本研究以水熱合成法製備YVO4螢光粉主體，摻雜稀土離子Eu3+當作發光中心並改變不同的製程條件，探討摻雜濃度對其晶體結構、表面型態與發光特性之影響。
第一部分以YVO4作為螢光粉主體，摻雜不同濃度之Eu3+離子，由XRD分析結果顯示，在煆燒溫度180℃持溫16小時條件下，為正方晶系(tetragonal) YVO4之結構，隨著Eu3+離子摻雜濃度的增加並沒有發現二次相的產生。SEM分析結果顯示摻雜不同濃度之Eu3+離子條件下，螢光粉體皆為不規則的顆粒狀，且顆粒尺寸大小不一致。在317 nm激發波長激發下，放射光譜主要由Eu3+離子的特徵峰組成，以5D0→7F1的磁偶極躍遷、5D0→7F2的電偶極躍遷和5D0→7F4的電子躍遷為主。當Eu3+離子摻雜濃度為8 mol%時，會有最強的放射強度。CIE色度座標顯示發光位置皆位在深紅光區，其座標為(x=0.666, y=0.321)。
第二部分為YVO4摻雜Eu3+離子濃度8 mol%，固定水熱法時間與溫度，調整不同pH值。由XRD結果顯示煆燒180℃持溫16小時，螢光粉仍保持正方晶系結構，且無雜相產生。SEM結果顯示隨著pH值的增加螢光粉體並沒有太大的改變，但有團聚的現象。而在317 nm激發波長下，隨著pH值的增加，位於放射波段594 nm和620 nm的Eu3+離子5D0→7F1和5D0→7F2電子躍遷也隨之增強，在pH值為12時具有最強的放射強度。CIE色度座標顯示隨著pH值的增加仍皆位於深紅光區。
第三部分為固定水熱法溫度、時間與pH=8，製備(Y0.92-xLaxEu0.08)VO4 (x=0-0.92)螢光粉。從XRD結果可看出，隨著La3+離子摻雜濃度的增加，螢光粉體逐漸從正方晶系的YVO4結構轉變為正方晶系的LaVO4結構。SEM圖顯示隨著La3+離子濃度的增加，螢光粉的表面型態由不規則的顆粒狀逐漸轉變為棒狀結構。光致發光方面在317 nm激發波長下，主要放射波段為594 nm (5D0→7F1)和620 nm (5D0→7F2)的Eu3+離子之電子躍遷，當La3+離子摻雜濃度為x=0.92時具有最強的放射強度。CIE色度座標顯示隨著La3+離子濃度的增加並無太大改變，均位在深紅光區。
第四部份則固定溫度與時間，改變pH值從8至12製備(La0.92Eu0.08)VO4螢光粉。XRD結果顯示隨著pH值的增加，螢光粉體皆為正方晶系LaVO4結構，並無雜相生成。SEM結果顯示隨著pH值的增加，螢光粉體的表面型態由長方體棒狀逐漸轉變為立方體。於317 nm激發波長下，主要放射波段仍為594 nm (5D0→7F1)和620 nm (5D0→7F2)的Eu3+離子之電子躍遷，當pH值為11時具有最強的放射強度。CIE色度座標顯示La0.92Eu0.08VO4螢光粉於不同pH值製備下，皆位於深紅光區。

In this study, YVO4 doped with rare earth ion Eu3+ phosphor was prepared by hydrothermal method, and different process conditions were changed to explore the effects of doping concentration and process conditions on the crystal structure, surface morphologies and luminescent properties.
In the first part, YVO4 doped with different concentrations of Eu3+ ions were prepared using the hydrothermal method. The XRD analysis results show that it is a tetragonal YVO4 structure at a heat treatment temperature of 180°C for 16 h. The formation of secondary phase did not be found when the Eu3+ ion doped concentrations increase. The SEM analysis results show that the phosphor powders are all irregular with different particle sizes as the different Eu3+ ion concentrations doped. Under the excitation wavelength of 317 nm, the emission spectra are mainly composed of characteristic peaks of Eu3+ ions, dominated by the magnetic dipole transition of 5D0→7F1, the electric dipole transition of 5D0→7F2 and the electronic transition of 5D0→7F4, respectively. There will be the strongest emission intensity when the Eu3+ ion doping concentration is 8 mol%. The CIE chromaticity coordinates show that the light-emitting positions are all located in the deep red light region, and the coordinates are (x=0.666, y=0.321).
