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研究生： 王柏勛
Wang, Po-Hsun
論文名稱： 鎢酸鹽螢光粉La2(WO4)3與LaBWO6之合成與光致發光性質研究
Synthesis and photoluminescent properties of tungstate phosphors La2(WO4)3 and LaBWO6
指導教授： 齊孝定
Qi, Xiao-Ding
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年： 2010
畢業學年度： 98
語文別： 中文
論文頁數： 127
中文關鍵詞： 螢光
外文關鍵詞： phosphor
相關次數： 點閱：90  下載：0 
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    • 　　本研究利用固相合成法製備以鎢酸鹽類為主體晶格之螢光粉體材料，分別將三價稀土金屬離子(Re3+=Dy3+、Tm3+、Er3+)等作為發光中心，並利用X光粉末繞射、掃描式電子顯微鏡、拉曼散射光譜儀、紫外-可見光吸收光譜儀以及光致發光光譜儀，對粉體進行結構與發光性質的分析、鑑定；探討活化劑摻雜濃度與La2(WO4)3和LaBWO6主體晶格對發光性質的影響。
    　　實驗結果顯示，於La2(WO4)3摻雜Dy3+離子可得到一個發暖白光的螢光粉體，CIE色度座標為(0.330,0.386)；若是以LaBWO6為主體晶格之情況下，摻雜Dy3+離子所得的螢光粉體之發光屬於冷白光，CIE色度座標為(0.254,0.307)，兩者皆已經屬於近白光。摻雜Tm3+離子在兩個主體晶格中，所得之發射光譜皆非常單純，峰值位於450 nm附近，屬於藍光，可作為高色純度的藍光螢光粉體。La2(1-x)Tm2x(WO4)3以及La1-xTmxBWO6之CIE色度座標分別為(0.152,0.029)以及(0.151,0.031)，色彩表現優於市面上常見之藍光螢光粉。
    　　兩主體晶格相比較，LaBWO6有高能量之聲子(~1450 cm-1)，雖其狀態密度(density of state)不高，但對某些能階的發光仍可能有較大的影響。此外，從Dy3+在兩主體晶格的發光光譜可知，La2(WO4)3中稀土離子的位置對稱性較LaBWO6低，所以前者的4F9/2 -> 6H13/2(黃光)發光較強, 而後者則是4F9/2 -> 6H15/2(藍光)發光較強。 

    　　Trivalent rare-earth (RE) ion doped tungstates, such as La1-xRExBWO6 and La2(1-x)RE2x(WO4)3 (RE=Dy3+, Tm3+, Er3+), were synthesized by solid-state reaction at 1000 C in air. The prepared powder samples were characterized by a range of techniques, including x-ray diffraction, scanning electron microscopy, Raman scatter spectroscopy, UV-visible absorption, and photoluminescence spectroscopy. The effects of host crystals and the concentration of RE ions on the luminescent properties were studied in terms of the potential applications as high efficient phosphors.
    　　When doped with the Dy3+ ions, La2(1-x)Dy2x(WO4)3 gave out a near white light with a warm color tone at the CIE chromaticity coordinate (0.330, 0.386). The La1-xDyxBWO6 powders also showed a near white fluorescence, but it had a cold color tone instead, with the CIE chromaticity coordinate at (0.254, 0.307). When doped with the Tm3+ ions, a simple blue emission peaked at about 450 nm were observed in the visible wavelength region for both hosts. The CIE chromaticity coordinates were calculated to be (0.152, 0.029) and (0.151, 0.031) for La2(1-x)Tm2x(WO4)3 and La1-xTmxBWO6, respectively, both of which have a better color purity than some of the commercial blue phosphors.
    　　Compared to La2(WO4)3, LaBWO6 has the additional phonons of a higher energy (~1450 cm-1). Although the density of state of these high-energy phonons is not very high, they may still have some effects on the luminescent properties of relevant energy levels. From the emission spectra of Dy3+ in the two hosts, it was found that the RE site symmetry in La2(WO4)3 was lower than in LaBWO6. As the consequence, the 4F9/2 -> 6H13/2 (yellow) emission was stronger for La2(WO4)3, whereas in LaBWO6 the 4F9/2 -> 6H15/2 (blue) emission was stronger.

