本論文係高效率與高可靠度玻璃螢光體於白光照明之研究，期能取代現今白光照明以螢光矽膠(低玻璃轉移溫度150℃)之架構。篩選鈉玻璃粉均勻混合黃色螢光粉(Y3Al5O12:Ce3+)後經燒結成玻璃螢光體，發現以700~850℃燒結完並切割拋光得到厚度0.5mm及直徑10mm的量子效率(QY)約68~65%，超過900℃燒結的QY降低至43%。經高解析度穿透式顯微鏡(HRTEM)觀察以700、800和900℃備製玻璃螢光體其擴散層寬度為2、5及25nm，表示玻璃螢光體以高溫燒結會使非晶矽擴散進YAG晶體，破壞發光機制而降低量子效率。以700℃燒結的玻璃螢光體構裝成白光發光二極體(WLED)後，其各角度色溫分佈(ACCTD)為350K。以150℃及250℃經1008小時的可靠度測試，證明玻璃螢光體的流明損失小於傳統矽膠螢光體7倍及38倍，與先前其他國外實驗室的玻璃螢光體/陶瓷螢光體技術研究比較，本研究提供高效率及高可靠度之玻璃螢光體製作技術。
本研究選用玻璃粉各別混合黃色螢光粉(Y3Al5O12:Ce3+)、綠色螢光粉(Lu3Al5O12:Ce3+)及紅色螢光粉(CaAlClSiN3:Eu2+)，分別以680、700及750℃燒結成玻璃螢光體，發現黃色與綠色玻璃螢光體在750℃下燒結可保持量子效率68~66%，而紅色玻璃螢光體量子效率隨著溫度上升而大幅降低。經HRTEM觀察擴散層寬度分別為10、150以及350nm，並分別在擴散層做元素分析發現隨溫度越高，紅色玻璃螢光體會有的碳化物產生而使量子效率下降。利用三種螢光粉混合鈉玻璃粉以680℃燒結後，切割拋光玻璃螢光體，量測其量子效率達55%。以445nm波長的LED與其構裝成WLED，色座標(CIE)及色溫(CCT)分別為(0.358, 0.288；3923K)，演色性(CRI)可達85，符合美國能源之星規範室內照明之CRI須大於80。以150℃、250℃經1008小時可靠度測試證明玻璃螢光體的流明損失小於傳統矽膠螢光體5倍及10倍。本研究成功研發兼具高效率及高可靠度之玻璃螢光體，此具有高玻璃轉移溫度(567℃)，擁有取代傳統商用矽膠螢光體的潛力，未來可應用於高功率固態照明系統上。

This doctorate dissertation is to study high-performance and high-reliability glass phosphors for WLED modules. The proposal glass phosphors are high reliability and expected to replace silica gel phosphors (low glass transition temperature, Tg, at 150℃) as the packaging materials for WLEDs. The mixture of sodium glass particles and phosphor crystals (Y3Al5O12:Ce3+) were sintered to form the glass phosphors. The quantum yield (QY) of the glass phosphors sintered at 750℃~850℃ was about 65~68%. The QY of the glass phosphors sintered at 900℃drops greatly to 43%. With the examination of high resolution transmission electron microscope (HRTEM), the distance of the diffusion of amorphous Si into YAG crystals were 2nm, 5nm and 25nm for the glass phosphors sintered at 700℃, 800℃, and 900℃, respectively. The diffusing Si atom damages the light-emitting mechanism of YAG crystals and decreases the QY of the glass phosphors. The WLED equipped with glass phosphor sintered under 700℃ has a angular correlated color temperature distribution (ACCTD) of 350K. In the 1008 hrs reliability tests, the luminescence loss of Ce3+:YAG doping silicone (CeYDS) were 7 and 38 times higher Ce3+:YAG doping glass (CeYDG) at 150℃ and 250℃, respectively. Compared with the study of glass/ceramic phosphor related technology revealed by other research groups, this study develops highly efficient and highly reliable glass phosphors.
The QY of glass phosphors with different phosphor crystals composition were also investigated. Yellow (Y3Al5O12:Ce3+), green (Lu3Al5O12:Ce3+), and red (CaAlClSiN3:Eu2+) phosphors were mixed uniformly with sodium glass and then sintered under 680℃, 700℃, and 750℃ to form glass phosphors. The yellow and green glass phosphor still keeps the QY at 66%~68% under 750℃ sintering temperature, while the QY of the red glass phosphors decreases dramatically with the rising sintering temperature. The diffusion widths were 10nm, 150nm and 350nm by HRTEM for the glass phosphors sintered at 680℃, 700℃, and 750℃. The result of HRTEM and element analysis both indicates that the red glass phosphor sintered at high temperature generates carbide, which has a bad influence on its QY.
High-CRI glass phosphors were realized by mixing multiple phosphors with sodium glass powder and then sintered at 680℃. The QY of the glass phosphor is up to 55%. A WLED packaging with the glass phosphors shows CIE and CCT at (x=0.358, y= 0.288；3923K). The CRI of the WLED reaches 85, which meets the regulation by USA Energy Star for interior lighting. In the 1008 hrs reliability tests, the luminescence loss of yellow, green, red phosphor doping silicone (YGRDS) were 5 and 10 times higher yellow, green, red phosphor doping glass (YGRDG) at 150℃ and 250℃, respectively. In summary, this study realizes color convention layer of WLEDs with high performance and high reliability. The glass phosphors have the potential to replace silicon phosphors for the application of high power solid state lighting.

