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Covering green to red part of the Visible spectrum
(ZnBe)2SiO4MnZn2SiO4Mn2+
of the Visible spectrum反射光譜
(Blasse amp Grabmeier (1994) Chap 6)
17
Chap 6)
17
MgWO4
1 100 ti t t ti h WO 2 ( t h d l) i bl t1 100 activator concentration each WO42- group (octahedral) is able to luminescence hellip
2 No concentration quenching (large Stokes shift) q g ( g )
3 Charge transfer luminescence mechanism in WO42- group
Zn SiO Mn2+Zn2SiO4Mn2
Emission due to Zn2SiO4Mn2+ is narrow
1 Zn2SiO4 Be2SiO4 are isostructural both Zn2+ Be2+ are in tetrahedral1 Zn2SiO4 Be2SiO4 are isostructural both Zn Be are in tetrahedral coordination (Mn2+ in tet Coordination)
Mn2+ (d5) all optical transitions within 3d5 configurations
均為spin- and parity-forbidden transitions
2 In (Zn Be)2SiO4 the crystal field of Mn2+ ion varies2 In (ZnBe)2SiO4 the crystal field of Mn ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases crystal field strength of Mn2+ ion emission
18
Introduction of Be increases crystal field strength of Mn ion emission shifted to longer wavelength
2 In (ZnBe)2SiO4 the crystal field of Mn2+ ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases CF of Mn2+ ion emission shifted to
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Covering green to red part of the Visible spectrum
(ZnBe)2SiO4MnZn2SiO4Mn2+
of the Visible spectrum反射光譜
(Blasse amp Grabmeier (1994) Chap 6)
17
Chap 6)
17
MgWO4
1 100 ti t t ti h WO 2 ( t h d l) i bl t1 100 activator concentration each WO42- group (octahedral) is able to luminescence hellip
2 No concentration quenching (large Stokes shift) q g ( g )
3 Charge transfer luminescence mechanism in WO42- group
Zn SiO Mn2+Zn2SiO4Mn2
Emission due to Zn2SiO4Mn2+ is narrow
1 Zn2SiO4 Be2SiO4 are isostructural both Zn2+ Be2+ are in tetrahedral1 Zn2SiO4 Be2SiO4 are isostructural both Zn Be are in tetrahedral coordination (Mn2+ in tet Coordination)
Mn2+ (d5) all optical transitions within 3d5 configurations
均為spin- and parity-forbidden transitions
2 In (Zn Be)2SiO4 the crystal field of Mn2+ ion varies2 In (ZnBe)2SiO4 the crystal field of Mn ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases crystal field strength of Mn2+ ion emission
18
Introduction of Be increases crystal field strength of Mn ion emission shifted to longer wavelength
2 In (ZnBe)2SiO4 the crystal field of Mn2+ ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases CF of Mn2+ ion emission shifted to
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Covering green to red part of the Visible spectrum
(ZnBe)2SiO4MnZn2SiO4Mn2+
of the Visible spectrum反射光譜
(Blasse amp Grabmeier (1994) Chap 6)
17
Chap 6)
17
MgWO4
1 100 ti t t ti h WO 2 ( t h d l) i bl t1 100 activator concentration each WO42- group (octahedral) is able to luminescence hellip
2 No concentration quenching (large Stokes shift) q g ( g )
3 Charge transfer luminescence mechanism in WO42- group
Zn SiO Mn2+Zn2SiO4Mn2
Emission due to Zn2SiO4Mn2+ is narrow
1 Zn2SiO4 Be2SiO4 are isostructural both Zn2+ Be2+ are in tetrahedral1 Zn2SiO4 Be2SiO4 are isostructural both Zn Be are in tetrahedral coordination (Mn2+ in tet Coordination)
Mn2+ (d5) all optical transitions within 3d5 configurations
均為spin- and parity-forbidden transitions
2 In (Zn Be)2SiO4 the crystal field of Mn2+ ion varies2 In (ZnBe)2SiO4 the crystal field of Mn ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases crystal field strength of Mn2+ ion emission
18
Introduction of Be increases crystal field strength of Mn ion emission shifted to longer wavelength
2 In (ZnBe)2SiO4 the crystal field of Mn2+ ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases CF of Mn2+ ion emission shifted to
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Covering green to red part of the Visible spectrum
(ZnBe)2SiO4MnZn2SiO4Mn2+
of the Visible spectrum反射光譜
(Blasse amp Grabmeier (1994) Chap 6)
17
Chap 6)
17
MgWO4
1 100 ti t t ti h WO 2 ( t h d l) i bl t1 100 activator concentration each WO42- group (octahedral) is able to luminescence hellip
2 No concentration quenching (large Stokes shift) q g ( g )
3 Charge transfer luminescence mechanism in WO42- group
Zn SiO Mn2+Zn2SiO4Mn2
Emission due to Zn2SiO4Mn2+ is narrow
1 Zn2SiO4 Be2SiO4 are isostructural both Zn2+ Be2+ are in tetrahedral1 Zn2SiO4 Be2SiO4 are isostructural both Zn Be are in tetrahedral coordination (Mn2+ in tet Coordination)
Mn2+ (d5) all optical transitions within 3d5 configurations
