金奈米棒(gold nanorod，AuNR)以二氧化矽包覆所組成之奈米粒子具有高度熱穩定性及光熱轉換效率，且其中二氧化矽殼層可提升生物相容性及提供優異的表面修飾潛力而被廣泛應用於光熱催化、光熱治療及藥物投遞等領域。吾人合成三種不同孔隙率之二氧化矽殼層修飾的金奈米棒，使用時間解析傅立葉轉換光譜儀擷取樣品受脈衝寬度7 ns之1064 nm雷射激發後於微秒時域的紅外放光光譜。樣品之熱輻射訊號波形包含矽氧橋鍵(Si-O-Si)聲子模(1000–1250 cm–1)與水分子彎曲振動模(1600–1650 cm–1)貢獻，推測金奈米棒受光激發後產生之熱能傳遞至二氧化矽殼層後，二氧化矽及其孔洞吸附水分子可受激發躍遷至較高振動能階，並以振動輻射緩解途徑將能量釋放。此外，樣品放光峰相較於二氧化矽吸收峰於 > 1250 cm–1有些微增寬現象，推測此訊號包含黑體輻射之貢獻。積分1000–1250 cm–1及1500–1750 cm–1放光強度之時間側寫皆顯示隨樣品孔隙率提高其放光訊號衰減速率較快。吾人皆以雙指數函數擬合兩波數區間的衰減曲線，得以分析Si-O-Si聲子及水分子彎曲振動能量之緩解動力學過程。結果顯示二氧化矽聲子緩解速率(k_SiO"2" )與水分子彎曲振動模緩解速率(k_(H"2" O))皆與樣品之孔隙率相依，且兩者皆包含輻射緩解(k_r)與非輻射緩解(k_nr)能量釋放途徑的貢獻。而穿透式顯微影像結果顯示僅有孔隙率最低之樣品受雷射激發後其二氧化矽殼層及金奈米棒核產生形貌變化，吾人推測係因其熱傳導效率最差，使奈米粒子因侷域高溫而熱致變形。吾人期望本論文探討二氧化矽與金奈米棒組成之核殼奈米粒子的光熱緩解過程及熱致形貌變化的研究成果，能協助了解金屬奈米粒子受光激發後與其周遭環境的能量傳遞過程。

Gold nanorods (AuNRs) manifested efficient conversion of light to heat. The SiO2 shell coating can further improve the thermal stability and the biocompatibility. The porous SiO2 shell also serves as a platform for chemical modification to advance the functionality of nanoparticles. All of these advantages enable AuNR@SiO2 to be widely utilized in miscellaneous photothermal studies. In this work, AuNR@SiO2 with different shell porosities (AuNR@SiO2_Y, Y = 711, 539 and 468, denoted the surface area in a unit of SiO2 shell (m2 g–1)) were synthesized. The transient infrared emissions of AuNR@SiO2_Y upon pulsed excitation of their longitudinal plasmonic bands were collected with a time-resolved Fourier-transform spectrometer. The infrared emission contours included the phonon mode of Si-O-Si bridge (1000–1250 cm–1) and the bending mode of adsorbed molecular water (1600–1650 cm–1) within the SiO2 pore surface. These observations revealed that SiO2 and water could be heated up and populated to their vibrationally excited states via the photothermal energy of AuNRs, partially followed by the thermalization through the radiative process. On top of that, the broadening emission contours > 1250 cm–1 comparing with the infrared absorption spectra of AuNR@SiO2_Y could be attributed to the blackbody radiation. The temporal profiles of the emission at 1000–1250 cm–1 and 1500–1750 cm–1 were characterized with the relaxation kinetics of Si-O-Si phonon mode and bending mode of adsorbed water, respectively. The decaying parts of these two modes were accelerated as the porosity of SiO2 increased. Upon bi-exponential fitting, the relaxation processes of both modes include intrinsic spontaneous emission and non-radiative process. The TEM images of AuNR@SiO2_468 after laser irradiation depicted that nanoparticles manifested a morphological alteration, suggesting that poor heat transfer might lead to local heating, which causes annealing. Thus, the heat transfer dynamics and reshaping phenomena of AuNR@SiO2 are expected to be applied in photothermal researches.