    摘要 I Abstract II 致謝 IV 目錄 VI 表目錄 XI 圖目錄 XII 第一章 序論 1 1-1 前言 1 1-2 研究動機與目的 2 第二章 理論基礎與文獻回顧 5 2-1 螢光材料簡介 5 2-2 螢光材料的分類與應用 5 2-2-1 螢光材料的分類 5 2-2-2 激發源種類及其應用 11 2-3 發光物理原理 11 2-3-1 能量轉換機構：螢光與磷光 13 2-3-2螢光體能量的激發與吸收 13 2-3-3 螢光放射 15 2-3-4 非輻射轉換 17 2-4 影響發光行為與效率的主要因素 18 2-4-1 主體晶格效應 (Host effect) 18 2-4-2 熱淬滅 (Thermal quenching) 18 2-4-3 濃度淬滅效應 (Concentration quenching effect) 19 2-4-4 毒劑效應 (Poisoning effect) 19 2-4-5 金屬離子間電子轉移的機制 20 2-5 螢光材料之組成與設計[26] 20 2-5-1 主體晶格之選擇 20 2-5-2 活化劑之選擇 22 2-5-3 抑制劑的避免 22 2-6 主體材料結構介紹 26 2-6-1 La2(WO4)3結構 26 2-6-2 LaBWO6結構 26 第三章 實驗方法與步驟 27 3-1 實驗流程 27 3-1-1 固相反應法之La2(WO4)3：(RE)3+螢光粉製備 27 3-1-2 固相反應法之LaBWO6：(RE)3+螢光粉製備 27 3-2 化學藥品 30 3-3 成分與結構分析 30 3-3-1 X光繞射分析 (X-Ray Diffraction analysis) 30 3-3-2 掃描式電子顯微鏡 (Scanning Electron Microscope)分析 30 3-4 光譜性質量測 31 3-4-1 螢光光譜儀 (Photoluminescence，PL) 31 3-4-2 吸收光譜儀 (Absorption Spectrometer) 31 3-4-3 色度座標分析 (Analysis of C.I.E Chromaticity Diagram) 32 3-4-4 拉曼光譜 (Raman Spectrometer) 32 第四章 結果與討論 36 4-1 固相反應法合成La2(WO4)3 36 4-1-1 X光繞射分析 36 4-1-2 拉曼光譜分析 36 4-1-3 吸收光譜分析 36 4-2 固相反應法合成La2(1-x)Dy2x(WO4)3 39 4-2-1 摻雜Dy3+對結構的影響 39 4-2-2 拉曼光譜分析 39 4-2-3 SEM表面型態分析 39 4-2-4 光譜分析 43 4-2-5 Dy3+摻雜濃度對發光之影響 47 4-2-6 光致發光的衰減現象 51 4-2-7 CIE色度座標分析 54 4-2-8 結論 56 4-3 固相反應法合成La2(1-x)Tm2x(WO4)3 57 4-3-1 摻雜Tm3+對結構的影響 57 4-3-2 拉曼光譜分析 57 4-3-3 SEM表面型態分析 57 4-3-4 光譜分析 61 4-3-5 Tm3+摻雜濃度對發光之影響 64 4-3-6 CIE色度座標分析 65 4-3-7 結論 68 4-4 固相反應法合成La2(1-x)Er2x(WO4)3 69 4-4-1 摻雜Er3+對結構的影響 69 4-4-2 拉曼光譜分析 69 4-4-3 SEM表面型態分析 69 4-4-4 光譜分析 73 4-4-5 Er3+摻雜濃度對發光之影響 76 4-4-6 CIE色度座標分析 78 4-4-7 結論 80 4-5 固相反應法合成LaBWO6 81 4-5-1 X光繞射分析 81 4-5-2 拉曼光譜分析 81 4-5-3 吸收光譜分析 81 4-6 固相反應法合成La1-xDyxBWO6 84 4-6-1 摻雜Dy3+對結構的影響 84 4-6-2 拉曼光譜分析 84 4-6-3 光譜分析 84 4-6-4 Dy3+摻雜濃度對發光之影響 90 4-6-5 光致發光的衰減現象 90 4-6-6 CIE色度座標分析 93 4-6-7 結論 95 4-7 固相反應法合成La1-xTmxBWO6 96 4-7-1 摻雜Tm3+對結構的影響 96 4-7-2 拉曼光譜分析 96 4-7-3 光譜分析 96 4-7-4 Tm3+摻雜濃度對發光之影響 102 4-7-5 CIE色度座標分析 102 4-7-6 結論 105 4-8 La2(WO4)3與LaBWO6摻雜不同稀土元素之比較 106 4-8-1 主體晶格之比較 106 4-8-2 摻雜Dy3+離子 109 4-8-3 摻雜Tm3+離子 117 第五章 總結 121 參考文獻 123

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