臺灣博碩士論文加值系統

依據近紫外光可激發雜質添加螢光粉設計原則，本研究利用的固態反應法，藉由Eu3+添加合成CaTiO3(紅色)、Eu2+添加合成Ca2MgSi2O7(綠色)及BaMgAl10O17(藍色)三色螢光粉，並且經光色混合產生白光。我們也設計不同參數條件合成三色螢光粉，且進行掃描式電子顯微鏡(Scanning Electron Microscope, SEM)、X-光粉末繞射儀(X-ray Diffraction, XRD)、光致發光光譜儀(Photoluminescence Spectrum, PL)、高解析電子能譜儀(High resolution X-ray Photoelectron Spectrometer, HR-XPS)以及色彩輝度計(Commission Internationale de L’Eclairage, CIE)，探討其微結構與光學特性。
SEM結果顯示，CaTiO3: Eu3+紅色螢光粉在合成溫度1450oC以及1500oC時，可以清楚觀察到疇壁。PL發光光譜得知，Ca2MgSi2O7: Eu2+綠色螢光粉隨著合成溫度的升高，發射光譜波段從藍色偏移至綠色區域。HR-XPS結果得知，添加Eu2+或Eu3+分別會產生不同之發光特性，因此可以開發出不同顏色螢光粉，及可以在不同狀況下應用。
本研究採用之三原色螢光粉能夠於300~400 nm有效地激發，且在近紫外光(near-UV)下產生白光，提供白色發光二極體(W-LED)製作螢光粉應用的新選擇。

In this study, because of the design principle of using UV to excite the dopant added phosphors, we used the solid-state reaction method to synthesize the phosphors with three different colors, including Eu3+-doped CaTiO3 (red color) and Eu2+-doped Ca2MgSi2O7 (green color) and BaMgAl10O17 (blue color). The synthesized phosphors were analyzed using a series of equipment with different functions to analyze the synthesized phosphors, including scanning electron microscope (SEM), x-ray diffraction (XRD) analyzer, photoluminescence spectrum (PL), high resolution x-ray photoelectron spectrometer (HR-XPS), and commission internationale de L'Eclairage (CIE) was also used.
From the SEM images, as the synthesis temperatures were 1450oC and 1500oC, the domain wall was really observed on the surfaces of CaTiO3: Eu3+ particles. With the increase of the synthesis temperature, the emission spectra of Ca2MgSi2O7: Eu2+ phosphors were changed from blue light to green light. From the analyzed results of HR-XPS, the emission wavelength (or color) was different because of the addition of Eu2+ or Eu3+. Such a result indicates that the investigated phosphors can achieve different colors and match the different applications.
For white light-emitting diodes (WLEDs), the mixed three-color phosphors can effective be excited by the near UV light in the wavelengths of 300 nm and 400 nm to form white light.

第一章 緒論
1.1 前言
1.2 研究動機
第二章 基礎理論
2.1 發光二極體(Light Emitting Diode, LED)之基本介紹[1, 2]
2.2 螢光材料簡介[9]
2.3 螢光材料分類
2.3.1 螢光材料之特性分類[9]
2.3.2 螢光材料發光分類[9]
2.3.3 螢光材料組成分類
2.4 發光之原理及種類[10]
2.5 固態材料中的光致發光[10]
2.5.1 本質型發光(Intrinsic luminescence)
2.5.2 外質型發光(extrinsic luminescence)
2.5.3 非侷限型(unlocalized type)發光材料
2.5.4 侷限型(localized type)發光材料
2.6 螢光粉之組成[11]
2.6.1 主體晶格
2.6.2 活化劑
2.6.3 敏化劑
2.6.4 淬滅劑[13]
2.7 發光行為與效率的因素[14]
2.7.1 濃度消淬效應 (concentration quenching)
2.7.2 毒劑現象(poisoning)
2.8 螢光材料合成方法[14]
2.8.1 固態反應法(Solid state method)
2.8.2 溶膠凝膠法(Sol gel method)
2.8.3 水熱法(Hydrothermal method)
2.8.4 共同沉澱法(Coprecipitation method)
2.9 色彩之介紹[15, 16]
2.9.1 CIE 色度座標
