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研究生:陳奕如
研究生(外文):Chen Yi-Ru
論文名稱:ZnS:Sm螢光體的製備與其發光性質之研究
論文名稱(外文):The study of Preparation and Photoluminescence on ZnS:Sm Phosphors
指導教授:唐自標
指導教授(外文):Tang Tzu-Piao
學位類別:碩士
校院名稱:國立臺北科技大學
系所名稱:材料及資源工程系碩士班
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2001
畢業學年度:89
語文別:中文
論文頁數:140
中文關鍵詞:螢光材料硫化鋅助熔劑活化劑發光機制
外文關鍵詞:LuminescenceZnSFluxActivatorLuminescent mechanism
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摘 要
本研究在探討合成ZnS:Sm螢光體時,而添加助熔劑對其發光性質之影響,而添加助熔劑有KF、LiCl、LiCl+ LiF、及KF + LiF等四種。
在燒成環境為還原燒成時,加入助熔劑中的Li+,因Li+的離子半徑小(0.059nm),容易進入ZnS的晶格之中,輔助電子的傳達,形成Sm離子化的發光機制,故使母體發光變弱,Sm的特性光增強;而添加助熔劑中的Cl—會和Sm反應,導致形成Sm-VZn-Cl—的機制,因Cl—離子半徑較大(0.181nm),所以只要Sm相化合物所佔的比例在一定的數量下,便能夠有效的抑制PL光譜中母體發光的出現,而加入助熔劑的K+(0.138nm)和F—(0.133nm)其離子半徑介於中間,對於F—也可能和Sm反應形成SmF3,跟Cl—比時則比較不容易形成此成份,K+則在ZnS外層,使ZnS顆粒成長。當ZnS有適量的α相(Hexagonal)(80%~90%)時會有較好的激光吸收,在低濃度的Sm,其發光機制為介穩定的Sm2O2S相,高濃度時,其發光機制則為Sm2O3六方晶及Sm2O2S相存在,有促進Sm的特性光譜產生。將不同種類的助熔劑之P.L.發光光譜取其最顯著的Sm發光特性峰(653nm)比較之,可發現ZnS:Sm加入不同助熔劑其發光效果由最強到最弱順序為(1)添加ZnS:0.20mol%Sm及助熔劑0.60mol%KF時所得到的發光強度最強,(2)ZnS:0.30 mol%Sm及助熔劑4.00mol%LiCl發光強度是其次,(3)再來發光強度就是ZnS:0.30 mol%Sm添加助熔劑0.90mol%LiCl+LiF,(4)最後發光強度就是ZnS:0.30mol%Sm添加助熔劑0.90mol% KF+LiF。
添加不同助熔劑的Sm發光機制,其電子遷移的路徑均為4G5/2 ===>6H9/2、4G5/2 ===>6H7/2與4G5/2 ===>6H5/2,各可得570nm、606nm和653nm的發光波峰,其波長都處在紅色光譜範圍內。

abstract
The study of Luminescence to Flux in Zinc Sulfide Doping Sm Red Phosphors, and Flux are four kinds compound of LiCl、KF、LiCl + LiF、and KF + LiF.
When Li+ added to ZnS:Sm that is easy into ZnS crystal lattice space in reduced-firing for Li+ radius is small size, electron can transmit speed up, and that form ZnS:Sm luminescence of luminescent mechanism, we can detect red Sm characteristic spectrum to increase and eliminate from host lattice luminescence. When Cl—added to ZnS:Sm, Cl—and Sm3+ together causes a reaction, it lead to form Sm-VZn-Cl—, The Cl— radius is big size that can easy reaction with Sm3+ form Sm compound, that can control effective, host lattice luminescence in PL spectrum. When K+ and F— add to ZnS:Sm, that F— can be react with Sm3+ to form SmF3 compound, Cl— easy reaction with Sm3+ than F—. The K+ surround particle of ZnS and make ZnS of particle grow up.
The main of ZnS for hexagonal phase that helps better Sm3+ excitation absorption. When Sm3+ into ZnS is lower concentration is Sm2O2S phase of luminescent mechanism, high concentration Sm3+ have Sm2O3(Hex) and Sm2O2S phase, sample can be found red characteristic spectrum and spectrum shades of color nice better. And all different kinds of flux of PL spectrum take 653nm wavelength can find flux better conditions and intensity order. ZnS:Sm added LiCl flux has better luminescence for 0.30mol%Sm, 4.00mol%LiCl. ZnS:Sm added KF flux has better luminescence for 0.20mol%Sm, 0.60mol%KF. ZnS:Sm added LiCl and LiF flux has better luminescence for 0.30mol%Sm, 0.90mol% LiCl and LiF. ZnS:Sm added KF and LiF flux has better luminescence for 0.30mol%Sm, 0.90mol% KF and LiF. All flux of luminescence occur ways are 4G5/2===>6H9/2(653nm),4G5/2===>6H7/2(606nm), 4G5/2 ===>6H5/2 (570nm) can get there wavelength in red spectrum region.