摘要………………………………………………………………………………………………………..i
Abstract………………………………………………………………………………………………….ii
誌謝………………………………………………………………………………………………………iii
索引………………………………………………………………………………………………………iv
內容目錄…………………………………………………………………v
圖目錄……………………………………………………………………ix
表目錄…………………………………………………………………..xiv
第一章 緒論…………….………………….………………..……………1
第一節 發光二極體的發展概述….………………………………..1
第二節 研究背景與動機………….………………………………..2
第三節 研究目標與章節介紹…….………………………………..4
參考文獻…………………..………………..………………………10
第二章LED構造及基本原理…………………………….……............11
第一節 WLED發光形式……….…………………………….........11
第二節 LED介紹及發展…………………………………………..12
第三節 LED晶片發光原理………………………………………..13
第四節 色彩學原理………………………………………………..15
壹、 色座標系統…………………………………….……..16
貳、 色溫系統…………………………………………..….18
參、 演色係數…………………………………………...…19
第五節 光致發光螢光機制………………………………………..21
壹、 振動-電子躍遷……………………………………….21
貳、 散射吸收……………………………………………..22
參、 視覺函數………………………………………...…...23
肆、 頻譜視覺效應……………………………………..….23
第六節 螢光粉物理機制
壹、 主體晶格……………………………………....……...24
貳、 稀土元素……………………………..………..…..….25
參、 YAG:Ce3+之結構與特性…..………..……………….26
肆、 LuAG:Ce3+之結構與特性…………………………....26
伍、 CaAlSiN3:Eu2+之結構與特性………………….…….26
第七節 玻璃物理特性
壹、 玻璃理論………………………………………….…..27
貳、 鈉玻璃熱學性質……………………….……….…….28
參考文獻………………………….………………………………..42
第三章 儀器設備與原理…..………………………….…….….............48
第一節 熱示差分析儀……………………………………….....….48
第二節 行星式球磨機……………………………………………..48
第三節 聚焦離子束……………………………………….……….49
第四節 場發射型穿透式電子顯微鏡……………………………..50
第五節 能量散佈分析儀…………………………………………..50
第六節 X光繞射儀……………………………………………......51
第七節 光致螢光光譜儀………………………………………..…51
第八節 積分球量測系統…………………………………………..52
第九節 視角機……………………………………………..………53
參考文獻…………………………………………..………………..62

第四章 玻璃螢光體研發與實驗結果討論…………….…....................63
第一節 玻璃螢光體文獻分析………………………….…….........63
第二節 玻璃螢光體製作流程……………………….…………….64
第三節 玻璃螢光體最佳化研發…………………….…………….65
壹、 玻璃粉徑對玻璃螢光體之影響………………….…..65
貳、 真空製程對玻璃螢光體之影響……………………...65
參、 燒結溫度對玻璃螢光體之影響.……….…………….67
肆、 螢光粉摻雜濃度對玻璃螢光體之影響………...……68
第四節 玻璃螢光體與矽膠螢光體之可靠分析…….…………….69
第五節 高演色性玻璃螢光體最佳化研發………….…………….70
壹、 黃、綠及紅色玻璃螢光體光學特性…..……………71
貳、 紅色玻璃螢光體微結構分析………………………..71
參、 高演色性玻璃螢光體………………………….….…72
第六節 高演色性玻璃螢光體與矽膠螢光體之可靠度分析….….73
參考文獻……………………………………………………..……..95
第五章 結論與建議…………….……………….……….………….….96
第一節 結論………………………………………………………..96
第二節 建議………………………………………………………..97

作者簡介……………………………………………………..…………99
學術著作……………………………………………………..………..100

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