臺灣博碩士論文加值系統

研究主要是以固態反應法製備BaY2ZnO5 作為螢光粉主體，並摻雜不同濃度之Tm3+離子作為發光中心，以及摻雜不同濃度之Li2CO3、Na2CO3、K2CO3離子作為電荷補償劑對螢光粉的晶體結構、表面型態以及光至發光特性之影響。
第一部分以BaY2ZnO5作為螢光粉主體，摻雜不同濃度之Tm3+ 離子，由XRD結果顯示，在煆燒1250℃持溫8小時條件下，摻雜濃度從1 mol% 增加至5 mol% 結果顯示並沒有二次相的生成，皆為斜方晶系BaY2ZnO5之結構。而從SEM分析得知摻雜不同濃度的Tm3+離子之條件下，可以發現螢光粉體之表面型態多為不規則狀。而在光致發光特性方面，於362nm波長激發下，由放射光譜得知主要由Tm3+離子特性放射峰所組成，來自於1D2→3F4、1G4→3H6、1D2→3H5、1G4→3F4、1G4→3H5之電子躍遷為主，當Tm3+離子濃度為2mol%時有最強的放射強度，CIE色度座標則是不會因為Tm3+離子摻雜濃度增加而離開深藍色區。
在第二部分以BaY2ZnO5作為螢光粉主體，固定Tm3+離子摻雜濃度2 mol%，並摻雜Li2CO3當作電荷補償劑，在煆燒1250℃持溫8小時條件下，摻雜濃度從1 mol% 增加至5 mol% 結果顯示並沒有二次相的生成，皆為斜方晶系BaY2ZnO5之結構。SEM分析方面得知摻雜不同濃度的Li2CO3補償離子條件下，可以發現螢光粉體之表面下多為不規則狀。而在光致發光特性方面，於362nm波長激發下，由放射光譜得知主要由Tm3+離子特性放射峰所組成，來自於1D2→3F4、1G4→3H6、1D2→3H5、1G4→3F4、1G4→3H5之電子躍遷為主，由於離子半徑的關係，摻雜Li2CO3補償離子的放射強度並沒有增強放射效果，CIE色度座標隨著Li2CO3補償離子的濃度增加，由藍光區偏移置綠光區。
在第三部分是以BaY2ZnO5作為螢光粉主體，固定Tm3+離子摻雜濃度2 mol%，並摻雜Na2CO3當作電荷補償劑，在煆燒1250℃持溫8小時條件下，摻雜濃度從1 mol%增加至5 mol%結果顯示並沒有二次相的生成，皆為斜方晶系BaY2ZnO5之結構。SEM分析方面得知摻雜不同濃度的Na2CO3補償離子條件下，可以發現螢光粉體之表面下多為不規則狀。而在光致發光特性方面，於362nm波長激發下，由放射光譜得知主要由Tm3+離子特性放射峰所組成，來自於1D2→3F4、1G4→3H6、1D2→3H5、1G4→3F4、1G4→3H5之電子躍遷為主，而當Na2CO3補償離子濃度為1 mol%時則有增強放射的效果，CIE色度座標隨著Na2CO3補償離子的增加，由深藍色光區逐漸變為淡藍色光區。
而第四部份是以BaY2ZnO5作為螢光粉主體，固定Tm3+離子摻雜濃度2 mol%，並摻雜K2CO3當作電荷補償劑，在煆燒1250℃持溫8小時條件下，摻雜濃度從1 mol%增加至5 mol%結果顯示並沒有二次相的生成，皆為斜方晶系BaY2ZnO5之結構。SEM分析方面得知摻雜不同濃度的K2CO3補償離子條件下，可以發現螢光粉體之表面下多為不規則狀。而在光致發光特性方面，於362nm波長激發下，由放射光譜得知主要由Tm3+離子特性放射峰所組成，來自於1D2→3F4、1G4→3H6、1D2→3H5、1G4→3F4、1G4→3H5之電子躍遷為主，而當K2CO3補償離子濃度為4 mol%時則有增強放射的效果，CIE色度座標隨著K2CO3補償離子的增加，CIE色度座標隨著K2CO3補償離子的增加，由淺綠色光區逐漸變為淺藍色光區。

In this study, BaY2ZnO5 was prepared by solid-state reaction as the main body of phosphor, and doping different concentrations of Tm3+ ions as luminescent centers, and doping different concentrations of Li2CO3, Na2CO3, K2CO3 ions as charge compensators on the crystal structure, surface morphology and light to luminescence properties of the phosphor powder.
