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作者(中文):葉柏成
作者(外文):Ye, Bo-Cheng
論文名稱(中文):利用飛秒瞬態吸收光譜技術研究奈米金棒以及包覆不同二氧化矽層厚度的奈米金棒熱釋解過程
論文名稱(外文):Ultrafast heat dissipation process of gold nanorods and gold nanorods coated different thickness silica core shell detected with femtosecond transient absorption spectroscopy
指導教授(中文):陳益佳
指導教授(外文):Chen, I-Chia
口試委員(中文):周佳駿
許良彥
口試委員(外文):Chou, Chia-Chun
Hsu, Liang-Yan
學位類別:碩士
校院名稱:國立清華大學
系所名稱:化學系
學號:107023527
出版年(民國):109
畢業學年度:108
語文別:中文
論文頁數:139
中文關鍵詞:奈米金棒超快熱釋解過程
外文關鍵詞:gold nanorodultrafast heat dissipation
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奈米金棒吸收光能後,會進行一連串的光熱轉換,因而產生高溫並可用於各種用途上。本研究中使用飛秒瞬態吸收光譜的技術偵測奈米金棒短時域的熱釋解過程,並提出一個合理的觀點以解釋整個實驗結果,本研究中使用3個自然指數衰退函數以及1個阻尼函數擬合偵測到的電漿共振譜帶瞬態動力曲線,分別指認為電子-聲子交互作用、聲子-聲子交互作用、熱傳導所需時間以及長軸端振盪的訊號。在奈米金棒熱釋解方面,我們所測得的電子-聲子交互作用衰減生命期約為4~5 ps,聲子-聲子交互作用衰減生命期約為200~300 ps,週期為75~110 ps,熱傳導至外圍環境的衰減生命期約為500~800 ps。我們觀察到較大顆的奈米金棒,其聲子-聲子交互作用、振盪週期以及熱傳導所需時間皆較長,電子-聲子交互作用時間則沒變化。在奈米金棒長短軸振盪部分,我們觀察到當奈米金棒AR越大時,會使得短軸振盪強度越小,最終看不到短軸振盪。我們使用2個阻尼函數加一個自然指數衰退函數進行擬合,分別指認為長軸振盪、短軸振盪以及熱傳導的訊號。我們擬合出長軸端振盪的阻尼常數為150~250 ps,對應的週期為75~110 ps,短軸端振盪的阻尼常數為40~60 ps,對應的短軸振盪週期為8~18 ps。我們觀察到長短軸振盪阻尼常數隨奈米金棒體積變小而有變小的趨勢,長短軸振盪週期則隨長短軸長度越小而有變小的趨勢,藉由所測得的振盪週期,我們可以估算奈米金棒楊氏係數以及其縱模聲速。為了探討環境對於奈米金棒熱釋解過程所造成的影響,我們使用了不同厚度的二氧化矽去包覆奈米金棒,以及移除CTAB去觀察其對於熱釋解過程的影響。對於未移除CTAB的樣品,我們測得電子-聲子交互作用衰減生命期為5~6 ps、聲子-聲子交互作用衰減生命期為140~190 ps、熱傳導衰減生命期為1 ns以上,振盪週期為80~90 ps;對於有移除CTAB的樣品,我們測得電子-聲子交互作用衰減生命期約為5 ps、聲子-聲子交互作用衰減生命期為140~160 ps、熱傳導衰減生命期為700~800 ps,振盪週期為80~90 ps。經由比較,我們發現電子-聲子交互作用生命期無明顯改變,聲子-聲子交互作用生命期則是奈米金棒最長,包覆SiO2的樣品則會明顯下降,熱傳導時間則是奈米金棒最短,其次為有移除CTAB的樣品,最後為未移除CTAB的樣品。奈米金棒,隨著激發能量上升,電子-聲子交互作用衰減生命期為2~5 ps、聲子-聲子交互作用衰減生命期為180~260 ps、熱傳導衰減生命期為300~800 ps,週期為92~98 ps;對於包覆SiO2的樣品,我們測得電子-聲子交互作用衰減生命期約為2~5 ps、聲子-聲子交互作用衰減生命期約為140~160 ps、熱傳導衰減生命期為1 ns以上,週期為80~90 ps;對於移除CTAB的樣品,我們測得電子-聲子交互作用衰減生命期約為2~5 ps、聲子-聲子交互作用衰減生命期為140~160 ps、熱傳導衰減生命期為570~700 ps,週期為80~90 ps。我們觀察到電子-聲子交互作用、熱傳導衰減生命期以及週期會隨激發能量越大而跟著變長,振盪強度也隨著激發能量越強而跟著變強,聲子-聲子交互作用衰減生命期在低能量時是隨著激發能量上升而上升,當激發能量高到一定強度後則會持平,說明這些物理量都是跟激發能量是有相關的。
After absorbing light energy, gold nanorods (AuNRs) would undergo a series of light-to-heat conversions. Therefore, AuNRs would generate high temperature and can be used in various application. In this study, we use transient absorption spectroscopy technology to detect the heat release process, and then propose a reasonable statement to explain experimental data. We use 3 exponential decay functions and 1 sine damping function to fit my experimental data. We assign these three exponential functions to electron-phonon interaction time(e-p interaction time), phonon-phonon interaction time (p-p interaction time), and heat conduction time (HC time). The damping function would be assigned to the oscillation of long axis in AuNRs. In AuNRs heat dissipation part, we measure the e-p interaction time is 4~5 ps, the p-p interaction