臺灣博碩士論文加值系統

本論文利用一鍋合成法合成碳量子點與氧化石墨烯量子點，其合成方法優點主要是可以大量製造且過程簡單又快速。本論文第一部分為改變氮摻雜濃度得到不同螢光波長的氧化石墨烯量子點，其螢光位移波長達225 nm，實現了氧化石墨烯量子點的能隙工程。經由穿透式電子顯微鏡及X射線光電子能譜的分析，推論氧化石墨烯量子點的能隙改變可能是由氮掺雜所產生結果而非來自量子侷限效應。另外將氧化石墨烯量子點塗佈於氮化鎵半導體表面，發現其具有提升氮化鎵螢光強度之現象，螢光強度最高可提升2.4倍。此結果對未來應用於藍光發光二極體上可能具有很大的效益。
第二部份我們利用葡萄糖作為前驅物，合成出量子產率達22%的藍綠光碳量子點。此量子點可應用於過氧化氫的偵測，結果顯示對於過氧化氫的偵測靈敏度可達0.1μM。另外我們設計出光波導式螢光共振能量轉移，由藍光氮化銦鎵量子井 (施子) 將能量轉移至碳量子點 (受子)，實驗結果計算出能量轉移效率最高可達84.2%，且轉移效率與距離四次方的倒數(d-4)成正比。

One pot synthesis of nanomaterials has shown promising advantages that enables production of nanomaterials in large quantity with facile synthesis process. In this thesis we present the synthesis of carbon quantum dots and graphene oxide quantum dots (GOQDs) using different precursors. In the first part of this thesis, the synthesis of the red to blue GOQDs were obtained by varying the nitrogen doping concentration having a fluorescence shift wavelength of 225 nm, implementing the band gap engineering for GOQDs. Based on the analysis of TEM and XPS, it is proved that the band gap engineering of the GOQDs is not attributed to the quantum confinement effect but due to the creation of a new energy level after nitrogen doping. Furthermore, the GOQDs were introduced on the surface of GaN, which presented an enhancement with a factor of 2.4 with respect to the fluorescence intensity of the pristine GaN.
For the second part of this thesis we synthesized the carbon quantum dots (CQDs) using glucose as precursor. The as-synthesized blue-carbon quantum dots having 22% quantum yield was used for hydrogen peroxide detection, with detection limit up to 0.1 μM. Fluorescence resonance energy transfer between CQDs and InGaN was also studied. The optical waveguiding fluorescence resonance energy transfer enables the transfer from the InGaN quantum well to the CQDs. The experimental results exhibited transfer efficiency as high as 84.2%. From the dependence of transfer efficiency on the cap thickness (d) of the quantum well, it was found that the transfer efficiency is proportional to the inverse of the fourth power (d-4).

摘要
Abstract II
致謝 III
目錄 IV
圖表目錄 VI
第一章 緒論 1
1-1 量子點的成長 1
1-2 氧化石墨烯量子點的能隙工程 3
1-2-1 氧化石墨烯量子點 3
1-2-2 能隙調整 5
1-3 碳量子點與量子井的螢光共振能量轉移 7
1-3-1 碳量子點 7
1-3-2 螢光共振能量轉移 9
1-3-3與量子井相關的能量轉移 12
第二章 實驗設計與原理 14
2-1 合成量子點 14
2-1-1 氧化石墨烯量子點 15
2-1-2 碳量子點 16
2-2 藍光氮化銦鎵/氮化鎵單層量子井 17
2-2-1氮化銦鎵/氮化鎵單層量子井及其能帶結構 18
2-3 螢光能量共振轉移之理論模型 19
第三章 量測系統與原理 21
3-1 光激螢光光譜測量系統與原理 21
3-2 時間解析光激螢光量測系統 23
第四章 結果與討論 25
4-1探討氧化石墨烯量子點的能隙調整 25
4-1-1 氧化石墨烯量子點的結構與光學特性 25
4-1-2 氧化石墨烯量子點與氮化鎵半導體間載子轉移之光學特性 37
4-2碳量子點及量子井的螢光能量共振轉移 43
4-2-1 螢光碳量子點的結構與光學特性 43
4-2-2 以碳量子點偵測過氧化氫 46
4-2-3 碳量子點的螢光共振能量轉移 48
第五章 結論 58
參考文獻 60



