无机荧光体材料化学

無機螢光體材料化學Materials Chemistry of Inorganic Phosphors
國立交通大學應用化學系
陳登銘
tmchen@.tw
Tel: 31695
無機螢光體材料化學
Materials Chemistry of Inorganic Phosphors
三13:30-14:20 四10:10-12:00
課程內容
1. 無機螢光材料簡介
2. 螢光材料發光原理與光學特性
3. 無機螢光材料之設計
4. 無機螢光材料之製備
5. 無機螢光材料之特性鑑定
6. 螢光材料之應用與研發展望Textbooks
1. G. Blasse and B. C. Grabmeier: “Luminescent Materials”,Spinger-Verlag, Berlin (1994)
2. R. C. Ropp: “Luminescence and the Solid State”, Elsevier Science Publishers, The Netherlands (1991)
References
發光學與發光材料」」化學工業出版社(中國1. 徐叙瑢、蘇勉曾:「發光學與發光材料
北京2004)
2. Phosphor Handbook: S. Shiyonoya and W. M. Yen,
CRC Press, Boca Raton, FL, USA, (1998).
3. Handbook of Luminescence, Display Materials and Devices, Vol. 3: H. S. Nalwa, American Scientific Publishers, USA (2003)
Grading
1. Midterm test 45%
2. Final exam 45%
3. Quizzes 10%
Luminescent Materials (1994)
G. Blasse(荷蘭University Utrecht) and B. C. Grabmeier(德國Siemens Research Lab)
Luminescence and the Solid State R. C. Ropp(Elsevier, 1991)
無機螢光材料之主要應用
一、螢光體相關的基本概念
1. 螢光與磷光(Fluorescence and phosphorescence)
2 .電子躍遷選擇律(Electronic transition rules)
3. 螢光衰減特性(Decay properties)
4. 激發光譜與發射光譜
(Excitation and emission spectra)
5. 長餘輝與餘輝衰減
(Long afterglow and afterglow decay)
凝態物質中常見發光凝態物質中常見發光((冷光冷光))之分類
Jablonski diagram –describing light absorption and emission and illustrating various molecular processes that occur in excited states.
F l u o r e s c e n c e Phosphorescence (103 -1 sec -1)
-h νp
Absorption
10-8sec -1
螢光與磷光產生之過程單態(singlet)
三態(triplet)
非輻射緩解(radiationless decay)
Introduction
Luminescence–emission of light from any substances occurs from the electronically excited states.
(Used for QE
measurements)
Structures of typical fluorescent molecules (fluorophores). Jablonski Diagrams
-Alexander Jablonski, generally regarded as the father of fluorescence spectroscopy of the 20th century
Characteristics of fluorescence
-Stokes’shift : fluorescence typically occurs at lower energy and longer λ
-Emission spectra are typically independent of λex (Kasha’s rule)
-Exception to the mirror image rule (deviations attributed to the different geometric arrangement of nuclei in the excited as compared to the ground state)
發光機制發光機制、、原理與實例
1. ns 2離子型發光中心KBr:Sn 2+, KCl:Pb 2+
2. 遷移型離子發光中心ZnS:Mn 2+, Zn 2SiO 4:Mn 2+
3. 稀土離子發光中心f →f (Eu 3+, Tb 3+), d →f (Ce 3+,Eu 2+)
4. 錯離子型發光中心Ca[WO 42-], Y[VO 43-]
5. 二-七族鹼土鹵化物半導體CaCl 2, SrCl 2, BaCl 2
6. 二-六族鹼土硫化物半導體SrS:Ce, CaS:Eu, CaS:Eu,Ce
7. 二-六族鋅(鎘)硫(硒)化物半導體ZnO, ZnS, ZnS, CdS
8. 三-五族化合物半導體
GaP, GaAs, (Ga,In,Al)N
交通大學螢光體實驗室Phosphors Laboratory
National Chiao Tung University
-螢光衰減特性交通大學螢光體實驗室
Phosphors Laboratory
National Chiao Tung University
Fluorescence measurements
-Steady state measurements
performed under constant illumination and observations
-Time resolved measurements
pulsed excitation and high speed detection, used for measuring intensity decays or anisotropy decays
Jobin-Yvon SPEX Fluorolog-3螢光光光譜儀
400500
600
700
I n t e n s i t y (a .u .)
Wavelength (nm)
Steady state fluorescence spectra for Zn 2GeO 4:x Mn 2+with different x values.
Time resolved fluorescence decay of green-emitting Mn2+ doped Zn2GeO4.
The fluorescence decay curves for Zn2GeO4:x Mn excited at 266 nm with a Nd:YAG laser and monitored at λem= 560 nm.
二、無機螢光材料簡介
無機螢光材料之設計
1. 主(母)體
2. 活化劑
3. 敏化劑
4. 螢光淬滅劑
無機螢光材料之製備
1. 固態燒結法
2. 共同沉澱法
3.溶膠凝膠法
Introduction of Inorganic Phosphors -Compositions (組成
)
Y 2O 3:Eu , Y 3Al 5O 12:Ce
(Sr,Ca)5(PO 4)3Cl:Sb ,Mn Activator
Sensitizer
Activator
Phosphsors: Host : A or Host:S,A
Self-activated(自身活化) phosphors:YVO 4, CaWO 4, ZnGa 2O 4
(Y 1-x Eu x )2O 3(0<x<1)
(Sr,Ca)5-x Sb x Mn y (PO 4)3Cl
Simple scheme describing the excitation, energy transfer and emission in a phosphor in a H:S,A in solid state.