time is 200~300 ps, the HC time is 500~800 ps, and the period is 75~110 ps. We find that p-p interaction time, HC time, and period would be longer in the bigger AuNRs. The e-p interaction time has no trend in different AuNRs sample. In AuNRs oscillation part, we find that the short oscillation intensity would become smaller as increasing aspect ratio of AuNRs. We use two sine damping functions and one exponential decay function to fit my experimental data. We assign these two damping functions as the oscillation of long axis and short axis in AuNRs. We assign the exponential function as HC part. We measure the damping constant of long axis is 150~300 ps, and its period is 75~110 ps. We measure the damping constant of short axis is 40~60 ps, and its period is 8~18 ps. We also observe that the damping constant and period would decrease, as AuNRs become smaller. By the oscillation periods obtained from experimental data, we can calculate the Young’s modulus and the longitudinal sound speed of AuNRs. In order to explore the emvironmental effect on the AuNRs thermal release process, we use AuNRs coated with different thickness SiO2 core shell, and remove the CTAB to explore the effect of CTAB on the thermal release process. For the sample without removed CTAB, we measure the e-p interaction time is 5~6 ps, p-p interaction time is 140~190 ps, HC time is above 1 ns, and the period is 80~90 ps. For the sample removed CTAB, we measure the e-p interaction time is about 5 ps, the p-p interaction time is 140~160 ps, the HC time is 700~800 ps, and the period is 80~90 ps. By comparison, we find that the e-p interaction time has no trend, and the p-p interaction time would decrease after AuNRs coated SiO2. The HC time is the shortest in AuNRs, followed by the sample removed CTAB, and finally the sample without removing CTAB. In the final part, we perform the power dependent experiment on the AuNRs, AuNRs coated SiO2 core shell sample, and the sample removed CTAB. For AuNRs, we measure the e-p interaction time is 2~5 ps, the p-p interaction time is 180~260 ps, the HC time is 300~800 ps, and the period is 92~98 ps. For the sample without removed CTAB, we measure the e-p interaction time is 2~5 ps, the p-p interaction time is 140~160 ps, the HC time is above 1 ns, and the period is 80~90 ps. For the sample removed CTAB, we measure the e-p interaction time is 2~5 ps, the p-p interaction time is 140~160 ps, the HC time is 570~700 ps, and the period is 80~90 ps. We find that e-p time, HC time, and the period would be longer as pump power increase. The oscillation intensity would be lager as pump power increase. The p-p interaction time would be longer as pump power increase at low pump power, and become almost the same at high pump power. Therefore, we can know these data are related to the excitation power.
