臺灣博碩士論文加值系統

根據研究顯示以固態反應法製備Ba2LaNbO6作為主體材料，並共摻4 mol% Dy3+以及0.25 mol% Eu3+離子時，螢光粉會產生白光，並且有最佳的發光效率[1]。因此本研究主要是以固態反應法製備Ba2(La0.9575Dy0.04Eu0.0025)NbO6單一相發白光螢光粉，並透過共摻或添加的方式加入不同濃度的助熔劑，藉此探討混和助熔劑後之Ba2(La0.9575Dy0.04Eu0.0025)NbO6單一相發白光螢光粉之結構與發光特性是否有改善。
本實驗大致分成兩個部分，第一部分為透過共摻方式，將助熔劑加入Ba2(La0.9575Dy0.04Eu0.0025)NbO6螢光粉中；第二部分為藉由添加方式，在完成Ba2(La0.9575Dy0.04Eu0.0025)NbO6螢光粉後，再加入助熔劑，並進行熱處理。最後藉由X光繞射、場發射掃描式電子顯微鏡以及螢光光譜儀對螢光粉進行晶體結構、表面型態與發光特性的分析，期望可以藉由助熔劑提升原始螢光粉的性能。
第一部分為Ba2(La0.9575Dy0.04Eu0.0025)NbO6單一相發白光螢光粉，並共摻不同濃度H3BO3助熔劑，在1250 ℃下煆燒6小時，以獲得螢光粉體。在X光繞射分析中，隨著H3BO3助熔劑共摻濃度增加，螢光粉體結構皆為單斜晶系Ba2LaNbO6之晶體結構，並且無雜相產生。透過場發射掃描式電子顯微鏡分析中，可觀察到表面型態並無太大差異，並且有團聚現象發生。在激發波長297 nm激發下所得之放射光譜圖中，主要放射峰波段街與原始螢光粉相同，僅有強度上的改變，其放射峰分別為Dy3+離子之4F9/2→6H15/2 (460~525 nm)、4F9/2→6H13/2 (550~630 nm) 與4F9/2→6H11/2電子躍遷(675~700 nm)以及Eu3+離子之5D0→7F1與5D0→7F2電子躍遷。其中共摻1 mol% H3BO3助熔劑具有最佳之放射峰強度。在CIE色度座標圖中，隨著H3BO3助熔劑濃度增加，發光位置皆位於白光區域，並且有接近NTSC標準白光的趨勢。
第二部分為Ba2(La0.9575Dy0.04Eu0.0025)NbO6單一相發白光螢光粉於1250 ℃下煆燒6小時後，再添加K2CO3、Li2CO3以及C6H8O7助熔劑，經混合後並在1000 ℃下熱處理2小時以獲得螢光粉體。在X光繞射分析中，隨著助熔劑濃度增加，其結構皆為單斜晶系Ba2LaNbO6之晶體結構，Li2CO3添加過多時會有雜相產生，但添加K2CO3以及C6H8O7則無雜相產生。在激發波長297 nm激發下所得之放射光譜圖中，僅有放射封強度上的改變，放射峰分別仍為Dy3+離子之4F9/2→6H15/2 (460~525 nm)、4F9/2→6H13/2 (550~630 nm) 與4F9/2→6H11/2電子躍遷(675~700 nm)以及Eu3+離子之5D0→7F1與5D0→7F2電子躍遷。。隨著K2CO3及Li2CO3助熔劑¬添加濃度增加，放射峰強度皆呈現下降的趨勢，而在添加C6H8O7時，放射峰強度則有增加，最佳添加濃度為6 wt%。在CIE色度座標圖中，隨著助熔劑濃度增加，發光位置皆位於白光區域，添加K2CO3及Li2CO3時有接近標準白光的趨勢，添加C6H8O7時則無。

According to the past research, the phosphor will produce white light emission and have the best luminous efficiency when Ba2LaNbO6 is co-doped with 4 mol.% Dy3+ and 0.25 mol.% Eu3+ ions prepared by the solid-state reaction method. In order to improve structure and luminous properties of the double-perovskite Ba2(La0.9575Dy0.04Eu0.0025)NbO6 single-phased white light emitting phosphor, Ba2(La0.9575Dy0.04Eu0.0025)NbO6 co-doped or added with different concentrations of fluxes was prepared by solid-state reaction method in this study.