A 活化劑
S 敏化劑H 主體主體//基質
(Sr,Ca)5(PO 4)3Cl:Sb ,Mn
Sb 3+
Mn 2+
螢光材料的合成
原料配置純化助熔劑之添加燒成氣氛與溫度研磨篩選(粒徑之控制) 表面處理激發(光)源_
X-射線
電場
陰極射線
紫外光
紅外光
螢光體可見光
三、無機螢光材料發光原理
-發光機制與實例
-發光光譜
-螢光衰減特性
Classification of Luminescence in Non-molecular Materials
Y 3Al 5O 12:Ce 3+
Gd 3Al 5O 12:Ce
3+
(Y,Gd)3Al 5O 12:Ce 3+
560+5
460+5
540+5
455+5
交通大學螢光體實驗室Phosphors Laboratory
National Chiao Tung University
光致發光(PL) 光譜
585+5
470+5
SrGa 2S 4:Eu
2+
交通大學螢光體實驗室Phosphors Laboratory
National Chiao Tung University
激發光譜
發射光譜
交通大學螢光體實驗室
Phosphors Research Laboratory
National Chiao Tung University CL(陰極射線發光)光譜
20 kV電子束
AC EL(交流電激)光譜
長餘輝(long afterglow)材料簡介
日本日亞化學公司長餘輝螢光材料(夜光粉)規格之比較
應用範圍：夜光標示、門牌、道路緊急標示、
戶外標示與裝飾
化學元素週期表
不同化學組成的夜光材料餘輝衰減之比較時間(分鐘)
餘輝強度(任意單位)
全球最大夜明珠現世
Light OFF
五、螢光材料色度學
-演色性(CRI, Color rendering index)
特定光源使物體真實顏色之表現或還原之程度
-色溫(Color temperature, K)
黑體受熱隨溫度升高所呈現之發光由深紅黑體受熱隨溫度升高所呈現之發光由深紅→→紅→橙黃橙黃→→白→藍白，當某一光源之發光與黑體之色光相同時當某一光源之發光與黑體之色光相同時，，所對應黑體之絕對溫度-量子效率與能量效率(Quantum and energy efficiency )-三波長照明螢光體
(Sr,Ca,Ba)5(PO 4)3Cl:Eu 2+/CaMgAl 11O 19:Ce,Tb /Y 2O 3:Eu -吸收與發射光譜–螢光光譜儀
-衰減壽命期
(Decay lifetime)
交通大學螢光體實驗室
Phosphors Laboratory
National Chiao Tung University
色光之混成
積分球(Integrating sphere)
1931CIE色度座標圖
色調
飽和度
六、無機螢光材料之主要應用
螢光材料應用實例
(一) 照明燈具
傳統照明
綠色照明
(二) 新世代半導體照明
(三) 傳統顯示器
(四) 新穎平面顯示器
省電螢光燈特殊用途螢光燈
Emission spectra of Ca5(F,Cl)(PO4)3 as a function of Mn:Sb:(PO4) ratio: (a)0:0.15:6(藍白), (b) 0.08:0.08:6(日光白), (c) 0.17:0.08:6(冷白), and (d)0.24:0.08:6(暖白)
Sb3+Mn2+
Excitation spectra of Ca5(F,Cl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b)Mn2+ emission wavelength (detector set at 590nm).
最佳激發波長
常見螢光照明用螢光材料(燈粉)組成(254 nm)
交通大學螢光體實驗室
Phosphors Laboratory
National Chiao Tung University
白光發光二極體
RGB 各式發光二極體
(LED)
白光發光二極體
交通大學螢光體實驗室Phosphors Laboratory National Chiao Tung University
文獻中各種白光LED的實例之比較
交通大學螢光體實驗室
Phosphors Laboratory
National Chiao Tung University
氮化鎵白光發光二極體(LED)發光原理
各種白光LED 常用的螢光材料
___________________________________________________________________________
激發光源(波長)
螢光材料組成. __________________________________________________________________________
1. (Ga,In)N chip (470 nm, Blue)YAG:Ce 3+(Y)
2. (Ga,In)N chip (420-470 nm, Blue)YBO 3:Ce 3+,Tb 3+(G)/SrGa 2S 4:Eu 2+(B)/Y 2O 2S:Eu 3+,Bi 3+(R)
3. (Ga,Al)N chip (370 nm )Ca 8Mg(SiO 4)4Cl 2:Eu 2+,Mn 2+(G)/Y 2O 3:Eu 3+, Bi 3+(R)
Ca 5(PO 4)3Cl:Eu 2+(B)or BaMg 2Al 16O 27:Eu 2+(B)
4. (Ga,In)N chip (460 nm,Blue) SrGa 2O 4:Eu 2+(G)/CaS:Eu(R)
5. LED (ultraviolet)ZnS:Ag,Ga/ CaS:Mn,Ce
6. Laser or laser diode (460-470 nm) SrS:Ce,K,Eu (white)
YBO 3:Ce,Tb(G)/SrS:Eu (R)
7. Laser or Laser diode (265 nm)
Ca 2SnO 4:Eu , Tb , Ce (白光(0.29, 0.28))8. LED (390 nm)Sr 5(PO 4)3Cl:Eu 2+(B)Y 2O 2S:Eu 3+(R)
__________________________________________________
______________交通大學螢光體實驗室
Phosphors Laboratory
National Chiao Tung University。