臺灣博碩士論文加值系統

本研究以固態反應法製備GaNbO4作為發光主體，並摻雜不同濃度的Eu3+與La3+離子作為發光中心，利用X光粉末繞射儀、掃描式電子顯微鏡、紫外-可見光光譜儀與光致發光光譜儀進行其結構和發光特性之鑑定，探討其製備條件與不同Eu3+離子摻雜濃度對晶體結構、光致發光特性之影響。
XRD繞射分析結果顯示在煆燒溫度1250 °C持溫4小時的條件下，可以得到單斜晶系GaNbO4之結晶結構。由紫外-可見光光譜圖觀察到GaNbO4：Eu3+螢光粉在200 - 400 nm間具有強吸收帶，主要來自於主體晶格(NbO4)3-陰離子團內部氧離子(O2-)與鈮離子(Nb5+)間電荷轉移帶的吸收所導致。
激發光譜顯示在225 - 310 nm間出現寬廣的激發帶，是由於Nb5+ - O2-間之電荷轉移躍遷所造成；在395 nm的激發下，其放射光譜由Eu3+離子的5D0→7F1,2,3,4,5電子躍遷所構成，發現最佳Eu3+離子的摻雜濃度為90 mol%。
另外在固定Eu3+離子濃度為90 mol%的情況下，摻雜不同濃度的La3+離子以調變Eu3+離子所處晶格環境進而改變其發光性質，放射光譜顯示發光強度與未摻雜La3+離子之發光強度相比較，可以發現摻雜後的發光強度高於未摻雜的強度。由SEM表面形態圖觀察到摻雜不同濃度的Eu3+與La3+離子對螢光粉體的外型並無明顯差異，不論摻雜濃度之多寡，粉體皆具有平滑表面並產生團聚現象。

In this study, GaNbO4 was prepared by solid-state reaction as the phosphors host and doped with different Eu3+ and La3+ ion concentrations as the luminescence center. The structure and luminescence properties of GaNbO4:Eu3+ phosphors were identified by X-ray diffraction (XRD), Scanning Electron Microscope (SEM), UV–visible spectrophotometry (UV-vis) and Photoluminescence Spectroscopy (PL). The effects of Eu3+ ion concentrations on the crystal structure and photoluminescence properties were investigated.
The XRD results showed that the crystalline structure of GaNbO4 with monoclinic crystal system could be obtained under the calcination temperature of 1250 °C for 4 h. A strong absorption band of GaNbO4:Eu3+ phosphors between 200-400 nm was observed by UV spectra, which was mainly caused by the absorption of charge transfer bands between oxygen ions (O2-) and niobium ions (Nb5+) in the 3-anion cluster of the main lattice (NbO4)3-.The excitation spectra show a broad excitation band between 225-310 nm, which is caused by the charge transfer transition between Nb5+-O2- in the anion group of (NbO4)3-. At excitation wavelength of 395 nm, the emission spectrum is composed of the 5D0→7F1,2,3,4,5 electron transitions of Eu3+ ions, the optimal Eu3+ ion concentrations was found to be 90 mol%.
In addition, under the Eu3+ ion concentrations fixed of 90 mol%, different concentrations of La3+ ion were co-doped to modify the lattice environment of Eu3+ ions lattice to change their luminescence properties, and the luminescence intensity was compared with that of unadulterated Eu3+ ions, the luminescence intensity of the ions doped is higher than that of the un-doped ions.From the SEM results, it is observed that there is no significant difference in the appearance of the GaNbO4 co-doped with Eu3+ and La3+ ions, and the powders have a smooth surface and agglomeration regardless of the both doping ion concentrations.