均為spin- and parity-forbidden transitions
2 In (Zn Be)2SiO4 the crystal field of Mn2+ ion varies2 In (ZnBe)2SiO4 the crystal field of Mn ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases crystal field strength of Mn2+ ion emission
18
Introduction of Be increases crystal field strength of Mn ion emission shifted to longer wavelength
2 In (ZnBe)2SiO4 the crystal field of Mn2+ ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases CF of Mn2+ ion emission shifted to
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Covering green to red part of the Visible spectrum
(ZnBe)2SiO4MnZn2SiO4Mn2+
of the Visible spectrum反射光譜
(Blasse amp Grabmeier (1994) Chap 6)
17
Chap 6)
17
MgWO4
1 100 ti t t ti h WO 2 ( t h d l) i bl t1 100 activator concentration each WO42- group (octahedral) is able to luminescence hellip
2 No concentration quenching (large Stokes shift) q g ( g )
3 Charge transfer luminescence mechanism in WO42- group
Zn SiO Mn2+Zn2SiO4Mn2
Emission due to Zn2SiO4Mn2+ is narrow
1 Zn2SiO4 Be2SiO4 are isostructural both Zn2+ Be2+ are in tetrahedral1 Zn2SiO4 Be2SiO4 are isostructural both Zn Be are in tetrahedral coordination (Mn2+ in tet Coordination)
Mn2+ (d5) all optical transitions within 3d5 configurations
均為spin- and parity-forbidden transitions
2 In (Zn Be)2SiO4 the crystal field of Mn2+ ion varies2 In (ZnBe)2SiO4 the crystal field of Mn ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases crystal field strength of Mn2+ ion emission
18
Introduction of Be increases crystal field strength of Mn ion emission shifted to longer wavelength
2 In (ZnBe)2SiO4 the crystal field of Mn2+ ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases CF of Mn2+ ion emission shifted to
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Covering green to red part of the Visible spectrum
(ZnBe)2SiO4MnZn2SiO4Mn2+
of the Visible spectrum反射光譜
(Blasse amp Grabmeier (1994) Chap 6)
17
Chap 6)
17
MgWO4
1 100 ti t t ti h WO 2 ( t h d l) i bl t1 100 activator concentration each WO42- group (octahedral) is able to luminescence hellip
2 No concentration quenching (large Stokes shift) q g ( g )
3 Charge transfer luminescence mechanism in WO42- group
Zn SiO Mn2+Zn2SiO4Mn2
Emission due to Zn2SiO4Mn2+ is narrow
1 Zn2SiO4 Be2SiO4 are isostructural both Zn2+ Be2+ are in tetrahedral1 Zn2SiO4 Be2SiO4 are isostructural both Zn Be are in tetrahedral coordination (Mn2+ in tet Coordination)
Mn2+ (d5) all optical transitions within 3d5 configurations
均為spin- and parity-forbidden transitions
2 In (Zn Be)2SiO4 the crystal field of Mn2+ ion varies2 In (ZnBe)2SiO4 the crystal field of Mn ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases crystal field strength of Mn2+ ion emission
18
Introduction of Be increases crystal field strength of Mn ion emission shifted to longer wavelength
2 In (ZnBe)2SiO4 the crystal field of Mn2+ ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases CF of Mn2+ ion emission shifted to
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Covering green to red part of the Visible spectrum
(ZnBe)2SiO4MnZn2SiO4Mn2+
of the Visible spectrum反射光譜
(Blasse amp Grabmeier (1994) Chap 6)
17
Chap 6)
17
MgWO4
1 100 ti t t ti h WO 2 ( t h d l) i bl t1 100 activator concentration each WO42- group (octahedral) is able to luminescence hellip
2 No concentration quenching (large Stokes shift) q g ( g )
3 Charge transfer luminescence mechanism in WO42- group
Zn SiO Mn2+Zn2SiO4Mn2
Emission due to Zn2SiO4Mn2+ is narrow
1 Zn2SiO4 Be2SiO4 are isostructural both Zn2+ Be2+ are in tetrahedral1 Zn2SiO4 Be2SiO4 are isostructural both Zn Be are in tetrahedral coordination (Mn2+ in tet Coordination)
Mn2+ (d5) all optical transitions within 3d5 configurations
均為spin- and parity-forbidden transitions
2 In (Zn Be)2SiO4 the crystal field of Mn2+ ion varies2 In (ZnBe)2SiO4 the crystal field of Mn ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases crystal field strength of Mn2+ ion emission
18
Introduction of Be increases crystal field strength of Mn ion emission shifted to longer wavelength
2 In (ZnBe)2SiO4 the crystal field of Mn2+ ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases CF of Mn2+ ion emission shifted to
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Covering green to red part of the Visible spectrum
(ZnBe)2SiO4MnZn2SiO4Mn2+
of the Visible spectrum反射光譜
(Blasse amp Grabmeier (1994) Chap 6)
17
Chap 6)
17
MgWO4
