中文摘要..............................I 英文摘要..............................II 目錄..................................IV 圖目錄................................VII 表目錄................................XIII 第一章 緒論...........................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.............4 2-1螢光材料簡介.......................4 2-2螢光材料的分類.....................4 2-3發光機制簡介.......................6 2-3.1螢光與磷光.......................6 2-3.2激發種類及應用...................7 2-4螢光材料的發光原理.................8 2-4.1螢光體能量的激發與吸收...........8 2-4.2螢光放射和非輻射轉移.............8 2-5螢光中心型螢光材料.................10 2-5.1 螢光體結構......................10 2-5.2 螢光體的設計....................11 2-5.3 螢光體的發光特性................12 2-5. 稀土離子的發光特性...............13 2-6螢光體發光的特性的測量.............14 2-6.1亮度量測.........................14 2-6.2放射光譜的量測...................14 2.6.3量子效率的量測...................14 2-6.4衰減期的量測.....................15 2-6.5色度座標.........................16 2-7 YAG型螢光材料的簡介...............17 2-7.1 歷史沿革........................17 2-7.2釔鋁柘榴石晶體結構介紹...........18 2-7.3 YAG:Ce3+的發光光譜..............19 2-8奈米螢光體簡介.....................19 2-8.1 超徵粒子粉體之簡介..............19 2-8.2 一次粒子與二次粒子..............20 2-8.3 超微粒子的特性..................20 2-8.4納米粒子的型態與組成分析.........22 2-8.5納米螢光體之特性.................22 2-9文獻回顧...........................22 2-10螢光體製程技術及原理..............25 2-10.1固態燒結法..............25 2-10.2膠體共沈法......26 2-10.3檸檬酸凝膠熱分解法法....26 3-1實驗藥品.....................49 3-2合成步驟與流程...............50 3-2.1膠體共沈法.......50 3-2.2固態燒結法...............50 3-2.3檸檬酸凝膠法.....50 3-3儀器設備...........................51 第四章 結果與討論.....................57 4-1螢光體之合成與XRD結構分析..........57 4-1.1膠體共沈法.......................57 4-1.1.1前驅物(precursor)之熱重分析....57 4-1.1.2不同燒結溫度改變粒徑大小.......57 4-1.1.3不同持溫時間改變粒徑大小.......57 4-1.1.4不同球磨時間改變粒徑大小.......57 4-1.1.5添加SiO2 粉末..................58 4-1.2檸檬酸凝膠法.....................58 4-1.2.1前驅物(precursor)之熱重分析....58 4-1.2.2不同燒結溫度改變粒徑大小.......58 4-1.2.3添加LiCl助熔劑.................59 4-1.2.4添加HMDS.......................59 4-1.3奈米固態法.......................60 4-1.3.1不同球磨時間改變粒徑大小.......60 4-2螢光粉體之粒徑大小分析、組成鑑定與FTIR分析.......75 4-2.1 XRD繞射法.......................75 4-2.1.1膠體共沈法.....................75 4-2.1.2檸檬酸凝膠法...................75 4-2.1.3奈米固態法.....................76 4-2.2螢光體微觀結構觀察...............76 4-2.3光散射法.........................76 4-2.4組成鑑定.........................76 4-2.5 FTIR 分析.......................77 4-3螢光體發光特性之研究...............92 4-3.1粒徑大小對YAG: Ce螢光體PL光譜之影響.........92 4-3.2添加HMDS及SiO2對YAG: Ce螢光體PL光譜之影響...92 第五章 結論...........................100 5-1粒徑對發光強度之影響...............100 5-2 Si對發光強度之影響................101 參考文獻..............................102 Fig.1-1 The mechanism of energy transform.......3 Fig.2-1 Jablonski diagram, which explains photophysical processes in molecular systems........32 Fig.2-2 Configurational coordinate diagram.......33 Fig.2-3 The diagram of Stokes shift.......34 Fig.2-4 The influence of coupling on emission spectra.......34 Fig.2-5 Nonradiative transitions in the configurational coordinate diagram.(a)strong coupling; (b) weak coupling; (c) combination of both.......35 Fig.2-6 Energy transfer of the activator A in its host lattice.......36 Fig.2-7 Energy transfer of a sensitizer S to an activator A in its host lattice .......36 Fig.2-8 Munsell coordinate diagram.......37 Fig.2-9 Tristimulous Response of the Human Eye.......37 Fig.2-10 CIE Chromaticity coordinate diagram.......38 Fig.2-11 The effect of activator concentration on phosphor efficiency.......39 Fig.2-12 The effect of poison centers on phosphor efficiency.......39 Fig.2-13 The effect of temperature on phosphor efficiency.......40 Fig.2-14 Concentration quenching occurs when the activator concentration becomes sufficiently high that efficient energy transfer permits the excitation energy to migrate through the host until it is trapped at a poison site.......40 Fig.2-15 The phase diagram of the Y2O3-Al2O3 system.......41 Fig.2-16 The unit cell and properties of the YAG compound.......42 Fig.2-17 Energy levels of trivalent lanthanide ions.......43 Fig.2-18 Energy-level diagram and absorption / fluorescence spectra of Ce3+ doped Y3Al5O12 at 295.......44 Fig 