臺灣博碩士論文加值系統

本研究是使用溶膠凝膠法合成堇青石摻雜過渡金屬（Mg2Al4Si5O18:Mn、Cr、Ti）螢光粉末，並探討不同活化劑和熱處理條件對其結構、微結構以及發光特性的影響。
粉末經熱處理到達900 ℃後，開始形成μ-Mg2Al4Si5O18結晶。隨著熱處理溫度升至1100 ℃，α- Mg2Al4Si5O18相開始出現，而在溫度達到1300 ℃時，則皆是純相的α- Mg2Al4Si5O18結晶。FTIR分析，證實煆燒至1300℃後，均為α- Mg2Al4Si5O18結晶。XPS光譜表示Mg2Al4Si5O18:Mn粉末中的Mn離子是以Mn2+為主，Mg2Al4Si5O18:Cr粉末中的Cr離子是以Cr3+為主，Mg2Al4Si5O18:Ti粉末中的Ti離子是以Ti4+為主。FE-SEM檢測顯示不同的活化劑會影響顆粒大小及結團狀況，UV-vis光譜顯示Mg2Al4Si5O18:Mn、Cr、Ti均呈現隨著摻雜濃度增加截止波長紅移及能隙值越小的趨勢。PL&PLE光譜顯示Mg2Al4Si5O18:Mn螢光粉末經波長為449 nm的激發後，顯示出在513 nm處的綠光發射波峰，最佳濃度為1%。對於Mg2Al4Si5O18:Cr螢光粉末，當波長為397 nm的激發作用時，產生的紅光發射波峰位於695 nm，最佳濃度為0.5%。Mg2Al4Si5O18:Ti螢光粉末，波長263 nm的激發後會導致471 nm處的藍光發射波峰，最佳濃度為1%。若共摻雜Mn、Cr、Ti，我們成功製備出近白光區域的螢光粉末。活化劑種類與濃度、熱處理條件會影響表面微結構及發光特性。

This research focuses on the synthesis of phosphor pow-ders(Mg2Al4Si5O18:Mn、Cr、Ti) using the sol-gel method, exploring the impact of different activators and heat treatment conditions on their structure, microstructure, and luminescent characteristics.
Upon heat treatment at 900 ℃, the formation of μ- Mg2Al4Si5O18 crystalline phase initiates. As the heat treatment temperature increases to 1100 ℃, the α- Mg2Al4Si5O18 phase begins to appear, and at 1300 ℃, a pure phase of α- Mg2Al4Si5O18 crystalline structure is obtained. FTIR analysis confirms the crys-tallization of α- Mg2Al4Si5O18 after sintering at 1300 ℃. XPS spectra reveal that Mn ions in Mg2Al4Si5O18:Mn powder are predominantly in the Mn2+ state, Cr ions in Mg2Al4Si5O18:Cr powder are mainly in the Cr3+ state, and Ti ions in Mg2Al4Si5O18:Ti powder are primarily in the Ti4+ state.
FE-SEM observations demonstrate that different activators influence particle size and agglomeration. UV-vis spectra indicate a redshift in the cutoff wave-length and a decrease in bandgap values with increasing doping concentrations for Mg2Al4Si5O18:Mn、Cr、Ti powders.PL&PLE spectra reveal that Mg2Al4Si5O18:Mn phosphor powder, excited at a wavelength of 449 nm, exhibits a green emission peak at 513 nm, with the optimal concentration being 1%. Mg2Al4Si5O18:Cr phosphor powder, excited at 397 nm, produces a red emission peak at 695 nm, with the optimal concentration being 0.5%. Mg2Al4Si5O18:Ti phosphor powder, excited at 263 nm, yields a blue emission peak at 471 nm, with the optimal concentration being 1%. The co-doping of Mn、Cr and Ti results in the successful preparation of phosphor powders in the near-white light region.
The type and concentration of activators, as well as heat treatment conditions, have a significant impact on the surface microstructure and luminescent proper-ties of the phosphor powders.

摘要..........................................................................i
Abstract....................................................................iii
誌謝..........................................................................v
目錄.........................................................................vi
表目錄......................................................................viii
圖目錄........................................................................ix
第一章 緒論.....................................................................1
1.1前言........................................................................1
第二章 基礎理論與文獻回顧.......................................................3
2.1堇青石......................................................................3
2.1.1堇青石的簡介...............................................................3
2.1.2堇青石的應用...............................................................4
2.1.3 堇青石合成方法............................................................8
2.1.4 溶膠凝膠法原理...........................................................10
2.2螢光材料介紹...............................................................12
2.2.1 螢光粉末發光原理.........................................................12
2.2.2螢光粉末的組成............................................................14
2.2.3史托克位移...............................................................16
2.3影響螢光粉發光因素.......................................................17
2.3.1主體晶格效應(Host effect).................................................17
2.3.2缺陷效應(Defect effect)..................................................17
2.3.3 濃度淬減效應............................................................18
第三章 實驗方法與步驟........................................................19
3.1 實驗流程.................................................................19
3.1.1 實驗材料............................................................19
3.1.2實驗步驟............................................................20
3.2 分析儀器與原理介紹.......................................................22
3.2.1 X光繞射分析儀(X-ray diffraction，XRD)....................................22
3.2.2 X射線電子能譜儀(XPS)....................................................22
3.2.3霍氏轉換紅外光譜儀(FT-IR).................................................23
3.2.4熱重分析/熱差掃描量熱分析 (TGA/DSC)........................................23
3.2.5電子順磁共振光譜 (EPR)....................................................24
3.2.6 場發射掃描式電子顯微鏡(Field Emission Scanning Electron Microscope,FE-SEM)...........................24
3.2.7紫外光/可見光光譜儀(UV-Vis).............................................24
3.2.8螢光光譜儀(Fluorescence spectrophotometer, PL)...........................25
第四章 結果與討論............................................................30
4.1 X光繞射分析(X-ray diffraction)...........................................30
4.1.1 不同熱處理溫度........................................................30
4.1.2摻雜不同活化劑............................................................31
4.2 熱重分析(TG)與熱差掃描量熱(DSC)分析........................................36
4.2.1 TGA/DSC曲線圖分析........................................................36
4.3傅立葉紅外線轉換光譜(FTIR)分析..............................................37
4.4掃描式電子顯微鏡分析(SEM)...................................................38
4.5 場發穿透式電子顯微鏡分析(TEM)...............................................42
4.6電子順磁共振光譜分析(EPR)..................................................44
4.7 X射線電子能譜儀分析(XPS)..................................................48
4.8紫外光/可見光光譜儀分析(UV-Vis)..............................................53
4.9螢光光譜儀分析(PL).......................................................59
4.9.1 PL分析............................................................59
4.9.2 衰減時間量測分析........................................................66
4.9.3 色度座標分析(CIE).......................................................70
第五章 結論............................................................75
參考文獻............................................................76

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