臺灣博碩士論文加值系統

本論文研究主要是以固態反應法製備雙鈣鈦礦Ba2LaNbO6當作螢光粉主體，藉由單摻雜不同濃度的稀土離子Dy3+、共摻雜Dy3+、Eu3+以及共摻雜Dy3+、Sm3+作為發光中心，並藉由X-Ray,場發射掃描式電子顯微鏡,螢光光譜儀進一步分析摻雜濃度對螢光粉之晶體結構、表面型態及光至發光特性之影響。
第一部分研究是以Ba2LaNbO6作為螢光粉主體，藉由摻雜不同濃度之Dy3+稀土離子，由X-Ray diffraction結果表明，當煆燒溫度1250C下持溫6小時，Dy3+離子的摻雜濃度由1mol%到9mol%，可觀察到結構為單斜晶系Ba2LaNbO6之晶體結構，並無二次相產生。在SEM分析下，隨著Dy3+摻雜濃度由1mol%上升至5mol%，可以觀察到螢光粉的表面型態皆為不規則狀且有顆粒團聚現象。粉末在293 nm激發波長下，主要放射光波長約位於460~520 nm和560~620 nm之間，分別對應於Dy3+離子之4F9/26H15/2磁偶極躍遷和4F9/26H13/2超靈敏躍遷所造成，當Dy3+離子濃度為4 mol%時有最強的放射之後發生濃度淬滅效應，CIE色度座標隨Dy3+稀土離子摻雜濃度增加由淺藍光區偏移至綠光區。
第二部分研究是以Ba2LaNbO6作為螢光粉主體，固定Dy3+離子摻雜濃度4 mol%，共摻雜不同濃度之Eu3+離子，由X-Ray diffraction結果表明，當煆燒溫度1250C下持溫6小時，Dy3+離子的摻雜濃度由0.25mol%到3mol%，可觀察到結構為單斜晶系Ba2LaNbO6之晶體結構，並無二次相產生。在SEM分析下，隨著Eu3+摻雜濃度由0.25mol%上升至3mol%，可以觀察到螢光粉的表面型態皆為不規則狀且有顆粒團聚現象。粉末在293 nm激發波長下，主要放射光波長除了Dy3+離子位於460~520 nm和560~620 nm之間，分別對應於之4F9/26H15/2磁偶極躍遷和4F9/26H13/2超靈敏躍遷外，還包括了Eu3+離子位於594nm的5D07F1強磁偶極躍遷，617nm的5D07F2電偶極躍遷以及652nm的5D07F3躍遷，導致Ba2La0.96-yNbO6: 0.04Dy3+/yEu3+的CIE色度座標由綠光區移至近白光區最後移至橙黃光區。
第三部分研究是以Ba2LaNbO6作為螢光粉主體，固定Dy3+離子摻雜濃度4 mol%，共摻雜不同濃度之Sm3+離子，由X-Ray diffraction結果表明，當煆燒溫度1250C下持溫6小時，Sm3+離子的摻雜濃度由0. 5mol%到3mol%，可觀察到結構為單斜晶系Ba2LaNbO6之晶體結構，並無二次相產生。在SEM分析下，隨著Sm3+摻雜濃度由0.5mol%上升至3mol%，可以觀察到螢光粉的表面型態皆為不規則狀且有顆粒團聚現象。粉末在293 nm激發波長下，主要放射光波長除了Dy3+離子位於460~520 nm和560~620 nm之間，分別對應於之4F9/26H15/2磁偶極躍遷和4F9/26H13/2超靈敏躍遷外，還包括了Sm3+離子位於579nm的4G5/26H5/2磁偶極躍遷，617nm的4G5/26H7/2躍遷以以及664nm的4G5/26H9/2電偶極躍遷，導致Ba2La0.96-yNbO6: 0.04Dy3+/ySm3+的CIE色度座標由綠光區移至近白光區。

In this study, a novel double-perovskite Ba2LaNbO6 as the host material and doped with Dy3+ ion, co-doped with (Dy3+, Eu3+) ions and co-doped with (Dy3+, Sm3+) ions was prepared busing the solid-state reaction. The effects of doping concentrations on the crystal structure, surface morphology and luminescence properties of phosphor were further analyzed by X-Ray diffraction, field emission scanning electron microscope and fluorescence spectrometer.