1 100 ti t t ti h WO 2 ( t h d l) i bl t1 100 activator concentration each WO42- group (octahedral) is able to luminescence hellip
2 No concentration quenching (large Stokes shift) q g ( g )
3 Charge transfer luminescence mechanism in WO42- group
Zn SiO Mn2+Zn2SiO4Mn2
Emission due to Zn2SiO4Mn2+ is narrow
1 Zn2SiO4 Be2SiO4 are isostructural both Zn2+ Be2+ are in tetrahedral1 Zn2SiO4 Be2SiO4 are isostructural both Zn Be are in tetrahedral coordination (Mn2+ in tet Coordination)
Mn2+ (d5) all optical transitions within 3d5 configurations
均為spin- and parity-forbidden transitions
2 In (Zn Be)2SiO4 the crystal field of Mn2+ ion varies2 In (ZnBe)2SiO4 the crystal field of Mn ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases crystal field strength of Mn2+ ion emission
18
Introduction of Be increases crystal field strength of Mn ion emission shifted to longer wavelength
2 In (ZnBe)2SiO4 the crystal field of Mn2+ ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases CF of Mn2+ ion emission shifted to
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Covering green to red part of the Visible spectrum
(ZnBe)2SiO4MnZn2SiO4Mn2+
of the Visible spectrum反射光譜
(Blasse amp Grabmeier (1994) Chap 6)
17
Chap 6)
17
MgWO4
1 100 ti t t ti h WO 2 ( t h d l) i bl t1 100 activator concentration each WO42- group (octahedral) is able to luminescence hellip
2 No concentration quenching (large Stokes shift) q g ( g )
3 Charge transfer luminescence mechanism in WO42- group
Zn SiO Mn2+Zn2SiO4Mn2
Emission due to Zn2SiO4Mn2+ is narrow
1 Zn2SiO4 Be2SiO4 are isostructural both Zn2+ Be2+ are in tetrahedral1 Zn2SiO4 Be2SiO4 are isostructural both Zn Be are in tetrahedral coordination (Mn2+ in tet Coordination)
Mn2+ (d5) all optical transitions within 3d5 configurations
均為spin- and parity-forbidden transitions
2 In (Zn Be)2SiO4 the crystal field of Mn2+ ion varies2 In (ZnBe)2SiO4 the crystal field of Mn ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases crystal field strength of Mn2+ ion emission
18
Introduction of Be increases crystal field strength of Mn ion emission shifted to longer wavelength
2 In (ZnBe)2SiO4 the crystal field of Mn2+ ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases CF of Mn2+ ion emission shifted to
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Covering green to red part of the Visible spectrum
(ZnBe)2SiO4MnZn2SiO4Mn2+
of the Visible spectrum反射光譜
(Blasse amp Grabmeier (1994) Chap 6)
17
Chap 6)
17
MgWO4
1 100 ti t t ti h WO 2 ( t h d l) i bl t1 100 activator concentration each WO42- group (octahedral) is able to luminescence hellip
2 No concentration quenching (large Stokes shift) q g ( g )
3 Charge transfer luminescence mechanism in WO42- group
Zn SiO Mn2+Zn2SiO4Mn2
Emission due to Zn2SiO4Mn2+ is narrow
1 Zn2SiO4 Be2SiO4 are isostructural both Zn2+ Be2+ are in tetrahedral1 Zn2SiO4 Be2SiO4 are isostructural both Zn Be are in tetrahedral coordination (Mn2+ in tet Coordination)
Mn2+ (d5) all optical transitions within 3d5 configurations
均為spin- and parity-forbidden transitions
2 In (Zn Be)2SiO4 the crystal field of Mn2+ ion varies2 In (ZnBe)2SiO4 the crystal field of Mn ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases crystal field strength of Mn2+ ion emission
18
Introduction of Be increases crystal field strength of Mn ion emission shifted to longer wavelength
2 In (ZnBe)2SiO4 the crystal field of Mn2+ ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases CF of Mn2+ ion emission shifted to
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Covering green to red part of the Visible spectrum
(ZnBe)2SiO4MnZn2SiO4Mn2+
of the Visible spectrum反射光譜
(Blasse amp Grabmeier (1994) Chap 6)
17
Chap 6)
17
MgWO4
1 100 ti t t ti h WO 2 ( t h d l) i bl t1 100 activator concentration each WO42- group (octahedral) is able to luminescence hellip
2 No concentration quenching (large Stokes shift) q g ( g )
3 Charge transfer luminescence mechanism in WO42- group
Zn SiO Mn2+Zn2SiO4Mn2
Emission due to Zn2SiO4Mn2+ is narrow
1 Zn2SiO4 Be2SiO4 are isostructural both Zn2+ Be2+ are in tetrahedral1 Zn2SiO4 Be2SiO4 are isostructural both Zn Be are in tetrahedral coordination (Mn2+ in tet Coordination)
Mn2+ (d5) all optical transitions within 3d5 configurations
均為spin- and parity-forbidden transitions
2 In (Zn Be)2SiO4 the crystal field of Mn2+ ion varies2 In (ZnBe)2SiO4 the crystal field of Mn ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases crystal field strength of Mn2+ ion emission
18
