金屬奈米粒子由於其表面電漿效應，可被應用於製作具有特殊的光電效應的元件，因而在各領域中被廣泛地研究。隨著各種有趣的現象與應用被逐一發展出來，金屬奈米粒子的重要性與日俱增，成為各個潛在研究中不可或缺的元素。本論文係以應用金屬奈米粒子於表面增益拉曼散射為主題，研究表面增益拉曼散射的增益機制，及其與金屬奈米粒子表面電漿效應的關係。除此之外，本論文亦藉由觀測繞射光強度的變化，來研究金屬奈米粒子在退火過程中，邊界效應對金屬奈米粒子形狀的影響。因此，本論文的研究可分成二部分來說明：
第一，觀測結晶紫分子於二氧化矽披覆銀奈米粒子的表面，其表面增益拉曼訊號強度，隨二氧化矽層厚度的變化而改變的現象。本實驗係藉由在銀奈米粒子表面上，沉積上梯度厚度的二氧化矽，來研究此增益機制。值得注意的事是梯度二氧化矽層的功用。因在同一片銀奈米粒子樣品上，即可量測不同厚度的二氧化對銀奈米粒子的影響，不需更換銀奈米粒子的樣品，所以可增加實驗的準確性。此外，二氧化矽亦可做為表面保護層，保護銀奈米粒子的活性，使得銀奈米粒子可作為重覆使用的基板。
第二，本研究利用黃光製程製作銀奈米粒的光柵。藉由觀測金奈米粒子光柵的繞射光的強度變化，來研究金奈米粒子在光柵中的形狀效應。在金奈米粒子的SEM影像中，我們發現金奈米粒子的形狀呈現橢圓形狀，且其平均長軸以57.8度的角度，略微垂直於光柵方向。這個形狀效應除了造成金奈米粒子的表面電漿共振波長，隨著入射光的偏振方向變化而位移外, 亦使得光柵的繞射光呈現偏振依賴性。在這實驗中，我們將探討這個金奈米粒子光柵的繞射特性，來了解光柵中金奈米粒子的形狀，受到光柵條邊界效應的影響。

Metallic nanoparticles due to surface plasmon effects are used to fabricate devices with particular electro-optic properties, so that, they have been widely studied in many fields. With progressive developments of interesting phenomena and applications, metallic nanoparticles have become an important role in different kinds of the studies. One interesting application is the surface enhanced Raman scattering associated with metallic nanoparticles. It is worthy to investigate the relationship between the surface plasmon effects of metallic nanoparticles and the enhancement mechanism of the Raman scattering. Besides, the shape effects of metallic nanoparticles in an array are interesting for a combination with optical circuits. On the basis of these properties of metallic nanoparticles, two studies will be introduced in this dissertation:
First, the intensity of surface-enhanced Raman scattering (SERS) light of crystal violet (CV) molecules are probed as the molecules adsorbs on silver nanoparticles with SiO2 coating. We find that the intensity of the SERS light from CV molecules varies with the thickness of the SiO2 coating. Hence, this experiment investigates the enhancement mechanism of surface enhanced Raman scattering by modulating the thickness of the SiO2 coating. In addition, the SiO2 coating can work as a preventer to remain the activity of the silver nanoparticles. This makes the silver nanoparticles with SiO2 coating as a reusable substrate, which can provide a possibility to increase the precession of SERS measurements.
Second, a gold nanoparticle grating is fabricated by lithographic method. The shape effect of gold nanoparticles in the grating is investigated by probing the diffraction light intensity of the array. A variation of the diffraction light intensity of the grating is revealed as rotating the polarization of the probe light. And, the peak of the diffraction spectra shifts with the increasing of the polarization angle of the probe light. Under observation of the SEM, gold nanoparticles of an ellipsoid-like shape are shown and the major axis of gold nanoparticles are parallel a direction with an averaged angle of 57.8o respect to grating direction. We thus considerably thought that this the varying of the diffraction spectra are attributed to the shifts of localized surface plasmon resonance. In addition, the boundary effect on the shape of gold nanoparticles in the grating is explored.

論文審定書 I
誌謝 II
摘要 III
Abstract V
目錄 VII
圖 次 XI
第一章 緒論 1
1.1 前言 1
1.2 研究動機與目的 2
1.3 文章架構 3
第二章 文獻回顧 3
2.1 金屬奈米粒子的表面電漿共振 9
2.1.1 金屬奈米粒子的光學性質 10
2.1.2 金屬奈米粒子的幾何形狀效應 11
2.1.3 金屬奈米粒的環境折射率效應 14
2.2 金屬奈米粒子的製備 17
2.3 金屬奈米粒子於表面增益拉曼散射的應用與發展 28
第三章 基本理論 42
3.1 拉曼散射 42
3.1.1 拉曼散射簡史 43
3.1.2 拉曼散射理論與分子振盪能階 44
3.1.2.1 拉曼散射的古典理論 47
3.1.2.2 拉曼散射的能態 51
3.1.3拉曼散射光譜與紅外線光譜 56
3.2金屬奈米粒子的表面電漿 60
3.2.1 金屬奈米粒子的介電係數函數 61
3.2.2 金屬奈米粒子於穩定電場的電位及電場 70
3.2.3 金屬奈米粒子於時變電場的電位及電場 74
3.2.5 金屬奈米粒子的光吸收及散射 79
3.3 表面增益拉曼散射 81
3.3.1 電磁增益機制 82
3.3.2 化學增益機制 84
3.3.3 表面增益拉曼散射之增益因子 87
第四章 二氧化矽披覆電漿奈米粒子場增益拉曼散射 90
4.1 實驗方法 90
4.1.1樣品製備 90
4.1.2樣品的特性分析 94
4.1.3 實驗量測裝置 96
4.2實驗結果與討論 97
4.2.1表面增益拉曼散射光譜 97
4.2.2 二氧化矽層的調制機制 100
4.2.3 表面增益拉曼散射機制的探討 101
4.2.4 基板的重覆使用性 102
第五章 金奈米粒子的形狀效應及其光柵繞射的偏振相依性 105
5.1 實驗方法 105
5.1.1樣品製備 105
5.1.2樣品的特性分析 107
5.1.3 實驗量測裝置 109
5.2實驗結果與討論 110
5.2.1金奈米粒子光柵繞射光譜圖 110
5.2.2 金奈米粒子的表面電漿共振 112
5.3 Echelon光柵 113
第六章 總結 116
(a) 二氧化矽披覆電漿奈米粒子場增益拉曼散射 116
(b) 金奈米粒子的形狀效應及其光柵繞射的偏振相依性 117
附錄 118
附錄A米氏理論 (Mie’s theory) 118
附錄B光柵繞射理論(Raman-Nath diffraction) 124
參考文獻 128
著作: 138

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