In the first part of the study, Ba2LaNbO6 as the host and the Dy3+ rare earth ion-doped Ba2LaNbO6 phosphor was prepared using solid state reaction under the calcination temperature at 1250°C for 6 h in the air. The X-Ray diffraction results show that all of the diffraction peaks were corresponding to the the monoclinic Ba2LaNbO6 structure for the Dy3+ ion concentrations from 1 mol% to 9 mol%. Under the SEM analysis, when the Dy3+ ion doping concentrations increased from 1 mol% to 9 mol%, the surface morphologies of the phosphors were irregular and the particle agglomeration was occurred. At the excitation wavelength of 293 nm, the main emission wavelengths are between 460~520 nm, and 560~620 nm, which correspond to the 4F9/26H15/2 magnetic dipole transition and 4F9/26H13/2 electronic transition of Dy3+ ions, respectively. When the Dy3+ ion concentration is more than 4 mol%, the concentration quenching effect occured after the strongest radiation. The CIE chromaticity coordinate shifts from the light blue region to the green region as the doping concentration increase of Dy3+ rare earth ions.
In the second part of the study, Dy3+ ion concentration is fixed 4 mol%, and co-doped with different concentrations of Eu3+ ion in the Ba2LaNbO6 host system. The XRD diffraction patterns show that the Ba0.96-xDy0.04EuxLaNbO6 (x=0.025~0.03) phosphors kept the monoclinic Ba2LaNbO6 crystal structure. Under the SEM analysis for the Eu3+ ion doping concentrations increased from 0.25 mol% to 3 mol%, the surface morphologies of the phosphor were still irregular and the particle agglomeration was occurred. At the excitation wavelength of 293 nm, the main emission wavelength is between 460~520 nm and 560~620 nm corresponding to he 4F9/26H15/2 magnetic dipole transition, and the 4F9/26H13/2 electronic transition for Dy3+ ions, and the 5D07F1 strong magnetic dipole transition at 594nm, 5D07F2 electric dipole transition at 617nm, and 5D07F3 transition at 652 nm of Eu3+ ion, respectively. The CIE chromaticity coordinates of Ba2La0.96-yNbO6: 0.04Dy3+/yEu3+ are moved from the green region to the near white region, and finally to the orange region as the Eu3+ ion concentration increased.
In the third part of the study, Dy3+ ion concentration is fixed 4 mol%, and co-doped with different concentrations of Sm3+ ion in the Ba2LaNbO6 host system. The XRD diffraction patterns show that the Ba0.96-yDy0.04SmyLaNbO6 (y=0.005~0.03) phosphors still kept the monoclinic Ba2LaNbO6 crystal structure. When the Sm3+ ion doping concentration is 3 mol%, a secondary phase is generated, and it can be attributed to the La3+ ion radius is larger than that of Sm3+ ion. Under the SEM analysis, when the Sm3+ ion doping concentrations increased from 0.5 mol% to 3 mol%, the surface morphologies of the phosphors were irregular and the particle agglomeration was occurred. At the excitation wavelength of 293 nm, the main emission wavelengths are between 460~520 nm and 560~620 nm corresponding to the 4F9/26H15/2 magnetic dipole transition, and 4F9/26H13/2 electronic transition of Dy3+ ion, and the 4G5/26H5/2 magnetic dipole transition at 579nm, 4G5/26H7/2 transition at 617 nm, and 4G5/26H9/2 electric dipole transition at 664 nm of Sm3+ ions, respectively. The CIE chromaticity coordinates of Ba2La0.96-yNbO6: 0.04Dy3+/ySm3+ are moved from the green region to the near white region.