Introduction of Be increases crystal field strength of Mn ion emission shifted to longer wavelength
2 In (ZnBe)2SiO4 the crystal field of Mn2+ ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases CF of Mn2+ ion emission shifted to
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Covering green to red part of the Visible spectrum
(ZnBe)2SiO4MnZn2SiO4Mn2+
of the Visible spectrum反射光譜
(Blasse amp Grabmeier (1994) Chap 6)
17
Chap 6)
17
MgWO4
1 100 ti t t ti h WO 2 ( t h d l) i bl t1 100 activator concentration each WO42- group (octahedral) is able to luminescence hellip
2 No concentration quenching (large Stokes shift) q g ( g )
3 Charge transfer luminescence mechanism in WO42- group
Zn SiO Mn2+Zn2SiO4Mn2
Emission due to Zn2SiO4Mn2+ is narrow
1 Zn2SiO4 Be2SiO4 are isostructural both Zn2+ Be2+ are in tetrahedral1 Zn2SiO4 Be2SiO4 are isostructural both Zn Be are in tetrahedral coordination (Mn2+ in tet Coordination)
Mn2+ (d5) all optical transitions within 3d5 configurations
均為spin- and parity-forbidden transitions
2 In (Zn Be)2SiO4 the crystal field of Mn2+ ion varies2 In (ZnBe)2SiO4 the crystal field of Mn ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases crystal field strength of Mn2+ ion emission
18
Introduction of Be increases crystal field strength of Mn ion emission shifted to longer wavelength
2 In (ZnBe)2SiO4 the crystal field of Mn2+ ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases CF of Mn2+ ion emission shifted to
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Covering green to red part of the Visible spectrum
(ZnBe)2SiO4MnZn2SiO4Mn2+
of the Visible spectrum反射光譜
(Blasse amp Grabmeier (1994) Chap 6)
17
Chap 6)
17
MgWO4
1 100 ti t t ti h WO 2 ( t h d l) i bl t1 100 activator concentration each WO42- group (octahedral) is able to luminescence hellip
2 No concentration quenching (large Stokes shift) q g ( g )
3 Charge transfer luminescence mechanism in WO42- group
Zn SiO Mn2+Zn2SiO4Mn2
Emission due to Zn2SiO4Mn2+ is narrow
1 Zn2SiO4 Be2SiO4 are isostructural both Zn2+ Be2+ are in tetrahedral1 Zn2SiO4 Be2SiO4 are isostructural both Zn Be are in tetrahedral coordination (Mn2+ in tet Coordination)
Mn2+ (d5) all optical transitions within 3d5 configurations
均為spin- and parity-forbidden transitions
2 In (Zn Be)2SiO4 the crystal field of Mn2+ ion varies2 In (ZnBe)2SiO4 the crystal field of Mn ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases crystal field strength of Mn2+ ion emission
18
Introduction of Be increases crystal field strength of Mn ion emission shifted to longer wavelength
2 In (ZnBe)2SiO4 the crystal field of Mn2+ ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases CF of Mn2+ ion emission shifted to
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Covering green to red part of the Visible spectrum
(ZnBe)2SiO4MnZn2SiO4Mn2+
of the Visible spectrum反射光譜
(Blasse amp Grabmeier (1994) Chap 6)
17
Chap 6)
17
MgWO4
1 100 ti t t ti h WO 2 ( t h d l) i bl t1 100 activator concentration each WO42- group (octahedral) is able to luminescence hellip
2 No concentration quenching (large Stokes shift) q g ( g )
3 Charge transfer luminescence mechanism in WO42- group
Zn SiO Mn2+Zn2SiO4Mn2
Emission due to Zn2SiO4Mn2+ is narrow
1 Zn2SiO4 Be2SiO4 are isostructural both Zn2+ Be2+ are in tetrahedral1 Zn2SiO4 Be2SiO4 are isostructural both Zn Be are in tetrahedral coordination (Mn2+ in tet Coordination)
Mn2+ (d5) all optical transitions within 3d5 configurations
均為spin- and parity-forbidden transitions
2 In (Zn Be)2SiO4 the crystal field of Mn2+ ion varies2 In (ZnBe)2SiO4 the crystal field of Mn ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases crystal field strength of Mn2+ ion emission
18
Introduction of Be increases crystal field strength of Mn ion emission shifted to longer wavelength
2 In (ZnBe)2SiO4 the crystal field of Mn2+ ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases CF of Mn2+ ion emission shifted to
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Covering green to red part of the Visible spectrum
(ZnBe)2SiO4MnZn2SiO4Mn2+
of the Visible spectrum反射光譜
(Blasse amp Grabmeier (1994) Chap 6)
17
Chap 6)
17
MgWO4
1 100 ti t t ti h WO 2 ( t h d l) i bl t1 100 activator concentration each WO42- group (octahedral) is able to luminescence hellip
2 No concentration quenching (large Stokes shift) q g ( g )
3 Charge transfer luminescence mechanism in WO42- group
Zn SiO Mn2+Zn2SiO4Mn2
Emission due to Zn2SiO4Mn2+ is narrow
