臺灣博碩士論文加值系統

螢光粉的功用與效能與其粒徑大小息息相關，一般而言，粉體粒徑小其表面積較大會有較最佳發光效率，且量子效率較佳。本研究之主旨在於探討釔鋁石榴石螢光粉體之發光特性與粒徑之關係，並於製程中添加含Si之有機物或氧化物以瞭解Si與發光強度之關係。
本研究係以膠體共沈法、檸檬酸凝膠法及奈米固態法合成釔鋁石榴石摻鈰螢光粉體，並以物理及化學的方法改變其粒徑大小，以探討粒徑對發光強度之關係。另外，為探討Si對YAG螢光發光光譜之影響，本研究亦在膠體共沈法及檸檬酸凝膠法之燒結過程分別添加SiO2及HMDS(含Si之有機物)比較其趨勢。實驗結果的分析，乃利用XRD、EDS、FTIR進行晶體結構與組成之鑑定，並利用XRD圖譜求得螢光粉體之平均粒徑，輔以其他量測粒徑之方法，如雷射粒徑分析儀、穿透式電子顯微鏡照片等，且作光激發光譜瞭解發光特性與粒徑之關係。
研究結果顯示，利用膠體共沈法以不同溫度、不同持溫時間燒結及研磨的方式，可合成出粒徑22.0至34.4nm之螢光粉體；檸檬酸凝膠法在不同溫度下亦可合成出粒徑24.4至34.8nm之螢光粉體；奈米固態法利用不同研磨時間，可得有粒徑粒徑51.8至57.9nm之螢光粉體。由光激發光譜可發現螢光體粒徑愈大，發光強度有愈佳的趨勢。
在膠體共沈法及檸檬酸凝膠法之燒結過程分別添加SiO2及HMDS，由光激發光圖譜顯示添加SiO2的濃度愈高有較佳的發光強度(10 mole%>5 mole%>1 mole%>20 mole%>0 mole% SiO2)，但過多反而變差；有加入HMDS的螢光粉體亦較未添加的發光強度強很多，故Si的存在確實有助於發光。

This research is to investigate the effect of particle size of Ce-doped Y3Al5O12 (YAG: Ce) phosphors on luminescence. The effect of Si elements on luminescence properties of YAG: Ce phosphor is also studied here.
The nano-scale with well crystalline and single phase powder of Ce-doped Y3Al5O12 was synthesized by heat treatment of co-precipitation method, citric gel method and nano solid state method. Then, the different particle size of phosphors were changed by chemical and physics methods, for example, by varying calcinations temperature, holding time and grinding time. The X-ray diffraction, EDS, and FTIR were utilized in the characterization of crystal structure and phase purity. The particle size of YAG: Ce phosphors were calculated by X-ray diffraction pattern. Particle size analyzer and TEM were also utilized in the characterization of particle size. Photoluminescence (PL) spectroscopy was used to characterize the optical properties (emission intensity).
The minimum grain size was found to be 22.0 to 34.4nm for YAG phase synthesized by co-precipitation method. The minimum grain size was found to be 24.4 to 34.8nm for YAG phase synthesized by citric gel method. The minimum grain size was found to be 51.8 to 57.9nm for YAG phase synthesized by nano solid state method. The intensity of luminescence emission for Ce-doped YAG phase was found to increase with increasing particle size.
The effect of Si in YAG PL property was studied by two processing method, (a) Silicon oxide (SiO2) powders was added co-precipitation YAG and (b) HMDS (the organics compound of Si) was added in the citric gel YAG, respectively. The intensity of luminescence emission for Ce-doped YAG phase was found to increase with increasing SiO2 concentration, then reach a maximum and decrease as it further increase. Therefore, the Si element enhances the PL intensity of luminescence emission.

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 2hrs65
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 method69
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 SiO298
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

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