中文摘要...i
Abstract...iii
誌謝...v
目錄...vi
表目錄...ix
圖目錄...x
第一章 緒論...1
1-1 前言...1
1-2 GaNbO4晶體介紹...2
1-3 研究動機與目的...3
第二章 理論基礎與文獻回顧...5
2-1 螢光材料簡介...5
2-1-1 有機螢光材料...5
2-1-2 無機螢光材料...5
2-1-3 激發源的種類及應用...7
2-2 固態材料中的光致發光...8
2-2-1 本質型發光(intrinsic luminescence)...8
2-2-1-1 能帶發光(band-to-band luminescence)...8
2-2-1-2 激子發光(exciton luminescence)...8
2-2-1-3 交叉發光(cross luminescence)...8
2-2-2 外質型發光(extrinsic luminescence)...9
2-2-2-1 非侷限型(unlocalized type)發光材料...9
2-2-2-2 侷限型(localized type)發光材料...9
2-3 發光機制...10
2-3-1 螢光(fluorescence)與磷光(phosphorescence)...10
2-3-2 發光原理與發光過程...10
2-3-3 組態座標(configuration coordination)...11
2-3-4 史托克位移(stokes shift)...12
2-3-5 能量轉移(energy transfer)...13
2-3-6 電子-聲子交互作用(electron-phonon interaction)...13
2-3-7 交叉緩解(cross relaxation)...13
2-4 影響發光行為及效率的主要因素...13
2-4-1 主體晶格效應(Host efect)...14
2-4-2 主體效應對活化劑發光性質的影響...14
2-4-3 濃度淬滅效應(concentration quenching effect)...14
2-4-4 熱淬滅(thermal quenching)...15
2-4-5 毒劑效應(poisoning effect)...15
2-4-6 螢光共振能量轉移...15
2-5 螢光體的組成與選擇...15
2-5-1 主體晶格的選擇...16
2-5-2 活化劑的選擇...16
2-5-3 抑制劑的避免...16
2-6 螢光粉體的合成技術...17
第三章 實驗方法與步驟...33
3-1 實驗流程...33
3-2 實驗材料...33
3-3 成分與結構分析...33
3-3-1 X光繞射(X-ray diffraction)分析...33
3-3-2 掃瞄式電子顯微鏡(Scanning Electron Microscope)分析...33
3-4 螢光粉體之光學特性分析...34
3-4-1 吸收光譜儀...34
3-4-2 光致發光光譜儀...34
3-4-3 CIE色度座標(C.I.E Chromaticity Diagram)分析...34
第四章 結果與討論...39
4-1 固態反應法合成GaNbO4螢光粉...39
4-1-1 TGA-DSC分析...39
4-1-2 XRD結構分析...39
4-1-3 SEM表面型態分析...39
4-1-4 吸收光譜(Absorption spectra)分析...40
4-1-5 光致發光光譜(Photoluminescence spectra)分析...40
4-1-6 煆燒溫度對發光影響...40
4-1-7 結論...40
4-2 固態反應法合成(Ga1-xEux)NbO4螢光粉...47
4-2-1 XRD結構分析...47
4-2-2 SEM表面型態分析...47
4-2-3 吸收光譜(Absorption spectra)分析...47
4-2-4 激發光譜(Excitation spectra)分析...48
4-2-5 放射光譜(Emission spectra)分析...48
4-2-6 Eu3+離子摻雜濃度對發光的影響...49
4-2-7 反對稱指數(Asymmetry ratio)分析...49
4-2-8 衰減時間(Decay time)分析...49
4-2-9 CIE色度座標...50
4-2-10 結論...50
4-3 固態反應法合成(Ga0.1-yLay)Eu0.9NbO4螢光粉...61
4-3-1 共摻La3+離子濃度對結構的影響...61
4-3-2 SEM表面形態分析...61
4-3-3 吸收光譜(Absorption spectra)分析...61
4-3-4 激發光譜(Excitation spectra)分析...62
4-3-5 放射光譜(Emission spectra)分析...62
4-3-6 反對稱指數(Asymmetry ratio)分析...62
4-3-7 衰減時間(Decay time)分析...63
4-3-8 CIE色度座標...63
4-3-9 結論...63
第五章 總結論...73
參考文獻...74
Extended Abstract...78

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