1 Zn2SiO4 Be2SiO4 are isostructural both Zn2+ Be2+ are in tetrahedral1 Zn2SiO4 Be2SiO4 are isostructural both Zn Be are in tetrahedral coordination (Mn2+ in tet Coordination)
Mn2+ (d5) all optical transitions within 3d5 configurations
均為spin- and parity-forbidden transitions
2 In (Zn Be)2SiO4 the crystal field of Mn2+ ion varies2 In (ZnBe)2SiO4 the crystal field of Mn ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases crystal field strength of Mn2+ ion emission
18
Introduction of Be increases crystal field strength of Mn ion emission shifted to longer wavelength
2 In (ZnBe)2SiO4 the crystal field of Mn2+ ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases CF of Mn2+ ion emission shifted to
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Covering green to red part of the Visible spectrum
(ZnBe)2SiO4MnZn2SiO4Mn2+
of the Visible spectrum反射光譜
(Blasse amp Grabmeier (1994) Chap 6)
17
Chap 6)
17
MgWO4
1 100 ti t t ti h WO 2 ( t h d l) i bl t1 100 activator concentration each WO42- group (octahedral) is able to luminescence hellip
2 No concentration quenching (large Stokes shift) q g ( g )
3 Charge transfer luminescence mechanism in WO42- group
Zn SiO Mn2+Zn2SiO4Mn2
Emission due to Zn2SiO4Mn2+ is narrow
1 Zn2SiO4 Be2SiO4 are isostructural both Zn2+ Be2+ are in tetrahedral1 Zn2SiO4 Be2SiO4 are isostructural both Zn Be are in tetrahedral coordination (Mn2+ in tet Coordination)
Mn2+ (d5) all optical transitions within 3d5 configurations
均為spin- and parity-forbidden transitions
2 In (Zn Be)2SiO4 the crystal field of Mn2+ ion varies2 In (ZnBe)2SiO4 the crystal field of Mn ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases crystal field strength of Mn2+ ion emission
18
Introduction of Be increases crystal field strength of Mn ion emission shifted to longer wavelength
2 In (ZnBe)2SiO4 the crystal field of Mn2+ ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases CF of Mn2+ ion emission shifted to
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Covering green to red part of the Visible spectrum
(ZnBe)2SiO4MnZn2SiO4Mn2+
of the Visible spectrum反射光譜
(Blasse amp Grabmeier (1994) Chap 6)
17
Chap 6)
17
MgWO4
1 100 ti t t ti h WO 2 ( t h d l) i bl t1 100 activator concentration each WO42- group (octahedral) is able to luminescence hellip
2 No concentration quenching (large Stokes shift) q g ( g )
3 Charge transfer luminescence mechanism in WO42- group
Zn SiO Mn2+Zn2SiO4Mn2
Emission due to Zn2SiO4Mn2+ is narrow
1 Zn2SiO4 Be2SiO4 are isostructural both Zn2+ Be2+ are in tetrahedral1 Zn2SiO4 Be2SiO4 are isostructural both Zn Be are in tetrahedral coordination (Mn2+ in tet Coordination)
Mn2+ (d5) all optical transitions within 3d5 configurations
均為spin- and parity-forbidden transitions
2 In (Zn Be)2SiO4 the crystal field of Mn2+ ion varies2 In (ZnBe)2SiO4 the crystal field of Mn ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases crystal field strength of Mn2+ ion emission
18
Introduction of Be increases crystal field strength of Mn ion emission shifted to longer wavelength
2 In (ZnBe)2SiO4 the crystal field of Mn2+ ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases CF of Mn2+ ion emission shifted to
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
1 100 ti t t ti h WO 2 ( t h d l) i bl t1 100 activator concentration each WO42- group (octahedral) is able to luminescence hellip
2 No concentration quenching (large Stokes shift) q g ( g )
3 Charge transfer luminescence mechanism in WO42- group
Zn SiO Mn2+Zn2SiO4Mn2
Emission due to Zn2SiO4Mn2+ is narrow
1 Zn2SiO4 Be2SiO4 are isostructural both Zn2+ Be2+ are in tetrahedral1 Zn2SiO4 Be2SiO4 are isostructural both Zn Be are in tetrahedral coordination (Mn2+ in tet Coordination)
Mn2+ (d5) all optical transitions within 3d5 configurations
均為spin- and parity-forbidden transitions
2 In (Zn Be)2SiO4 the crystal field of Mn2+ ion varies2 In (ZnBe)2SiO4 the crystal field of Mn ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases crystal field strength of Mn2+ ion emission
18
Introduction of Be increases crystal field strength of Mn ion emission shifted to longer wavelength
2 In (ZnBe)2SiO4 the crystal field of Mn2+ ion varies
The emission band broadens relative to that of Zn2SiO4Mn2+
Introduction of Be2+ increases CF of Mn2+ ion emission shifted to
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Emission spectra of Ca5(FCl)(PO4)3 as a function of MnSb(PO4) ratio (a) 00156(藍白) (b) 0080086(日光白) (c) 0170086(冷白) and (d) ( ) ( ) ( ) ( ) ( ) ( ) ( )0240086(暖白)
