臺灣博碩士論文加值系統

我們將電化學方法製備出懸浮於水溶液中的金奈米圓柱粒子（Aunanorods），用sol-gel的方法將表面修飾上一層不均勻的鍍層，製備出核層奈米結構─（Aunanorod@SiO2）。由於sol-gel製備出的材料具有多孔洞性；及良好的透光性，且可當成導體外表包覆的絕緣體，更進一步可利用其特性增加金奈米圓柱的功能，成為多功能的奈米複合材料。同時研究當環境介質改變成時，光學現象上有何變化，進一步探討此種核層奈米結構對於金奈米圓柱本身之光誘導形狀轉換的影響，讓我們有機會了解光熔融現象的Matrix effect。
為了探討金奈米圓柱粒子的Matrix effect，所以必須達到單顆金奈米圓柱粒子鍍層SiO2，而非多顆粒子被sol-gel產物包覆，我們利用MPTMS(3-mercaptopropyltrimethoxy silane)當作轉接層，利用TEOS（Tetraethoxysilan）經Sol-gel反應過程後，控制PH值等種種條件，可達到最佳化的不均勻鍍層結果。之後再藉由控制sol-gel反應時間來合成厚度不同的不均勻鍍層─短軸鍍層厚﹔長軸鍍層薄，並且利用離心濃縮方式對作Aunanorod@SiO2純化處理。
而在形狀轉換及探討Matrix effect的實驗得知：當金奈米圓柱粒子經sol-gel反應，鍍上短軸鍍層厚﹔長軸鍍層薄的不均勻鍍層後，在吸收雷射能量後，相較於無鍍層或均勻鍍層的金奈米圓柱粒子而言，會產生高比率的「2-sphere@SiO2」甚至發現前所未有的「3-sphere@SiO2」的產物，整合早期實驗室的實驗結果與推論，推測此高比率的光分解（Photo dissociation）產物，是因為此奈米核層結構物的殼層（Shell）也就是我們所謂的Matrix的厚度不均造成不均勻的散熱，而影響其光熔融過程，產生高比率的光分解（Photo dissociation）產物。

We have fabricated colloidal Au nanorods via electrochemical method and they are embedded in a thin layer of silica with uneven thickness. The sol-gel process is responsible for the production of such core-shell nanostructure, AuNanorod@SiO2. The sol-gel material is not only porous and transparent but also electrically insulating. It can mimic the shielding layer of a bulk conducting wire. Furthermore, taking advantage of the characters of the sol-gel, we can further put additional function onto the Au nanorod particles via surface modification and turn them into multifunctioned nanocomposites. The context in this thesis is focused on the optical responses of the Au nanorods before, during and after the surface modification. Also, the second subject is to investigate how the shell structure influences the shape transitions of the core Au nanorod during a photoannealing process. It turns out to be a sensitive and perfect system to unravel the matrix effect of photoannealing for AuNanorod@SiO2 particles.
The core-shell nanostructures of AuNanorod@SiO2 with uneven thickness of silica are demonstrated successfully to comprise a couple of coating processes: the coating of an adapting layer of MPTMS (3-mercaptopropyltrimethoxy silane) and the coating of shell silica via a hydrolysis and condensation of siloxane precursor, TEOS. The single particle coating is then completed. Adjusting the pH value during the second process and the reaction time allow us not only carefully control the geometric shell structure but also the shell thickness. The cladding along the long axis is much thinner relative to the thickness along the short axis.
The studies on the matrix effect of photoannealing were conducted by irradiating the core-shell nanoparticles by either 532 nm or 1064 nm. The former excites the transverse surface plasmon of the embedded Au nanorod and the later cause the excitation of the longitudinal surface plasmon. The experimental results reveal that the excitation of long axis surface plasmon on the particles with 12 hrs coating time gives much higher yields of the fission products, 2-sphere@SiO2. In addition, the shape transformed products of the photoannealing process for particles with relatively high aspect ratios include a unique structure of 3-sphere@SiO2. We have summarized the results regarding the photo-induced shape transition of the Au nanorod@SiO2 and demonstrate clearly the effect of the heat release within the shell structures. The unequal heat release rates along the major and minor axis influence the particle shape transformation sensitively.

總目錄i
圖目錄iv
中文摘要x
英文摘要xi
第一章 緒論1
1.1 1.1奈米材料1
1.2金屬奈米材料的研究及應用2
1.3金屬奈米材料的合成及控制3
1.4金屬奈米材料之表面修飾──表面matrix的改變3
1.5金屬奈米材料之形狀轉換研究4
1.5.1金奈米圓柱之理論光譜4
1.5.2 金奈米圓柱之製備5
1.5.3 金奈米圓柱之合成結果與鑑定5
1.6研究內容動機及目標6
第二章用sol-gel 方法製備奈米核層結構複合材料─Aunanorod@SiO2…………………………………..…...15
2.1 前言15
2.2 實驗內容17
2.2.1 反應物及藥品18
2.2.2 鑑定、檢測樣品18
2.2.3 Sol-gel方法製備Aunanorod@SiO2的步驟18
2.3實驗結果與討論19
2.3.1濃縮處理及製備TEM樣品的方法19
2.3.2 PH值的選擇………...…………………………………..20
2.3.2反應時間之影響…………………………...………….…20
2.4結果與鑑定………….…………………………………..………20
2.5.Aunanorod@SiO2結構進一步的控制.20
2.5.1.結構控制的動機及方法.20
2.5.2.此不均勻的鍍層結構的重要性……………………….21
2.6進一步探討表面電漿共振的效應………………………21
第三章光融熔性質的Matrix Effect探討..42
3.1 前言42
3.1.1以界面活性劑穩定的金奈米圓柱的形狀轉換.42
3.1.2「ψ」型金奈米粒子的發現……..42
3.1.3金奈米圓柱包覆均勻厚度二氧化矽的形狀轉換43
3.1.4 照射532nm雷射光的形狀轉換43
3.1.5. 照射1064nm雷射光的形狀轉換44
3.2形變的機制的推測44
3.3實驗45
3.3.1實驗流程45
3.4結果討論46
3.4.1吸收1064nm低強度雷射光的變化46
3.4.2吸收1064nm高強度雷射光的變化47
3.5形變機制的整合探討48
3.5.1吸收1064nm低強度雷射光的形變探討48
3.5.2吸收1064nm高強度雷射光的形變探討48
第四章 結論與未來發展方向73
參考文獻………………………………………………...……………...74

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