In the first part, XRD results show that there was no formation of secondary phases at 1250℃ for 8 h and the increase of Tm3+ dosage from 1 mol% to 5 mol%. All of them were the structures of orthorhombic BaY2ZnO5. From the SEM analysis, the surface morphology of the phosphor powder is irregular mostly. Under an excitation wavelength of 362 nm, the emission spectrum consists of 1D2→3F4, 1G4→3H6, 1D2→3H5, 1G4→3F4, and 1G4→3H5 electronic transitions of Tm3+ ions. The CIE chromaticity coordinates was dark blue area.
In the second part, XRD results show that the structure is orthorhombic BaY2ZnO5 crystal structure under the condition of calcination temperature of 1250 °C for 8 h. With the increase of the Li2CO3 concentration, no secondary phase was observed. In the SEM analysis, the surface morphology of the phosphor powder is irregular mostly. Under an excitation wavelength of 362 nm, the emission spectrum consists of 1D2→3F4, 1G4→3H6, 1D2→3H5, 1G4→3F4, and 1G4→3H5 electronic transitions of Tm3+ ions. The CIE chromaticity coordinates shift from blue to green region with the increase of the Li2CO3 concentration.
In the third part, XRD results show that the structure is orthorhombic BaY2ZnO5 crystal structure under the condition of calcination temperature of 1250 °C for 8 h. With the increase of the Na2CO3 concentration, no secondary phase was observed. In the SEM analysis, the surface morphology of the phosphor powder is irregular mostly. Under an excitation wavelength of 362 nm, the emission spectrum consists of 1D2→3F4, 1G4→3H6, 1D2→3H5, 1G4→3F4, and 1G4→3H5 electronic transitions of Tm3+ ions. The CIE chromaticity coordinates shift from dark blue to Light blue region with the increase of the Na2CO3 concentration.
In the fourth part, XRD results show that the structure is orthorhombic BaY2ZnO5 crystal structure under the condition of calcination temperature of 1250 °C for 8 h. With the increase of the K2CO3 concentration, no secondary phase was observed. In the SEM analysis, the surface morphology of the phosphor powder is irregular mostly. Under an excitation wavelength of 362 nm, the emission spectrum consists of 1D2→3F4, 1G4→3H6, 1D2→3H5, 1G4→3F4, and 1G4→3H5 electronic transitions of Tm3+ ions. The CIE chromaticity coordinates shift from green to blue region with the increase of the K2CO3 concentration.

摘要...i
Abstract.....iii
誌謝..v
目錄..vi
表目錄...x
圖目錄....xi
第一章 緒論....1
1-1前言...1
1-2 BaY2ZnO5主體介紹...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螢光材料簡介....7
2-1-1有機螢光材料....7
2-1-2無機發光材料.........7
2-1-3 依激發源種類及其應用.....8
2-2 發光機制簡介...............................9
2-2-1螢光(fluorescence)與磷光(phosphorescence)......9