2.9.2 演色性指標(Colorrendering，CRI)
2.9.3 色溫
2.9.4 光致發光衰減現象
第三章 文獻回顧
3.1 螢光體文獻回顧
3.2 晶體結構簡介
3.2.1 CaTiO3晶體結構[21-23]
3.2.2 Ca2MgSi2O7晶體結構
3.2.3 BaMgAl10O17晶體結構[27]
第四章 實驗方法與流程
4.1 實驗藥品
4.2 儀器設備
4.2.1 輕巧型紫外線燈(UV light)
4.2.2 高溫箱型爐(High-Temperature Furnace)
4.2.3 管狀高溫爐
4.2.4 烘箱(Oven)
4.2.5 光致發光光譜儀(Photoluminescence, PL)
4.2.6 場發射式掃描式電子顯微鏡(Field-Emission Scanning Electron Microscopy, FE-SEM)
4.2.7 高精度X光繞射儀(X-Ray Diffraction, XRD)
4.2.8 色彩輝度計(Commission Internationale de L’Eclairage ,CIE)
4.2.9 高解析電子能譜儀(High resolution X-ray Photoelectron Spectrometer, HR-XPS)之分析
4.3 實驗方法
4.3.1 實驗流程
4.3.2 紅色螢光粉CaTiO3: x Eu3+(x=0.07~0.088)之合成
4.3.3 綠色螢光粉Ca2-xMgSi2O7: x Eu2+(x=0.005~0.045)之合成
4.3.4 藍色螢光粉BaMgAl10O17: x Eu2+ (x=0.02~0.1)之合成
第五章 結果與討論
5.1 利用固態反應法合成CaTiO3: x Eu3+紅色螢光粉之研究
5.1.1 X 光繞射圖譜分析
5.1.2 螢光圖譜分析
5.1.3 光致發光衰減現象(Decay time)
5.1.4 SEM 表面型態分析
5.1.5 HR-XPS高解析電子能譜儀
5.1.6 CIE發光的色度座標值
5.2 利用固態反應法合成 Ca2-xMgSi2O7: x Eu2+綠色螢光粉之研究。
5.2.1 X 光繞射圖譜分析
5.2.2 螢光圖譜分析
5.2.3 光致發光衰減現象(Decay time)
5.2.4 SEM 表面型態分析
5.2.5 XPS高解析電子能譜儀
5.2.6 CIE發光的色度座標值
5.3 利用固態反應法合成 BaMgAl10O17: x Eu2+藍色螢光粉之研究
5.3.1 X 光繞射圖譜分析
5.3.2 螢光圖譜分析
5.3.3 光致發光衰減現象(Decay time)
5.3.4 SEM 表面型態分析
5.3.5 XPS高解析電子能譜儀
5.3.6 CIE發光的色度座標值
5.4 近紫外光激發三色螢光粉混合一白光光源
5.4.1 三色螢光粉混合白光之螢光圖譜分析
5.4.2 CIE發光的色度座標值
第六章 結論
6-1 利用固態反應法製備CaTiO3：x Eu3+紅色螢光粉微結構與發光特性之研究
6-2 利用固態反應法製備Ca2-xMgSi2O7：x Eu2+綠色螢光粉微結構與發光特性之研究
6-3 利用固態反應法製備BaMgAl10O17：x Eu2+藍色螢光粉微結構與發光特性之研究
6-4 利用三色螢光粉之最佳組成混合產生白光
第七章 參考文獻

[1]經濟部能源局委託工業技術研究院, 白熾燈泡能源效率管理系統, 2001.
[2]"中華民國光電學會叢書," 台北:五南, p. p.95, 2012.
[3]R. Patil and S. Moharil, "Cu+ luminescence in new hosts," physica status solidi (a), vol. 187, pp. 557-562, 2001.
[4]R. Patil, S. Moharil, S. Dhopte, P. Muthal, and V. Kondawar, "Thermoluminescence in some copper‐doped compounds," physica status solidi (a), vol. 199, pp. 527-532, 2003.
[5]Z. Wu, J. Shi, J. Wang, M. Gong, and Q. Su, "A novel blue-emitting phosphor LiSrPO4: Eu2+ for white LEDs," Journal of Solid State Chemistry, vol. 179, pp. 2356-2360, 2006.
[6]Z. Yang, G. Yang, S. Wang, J. Tian, X. Li, Q. Guo, et al., "A novel green-emitting phosphor NaCaPO4: Eu2+ for white LEDs," Materials Letters, vol. 62, pp. 1884-1886, 2008.
[7]劉如熹，林群哲, "高演色性白光發光二極體螢光粉材料近況發展," 工業材料雜誌, vol. 258期, 2008.
[8]Z. Wu, J. Liu, Q. Guo, and M. Gong, "A novel blue-green-emitting phosphor LiBaPO4: Eu2+ for white light-emitting diodes," Chemistry letters, vol. 37, pp. 190-191, 2008.
[9]楊素華, "螢光粉在發光上的應用," 科學發展, Lett, vol. 358, pp. 57-66, 2002.
[10]X. F. Wang and B. Herman, "Fluorescence imaging spectroscopy and microscopy," CHEMICAL ANALYSIS-NEW YORK-INTERSCIENCE THEN JOHN WILEY-, vol. 1, pp. ALL-ALL, 1996.
[11]G. Blasse and B. Grabmaier, "Springer-Verlag: Berlin," Luminescent Materials, 1994.