2-19 The schematic aggregate and agglomerate.......45 Fig 2-20(a) The formula of citrate acid.......46 Fig 2-20(b) The formula of ethylene glycol.......46 Fig 2-21 The schematic of esterification and Polymerization .......47 Fig 2-22 The formula of Citric gel.......48 Fig.3-1 The flow chart of synthesis of YAG:Ce phosphor powders by co-precipitation.......53 Fig.3-2 The flow chart of synthesis of YAG:Ce phosphor powders by solid state .......54 Fig.3-3 The flow chart of synthesis of YAG:Ce phosphor powders by citric gel method.......55 Fig.3-4 The equipment of Labgide spectrofluorophotometer.......56 Fig. 4-1 The XRD pattern of YAG powders by co-precipitation and calcinated at 850℃ for 2hrs 65 Fig. 4-2 DTA-TGA analysis of YAG precursor powders by co-precipitation method .......65 Fig.4-3 The XRD patterns of YAG: Ce phosphor prepared by co-precipitation and calcinate 8 hrs at (a)980℃ (b)900℃ (c)850℃ (d)800℃.......66 Fig.4-4 The XRD patterns of YAG: Ce phosphor prepared by co-precipitationand calcinate at 850℃for (a) 8 hr (b) 32 hr (c) 64 hr (d) 128hr.......66 Fig.4-5 The XRD patterns of YAG: Ce phosphor prepared by co-precipitation and calcinate at 850℃for 128hr with grinding time (a)12 hr (b)25 hr (c)50 hr (d)100 hr.......67 Fig.4-6 The XRD (420) peak intensity of YAG: Ce phosphors with different grinding time.......67 Fig.4-7 The XRD patterns of YAG: Ce phosphor prepared by co-precipitation method and adding (a) 0mole% (b) 1mole% (c) 5mole% (d) 10mole% SiO2.......68 Fig. 4-8 The XRD pattern of YAG powders by citric gel method and calcinated at 900℃ for 2hrs.......69 Fig. 4-9 DTA-TGA analysis of YAG precursor powders by citric gel method 69 Fig.4-10 The XRD patterns of YAG: Ce phosphor prepared by citric gel method and calcinate 2 hrs at (a) 1100℃(b) 1000℃(c) 900℃(d)800℃(e)700℃.......70 Fig.4-11 The XRD patterns of YAG: Ce phosphor prepared by citric gel method and calcinate for 2 hrs at (a) 650℃with adding LiCl flux (b) 800℃no flux.......70 Fig 4-12 金屬氧化物利用sol-gel法所製成之非晶質材料經熱處理過程其微觀結構之示意圖 .......71 Fig 4-13 經由HMDS 處理之前驅物，其粒子與粒子之間在熱處理過程中，不會因為表面官能基的反應而拉近，而各自單獨進行局部性的結晶過程.......72 Fig.4-14 The FTIR spectra patterns of YAG: Ce phosphor precursor by citric gel method.......73 Fig.4-15 The XRD patterns of YAG: Ce phosphor prepared by citric gel method calcinated at 800℃ for 2hr (a) no HMDS (b) adding HMDS.......73 Fig. 4-16 The XRD pattern of YAG by nano solid state sintered at 1200℃ for 4hr .......74 Fig.4-17 The XRD patterns of YAG: Ce phosphor prepared by nano solid state sintered at 1200℃ for 4hr and with a grinding time (a)12 hr (b)50 hr (c)100 hr .......74 Fig 4-18 A plot of log(grain size) (log D) versus the reciprocal of absolute temperature(1/T) of samples processed by co-precipitation method.......81 Fig 4-19 A plot of log(grain size) (log D) versus the reciprocal of absolute temperature(1/T) of samples processed by citric gel method.......81 Fig. 4-20.The TEM picture and SAD of YAG:Ce powder by citric gel method.......82 Fig. 4-21 The TEM picture and SAD of YAG:Ce powder by co-precipitation method.......82 Fig. 4-22 The TEM picture and SAD of YAG:Ce powder by nano solid state method .......83 Fig. 4-23 The particle size analysis of YAG:Ce by co-precipitation method calcinated at 980℃ for 8hr.......83 Fig. 4-24 The particle size analysis of YAG:Ce by co-precipitation method calcinated at 900℃ for 8h.......84 Fig. 4-25 The particle size analysis of YAG:Ce by co-precipitation method calcinated at 850℃ for 8hr.......84 Fig. 4-26 The particle size analysis of YAG:Ce by co-precipitation method calcinated at 850℃ for 32hr.......85 Fig. 4-27 The particle size analysis of YAG:Ce by co-precipitation method calcinated at 850℃ for 64hr.......85 Fig. 4-28 The particle size analysis of YAG:Ce by co-precipitation method calcinated at 850℃ for 128hr and with grinding 12hr.......86 Fig. 4-29 The particle size analysis of YAG:Ce by co-precipitation method calcinated at 850℃ for 128hrfor 850℃ 128hr with grinding 25hr.......86 Fig. 4-30 The particle size analysis of YAG:Ce by co-precipitation method calcinated at 850℃ for 128hr with grinding 50hr.......87 Fig. 4-31 The particle size