圖表目錄
圖1-1-1 Top-down與Bottom-up的合成方法 2
圖1-2-1 利用Hammers方法合成氧化石墨烯 4
圖1-2-2 煤衍生石墨烯量子點能隙工程 5
圖1-3-1 Xu 等研究團隊於實驗中發現之螢光物質 8
圖1-3-2 Sun等研究團隊以雷射消融及表面鈍化和成碳點 8
圖1-3-3 螢光共振能量轉移 (FRET) 效應能階圖 10
圖1-3-4 Donor放光光譜 (藍色實線) 與Acceptor吸收光譜 (綠色實線) 重疊面積J(λ) 10
圖1-3-5 氮化銦鎵/氮化鎵量子井與量子點之間的能量轉移示意圖 12
圖1-3-6 氧化石墨烯與發光物質之間的能量轉移示意圖 13
圖2-1-1 合成碳量子點之實驗架設示意圖 14
圖2-2-1 藍光氮化銦鎵/氮化鎵單層量子井之結構示意圖 17
圖2-2-2 藍光氮化銦鎵/氮化鎵單層量子井之能帶結構示意圖 18
圖2-3-1 能量轉移效率與距離的關係圖 20
圖3-1-1 光激螢光原理示意圖 22
圖3-1-2 光激螢光光譜量測系統架設示意圖 22
圖3-2-1 TCSPC示意圖。 24
圖3-2-1 時間解析光激螢光光譜儀器架設圖 24
圖4-1-1 GOQDs-660 (a)的穿透式電子顯微鏡圖像(b) 高解析穿透式電子顯微鏡之晶格結構(c)高斯尺寸分布圖；GOQDs-425(d)的穿透式電子顯微鏡圖像(e) 高解析穿透式電子顯微鏡之晶格結構(f)高斯尺寸分布圖。 26
圖4-1-2 氧化石墨烯量子點於紫外燈下的側視圖 27
圖4-1-3 (a) 氧化石墨烯量子點之光激螢光光譜圖;(b) 摻雜不同濃度二乙烯三胺與螢光波長之關係圖 28
圖4-1-4 (a) GOQDs-650 (b) GOQDs-535 (c) GOQDs-425 之能階示意圖 28
圖4-1-5 (a) 氧化石墨烯量子點的X射線光電子能譜全譜圖譜 (b) 不同氮摻雜濃N/C比 29
圖4-1-6 不同氮摻雜濃度 (a) GOQDs-550 (b) GOQDs-535 (c) GOQDs-470 (d) GOQDs-425的氧化石墨烯量子點之X射線光電子能譜 N1s圖譜 31
圖4-1-7吡啶氮 (pyridinic N)、吡咯氮 (pyrrolic N)、石墨氮 (graphitic N) 氮原子示意圖 31
圖4-1-8 不同氮摻雜濃度的氧化石墨烯量子點之N-鍵結百分比 32
圖4-1-9 (a) 紅光與 (b) 藍光氧化石墨烯量子點之不同波長激發的光激螢光光譜 33
圖4-1-10 (a) GOQD-650與 (b) GOQD-425改變波長之時間解析螢光光譜 34
圖4-1-11 (a) GOQD-650與 (b) GOQD-425改變波長之螢光衰減時間
34
圖4-1-12 PL光激螢光光譜圖與不同發射波長衰減時間(a) GOQD-650 (b) GOQD-425；紅色虛線為利用載子侷限態模型所擬合曲線 36
圖4-1-13 實驗架設圖 38
圖4-1-14 (a) GOQD-660 (b) GOQD-570 (c) GOQD-535 (d) GOQD-425以不同體積塗佈於.氮化鎵之光激螢光光譜 38
圖4-1-15 氮化鎵半導體塗佈前後強度相除之圖譜 39
圖4-1-16 (a) GOQD-660 (b) GOQD-425之吸收光譜與光激螢光光譜圖 40
圖4-1-17 (a) GOQD-660 (b) GOQD-570 (c) GOQD-535 (d) GOQD-425塗佈於氮化鎵之時間解析光譜 41
圖4-1-18(a) GOQD-660 (b) GOQD-570 (c) GOQD-535 (d) GOQD-425塗佈於氮化鎵之螢光增強比例與載子轉移率 42
圖4-2-1 碳量子點 (a) 穿透式電子顯微鏡圖像 (b) 粒徑分布圖43
圖4-2-2 碳量子點的 (a) X射線光電子能譜C1s光譜 (b) 傅立葉轉換紅外線光譜儀光譜圖 44
圖4-2-3 碳量子點 (a) 光激螢光光譜與光激螢光激發光譜光譜圖 (b) 時間解析光激螢光光譜圖與擬合結果 45
圖4-2-4 (a) 存在不同H2O2濃度 (10 M~0.1 μM) 的碳量子點之光激螢光光譜 (b) 原始碳量子點與加入H2O2 (10 M) 後之碳量子點的時間解析螢光光譜 47
圖4-2-5 為過氧化氫濃度與碳量子點的螢光衰減時間之關係圖 47
圖4-2-6 氮化銦鎵量子井與碳量子點能量轉移示意圖 48
圖4-2-7黑線為氮化銦鎵/氮化鎵單層量子井 (施子) 光激螢光光譜；紅線為碳量子點 (受子) 的吸收光譜；藍線為碳量子點的光激螢光光譜
49
圖4-2-8 光波導式螢光共振能量轉移示意圖 50
圖4-2-9 黑線為未塗佈碳量子點的光譜；紅線為塗佈後的光激螢光光譜；插圖為波導式螢光共振能量轉移照片 51
圖4-2-10 (a) 碳量子點 (受子) 螢光強度與雷射距離之光激螢光光譜；插圖為塗佈前後的螢光光譜圖；(b) 其螢光強度與距離之關係圖
52
圖4-2-11 塗佈前後碳量子點 (受子) 之時間解析螢光光譜圖
52
圖4-2-12 單純氮化銦鎵量子井與量子井塗佈碳量子點後在不同氮化銦厚度 (a) 2 nm (b) 4 nm (c) 6 nm (d) 8 nm的之時間解析光激螢光光譜。紅色實線為理論擬合曲線 54
表4-2-1 施子與受子/碳量子點之時間解析將螢光光譜擬合數據 54
圖4-2-13 隨著厚度改變的能量轉移效率。 57

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