[12]吳佳蓁,陳登銘, "真空紫外線激發螢光粉之設計, 製備與發光特性鑑定," 2007.
[13]陳文成, "銪活化 Sr2-xBaxSiO4及Sr3-xBaxSiO5螢光材料," 成功大學材料科學及工程學系學位論文, pp. 1-112, 2008.
[14]傅玟娟, "以固相反應法合成 YAG 之研究," 南台科技大學碩士論文, 2006.
[15]楊子蘊,陳登銘, "新穎鹼土多磷酸鹽螢光體合成, 發光特性與能量轉移之研究," 2009.
[16]宋曉芳, "白光發光二極體的發光光譜穩定性之研究," 2008.
[17]A. K. Vijh, "Relation Between Solid‐State Cohesion of Metal Fluorides and the Electrochemical Behavior of Metals in Hydrogen Fluoride," Journal of The Electrochemical Society, vol. 115, pp. 1096-1098, 1968.
[18]L. Jiang, C. Chang, and D. Mao, "Luminescent properties of CaMgSi2O6 and Ca2MgSi2O7 phosphors activated by Eu2+, Dy3+ and Nd3+," Journal of alloys and compounds, vol. 360, pp. 193-197, 2003.
[19]S. Poort, H. Reijnhoudt, H. Van der Kuip, and G. Blasse, "Luminescence of Eu2+ in silicate host lattices with alkaline earth ions in a row," Journal of Alloys and Compounds, vol. 241, pp. 75-81, 1996.
[20]N. Lakshminarasimhan and U. Varadaraju, "White-light generation in Sr2SiO4: Eu2+, Ce3+ under near-UV excitation a novel phosphor for solid-state lighting," Journal of the Electrochemical Society, vol. 152, pp. H152-H156, 2005.
[21]G. Blasse and B. Grabmaier, "How Does a Luminescent Material Absorb Its Excitation Energy?," in Luminescent materials, ed: Springer, 1994, pp. 10-32.
[22]S. Marchionna, F. Meinardi, M. Acciarri, S. Binetti, A. Papagni, S. Pizzini, et al., "Photovoltaic quantum efficiency enhancement by light harvesting of organo-lanthanide complexes," Journal of luminescence, vol. 118, pp. 325-329, 2006.
[23]P. Chung, H.-h. Chung, and P. H. Holloway, "Phosphor coatings to enhance Si photovoltaic cell performance," Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, vol. 25, pp. 61-66, 2007.
[24]M. G. Ha, J. H. Lee, J. S. Bae, J. P. Kim, K. S. Hong, and H.-S. Yang, "Photophysical properties of highly efficient red-emitting CaTiO3:Eu3+ phosphors under near ultra-violet excitation," Current Applied Physics, vol. 11, pp. 1379-1383, 2011.
[25]A. Le Donne, M. Acciarri, D. Narducci, S. Marchionna, and S. Binetti, "Encapsulating Eu3+ complex doped layers to improve Si‐based solar cell efficiency," Progress in Photovoltaics: Research and Applications, vol. 17, pp. 519-525, 2009.
[26]H. He, R. Fu, X. Song, R. Li, Z. Pan, X. Zhao, et al., "Observation of Fluorescence and Phosphorescence in Ca2MgS2O7:Eu2+,Dy3+ Phosphors," Journal of The Electrochemical Society, vol. 157, p. J69, 2010.
[27]Y.-I. Kim, K.-B. Kim, M.-J. Jung, and J.-S. Hong, "Combined Rietveld refinement of BaMgAl10O17: Eu2+ using X-ray and neutron powder diffraction data," Journal of luminescence, vol. 99, pp. 91-100, 2002.
[28]N. Pradal, A. Potdevin, G. Chadeyron, P. Bonville, B. Caillier, and R. Mahiou, "Spectroscopic study and enhanced thermostability of combustion-derived BaMgAl10O17:Eu2+ blue phosphors for solid-state lighting," Optical Materials, vol. 64, pp. 334-344, 2017.
[29]G. Gumenchuk, M. Bludov, and A. Belov, "Photon-stimulated recombination of self-trapped holes with electrons in pre-irradiated solid Ar," Low temperature physics, vol. 31, pp. 179-181, 2005.
[30]Y. Li, Y. Wang, X. Xu, G. Yu, and F. Zhang, "Photoluminescence properties and valence stability of Eu in CaMgSiO4," Journal of The Electrochemical Society, vol. 157, pp. J39-J43, 2010.
[31]M. Peng and G. Hong, "Reduction from Eu3+ to Eu2+ in BaAl2O4: Eu phosphor prepared in an oxidizing atmosphere and luminescent properties of BaAl2O4: Eu," Journal of Luminescence, vol. 127, pp. 735-740, 2007.