analysis of YAG:Ce by co-precipitation method calcinated at 850℃ for 128hr with grinding 100hr.......87 Fig. 4-32 The particle size analysis of YAG:Ce by citric gel method calcinated at 800℃ for 2hr.......88 Fig. 4-33 The particle size analysis of YAG:Ce by citric gel method calcinated at 900℃ for 2hr.......88 Fig. 4-34 The particle size analysis of YAG:Ce by citric gel method calcinated at 1000℃ for 2hr.......89 Fig. 4-35 The particle size analysis of YAG:Ce by citric gel method calcinated at 1100℃ for 2hr.......89 Fig. 4-36 The particle size analysis of YAG:Ce by nano solid state method calcinated at 1200℃ for 4hr with grinding 12hr.......90 Fig. 4-37 The particle size analysis of YAG:Ce by nano solid state method calcinated at 1200℃ for 4hr with grinding 50hr.......90 Fig. 4-38 The particle size analysis of YAG:Ce by nano solid state method calcinated at 1200℃ for 4hr with grinding 100hr.......91 Fig. 4-39 The FTIR analysis of YAG:Ce phosphor processed by (a) nano solid state (b) citric gel method (c) co-precipitation method.......91 Fig. 4-40 Effect of sintering temperature on the PL of YAG:Ce phosphors by co-precipitation method.......94 Fig. 4-41 Effect of different holding time at 850℃ on the PL of YAG:Ce phosphors by co-precipitation method.......94 Fig. 4-42 Effect of different grinding time on the PL of YAG:Ce phosphors prepared by co-precipitation method.......95 Fig. 4-43 Effect of different sintering temperatures on the PL of YAG:Ce phosphors prepared by citric gel method.......95 Fig. 4-44 Effect of different grinding time on the PL of YAG:Ce phosphors by nano solid state method.......96 Fig. 4-45 The integration intensity of emission spectra of YAG:Ce phosphor vs. particle size by different synthesis methods.......96 Fig. 4-46 Effect of adding HMDS on the PL of YAG:Ce phosphors by citric gel method.......97 Fig. 4-47 The integration intensity of emission spectra of YAG:Ce phosphor vs. particle size by citric gel method with(out) HMDS.......97 Fig. 4-48 Effect of adding SiO2 on the PL of YAG:Ce phosphors by co-precipitation method.......98 Fig. 4-49 The integration intensity of emission spectra of YAG:Ce phosphor vs. particle size by co-precipitation method added different amounts SiO2 98 Fig. 4-50 Effect of adding (or not adding) 10mole% SiO2 on the PL of YAG:Ce phosphors by co-precipitation method.......99 Fig. 4-51 The integration intensity of emission spectra of YAG:Ce phosphor prepared by co-precipitation method added 10mole% SiO2 after(or before calcinations).......99 Table 2-1 Phosphor Devices.......28 Table 2-2 Anions that can be used to form Phosphor.......29 Table 2-3 Anions that are optically active-“self-activation’.......29 Table 2-4 Cations that can be used to form phosphors.......30 Table 2-5 Cations that can be used as activator center.......30 Table 2-6 Cations with unpaired spins which function as quenchers of luminescence.......31 Table 2-7 The measurement of particle size.......31 Table 2-8 The radius of metal ion.......31 Table 4-1 Experimental design of different calcination temperatures by co-precipitation method.......61 Table 4-2 Experimental design of different holding times by co-precipitation method.......61 Table 4-3 Experimental design of different grinding times by co-precipitation method.......62 Table 4-4 Experimental design of adding different amounts SiO2 powders by co-precipitation method.......62 Table 4-5 Experimental design of different calcination temperatures by citric gel method.......63 Table 4-6 Experimental design of citric gel method adding 20wt% LiCl flux .......63 Table 4-7 Experimental design of different calcination temperatures by citric gel method adding HMDS.......63 Table 4-8 Experimental design of different grinding times by Nano solid state method.......64 Table 4-9 YAG:Ce particle size from Scherrer’s equation (by XRD pattern) .......78 Table 4-10 EDS analysis of th YAG:Ce phosphors prepared by co-precipitation method.......80 Table 4-11 EDS analysis of th YAG:Ce phosphors prepared by citric gel method .......80 Table 4-12 EDS analysis of th YAG:Ce phosphors prepared by nano solid state method.......80