目 次
摘 要 -------------------------------------------------------------------------------------- iii
Abstract ----------------------------------------------------------------------------iv
誌 謝 -------------------------------------------------------------------------------------v
List of Table ---------------------------------------------------------------------------------- ix
List of Figure ----------------------------------------------------------------------------------x
第一章 前 言 ----------------------------------------------------------------------------- 1
1.1 螢光材料的發展歷史 ---------------------------------------------------------- 2
1.1.1 第二次世界大戰戰前 -------------------------------------------- 2
1.1.2 第二次世界大戰戰後 -------------------------------------------- 3
1.2 螢光材料之分類 --------------------------------------------------------------- 5
1.2.1 依螢光材料組成分類 ------------------------------------------- 5
1.2.2 依螢光材料發光物性分類 --------------------------------------6
1.2.3 依螢光材料性質分類 -------------------------------------------8
1.3 螢光材料的應用 -------------------------------------------------------------9
1.4 影像顯示器之歷史 ----------------------------------------------------------9
1.5 研究背景 ----------------------------------------------------------------------11
1.6 研究目的 ----------------------------------------------------------------------12
第二章 ZnS螢光材的發光原理及性質 ----------------------------------------------23
2.1 ZnS螢光粉的結構 ----------------------------------------------------------23
2.2 助熔劑之影響 ----------------------------------------------------------------24
2.3 發光原理 ----------------------------------------------------------------------24
2.3.1 激光 ( Excitation ) -----------------------------------------------25
2.3.2 發光 ( Luminescence ) -------------------------------------------27
2.4 ZnS:Sm發光原理 ----------------------------------------------------------29
第三章 實 驗 步 驟 ----------------------------------------------------------44
3.1 材料與設備 -------------------------------------------------------------------44
3.2 螢光粉的製作流程及燒成方式 -------------------------------------------46
3.3 特性測試 ----------------------------------------------------------------------48
3.3.1 X射線測試 -------------------------------------------------------48
3.3.2 掃瞄式電子顯微鏡測定 ----------------------------------------48
3.3.3 發光光譜測定------------------------------------------------------48
第四章 結 果 與 討 論 -------------------------------------------------------60
4.1 助熔劑LiCl的影響 ----------------------------------------------------------60
4.1.1 PL光譜之分析 ----------------------------------------------------60
4.1.2 X-ray 相結構分析 ------------------------------------------------61
4.1.3 SEM之分析 --------------------------------------------------------62
4.2 助熔劑KF的影響 ------------------------------------------------------------63
4.2.1 PL光譜之分析 ----------------------------------------------------63
4.2.2 X-ray 相結構分析 -----------------------------------------------64
4.2.3 SEM之分析 -------------------------------------------------------64
4.3 助熔劑LiCl&LiF的影響 ---------------------------------------------------65
4.3.1 PL光譜之分析 ----------------------------------------------------65
4.3.2 X-ray 相結構分析 ------------------------------------------------66
4.3.3 SEM之分析 -------------------------------------------------------66
4.4 助熔劑KF+LiF 的影響------------------------------------------------------68
4.4.1 PL光譜之分析 ---------------------------------------------------68
4.4.2 X-ray 相結構分析 ------------------------------------------------69
4.4.3 SEM之分析 -------------------------------------------------------69
4.5 總 結 ------------------------------------------------------------------------71
第五章 結論及建議 --------------------------------------------------------------118
第六章 參 考 資 料 ----------------------------------------------121
Appendix -----------------------------------------------------------------123
A Energy unit, Frequency and wavelength. --------------------125
B α-ZnS、β-ZnS and ZnO of PDF standard peak intensity. ---------126

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