第一章 緒論 1
1.1 前言 1
1.2 金屬奈米粒子光致侷域加熱的應用 1
1.2.1 生醫領域之光熱應用 1
1.2.2 化學催化領域之光熱應用 2
1.3 光熱效應中之聲子–聲子耦合過程與環境介質的關係 3
1.3.1 介面熱傳導係數 3
1.3.2 環境介質之熱傳導係數 4
1.4 二氧化矽核殼奈米粒子光熱緩解過程分析 5
1.5 研究動機 6
參考文獻 14
第二章 金屬奈米粒子之光熱性質及二氧化矽之熱傳導特性 19
2.1 侷域性表面電漿共振 19
2.1.1 米氏理論 19
2.1.2 甘斯理論 22
2.2 光熱效應 23
2.2.1 光熱效應過程 23
2.2.2 時間解析法偵測光熱現象 24
2.2.3 偵測光熱效應造成周遭環境介質之溫度變化 26
2.3 二氧化矽之熱傳導特性 27
參考文獻 44
第三章 儀器原理、樣品製備、實驗系統架設與儀器參數設定 51
3.1 紫外–可見–近紅外光靜態吸收光譜 51
3.2 電子顯微鏡 52
3.2.1 穿透式電子顯微鏡 53
3.2.2 掃描式電子顯微鏡 53
3.3 氮氣等溫吸附/脫附 54
3.3.1 氣體吸脫附曲線 54
3.3.2 氣體吸脫附曲線數據分析 55
3.4 傅立葉轉換紅外光譜儀 57
3.4.1 麥克森干涉儀 57
3.4.2 單色光與多色光干涉 58
3.4.3 傅立葉轉換 59
3.4.4 截斷函數與削足函數 59
3.4.5 相位誤差與相位校正 61
3.4.6 連續掃描模式 62
3.5 步進式掃描時間解析紅外放光光譜法 62
3.5.1 工作原理 62
3.5.2 跳點取樣 63
3.5.3 放光光譜數據擷取原理 64
3.6 實驗樣品製備 64
3.6.1 金奈米棒合成 64
3.6.2 修飾不同孔隙率之二氧化矽殼層於金奈米棒表面 65
3.6.3 移除二氧化矽包覆之金奈米棒中的介面活性劑 66
3.6.4 樣品薄膜製備 67
3.6.5 實驗樣品 68
3.7 實驗系統架設 68
3.7.1 雷射激發系統 68
3.7.2 樣品槽 68
3.7.3 步進式掃描傅立葉轉換紅外光譜儀 68
3.7.4 數據擷取系統 69
3.7.5 黑體輻射偵測系統 69
3.8 儀器參數設定 70
3.8.1 吸收光譜儀 70
3.8.2 掃描式電子顯微鏡 70
3.8.3 穿透式電子顯微鏡 70
3.8.4 連續掃描式傅立葉轉換紅外光譜儀 70
3.8.5 步進式掃描傅立葉轉換紅外光譜儀 71
參考文獻 94
第四章 實驗結果與討論 97
4.1 樣品之定性分析 97
4.1.1 靜態可見–近紅外消光光譜 97
4.1.2 氮氣等溫吸附/脫附量測 98
4.1.3 電子顯微影像 99
4.1.4 以能量散射X射線譜求樣品孔隙率 100
4.1.5 靜態紅外光吸收光譜 101
4.1.5.1 樣品吸收峰指認 101
4.1.5.2 定量二氧化矽孔洞中之物理吸附水分子 101
4.1.5.3 不同抽真空時間對二氧化矽孔洞吸附水分子含量之影響 102
4.2 樣品受雷射激發後之輻射緩解過程 102
4.2.1 時間解析紅外放光光譜之再現性 102
4.2.2 瞬態紅外放光峰指認 103
4.2.3 紅外放光時間側寫分析 104
參考文獻 132
第五章 結論 137

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第二章
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