圖目錄 X
表目錄 XVIII
縮寫表 XIX
第一章 序論 1
第二章 奈米金的物理基本性質介紹 6
2-1 奈米金棒的表面電漿共振光譜介紹 6
2-2 費米-狄拉克分佈(Fermi-Dirac distribution) 6
2-3 米氏理論(Mie theory)的簡單介紹 7
2-4 甘氏理論(Gans theory) 9
2-5 奈米金介電係數計算 10
2-6 奈米金棒熱釋解過程 12
2-6-1 表面電漿共振去相位化 13
2-6-2 電子-電子交互作用 13
2-6-3 電子-聲子交互作用 14
2-6-4 聲子-聲子交互作用力 15
2-6-5 熱傳導 16
2-7 研究動機與目的 18
第三章 實驗方法、儀器架設與樣品製備 26
3-1 靜態紫外可見吸收光譜 26
3-2 掃描式傅立葉紅外光譜儀(Scanning Fourier-Transform Infrared Spectroscopy) 26
3-3 熱場發射掃描式電子顯微鏡(Thermal type Field Emission Scanning Electron Microscope, FESEM) 26
3-4 高解析穿透式電子顯微鏡(High Resolution Transmission Electron Microscope, HRTEM) 27
3-5 調變雷射波長 27
3-6 飛秒雷射部分 28
3-6-1 超快雷射系統 28
3-6-2 光纖雷射(Fiber seed laser) 29
3-6-3 共振再生放大系統(Regenerative amplifier) 29
3-6-4 OPCPA front-end 30
3-6-5脈衝拉寬器(Stretcher) 30
3-6-6 OPCPA主體 31
3-7 瞬態吸收光譜法(Transient absorption spectroscopy) 31
3-7-1 瞬態吸收簡介 31
3-7-2 實驗儀器架設 32
3-7-3 瞬態吸收光譜數據處理 33
3-8 樣品介紹 34
3-8-1 實驗藥品 34
3-8-2 奈米金棒的合成步驟 34
3-8-3 奈米金棒包覆二氧化矽層的合成步驟 36
3-8-4 已包覆二氧化矽的奈米金棒移除CTAB步驟 36
3-9 瞬態吸收光譜實驗條件 37
3-9-1 光源 37
3-9-1-1 脈衝寬度的量測 37
3-9-1-2 激發脈衝波長的量測 38
3-9-1-3 激發脈衝強度 38
3-9-2 實驗樣品 39
第四章 實驗結果 46
4-1 樣品靜態吸收光譜/SEM/TEM光譜的鑑定 46
4-1-1 奈米金棒的靜態吸收光譜/SEM光譜 46
4-1-2 包覆不同二氧化矽厚度奈米金棒靜態吸收光譜/SEM/TEM光譜 46
4-1-3 包覆不同二氧化矽厚度奈米金棒去除CTAB的靜態吸收光譜/SEM/TEM光譜 47
4-1-4 實驗後樣品性質檢測 48
4-2 瞬態吸收光譜 49
4-2-1 數據擬合 49
4-2-2 不同大小/AR的奈米金棒瞬態吸收光譜 51
4-2-3 不同二氧化矽厚度的奈米金棒瞬態吸收光譜 52
4-2-4 激發能量相依性的瞬態吸收光譜 54
第五章 討論 117
5-1 不同奈米金棒樣品的生命期指認以及熱釋解機制的探討 117
5-1-1 奈米金棒吸收光能後達平衡時的溫度計算 117
5-1-2 不同奈米金棒樣品間的熱釋解過程的探討 118
5-1-2-1 奈米金棒熱釋解部分擬合參數的指認 118
5-1-2-2 奈米金棒熱釋解部分機制探討 118
5-1-3 不同奈米金棒樣品間的長短軸振盪部分探討 120
5-2 包覆不同二氧化矽厚度以及有無去CTAB對於整個熱釋解過程的探討 122
5-2-1 包覆不同二氧化矽層厚度對於奈米金棒熱釋解影響探討 122
5-2-2 包覆不同二氧化矽層厚度以及去完CTAB後對於奈米金棒熱釋解影響探討 124
5-3 激發能量對於不同樣品熱釋解速率的影響 125
5-3-1 激發能量對於奈米金棒熱釋解速率的影響 125
5-3-2激發能量對於AuNR@40-SiO2以及AuNR@40-SiO2-CTAB的熱釋解速率影響 126
第六章 結論 133
參考文獻 135

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