Sb3+ Mn2+ [Mn][Sb]
Color Temperature
22
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Excitation spectra of Ca5(FCl)(PO4)3 monitored at Sb3+ emission wavelength (detector set at 476 nm) and (b) Mn2+ emission g ( ) ( )wavelength (detector set at 590nm)
最佳激發波長
23
Phosphors for Tricolor Lamps
Year Phosphors
1960 Ca5(PO4)3ClSb3+Mn2+ (white)
1974 BaMg2Al16O27Eu2+ CeMgAl10O19Tb3+ Y2O3Eu3+
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
1990 BaMgAl O Eu2+ (B) (La Ce)PO Tb3+ Y O Eu3+1990 BaMgAl10O17Eu2+ (B) (SrCa)5(PO4)3ClEu2+
(LaCe)PO4Tb3+
CeMgAl10O19Tb3+
(GdCe)MgB5O10Tb3+
Y2O3Eu3+
2005 BaMgAl10O17Eu2+ (B) (LaCe)PO4Tb3+ Y2O3Eu3+
24
CeMgAl11O19
GdMgAl5O10
Gd(MgMn)B5O10Ce3+
S Al O E 2+色溫4000K
BaMgAl10O17Eu2+Sr2Al6O11Eu2+
(magnetoplumbite-type)
25 25
Phosphors for Tricolor Lamps
Keodam and Opstelten
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
A luminescent lamp with an efficacy(功效) of 100 lmW and CRI ofA luminescent lamp with an efficacy(功效) of 100 lmW and CRI of 80-85 can be obtained by combining three phosphors which emit in narrow λ intervals centered at 450 550 and 610 nm
色溫4000K三波長螢光燈燈粉發射光譜
26
A lamp containing a mixture of Sr2Al6O11Eu2+ GdMgB5O10Ce3+Tb3+ Mn2+
and Ca5(PO4)3(FCl)SbMn has a CRI of 95 and an efficacy of 65 lmW
色溫為4000K之deluxe lamp
Can be suppressed by adding yellow-
3emittingYAGCe3+
27 26
500
400
PL Electronic Helix 20WDY2O3Eu3+ SrAl12O19Mn2+
(cps
)
300
Ca (PO ) FSb3+LaPO Tb3+Y O Eu3+
Inte
nsity
(
200
M-廠 FL40D Ca5(PO4)3FSb3+LaPO4Tb3+Y2O3Eu3+
100
GE Lighting FL40D Ca5(PO4)3FSb3+Y2O3Eu3+ LaPO4Tb3+
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Operations Y Scale Add 200 | Import2 - File 2raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 300 | Import1 - File 1raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 13 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
2-Theta - Scale10 20 30 40 50 60 70 8
Comparison of XRD profiles for fluorescent lamp phosphors from
28Operations Import4 - File 4raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X Operations Y Scale Add 100 | Import3 - File 3raw - Type 2ThTh locked - Start 10000 - End 80000 - Step 0100 - Step time 04 s - Temp 25 (Room) - Time Started 14 s - 2-Theta 10000 - Theta 5000 - Chi 000 - Phi 000 - X
different sources
25
Red phosphors for tricolor lamps
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
It has been estimated that 5 ppm of Fe lowers the efficiency of Y2O3Eu by 7
J = 2 dominates because of hypersensitivity
Dominating ndash a hypersensitive forced electric dipole emissionelectric dipole emission Eu3+ occupies a lattice site without a inversion symmetry
5D0 rarr 7FJ
29 27
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Red phosphors for tricolor lamps實際上 中提供兩種供 3 取代並具有 與 點對稱之格位實際上Y2O3中提供兩種供Eu3+取代並具有 與 點對稱之格位S6 C2
Eu3+ on S6 site only shows the 5D0-7F1
The unwanted 5D0-7F1 emission of the S6 site is suppressed in the commercial 3 Eu3+Eu on S6 site only shows the D0- F1
magnetic-dipole emission (595 nm)
τe = 8 msec
suppressed in the commercial 3 Eu3
samples due to energy transfer from Eu3+ (S6) to Eu3+ (C2) rc = 8 Aring
C2 sites are 3 times more than S6
τe = 11 msec
S6 C2
30
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Blue phosphors for Tricolor LampsHighest lamp output is expected for a B-emitting phosphor with an emission max at 450 nm the best CRI is found with an emission max at 480 nm
基於對兩者之要求 only phosphors with emission (max) 440-460 nm are of interest
B M Al O E 2+BaMgAl10O17Eu2+
(magnetoplumbite-type)
Ca5(PO4)3(ClF) SbMn(halophosphate)
Sr2Al6O11Eu2+
QE = 90
31
Blue phosphors for tricolor lamps
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Built up of alternating l f AlO h dlayer of AlO4-tetrahedra and of AlO6-octahedra
32
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Green phosphors for Tricolor Lamps (mainly Tb3+)Green phosphors for Tricolor Lamps (mainly Tb )
1 First allowed transition is 4f8 rarr 4f75d1 and it often lies too high energy to make 254 nm excitation effective A sensitizer (Ce3+ 4frarr 5d is situated at lower energy than the ( gyTb3+ 4f8 rarr 4f75d1) must be used to absorb the 254 nm radiation effectively
2 CeMgAl11O19 magnetoplumbite (1-12-19) structure
GdMgAl5O10 structure consists of a 2-D framework of BO3 and BO4groups in which Mg2+ are in oct coordination and Gd3+ in ten-coordination The Gd3+ polyhedra form isolated zig-zag chains d(Gd-Gd) = 4 AringThe Gd polyhedra form isolated zig zag chains d(Gd Gd) 4 Aring
