臺灣博碩士論文加值系統

本研究是以三種不同主體材料為對象，分別為Y1-xBixVO4、SrAl12O19、Sr3MgSi2O8，以固態反應法及還原固態反應法製備，摻雜二價或三價的Eu離子，製成三原光（紅、綠、藍）之螢光粉末，探討其材料的合成及不同參數對螢光特性之影響。取三原色螢光粉體之最佳參數進行不同莫耳數比之混光，並以近紫外光確認白光初步成果，再進一步探討其混成後之螢光特性。
本實驗以固態反應法製備Y1-x-yBixVO4:yEu3+紅光螢光粉末(x=0.025~0.125，y=0.02~0.1)，Y1-x-yBixVO4:Eu3+主要的發光光譜位於波長620 nm處，並展現出明亮且顯著的紅光，其中在545nm時，有來自於Bi3+ 電子軌域之3P1 → 1S0躍遷及在592nm、620nm時有Eu3+電子軌域之5D0 → 7F1、5D0 → 7F2躍遷，而主要能使粉體發出紅光的主因即為Eu3+電子軌域之5D0 → 7F2電偶極躍遷，且其激發光譜寬敞介於260~340nm之間，皆可使其發出顯著的紅光。當Bi3+離子摻雜濃度增加到0.1mol、Eu3+濃度達到0.1 mol時，在365nm激發下可得到最佳之螢光強度。而在278nm激發下，Eu3+濃度在0.06mole且 Bi3+濃度大於0.05mole後，即出現濃度淬滅之現象使其發光強度開始大幅下降。
接者，以還原固態反應法製備Sr1-xEuxAl12O19綠光螢光粉末(x=0.03~0.18)，使其在還原氣氛(96%N2+4%H2)中合成，Sr1-xEuxAl12O19主要的發光光譜位於波長513 nm處，其發光光譜為單一波峰故可顯現出明亮且顯著的綠光，其電子躍遷是來自於Eu2+離子4f65d1→4f7的電偶極躍遷，且其激發光譜寬敞介於275~375nm之間，皆可使其發出顯著的綠光。此綠色螢光粉體之螢光強度會隨合成溫度、Eu2+摻雜濃度增加及關氣溫度下降而增強。在365nm激發下，當Eu2+濃度達到0.15 mole時，即得最佳之發光強度，而在大於此最佳濃度之後，出現濃度淬滅之現象使其發光強度開始大幅降低。當合成溫度提升時，粉末顆粒表面之絨毛及塊狀顆粒會漸漸消失，使其二次相漸漸消失並提升其螢光強度。
再者，在還原氣氛下(96%N2+4%H2)以固態反應法製備[Sr1-xEux]3MgSi2O8藍光螢光粉末(x=0.005~0.015)，[Sr1-xEux]3MgSi2O8主要的發光光譜位於波長457 nm處，可展現出明亮且顯眼的藍光，其電子躍遷也是來自於Eu2+離子4f65d1→4f7的電偶極躍遷。當Eu2+濃度達到0.03mole時，可得最佳之發光強度，並在大於此最佳濃度之後出現濃度淬滅之現象，使其發光強度開始大幅減弱。此藍色螢光粉體螢光強度會隨合成溫度、持溫時間增加增強，其顆粒表面之絨毛也會隨之變短並減少。
最後，將固態反應法及還原固態反應法所製備出的三原色螢光粉取其發光強度最佳者進行R.G.B不同莫耳數比之混光，其莫耳數比分別為1:1:1、2:3:2、1:2:1及2:5:2，並使用254nm、270nm、280nm、320nm及近紫外光350nm、365nm等光源進行激發，確認其混成結果並得到莫耳比在2:3:2及1:2:1時，在365nm激發下可得到白色光源，此研究成果可有利於後續白光mini LED之應用。

In this research, three host materials, Y1-xBixVO4, SrAl12O19, and Sr3MgSi2O8, were doped with divalent or trivalent Eu ions and they were synthesized by solid-state reaction method in air or reduction atmosphere to prepare the red, green, and blue phosphors. The influences of different parameters on the luminescence properties of three phosphors were investigated in this study.
Red Y1-x-yBixVO4:yEu3+ phosphors were synthesized by solid-state method (x=0.025-0.125, y=0.02-0.1). The red phosphors emitted bright and significant red luminescence centered at 620 nm due to the 5D0→7F2 electric dipole transition of Eu3+ ions and the excitation spectra were within the wavelength range of 260 ~ 340 nm. Another characteristic emission peak of 545 nm was also observed, which is corresponding to3P1 → 1S0 transitions of Bi3+ ions. The other characteristic emission peaks of 592 nm, which is corresponding to 5D0 → 7F1 transitions of Eu3+ ions. When the doping concentration of Eu3+ ions increased to 0.1 mol and Bi3+ concentration reached 0.1 mol, the optimum luminescence intensity was obtained with the excitation of 365 nm UV light. However, when the concentration of Eu3+ was 0.06 mole and the concentration of Bi3+ was more than 0.05 mole excited with the excitation of 278 nm UV light, the concentration quenching effect occurred and the luminescence intensity of emission spectra began to decrease dramatically.
In addition, Sr1-xEuxAl12O19 green phosphors (x=0.03~0.18) was prepared by solid-state reaction method in a reducing atmosphere (96% N2+4% H2). The main luminescence spectra of the green phosphors located at 513 nm, and they emitted bright and remarkable green light due to 4f65d1→4f7 electric dipole transition of Eu2+ ions. Their wavelengths of excitation spectra were between 275 and 375 nm. The luminescence intensity of Sr1-xEuxAl12O19 green phosphors increased with the increase of synthesis temperature, doping concentration of Eu2+ ions, and the shot-off temperature. The maximum PL intensity was obtained at Eu2+ ions concentration of 0.15 mole. As the synthesis temperature increased, the bulk particles and the villus on the surface of the powder particles gradually disappeared, and those microstructures would affect the luminescent properties of Sr1-xEuxAl12O19 green phosphors.
Furthermore, blue [Sr1-xEux]3MgSi2O8 phosphors (x=0.005-0.015) were also prepared by solid-state method in a reduction atmosphere of 96% N2 + 4% H2. The main luminescence spectra of those phosphors were located at 457 nm, which emitted bright and conspicuous blue light, and they were also due to 4f65d1→4f7 electric dipole transition of Eu2+ ions. When the concentration of Eu2+ ions reached 0.03 mole, the optimum luminescence intensity could be obtained. The luminescence intensity of the blue phosphors increased with the increase of synthesis temperature and holding times, and the villus on the surfaces of the particles decreased accordingly.
Finally, the red, green, and blue phosphors were mixed with different molar ratios of 1:1:1, 2:3:2, 1:2:1, and 2:5:2, respectively, and excited with 254, 270, 280, 320, 350, and 365 nm near-UV light. The results showed that white light could be obtained at the composition of 2:3:2 and 1:2:1mole under 365 nm excitation, which is beneficial to the application of white mini LEDs in the future.

