藍光發光二極體 (light emitting diode, LED) 晶片，搭配鈰摻雜之釔鋁石榴石 (yttrium aluminum garnet doped with cerium, YAG:Ce) 黃色螢光粉的白光產品，肇始了 LED 應用的新紀元，其中高可靠性、製作簡便與低成本等優點是使 YAG 系列產品於光源市場上佔重要地位的依據。本論文除了利用噴霧乾燥製備球形 YAG:Ce 與 YAG:Tb (terbium, 鋱) 螢光粉外，另於 YAG 中大量添加鋱離子並促使螢光主體由 YAG 轉變為鋱鋁石榴石 TbAG (terbium aluminum garnet)，主要探討添加濃度、合成溫度與氣氛等對此螢光粉之結構與特性上的影響，內容依序如下。
1. 透過 pH 控制方法，純相的 YAG:Ce 能夠順利被合成出，其中氫氧化鈉 (NaOH) 助熔劑是扮演重要的角色，除此之外，由噴霧乾燥方法所產出球形顆粒也幫助螢光粉達到均勻的凝聚，並產生更適合的光致發光 PL (photoluminescence) 特性。
2. 活化物濃度、相雜質、煆燒條件與粉體結晶性等因素主導螢光粉的 PL 特性，雖本研究產品 (YAG:Ce) 在煆燒後發現大部分有二氧化鈰 (CeO2) 殘留，但是因為有更高的結晶度與較少缺陷 (煆燒在 1500oC/8 h) 而促使產品有更高的發光強度；相反的，殘留 CeO2 的產品 (Ce3+ 添加量: 2.50 at.%) 被發現有較低的發光強度，也因此降低結構參數分析擬合的信賴度與品質。
3. Tb3+ 離子在氧化環境下很容易轉變為 Tb4+，且 Tb4+ 也能藉由在YAG 主體中共添加 Mg2+ (鎂) 離子而被誘導出，比單添加 Tb 離子於 YAG 的螢光粉來說，共添加氧化鎂 (MgO) 會抑制晶粒成長的行為，除此之外，PL 發光強度的降低主要是由 Tb4+ 離子與微結構的缺陷所引起，同時存在 Mg2+ 和 Tb4+ 離子也會對 YAG 晶體結構造成一定的影響。
4. 在 YAG 中釔離子完全的被鋱離子取代可形成 TbAG，PL 和陰極發光 CL (cathodoluminescence) 強度在更高的鋱離子添加時會因濃度而發生粹滅，本研究中比較適當的鋱離子添加量為 15 ~ 20 at.%，且鋱離子濃度是此 YAG/TbAG 固溶系統中最重要的因素，同時影響到粉體微結構、反射和螢光特性、激發光能轉移和晶體結構。
5. Theta-Al2O3 (氧化鋁) 在本階段研究被 alpha-Al2O3 取代成為起始材料，且由與鹽酸(HCl) 溶液比較下，NaOH 溶液也被證實對合成是更有幫助，在 YAG/TbAG 主體中，Ce3+ 離子的晶格場分裂與 Ce3+-O2- 鍵長縮減是被關連到 Ce3+ 的發光特性，其中結構因 Tb3+ 離子添加而膨脹之時，Ce3+ 離子的激發 PL excitation (PLE) 與發光 (PL) 光譜和色度圖也偏移到更長的波長位置，且 Tb3+ 離子 (或 TbAG 主體) 不僅扮演一個不發光角色，也使 (Y/Tb)AG:Ce 系統因高濃度而發光粹滅。
6. 在氮氫混和氣 (N2/H2) 與空氣下分別合成的兩種 YAG-TbAG 固溶體，其吸收與發光光譜特性明顯不同，在空氣氣氛下，Tb 離子由三價轉變成四價是這些光譜改變的重要依據，也因此造成更小的晶格參數，非均勻性加寬的發光光譜明顯出現在 N2/H2 合成的樣品中，但消失於空氣製備的樣品，本系統中，當 Tb3+ 添加量超過 20 at.%，濃度粹滅效應仍然存在。

Blue light emitting diode (LED) chip coated with a yellow yttrium aluminum garnet doped with cerium ions (YAG:Ce) phosphor has led to the commercial production of white LED. The advantages of good reliability, simple preparation, low cost and so on are the reasons why this YAG product has been popular on the market for a long time. This dissertation not only investigates the spherical YAG:Ce and YAG:Tb (terbium) phosphors granulated by a spray-drying method, but also studies the host transition from YAG to TbAG (terbium aluminum garnet) synthesized with the maximum replacement of yttrium ions in YAG. The effects of dopant concentration, temperature and atmosphere used in the synthesis and so forth on structure and property of the system are mainly studied in the dissertation as follows:
1. Pure YAG:Ce can be successfully synthesized without second phase through the pH control. The flux, sodium hydroxide (NaOH) solution, actually acts as an important role. In addition, the spherical particles granulated with the spray-drying method produce the homogeneous agglomerate of phosphors and consequently achieve more favorable photoluminescence (PL) properties in this study.