33
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
1 some UV emission originating from Ce3+ and Gd3+ is present
2 The energy transfer mechanisms are different
CeMgAl11O19Tb330
3 CeMgAl11O19Tb has first excitation max at 270 nm Stokes shift is large CeMgAl11O19Tb
(Ce Gd)MgB O Tb
約 8000 cm-1 energy transfer between Ce3+
does not occur and i hi (CeGd)MgB5O10Tbconcentration quenching
is absent
3 3 (LaCe)PO4Tb4 The Ce3+rarr Tb3+
transfer is one-step process Transfer is
t i t d t i hbrestricted to neighbors high concentration of Tb3+ ( gtgt 33) is necessary to quench
34
necessary to quench the Ce3+ emission
(LaCe)PO4Tb = LaPO4 CeTb
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
- Stokes of the emission is small (約6000 cm-1) emission of CePO4 is partly- Stokes of the emission is small (約6000 cm ) emission of CePO4 is partly concentration quenched
- energy migration over the Ce3+ assists in transfer to Tb3+
- the UV output is high (due to the fact that Ce3+-Ce3+ transfer more efficient than Ce3+-Tb3+ transfer rate 1011 sec-1 versus 3 x 108 sec-1 at the shortest internuclear rare-earth distance))
GdMgB5O10CeTb
- excitation with 254 nm occurs in the Ce3+ which transfers its energy to Gd3+ all of Ce3+ exc energy is transferred to Gd3+ Then the energy migrated over to the Gd3+ sublattice (次晶格) It is trapped by the emittingmigrated over to the Gd3 sublattice (次晶格) It is trapped by the emitting Tb3+ ions
35
不同Ce3+rarrTb3+能量轉移機制之比較不同Ce rarrTb 能量轉移機制之比較
36
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
- The eye sensitivity curve drops sharply in the red spectral area
- The 5D1 emission of Eu3+ should be quenched by cross relaxation as in the lamp phosphors
- The high value of lumen equiv of Y2O3Eu and Y2(WO4)3Eu3+ are due to 5D0-7F4
Eye-sensitivitylamp phosphors
(ZnCd)SAg低流明當量
Eu3+
5D0-7F4 tend to d l idecrease lumen eqiv
37
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Phosphors for HPMV (High Pressure Mercury Vapor) Lamp
高壓水銀燈用螢光粉 - 街道照明的主力
250-300
700-800
38
HPMV Lamps
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
-Internal pressure of the lamp ranging from a few mm to several atmospheres gtgt 760 mm Hg a quartz envelope is employed for high pressure operation
Th b f lli i d b t H t i-The number of collision per second between Hg atoms increases enormously in the discharge
-This has the effect of shifting the resonance of radiation to longer wavelengths including the visible 430 nm 546 nm and 5785 nm resulting in a green white emitting lamp Thus a red emittingresulting in a green-white emitting lamp Thus a red-emitting phosphor is needed so as to correct for the lack of red emission
- Considerable amount of 365 nm is also present
- The HPMV lamp has been used extensively in street-lighting (街道照明) li ti
39
(街道照明)applications
Phosphors for HPMV Lamps (高壓水銀燈用螢光粉)
螢光粉化學組成 YVO4Eu YVO4Dy and (SrMg)3(PO4)2Sn2+
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Better phosphor Y(P020V080)O4Eu ndash a superior temperature dependence of emission Though Y O Eu has a good temperature dependence of emissionemission Though Y2O3Eu has a good temperature dependence of emission but it does not respond to 365 nm radiation
I t f HPMV LPMV lImprovements of HPMV or LPMV lamps- The Hg vapor has been augmented with metal vapors of Tl In and others (the iodides of these metals are volatile so that the metal emission spectra result 含部分紅光) 此種照明稱之為metal vapor lamps
- LPMV lamps
result含部分紅光) 此種照明稱之為metal vapor lamps
the newest lamps contain three essential line-emitters using Eu2+ as blue Tb3+ for green emission and Eu3+ for red emission此種照明稱之為high output lamps which have line emission in contrast to the broad bandoutput lamps which have line emission in contrast to the broad band emission Eventually human eyes integrate the three wavelengths and perceive as white light
40
各式發光二極體(LED)
(二) 新世代半導體照明
各式發光二極體(LED)
(二) 新世代半導體照明
白光發光二極體白光發光二極體41
白光發光二極體白光發光二極體
Diodes (LED) the future for lighting
Lampe fluorescenteLampe agrave incandescence
Diodes (LED)
19951970Hg
incandescence
g
P t th i i i i i
Energy saving
Pertes thermiquesbull100W geacutenegraverent seulement 18W de lumiegravere
bullElimination des pertes thermiquesbull 55 de leacutenergie sont perduslors de la conversion de lUV en
h t i ibl
35 de leacutenergie sont Perdus lors de la conversion de lexcitation UV h i iblde lumiegravere photons visibles UV en photons visibles