謝誌 I
目錄 III
表目錄 VII
圖目錄 IX
中文摘要 XVIII
英文摘要 XXI
第一章 緒論 1
1-1前言 1
1-2研究動機與目的 1
第二章 基礎理論與文獻回顧 3
2-1螢光材料基本介紹 3
2-2螢光粉合成方法 4
2-2-1固態反應法 4
2-2-2溶膠凝膠法 5
2-2-3共同沉澱法 6
2-2-4水熱合成法 6
2-2-5還原固態反應法 7
2-3影響螢光特性與效率之主要因素 7
2-3-1主體晶格效應 7
2-3-2熱淬滅現象 8
2-3-3濃度淬滅現象 8
第三章 實驗方法 12
3-1實驗流程 12
3-2實驗方法 12
3-2-1以固態反應法製備Y1-xBixVO4:yEu3+(x=0.025~0.125，y=0.02~0.1)之紅光螢光粉體 12
3-2-2以還原固態反應法製備Sr1-xEuxAl12O19(x=0.03~0.18)之綠光螢光粉體 13
3-2-1以還原固態反應法製備[Sr1-xEux]3MgSi2O8 (x=0.005~0.015)之藍光螢光粉體 13
3-3螢光粉成份與結構之分析 14
3-3-1 X光繞射儀(XRD)之分析 14
3-3-2 高解析場發射掃描式電子顯微鏡(SEM)之分析 14
3-3-3 解析型掃描穿透式電子顯微鏡(TEM)之分析 15
3-3-4 高解析電子能譜儀(XPS)之分析 15
3-4螢光粉體性質測量 16
3-4-1 螢光光譜儀(PL)之分析 16
3-4-2 色度座標(C.I.E.)之分析 16
第四章 結果與討論 18
4-1以固態反應法合成Y1-xBixVO4:yEu3+(x=0.025~0.125，y=0.02~0.1)紅色螢光粉之研究 18
4-1-1 X光繞射(XRD)之分析結果 18
4-1-2 場發射掃描式電子顯微鏡(SEM)分析結果 18
4-1-3 螢光光譜儀(PL)之分析結果 25
4-1-3-1 不同合成溫度對紅光螢光粉之影響 25
4-1-3-2 摻雜不同Bi3+之濃度對紅光螢光粉之影響 26
4-1-3-3 摻雜不同Eu3+之濃度對紅光螢光粉之影響 26
4-1-4 色度座標(C.I.E.)之分析結果 27
4-2以還原固態法製備Sr1-xEuxAl12O19 (x=0.03~0.18)綠色螢光粉之研究 39
4-2-1 X光繞射(XRD)之分析結果 39
4-2-2 場發射掃描式電子顯微鏡(SEM)分析結果 39
4-2-3 解析型掃描穿透式電子顯微鏡(TEM)分析結果 40
4-2-4 螢光光譜儀(PL)之分析結果 49
4-2-4-1 不同持溫時間對綠光螢光粉之影響 49
4-2-4-2 不同合成溫度對綠光螢光粉之影響 49
4-2-4-3 摻雜不同Eu2+之濃度對綠光螢光粉之影響 50
4-2-4-4 在還原氣氛下不同關氣溫度對綠光螢光粉之影響 51
4-2-5 高解析電子能譜儀(HRXPS)分析結果之分析結果 51
4-2-6 色度座標(C.I.E.)之分析結果 52
4-3以還原固態法製備[Sr1-xEux]3MgSi2O8(x=0.005~0.015)藍色螢光粉之研究 63
4-3-1 X光繞射(XRD)之分析結果 63
4-3-2 場發射掃描式電子顯微鏡(SEM)分析結果 63
4-3-3 解析型掃描穿透式電子顯微鏡(TEM)分析結果 63
4-3-4 螢光光譜儀(PL)之分析結果 73
4-3-4-1 不同持溫時間對藍光螢光粉之影響 73
4-3-4-2 摻雜不同Eu2+之濃度對藍光螢光粉之影響 74
4-3-4-3 不同合成溫度對藍光螢光粉之影響 74
4-3-4-4 在還原氣氛下不同關氣溫度對藍光螢光粉之影響 75
4-3-5 色度座標(C.I.E.)之分析結果 76
4-4利用三原色螢光粉混成一白光源 88
4-4-1 取三原色螢光粉之不同莫耳數比混成白光結果之分析 88
第五章 結論 95
第六章 參考文獻 98

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