被還原劑還原沉積於粒子上，且因高溫擴散作用，最後所得為中空結構之合金型奈米粒子，此外為了達熱力學上的穩定狀態，中空結構之粒子隨反應時間增長趨向於實心結構。合金型奈米粒子其特性吸收峰隨著成份比例不同而有所偏移；中空結構之奈米粒子其特性吸收峰不僅隨著成份比例不同而偏移，亦受中空程度不同而有所偏移。

This thesis includes two parts: (1) Phase transformation of the PVP protected metallic nanoparticles upon heating in air via in situ synchrotron radiation X-ray diffraction. (2) The optical properties of nanoparticles(NPs) with different structures and compositions
For the first part, through monitoring the evolution of the X-ray diffraction peaks, the phase transformation of PVP-protected Ag and Au nanoparticle deposits (NPDs) on electronic substrates of Cu and Ni upon heating in air was investigated via in situ synchrotron radiation X-ray diffraction. With an increasing temperature, the broad diffraction peak of nano-sized Ag and Au particles with the original average diameters of 4.2 nm and 9.6 nm respectively became sharp because of particle coarsening and coalescence. Complex phase transitions among Au, Cu, AuCu3 and CuOx were observed, mainly due to the negative enthalpy of mixing between Au and Cu. The interactions between NPDs and the substrates affected the shift of diffraction peaks to lower angles caused by thermal expansion and also the temperature for the oxide formation. Compared to Au, Ag NPDs did not form intermetallic compounds with Cu and the formation of copper oxides can also be retarded mainly due to the phase separation feature of the Ag-Cu system.
For the second part, the structures and compositions of Ag-Au bimetallic nanoparticles are investigated by transmission electron microscopy (TEM) and EDS. The experimental results show that ring-like alloy NPs were formed by using successive reduction method. The optical properties of the NPs were measured by UV-vis spectroscopy. It was found that the absorption spectra strongly related to the compositions, structures, and like of the bimetallic NPs. Combined with the optical properties, the formation mechanism of ring-like alloy NPs were proposed in this study.

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