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研究生：	王文靖 Wang, Wen-Jing
論文名稱：	銀顆粒於氮化鎵奈米線在表面增顯拉曼散射之研究 Study of surface-enhanced Raman scattering from silver-coated GaN nanowires
指導教授：	陳引幹 Chen, In-Gann
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學及工程學系 Department of Materials Science and Engineering
論文出版年：	2010
畢業學年度：	98
語文別：	中文
論文頁數：	112
中文關鍵詞：	表面增顯拉曼散射、氮化鎵奈米線
外文關鍵詞：	surface-enhenced Raman scattering (SERS), GaN nanowires
相關次數：	點閱：65 下載：0
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本實驗利用化學氣相沈積反應，以鉑做為催化劑成長氮化鎵奈米線於矽基板上。並分別比較三種不同製程方法：紅外線爐加熱法、濺鍍法及電子束蒸鍍法，將銀顆粒附著於氮化鎵奈米線表面，製備具表面增顯拉曼散射效果(Surface-Enhanced Raman Scattering, SERS)之基板，檢測吸附在銀顆粒表面的分子探針Rhodamine 6G (R6G)濃度。
比較三種銀顆粒附著方法的SERS增顯效果，紅外線加熱法所製備的SERS基板，增顯因子僅5×103，R6G檢測濃度可達10-3M；濺鍍法所製備的SERS基板，增顯因子為9×104，R6G檢測濃度可達10-6M；電子束蒸鍍法所製備的SERS基板，其增顯因子為4×105 ，R6G檢測濃度可達10-12M。
在使用電子束蒸鍍法附著銀顆粒於氮化鎵奈米線的實驗中，隨著蒸鍍銀膜厚的增加，氮化鎵奈米線上的銀顆粒會由獨立圓球形奈米銀顆粒逐漸團聚而形成不規則島狀。隨著銀蒸鍍膜厚由10Å增加至1800Å，銀覆蓋率由20%增加至30%，但獨立圓球形奈米銀顆粒的覆蓋率由15%降低至2%。
將上述試片滴上10-3 M的R6G溶液並進行表面增顯拉曼量測，其結果顯示，隨著銀蒸鍍膜厚由10Å增加至1800Å，SERS強度由20000降低至8000。此結果顯示獨立圓球形的奈米銀顆粒有助於增強SERS的增顯效果。
電子束蒸鍍法為三種方法中最能有效產生獨立圓球形銀顆粒於奈米線表面的方法，使其SERS增顯效果最為顯著。
以電子束蒸鍍法所製備的活性基板檢測不同R6G溶液濃度，結果顯示，在 10-3 到 10-12M 濃度之間，表面增顯拉曼訊號的強度變化有隨 R6G 濃度變化呈現近似線性的變化趨勢。此趨勢說明，有銀顆粒附著的氮化鎵奈米線，具有作為表面增顯拉曼活性基板的應用潛力。

In this study, Surface Enhanced Raman Scattering (SERS) phenomena of silver-coated GaN nanowires has been investigated. SERS substrates were fabricated by deposition of Ag nanoparticles on GaN nanowires. Three different deposition strategies has been carried out: IR furnace heating treatment, sputtering method and electron beam evaporation method. Characterization of Raman scattering has been investigated in the presence of Rhodamine 6G (R6G).
Comparison between these three different methods shows that the enhancement factor was 5×103, 9×104, 4×105 for IR furnace heating treatment, sputtering and e-beam method, respectively. The lowest detectable R6G concentration in SERS spectra was 10-3M, 10-6M and 10-12M for IR furnace heating treatment, sputtering and E-beam evaporation method, respectively.
Using E-beam method, which increase the Ag deposition thickness from 10Å to 1800Å, induce Ag nanoparticles agglomeration to form non-uniform islands.
Increasing the Ag deposition thickness from 10Å to 1800Å leads to an increase of the total Ag coverage from 20% to 30%. However, the Ag nanoparticles coverage was decreased from 15% to 2%. SERS measurement of 10-3M R6G showed that the SERS intensity was decreased from 20,000 to 8,000 when Ag deposition thickness was increased from 10Å to 1800Å. These results indicate that nanoparticles are suitable for the SERS performance.
Substrate that we fabricated by the e-beam method shows linear relationship between R6G concentration and SERS intensity. In conclusion, we believe that Ag nanoparticles adsorbed on GaN nanowires can be a potential SERS active substrate.