2-3 固態材料中的光致發光..................10
2-3-1 本質型發光(Intrinsic Luminescence).....10
2-3-2 外質型發光(extrinsic luminescence)......10
2-3-2-1 侷限型(localized type)發光材料....10
2-3-2-2 非侷限型(unlocalized type)發光材料.....11
2-3-3能帶發光 (band-to-band luminescence)...11
2-3-3-1激子發光 (exciton luminescence)....11
2-3-3-2交叉發光 (cross-luminescence)....11
2-4 螢光體的發光機制....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).....13
2-4-5電子-聲子交互作用(electron-phonon interaction)....14
2-4-6 交叉緩解(cross-reaxation).....14
2-5 影響發光行為與效率的因素.....14
2-5-1 主體晶格.....14
2-5-2 濃度淬滅效應 (concentration quenching effect).....15
2-5-3 熱消淬效應(thermal quenching).....15
2-5-4 毒劑效應(poisoning effect).....15
2-5-5 螢光共振能量轉移(resonance energy transfer).....15
2-6 螢光體的組成與選擇.....16
2-6-1 主體晶格的選擇......16
2-6-2 活化劑的選擇......16
2-6-3 抑制劑的避免.......16
2-7 螢光粉體之合成技術......17
2-7-1固相反應法(Solid-state method)......17
2-7-2助熔劑法......17
2-8 電荷補償劑.....18
第三章實驗方法與步驟.....32
3-1 實驗流程.....32
3-2 實驗材料.....32
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......33
3-4 螢光粉體之光學特性分析......33
3-4-1 吸收光譜 (absorption spectrum)............33
3-4-2 螢光光譜儀 (photoluminescence, PL)特性量測...33
3-4-3 化學分析電子能譜儀 (electron spectroscope for chemical analysis ，ESCA).....33
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....41
4-1 以固態反應法製備 Ba1-xTmxY2ZnO5 (x = 0.1 ~ 0.5) 螢光粉....41
4-1-1 Ba1-xTmxY2ZnO5 螢光粉之XRD結構分析......41
4-1-2 場發射掃描式電子顯微鏡(FE-SEM)表面形態分析....41
4-1- 3 (Ba1-xTmx)Y2ZnO5螢光粉之吸收光譜分析.....41
4-1-4 (Ba1-xTmx)Y2ZnO5螢光粉之激發光譜分析......41
4-1-5 (Ba1-xTmx)Y2ZnO5螢光粉之放射光譜分析......42
4-1-6 CIE色度座標.....43
4-1-7 結論.....43
4-2 以固態反應法製備(Ba0.98-xLixTm0.02)Y2ZnO5 (x = 0.1 ~ 0.5) 螢光粉.....53
4-2-1 (Ba0.98-xLixTm0.02)Y2ZnO5螢光粉之XRD結構分析......53
4-2-2 FE-SEM表面形態分析.....53
4-2-3 (Ba0.98-xLixTm0.02)Y2ZnO5螢光粉之吸收光譜分析.....53
4-2-4 (Ba0.98-xLixTm0.02)Y2ZnO5螢光粉之激發光譜分析.....53
4-2-5 (Ba0.98-xLixTm0.02)Y2ZnO5螢光粉之放射光譜分析.....54
4-2-6 摻雜Li+離子對氧空缺的影響......54
4-2-7 CIE色度座標.....55
4-2-8 結論....55
4-3 以固態反應法製備(Ba0.98-xNaxTm0.02)Y2ZnO5 (x = 0.1 ~ 0.5) 螢光粉....66
4-3-1 (Ba0.98-xNaxTm0.02)Y2ZnO5螢光粉之XRD結構分析.....66
4-3-2 FE-SEM表面形態分析.....66
4-3-3 (Ba0.98-xNaxTm0.02)Y2ZnO5螢光粉之吸收光譜分析.....66
4-3-4 (Ba0.98-xNaxTm0.02)Y2ZnO5螢光粉之激發光譜分析.....66
4-3-5 (Ba0.98-xNaxTm0.02)Y2ZnO5螢光粉之放射光譜分析.....66
4-2-6 摻雜Na+離子對氧空缺的影響....67
4-2-7 CIE色度座標....67
4-2-8 結論....67
4-4 以固態反應法製備(Ba0.98-xKxTm0.02)Y2ZnO5 (x = 0.1 ~ 0.5) 螢光粉.....79
4-3-1 (Ba0.98-xKxTm0.02)Y2ZnO5螢光粉之XRD結構分析......79
4-4-2 FE-SEM表面形態分析......79
4-3-3 (Ba0.98-xKxTm0.02)Y2ZnO5螢光粉之吸收光譜分析....79
4-3-4 (Ba0.98-xKxTm0.02)Y2ZnO5螢光粉之激發光譜分析....79
4-3-5 (Ba0.98-xKxTm0.02)Y2ZnO5螢光粉之放射光譜分析....80
4-2-6 摻雜K+離子對氧空缺的影響.....80
4-2-7 CIE色度座標.....80
4-2-8 結論....81
第五章 總結論.....92
參考文獻.....94

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