2. The factors, such as activator concentration, phase impurity, calcination term, and powder crystallinity dominate the PL properties of phosphors. Most of these products (YAG:Ce) are identified as YAG and CeO2 phases after calcination, showing higher emission intensity resulted from higher crystallinity and less defect of phosphor (calcined at 1500oC/8 h). On the contrary, the product with CeO2 is found to have lower emission intensity (Ce3+ doping content: 2.50 at.%), and therefore decrease the reliability and goodness of fit when refining its atomic parameters.
3. Tb3+ ions have a strong trend to transform into Tb4+ ions under an oxidizing environment, and Tb4+ is induced and obtained by incorporating magnesium (Mg2+) ions into YAG host in the study. MgO co-doping restrains the grain growth behavior than single-doped YAG:Tb phosphors. Furthermore, the decrease of PL intensity is mainly caused by Tb4+ ions and the defect of microstructure of phosphor, and the co-existence of Mg2+ and Tb4+ in the YAG matrix also results in some changes in crystal structure.
4. TbAG is the complete solid solution with the maximum replacement for Y ion in YAG. The Tb3+ concentration quenchings of PL and cathodoluminescence (CL) emission intensities with higher Tb doping levels are shown, and the suitable Tb3+ concentration is between 15 ~ 20 at.% in this work. The Tb3+ concentration is the most important factor in YAG/TbAG system in the study, influencing the microstructure of powder, reflective and fluorescent properties, energy transfer of excitation light, and crystal structure.
5. Theta-Al2O3 is replaced by alpha-Al2O3 as one of the starting materials in the system. In addition, NaOH solution is selected for the synthesis as comparing with hydrochloric acid (HCl). The crystal field splitting of Ce3+ in YAG/TbAG host and the lowering of Ce3+-O2- bond lengths are correlated with luminescent properties in this study. PL excitation (PLE) and PL spectra, and chromaticity diagram of Ce3+-garnet shift to a longer wavelength while the structures expand with the increasing content of Tb3+ ions. The Tb3+ ions (or TbAG) not only act as a non-radiative role, but bring the concentration quenching in the (Y/Tb)AG:Ce material.
6. The absorption and luminescence spectra of compounds in YAG-TbAG solid solution synthesized in a N2/H2 (nitrogen/hydrogen) are significantly different from those synthesized in air. The oxidation of Tb from 3+ to 4+ when synthesized in air is the key factor in the variation of spectra, and it also results in smaller lattice constants for the Tb-garnets. The inhomogeneous broadening effect obviously occurs in the phosphors synthesized in N2/H2, but it disappears in the air-prepared system. The concentration quenching is still found because of an excess of Tb3+ doping, at more than 20 at.%, in the system.

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