目錄
摘要................................................................................................................	Ⅰ
Abstract..........................................................................................................	Ⅱ
目錄................................................................................................................	Ⅲ
表目錄............................................................................................................	Ⅴ
圖目錄............................................................................................................	Ⅵ
第一章 緒論..................................................................................................	1
1.1 前言.................................................................................................	1
1.2 奈米材料的基本物理效應.............................................................	3
1.3 研究動機.........................................................................................	4
第二章 理論基礎..........................................................................................	7
2.1 氮化鎵奈米線(GaN Nano-Wire)慨述............................................	7
2.1.1 氮化鎵材料……..................................................................	7
2.1.2 奈米線成長原理..................................................................	8
2.1.3 VLS(Vapor-Liquid-Solid)法.................................................	8
2.2 表面增顯拉曼散射.........................................................................	10
2.2.1. 拉曼散射原理.....................................................................	10
2.2.2. 表面增顯拉曼散射............................................................	12
2.3 表面增顯拉曼光譜之影響因子.....................................................	14
2.3.1 表面粗糙度..........................................................................	14
2.3.2 表面高低起伏及熱區(hot-spot)..........................................	16
2.3.3 分子探針(molecular probe)進行SERS檢測......................	16
2.4 表面增顯拉曼光譜機制.................................................................	18
        2.4.1 電磁增顯機制(Electro-magnetic Enhancement
             Mechanism, EM)..................................................................	
18
        2.4.2 化學增顯機制(Chemical Enhancement Mechanism,  
             CHEM).................................................................................	
23
第三章 實驗流程與分析儀器......................................................................	36
3.1 實驗流程.........................................................................................	36
        3.1.1 氮化鎵(GaN)奈米線的製備...............................................	36
             3.1.1.1 實驗材料.................................................................	36
             3.1.1.2 基板前處理.............................................................	37
             3.1.1.3 化學氣相沉積(CVD)實驗步驟..............................	38
        3.1.2 奈米銀顆粒附著於氮化鎵奈米線上..................................	39
             3.1.2.1 電子束蒸鍍法(Electron beam evaporation，EBE)	39
             3.1.2.2 紅外線(IR)加熱爐熱處理......................................	39
             3.1.2.3 濺鍍法(Sputter)......................................................	40
       3.1.3 分子探針溶液製備................................................................	40
   3.2 實驗分析儀器...................................................................................	41
       3.2.1 低掠角X光薄膜繞射儀(Grazing Incident Angle X-ray
            Diffraction，GIAXD)..............................................................	
41
       3.2.2 掃描式電子顯微鏡(SEM).....................................................	42
       3.2.3 穿透式電子顯微鏡(TEM).....................................................	43
       3.2.4 微拉曼光譜儀(Micro-Raman-Spectrometer)........................	43
   3.3 拉曼光譜的訊號處理.......................................................................	44
第四章 結果與討論......................................................................................	53
   4.1 氮化鎵奈米線性質分析...................................................................	53
       4.1.1奈米線晶體結構及表面形貌分析..........................................	53
   4.2 以紅外線加熱爐熱還原奈米銀顆粒於氮化鎵奈米線...................	58
       4.2.1 銀顆粒附著於氮化鎵奈米線表面之晶體結構分析............	58
       4.2.2 銀顆粒附著於氮化鎵奈米線之表面形貌分析與表面元素 
            分析........................................................................................	
59
       4.2.3 銀顆粒附著於氮化鎵奈米線之表面增顯拉曼散射分析....	60
   4.3 濺鍍法濺鍍奈米銀顆粒於氮化鎵奈米線..............................	70
       4.3.1 銀顆粒附著於氮化鎵奈米線表面之晶體結構分析與表面
            元素分析................................................................................	
70
       4.3.2 銀顆粒附著於氮化鎵奈米線之表面形貌分析....................	70
       4.3.3 銀顆粒附著於氮化鎵奈米線之表面增顯拉曼散射分析....	71
   4.4 電子束蒸鍍法蒸鍍奈米銀顆粒於氮化鎵奈米線...........................	76
       4.4.1 銀顆粒附著於氮化鎵奈米線表面之晶體結構分析與表面 
            元素分析................................................................................	
76
       4.4.2 銀顆粒附著於氮化鎵奈米線之表面形貌分析....................	77
       4.4.3 銀顆粒附著於氮化鎵奈米線之表面增顯拉曼散射分析....	77
            4.4.3.1 相同蒸鍍時間下，不同R6G濃度對試片的SERS
                   強度變化分析..........................................................	
77
            4.4.3.2 R6G濃度10-3 M下，不同銀蒸鍍膜厚對SERS強                
                   度變化分析..............................................................	
78
            4.4.3.3 綜合比較:銀顆粒形貌及覆蓋率與SERS增顯效果
                   的關係......................................................................	
81
       4.4.4 不同奈米銀顆粒附著方法之比較........................................	82
   4.5 表面增顯拉曼散射光譜探討...........................................................	95
       4.5.1 不同雷射波長檢測結果........................................................	95
       4.5.2 不同R6G 濃度檢測結果......................................................	95
       4.5.3 表面增顯拉曼散射增顯因子計算........................................	96
第五章 結論..................................................................................................	101
參考文獻........................................................................................................	103

                                    

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