臺灣博碩士論文加值系統

微拉曼光譜學是一項檢驗單壁奈米碳管性質快速且不具破壞性的檢測工具。特別是共振拉曼光譜學更是應用在少量或是單根的單壁奈米碳管量測上的一項檢測利器。本論文中主要就是針對單根懸空的單壁奈米碳管進行由常溫到700 K之間,其拉曼訊號隨著溫度升高所產生的變化的研究。從實驗中，我們可以清楚的發現，當溫度增高時，單壁奈米碳管的拉曼特徵譜線會隨之而有往較低頻部分位移的情形發生。因為本論文主要就是注重在溫度變化上的分析，所以為了能夠較精準的得到試片表面的溫度，我們利用矽的單晶拉曼訊號來進行試片表面的溫度校準。溫度升高時，G+ band的頻率往低頻部份位移的原因主要來自於在昇溫的過程中，碳-碳鍵伸長導致鍵強的減弱，使得碳原子的振動頻率下降。溫度係數在此被我們用來作為估計各個不同的單壁奈米碳管振動模式的拉曼頻率位移量。我們發現不同結構(chirality)的單壁奈米碳管在溫度增加時，會具有不同的溫度係數。碳管中存在有許多不同的振動模式，而我們所觀察到的拉曼訊號來自於所有模式的加成結果。單壁奈米碳管的起始力常數、單位晶格大小、管徑以及捲曲時的角度(chiral angle)皆是影響溫度係數的因素。

In this study, resonance Raman spectroscopy (RRS) is employed to probe the structural information of CVD-synthesized single-walled carbon nanotubes (SWNTs) in ambient environment at various temperatures ranged from 300 K to 700 K. SWNTs are fabricated crossing as-formed deep trench on SiO2/Si to avoid the interferences from surrounding media such as the substrates. Furthermore, the enhanced RRS from suspended SWNTs (su-SWNTs) also helps to observe the slight changes of principal peaks as the temperature increased. We specially use the well-established Si Raman thermology to monitor and determine the accurate surface temperature of the measured su-SWNTs. The frequency of G+ peak is found downward shifted with the increase of temperatures due to the softening of C-C bonding strengths, where the changes are reversible during different temperature cycles. Temperature coefficients of the characteristics peaks are estimated respectively. The force constant of C-C bond is used to explain why the temperature coefficients of different chiralities are different. The initial force constant, the chiral angle, and the tube diameter all might be the causes of the different temperature coefficients of the individual suspended-SWNTs. However, there are too many phonon modes in various chiralities, so the temperature-dependent Raman feature is affected by other factors. The Raman feature would not be influenced by one factor only.

Contents
Abstract.............................................Ⅰ
摘要.................................................Ⅱ
誌謝.................................................Ⅲ
Content............................................ⅤⅡ
List of Figures....................................ⅠⅩ
List of Tables.....................................ⅩⅢ

Chapter 1 Introduction...............................1

Chapter 2 Basic property of carbon nanotubes.........5
2.1 Geometric and electronic structure of single-walled carbon nanotube......................................5
2.2 Raman spectroscopy of single-walled carbon nanotube.............................................9
2.2.1 Raman scattering.............................. 9
2.2.2 Raman characteristic modes of SWNT............10
2.2.2.1 Radial Breathing Mode (RBM).................10
2.2.2.2 G-band......................................11

Chapter 3 Motivation................................14

Chapter 4 Literature review.........................15
4.1 Chirality assignment............................15
4.2 Temperature-dependent Raman feature of SWNTs....17

Chapter 5 Methodology...............................21
5.1 Sample preparation..............................21
5.2 Raman spectrum of the isolated suspended SWNT measurement.........................................21
5.3 The RBM and the (n,m) assignment................24

Chapter 6 Results and discussion....................27
6.1 Introduction....................................27
6.2 Characterization................................31
6.3 Temperature-dependent Raman feature.............33
6.4 Discussion......................................46

Chapter 7 Conclusion................................54

Chapter 8 Outlook and perspective...................55

Appendix A Calculated allowed transition energies of metallic and semiconducting SWNTs...................57

Appendix B Empirical-calibrated Kataura plot........59

Appendix C Experimental results.....................62

Appendix D Two atoms force constant model...........70

Reference...........................................71

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