摘要......i
Abstract......iii
誌謝......vi
目錄......vii
表目錄......x
圖目錄......xi
第一章 緒論......1
1-1 前言......1
1-2 Ba2LaNbO6主體晶體介紹......2
1-3 研究動機與目的......2
第二章 理論基礎與文獻回顧......7
2-1 發光的定義......7
2-1-1 螢光與磷光之關係......7
2-1-2 激發源的種類與應用......7
2-1-3 螢光材料簡介......8
2-2 螢光材料種類......8
2-2-1 有機螢光材料......8
2-2-2 無機發光材料......9
2-2-3 半導體發光材料......10
2-3 固態材料中的光致發光現象......10
2-3-1 本質型發光(Intrinsic Luminescence)......10
2-3-1-1 能帶發光(band-to-band luminescence)......10
2-3-1-2 激子發光(exciton luminescence)......11
2-3-1-3 交叉發光(cross-luminescence)......11
2-3-2 外質型發光(extrinsic luminescence)......11
2-3-2-1 侷限型(localized type)......11
2-3-2-2 非侷限型(unlocalized type)......12
2-4 發光機制簡介......12
2-4-1 發光原理與發光過程......12
2-4-2 組態座標(configuration coordination)......12
2-4-3 史托克位移(stokes shift)......13
2-4-4 能量轉移(energy transfer)......14
2-4-5 電子-聲子交互作用(electron-phonon interaction)......14
2-4-6 交叉緩解(cross relaxation)......14
2-4-7 非輻射躍遷(non-radiative transition)......14
2-5 影響發光性質的主要因素......14
2-5-1 主體晶格效應(host lattice effect)......15
2-5-2 熱淬滅效應(thermal quenching)......15
2-5-3毒劑效應(poisoning effect)......15
2-5-4 濃度淬滅效應(concentration quenching effect)......15
2-5-5 光游離效應(photoionization effect)......16
2-5-6 補償效應(offset effect)......16
2-6 螢光體的組成與選擇......16
2-7 螢光粉體之合成技術......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 analysis, XRD)分析......33
3-3-2 場發射掃描式電子顯微鏡(Field emission scanning electron microscopy, FE-SEM)分析......34
3-3-3 熱分析儀(Thermal analyzers，TGA)......34
3-4 螢光粉體之光學特性分析......34
3-4-1 吸收光譜(Absorption spectrum)......34
3-4-2 螢光光譜儀(Photoluminescence, PL)特性量測......34
3-4-3 衰減時間(Decay time)分析......34
3-4-4 CIE色度座標分析(analysis of C.I.E chromaticity diagram)......34
第四章 結果與討論......39
4-1以固態反應法製備Ba2(La1-xDyx)NbO6 (x = 0 ~ 0.09)之螢光粉......39
4-1-1 Ba2LaNbO6:Dy3+螢光粉之X-ray結構特性分析......39
4-1-2 場發射掃描式電子顯微鏡(FE-SEM)表面形態分析......39
4-1-3 Ba2LaNbO6:Dy3+螢光粉之吸收光譜分析......39
4-1-4 Ba2LaNbO6:Dy3+螢光粉之激發光譜分析......40
4-1-5 Ba2LaNbO6:Dy3+螢光粉之放射光譜分析......40
4-1-6 Ba2LaNbO6:Dy3+螢光粉之衰減曲線......41
4-1-7 CIE色度座標......41
4-1-8結論......41
4-2以固態反應法製備Ba2(La0.96-x Dy0.04)NbO6: xEu3+ (x = 0.0025 ~ 0.03)之螢光粉......57
4-2-1 Ba2LaNbO6:Dy3+,Eu3+螢光粉之X-ray結晶結構分析......57
4-2-2場發射掃描式電子顯微鏡(FE-SEM)表面形態分析......57
4-2-3 Ba2LaNbO6:Dy3+,Eu3+螢光粉之吸收光譜分析......57
4-2-4 Ba2LaNbO6:Dy3+,Eu3+螢光粉之激發光譜分析......57
4-2-5 Ba2LaNbO6:Dy3+,Eu3+螢光粉之放射光譜分析......57
4-2-6 Ba2LaNbO6:Dy3+,Eu3+螢光粉之衰減曲線......58
4-2-7 CIE色度座標......59
4-3以固態反應法製備Ba2(La0.96-xDy0.04)NbO6:ySm3+ (y = 0.005 ~ 0.03)之螢光粉......72
4-3-1 Ba2LaNbO6:Dy3+,Sm3+螢光粉之X-ray結構分析......72
4-3-2 場發射掃描式電子顯微鏡(FE-SEM)表面形態分析......72
4-3-3 Ba2LaNbO6:Dy3+,Sm3+螢光粉之吸收光譜分析......72
4-3-4 Ba2LaNbO6:Dy3+,Sm3+螢光粉之激發光譜分析......73
4-3-5 Ba2LaNbO6:Dy3+,Sm3+螢光粉之放射光譜分析......73
4-3-6 Ba2LaNbO6:Dy3+,Sm3+螢光粉之衰減曲線......73
4-3-7 CIE色度座標......74
4-3-8結論......74
第五章 總結論......87
參考文獻......89
Extended Abstract......93

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