Adantages des LEDs puissance eacutelectrique brillance pureteacute de couleur taille dureacutee deg p q p vie sans mercure
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
單晶片型與多晶片型白光單晶片型與多晶片型白光 LEDLED之比較之比較((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))((pc LED Phosphor Converted LEDpc LED Phosphor Converted LED))
產生白光的方法
From Chaddok NETL DOE (2009 Phosphor Global Summit)
51
Phosphor-Converted LEDHigh-Efficiency White LED UV-Pumped White-LED
ηpc-LED= ηchip times ηpackage times ηphosphor times ηStokes conversion
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
blue LED + phosphor (yellow green orange-red)UV-LED + phosphor (blue green yellow orange red)
2粒徑適中且分布範圍窄分散性良好過粗或過細光效差
EuEu2+ 2+ and Ceand Ce3+3+ are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDsEuEu and Ceand Ce are the best activator ions for excitation based on LEDsare the best activator ions for excitation based on LEDs
白光白光LEDsLEDs用螢光粉用螢光粉
UV紫外254 nm 365 nm 400 nm 460 nm 540 nm 610 nm
Aluminates Y3Al5O12Ce3+(YAG)Tb3Al5O12Ce3+(TAG)
L Al O C 3+(L AG)(CaSrBa)Al2O4Eu2+CaAl4O7Eu2+
(MgCaSrBa)4Al14O25Eu2+
BaMg2Al16O27Eu2+(BAM)
Silicates
Lu3Al5O12Ce3+(LuAG)
Sr2SiO4Eu2+Ba2SiO4Eu2+
Ca2Al12O19 Mn4+
Ca8Mg(SiO4)4Cl2Eu2+(CS)
Nitrides
(MgCaSrBa)3Si2O7Eu2+
(MgCaSrBa)2SiO4Eu2+
2 42 4
Ca2Si5N8Eu2+Nitrides
(CaMgY)SiwAlxOyNzEu2+
(SrCaBa)SixOyNzEu2+
(CaMgY)SiwAlxOyNzCe2+
Ca5(PO4)3Cl Eu2+ Mn2+Ca5(PO4)3Cl Eu2+
(CaSrBa)SEu2+
Others
Sr3B2O3Eu2+
Z CdS A 1+ Cl 1-
SrGa2S4Eu2+ LiEuW2O8
35MgO05MgF2GeO2Mn4+(MGM)
Na2Ln2 B2O7Ce3+Tb3+ ZnCdS Ag 1+Cl 1-
ZnSCu1+Al3+64
(C S )SiN E 2+
(CaSr)SEu2+
(CaSr)SiN3Eu2+
From J Strauβ Osram (2009 Phosphor Global Summit)
57
Golden Phosphor Combination for UVGolden Phosphor Combination for UV--Chip Pumped WLChip Pumped WL--LEDLED
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
(Fukuda Toshiba Corp Japan Global Phosphor Summit 2007)
氮氮((氧氧))化物螢光粉與其他組成螢光粉之比較化物螢光粉與其他組成螢光粉之比較
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Oxynitridenitride phosphorsOxynitridenitride phosphors- a large family and structural diversity- full colors- a very interesting novel class of luminescent materials
(RJ Xie et al NIMS Japan Phosphor Global Summit 2007 Korea)
文獻專利中所揭露多種氮文獻專利中所揭露多種氮((氧氧))化物螢光體化物螢光體
B LaSi3N5Ce K Uheda et al 440470nm
L Si Al ON C N Hi ki t l 465 495LaSi5Al2ON9Ce N Hirosaki et al 465-495nm
SrSiAl2O3N2Eu H T Hintzen et al 480nm
SrSi AlO N Eu R J Xie et al 490nmSrSi5AlO2N7Eu R-J Xie et al 490nm
G β-SiAlONEu N Hirosaki et al 540nm
Ln2Si3O3N4Tb H T Hintzen et al 545nm etc
AESi2O2N2Eu W S Schnick et al 505-565nm
Y Ln-α-SiAlONEu J H W van Krevel et al 560-600nm
R AE2Si5N8Eu H A Hӧppe et al 580-625nmR AE2Si5N8Eu H A Hӧppe et al 580-625nm
(CaSr)AlSiN3Eu K Uheda et al 620-650nmThe wavelength of emission can be varied in a wide rangeThe wavelength of emission can be varied in a wide range
(From Fukuda Toshiba Corp Japan)
Preparation of Nitride and Oxynitride Phosphors Methodology
2 Solid-state reaction
2 M t l i id tiTemperature 1600 ndash 2000oC N2 pressure 05 ndash 10 MPa
2 Metal-imide reaction
cf HAHӧppe et al JPhysChemSol 61 2001 (2000)
2 Reduction-nitridation (RN) method Ba2-xEuxSi5N8 image with various x
NH3-CH4gas mixture
Powder sample
Alumina tubeTubular furnace
Gas-tightend cap
Precursor powder CaO Al O SiO
cf TSuehiro et al Chem Mater 17 308(2005) SEM of Ca-α-SiAlON
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Toyada Gosei開發SrO(BaSr)2SiO4P2O5B2O3螢光粉配方以取代Y Al O C 3+迴避智財權Y3Al5O12Ce3+迴避智財權
單一螢光粉之白光LED
色溫偏高(高操作電流密度)缺紅光演色性不足色溫偏高(高操作電流密度)缺紅光演色性不足
88
使用螢光粉搭配LED的發光原理與代表性廠商
產生白光原理 具代表性廠商
Blue-LED + YAGCe粉 Nichia Osram Opto
Blue-LED +YAGCe + R 粉 Nichia
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Blue-LED + R + G Luminled Osram Opto Simens Phili 詮興Philips 詮興
UV-LED + R + G + B 粉 TG GELcore Osram Opto日本21世紀光計畫
89
世紀光計畫
(Source PIDA 2003)
90
Phosphors Excitable with Blue LEDs
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
(a) Oxysulfides ldquoSr5Al2O7SEu2+rdquo (red emitting)(a) O ysu des S 5 2O7S u ( ed e tt g)(b) Silicates (BaSr)2SiO4Eu2+ Sr3SiO5Eu2+ (yellow emitting)(c) Sulfides (CaSr)SEu (CaSr)SCe3+(c) Sulfides (CaSr)SEu (CaSr)SCe(d) Nitridosilicates yellow to red emitting
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong
Asia Pacific Beihua Fine ChemDaming IricoGuogang JiangnanJingneng KehengIntegration DisplaysNanfang 706 New EraNemoto OdeSunlight TiancaiTokyo Kagaku K YaohuaYixing Yuelong