This experiment is divided into two parts. The first part is that the Ba2(La0.9575Dy0.04Eu0.0025)NbO6 phosphor co-doped with different concentrations of H3BO3 flux, then calcining at 1250 ℃ for 6 h to obtain phosphors powder. In X-ray diffraction analysis, as the H3BO3 flux concentration increases, the crystal structure belongs to the monoclinic Ba2LaNbO6 structure, and no secondary phase appears. By the field emission scanning electron microscopy (FE-SEM) analysis, it can be observed that the surface morphology is roughly, and some agglomeration occurs. In the emission spectra obtained under the excitation wavelength of 297 nm, the main emission band is the same as that of the original Ba2(La0.9575Dy0.04Eu0.0025)NbO6 phosphor, but the intensity changes. The emission peaks are belongs to the 4F9/2→6H15/2 transition at 460~525 nm, the 4F9/2→6H13/2 transition at 550~630 nm, the 4F9/2→6H11/2 transition at 675~700 nm of Dy3+ ion, respectively. In addition, two emission peaks attributing to the 5D0→7F1 and 5D0→7F2 transition of Eu3+ ion are observed in the emission spectra. The radiation intensity of co-doped 1mo.l% H3BO3 flux is the best. In the CIE chromaticity coordinates diagram, as the flux contents increase, the light-emitting positions are all located in the white light region, and there is a tendency to approach the NTSC standard white light coordinates.
The second part is Ba2(La0.9575Dy0.04Eu0.0025)NbO6 phosphor prepared at 1250 ℃ for 6 h. After calcining, the phosphor added with fluxes including K2CO3, Li2CO3 and C6H8O7 and heat treated at 1000 ℃ for 2 h to obtain fluorescent powder. In the XRD analysis results, when the flux concentration increases, the structure keeps the monoclinic structure of Ba2LaNbO6 but the secondary phase will be observed when Li2CO3 contents is too much, whereas K2CO3 and C6H8O7 are not. In the emission spectra obtained under the excitation wavelength of 297 nm, the main emission band is the same as that of the Ba2(La0.9575Dy0.04Eu0.0025)NbO6 phosphor, but the intensity changes. The emission peaks are belongs to the 4F9/2→6H15/2 transition at 460~525 nm, the 4F9/2→6H13/2 transition at 550~630 nm, the 4F9/2→6H11/2 transition at 675~700 nm of Dy3+ ion, respectively. Two emission peaks attributing to the 5D0→7F1 and 5D0→7F2 transition of Eu3+ ion are also observed. When the concentrations of K2CO3 and Li2CO3 increased, the emission peaks showed a downward trend. The emission peak intensity is increased when C6H8O7 was added and the optimum value was 6 wt% for C6H8O7 contents. In the CIE chromaticity coordinate diagram, the light-emitting positions are all located in the white light region for all the flux contents increase. There is a tendency to approach the NTSC standard white light coordinates when K2CO3 and Li2CO3 are added.