The second part is that (Y0.92Eu0.08)VO4 phosphor is synthesized using the hydrothermal method with various pH values at 180℃ for 16 h. XRD results show that the structure keeps the tetragonal YVO4 structure, and there is no obvious impurity phase observed in the XRD pattern. SEM images showed that the phosphor powders still display agglomeration phenomenon, but did not change much with the increase of pH value. In the photoluminescence properties, at the excitation wavelength of 317 nm, the intensities of the emission peaks located at the emission bands of 594 nm and 620 nm corresponding to the 5D0→7F1 and 5D0→7F2 transition of Eu3+ ions increase with the increase of pH, respectively., and the strongest emission intensity was observed for the pH=12. The CIE chromaticity coordinates show that they are all located in the deep red region with the increase of pH value.
The third part is that the (Y0.92-xLax)Eu0.08VO4 (x=0-0.92) phosphor was synthesized by the hydrothermal method under the pH=8. From the XRD analysis results, it can be seen that the phosphor powder gradually changes from the tetragonal YVO4 structure to the tetragonal LaVO4 structure with the increase of La3+ ion. the surface morphologies of the phosphors gradually changed from irregular granular to rod-like structure. Under the excitation wavelength of 317 nm, the main emission bands are located at 594 and 620 nm, which are corresponding to the 5D0→7F1 and the 5D0→7F2 electron transitions of Eu3+ ions, respectively. When the La3+ ion doping concentration is 92 mol%, it will have the strongest emission intensity. The CIE chromaticity coordinates show that they are still all located in the deep red region as the increase of La3+ ion concentration.
In the fourth part, (La0.92Eu0.08)VO4 is prepared using the hydrothermal method under the pH value is between 8 and 12. The XRD results show that the phosphor powders belong to tetragonal LaVO4 structure as the pH value increases, and there is no obvious impurity phase was presented. The SEM images results showed that with the increase of pH value, the surface morphologies of the phosphor powder gradually changed from rod shape to cuboid shape. Under the excitation wavelength of 317 nm, the main emission bands still located at 594 nm and 620 nm which is attributed to the 5D0→7F1, and the 5D0→7F2 electron transition of Eu3+ ions, respectively. The CIE chromaticity coordinates show that the (La0.92Eu0.08)VO4 phosphor are all located in the deep red region prepared using the hydrothermal method with pH=8-12.

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
1-4 研究動機與目的...3
第二章 理論基礎與文獻回顧...8
2-1 發光的定義...8
2-1-1 螢光與磷光之關係...8
2-1-2 激發源的種類與其應用...8
2-2 螢光材料種類...10
2-2-1 有機螢光材料...10
2-2-3 半導體發光材料...11
2-3 固態材料中的光致發光現象...11
2-3-1 本質型發光 (Intrinsic Luminescence)...12
2-3-1-1 能帶發光 (band-to- band luminescence)...12
2-3-1-2 激子發光 (exciton luminescence)...12
2-3-1-3 交叉發光 (cross-luminescence)...12
2-3-2 外質型發光 (extrinsic luminescence)...13
2-3-2-1 侷限型 (localized type)...13
2-3-2-2 非侷限型 (unlocalized type)...13
2-4 發光機制簡介...14
2-4-1 發光原理與發光過程...14
2-4-2 組態座標 (configuration coordination)...14
2-4-4 能量轉移 (energy transfer)...15
2-4-5 電子-聲子交互作用 (electron-phonon interaction)...16
2-4-6 交叉緩解 (cross relaxation)...16
2-5 影響發光效率及性質的主要因素...16
2-5-1 主體晶格效應...17
2-5-3 熱淬滅效應 (thermal quenching)...17
2-5-4 濃度淬滅效應 (concentration quenching effect)...17
2-5-6 補償效應 (offset effect)...18
2-6 螢光體的組成與選擇...18
2-7 螢光粉體之合成技術...19
第三章 實驗方法與步驟...35
3-1 實驗流程...35
3-2 實驗材料...35
3-3 成分與結構分析...36
3-3-1 X光繞射 (X-ray diffraction analysis, XRD)分析...36
3-3-2 場發射掃描式電子顯微鏡 (Field emission scanning electron microscopy, FE-SEM) 分析...36
3-3-3 場發射解析型穿透式電子顯微鏡 (Field emission Analytical Scanning Transmission Electron Microscope, FE-TEM)分析...36
3-4 螢光粉體之光學特性分析...36
3-4-1 吸收光譜 (Absorption spectrum)...36
3-4-2 螢光光譜儀 (Photoluminescence, PL)特性分析...37
3-4-3 衰減時間 (Decay time)分析...37
3-4-4 CIE色度座標分析 (analysis of C.I.E chromaticity diagram)...37
第四章 結果與討論...43
4-1 以水熱合成法製備YVO4：Eu3+螢光粉...43
4-1-1 YVO4：Eu3+ 螢光粉之XRD結構分析...43
4-1-2 場發射掃描式電子顯微鏡(FE-SEM)表面型態分析...43
4-1-3 YVO4：Eu3+螢光粉之吸收光譜分析...43
4-1-4 YVO4：Eu3+螢光粉之激發光譜分析...44
4-1-5 YVO4：Eu3+螢光粉之放射光譜分析...44
4-1-6 YVO4：Eu3+螢光粉之衰減曲線...44
4-1-7 CIE色度座標...45
4-1-8 (Y0.92Eu0.08)VO4螢光粉之熱淬滅分析...45
4-1-9 結論...45
4-2 以水熱合成法製備(Y0.92Eu0.08)VO4調整pH值之螢光粉...59
4-2-1 (Y0.92Eu0.08)VO4調整pH值螢光粉之XRD結構分析...59
4-2-2 場發射掃描式電子顯微鏡(FE-SEM)表面型態分析...59
4-2-3 (Y0.92Eu0.08)VO4調整pH值螢光粉之吸收光譜分析...59
4-2-4 (Y0.92Eu0.08)VO4調整pH值之激發光譜分析...59
4-2-5 (Y0.92Eu0.08)VO4 調整pH值之放射光譜分析...60
4-2-6 (Y0.92Eu0.08)VO4 調整pH值之衰減曲線...60
4-2-7 CIE色度座標...60
4-2-8 (Y0.92Eu0.08)VO4 固定pH = 12之熱淬滅分析...60
4-2-9 結論...61
4-3 固定pH 8以水熱合成法製備(Y0.92-xLaxEu0.08)VO4螢光粉...74
4-3-1 固定pH 8 (Y0.92-xLaxEu0.08)VO4螢光粉之XRD結構分析...74
4-3-2 固定pH 8 (Y0.92-xLaxEu0.08)VO4螢光粉之晶格應變分析...74
4-3-3 場發射掃描式電子顯微鏡(FE-SEM)表面型態分析...75
4-3-4 (Y0.92-xLaxEu0.08)VO4固定pH 8之吸收光譜分析...75
4-3-5 (Y0.92-xLaxEu0.08)VO4固定pH = 8之激發光譜分析...75
4-3-6 (Y0.92-xLaxEu0.08)VO4固定pH8之放射光譜分析...75
4-3-7 (Y0.92-xLaxEu0.08)VO4固定pH = 8之衰減曲線...76
4-3-8 CIE色度座標...76
4-3-9 (La0.92Eu0.08)VO4固定pH = 8之熱淬滅分析...76
4-3-10 結論...76
4-4 以水熱合成法調整不同溶液pH值以製備(La0.92Eu0.08)VO4螢光粉...91
4-4-1 不同pH值製備之(La0.92Eu0.08)VO4螢光粉之XRD結構分析...91
4-4-2 場發射掃描式電子顯微鏡(FE-SEM)表面型態分析...91
4-4-3 場發射穿透式電子顯微鏡(FE-TEM)結構型態分析...91
4-4-4 (La0.92Eu0.08)VO4於不同pH值製備下之吸收光譜分析...91
4-4-5 (La0.92Eu0.08)VO4於不同pH值製備下之激發光譜分析...91
4-4-6 (La0.92Eu0.08)VO4於不同pH值製備下之放射光譜分析...92
4-4-7 (La0.92Eu0.08)VO4於不同pH值製備下之衰減曲線...92
4-4-8 CIE色度座標...92
4-4-9 (La0.92Eu0.08)VO4固定pH=11之熱淬滅分析...92
4-4-10 結論...93
第五章 總結論...107
5-1 第一部分：...107
5-2 第二部分：...107
5-3 第三部分：...108
5-4 第四部分：...108
參考文獻...109
Extended Abstract...113

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