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 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......6
2-1 發光之定義...............6
2-1-1 螢光材料簡介............6
2-1-2 螢光與磷光之關係.........6
2-1-3 激發源的種類與應用......7
2-2 螢光材料種類...............8
2-2-1 有機螢光材料............8
2-2-2 無機螢光材料............8
2-2-3 半導體發光材料............9
2-3 固體材料中的光致發光現象......9
2-3-1 本質型發光 (Intrinsic Luminescence).........9
2-3-2 外質型發光 (Extrinsic Luminescence).........10
2-4 發光機制簡介....................................11
2-4-1 發光原理與發光過程...........................11
2-4-2 組態座標 (Configuration Coordination).........11
2-4-3 史托克位移 (Stokes Shift).....................12
2-4-4 能量轉移 (Energy Transfer).....................12
2-4-5 電子-聲子交互作用 (Electron-Phonon Interaction).........13
2-4-6 交叉緩解 (Cross Relaxation).....................13
2-4-7 非輻射躍遷 (Non-Radiative Transition)............13
2-5 影響發光性質的因素.................................13
2-5-1 主體晶格效應 (Host Lattice Effect)...............13
2-5-2 熱淬滅效應 (Thermal Quenching)..................14
2-5-3 毒劑效應 (Posisoning Effect).....................14
2-5-4 濃度淬滅效應 (Concentration Quenching Effect)......14
2-5-5 光游離效應 (Photoionization Effect)...............14
2-5-6補償效應 (Offset Effect).....................14
2-6 螢光體的組成與選擇...........................15
2-7 稀土金屬離子的發光特性........................16
2-8 螢光粉體之合成技術...........................16
2-8-1 固態反應法 (Solid-State Reaction).........16
2-8-2 水熱合成法 (Hydrothermal Synthesis).........16
2-8-3 溶膠-凝膠法 (Sol-Gel Method)...............17
2-9 助熔劑.......................................17
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光繞射分析 (X-ray diffraction analysis, XRD)......36
3-3-2 場發射掃描式電子顯微鏡分析 (Field emission scanning electron microscopy, FE-SEM).............................................36
3-4 螢光粉體之光學特性分析........................36
3-4-1 吸收光譜分析 (Absorption spectrum).........36
3-4-2 螢光光譜儀特性分析 (Photoluminescence, PL)...36
3-4-3 衰減時間分析 (Decay time)..................37
3-4-4 CIE色度座標分析...........................37
第四章 結果與討論.................................41
4-1 以固態反應法製備Ba2(La0.9575Dy0.04Eu0.0025)NbO6螢光粉共摻H3BO3助熔劑......41
4-1-1 共摻H3BO3助熔劑之XRD結構分析...............41
4-1-2 場發射掃描式電子顯微鏡(FE-SEM)表面型態分析...41
4-1-3 共摻H3BO3助熔劑之吸收光譜分析...............42
4-1-4 共摻H3BO3助熔劑之激發光譜分析...............42
4-1-5 共摻H3BO3助熔劑之放射光譜分析...............42
4-1-6 衰減時間(Decay time)分析.....................43
4-1-7 CIE色度座標分析..............................43
4-1-8 結論.......................................44
4-2 以固態反應法製備Ba2(La0.9575Dy0.04Eu0.0025)NbO6螢光粉添加K2CO3助熔劑......58
4-2-1 添加K2CO3助熔劑之XRD結構分析..................58
4-2-2 場發射掃描式電子顯微鏡(FE-SEM)表面型態分析......58
4-2-3 添加K2CO3助熔劑之吸收光譜分析...............58
4-2-4 添加K2CO3助熔劑之激發光譜分析...............59
4-2-5 添加K2CO3助熔劑之放射光譜分析...............59
4-2-6 衰減時間(Decay time)分析.....................59
4-2-7 CIE色度座標分析..............................60
4-2-8 結論.......................................60
4-3 以固態反應法製備Ba2(La0.9575Dy0.04Eu0.0025)NbO6螢光粉添加Li2CO3助熔劑......72
4-3-1 添加Li2CO3助熔劑之XRD結構分析..................72
4-3-2 場發射掃描式電子顯微鏡(FE-SEM)表面型態分析......72
4-3-3 添加Li2CO3助熔劑之吸收光譜分析...............72
4-3-4 添加Li2CO3助熔劑之激發光譜分析...............73
4-3-5 添加Li2CO3助熔劑之放射光譜分析...............73
4-3-6 衰減時間(Decay time)分析.....................73
4-3-7 CIE色度座標分析..............................74
4-3-8 結論..........................................74
4-4 以固態反應法製備Ba2(La0.9575Dy0.04Eu0.0025)NbO6螢光粉添加C6H8O7助熔劑......86
4-4-1 添加C6H8O7助熔劑之XRD結構分析..................86
4-4-2 場發射掃描式電子顯微鏡(FE-SEM)表面型態分析......86
4-4-3 添加C6H8O7助熔劑之吸收光譜分析...............86
4-4-4 添加C6H8O7助熔劑之激發光譜分析...............87
4-4-5 添加C6H8O7助熔劑之放射光譜分析...............87
4-4-6 衰減時間(Decay time)分析.....................87
4-4-7 CIE色度座標分析..............................88
4-4-8 結論.......................................88
第五章 總結論....................................100
參考文獻..........................................101
Extended Abstract.................................105

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