PHOSPHOR CONVERTED

1
PHOSPHOR CONVERTED WHITE LED
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Contents
1. White LED 2. Phosphor Converted White LED 3.
Characteristics of Phosphors for White LED
application 4. Phosphors Claimed, Studied and
Used in LED Application 5. Phosphor Mounting A.
Fabrication B. LED Efficiency C. Epi Growth D.
Extraction Efficiency E. Junction F. LED
Basics G. LED Business H. LED Applications
3
1. White LED Introduction
LED
???
G
?
B
(A)
multi chip (single color LED)
R
(1)
R, G, B LED
??
G
B
Advantage (vs. CCFL)
(B)
R
single chip (multi color LED)
Increased Color Gamut Mechanical Stability
Fast switching Time
?
?
(A)
Y
B
Y Ph
(2)
?
B LED Phosphor
(B)
R/G
B
R, G Ph
R/G/B
(3)
UV
UV LED Phosphor
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1. White LED Characteristics
LCD BLU
color stability chip degradation
LED
???
color gamut
Advantages vs. Disadvantages
?
(1-A)
Adv adjustable white point
sequential color potential Dis complexity in
control circuit large mixing
compensation area efficiency of green
LED (e.g.) Lumileds (LCD TV, monitor) Adv
adjustable white point sequential color
potential small mixing compensation
area Dis complexity in control circuit
complexity in chip design
efficiency of green LED (e.g.) Osram opto.,
Nichia (LCD monitor) Adv simple control
circuit small mixing compensation
area Dis fixed white point no
sequential color potential (e.g.) 2-A
small sized BLU, flash lamp 2-B CRI ? for
lighting, BLU for LCD TV ? 3
development of near UV LED
G
excellent (100) excellent (100)
good (70) very good (90) excellent
(100)
good good very good very good
excellent
2G/1B/1R
B
R
??
(1-B)
G
B
R
(2-A)
Y
B
?
(2-B)
R/G
B
(3)
?
R/G/B
UV
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1. White LED Application (Backlight)
? LCD Backlight Lumileds
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1. White LED Application (Backlight)
? LCD Backlight Lumileds
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1. White LED Application (Backlight)
? LCD Backlight presented at 2004 FPD (Japan)
by HannStar (Taiwan)
Using R, G, B LED
Using White LED
What kind of white LED?
8
1. White LED Application (Backlight)
? Mixing Compensation Area
Osram Opto, Nichia
G
B
R
Lumileds
G
B
R
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2. Phosphor Converted White LED Need for
Phosphors (I)
Efficiency of Green LED
gt
B LED G Phosphor (530nm) 60 70 87
37
G LED 20
? 2 G LED 1 B LED 1 R LED
Why? Transition to indirect band-gap material
at above 0.53 of Al
Why? difficult to obtain high quality InGaN epi-
layer due to re-evaporation of In from
growth surface ? wider FWHM of green
LED and the subsequent low color
purity
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2. Phosphor Converted White LED Need for
Phosphors (I)
White? ?? 3.0 lm, 5.7 lm, 0.57 lm ? ??? R
LED? ?? 85, B LED? ?? 65 ? ?? current ratio?
?? ????? or 2 G LED 1 B, R LED HB LED? ?? I?
T? ?? ??? ???
11
2. Phosphor Converted White LED Need for
Phosphors (II)
efficiency vs. temperature
efficiency vs. time (life time)
- same effect for PC white LED
- less effect for PC white LED
optical feedback
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2. Phosphor Converted White LED Need for
Phosphors (II)
13
3. Characteristics of Phosphors for White LED
Application
Parameters
? Excitation WL ? Absorption efficiency
(Reflection) ? Quantum efficiency ? Stock shift ?
Luminance (Peak WL Eye factor) ? Emission color
(Peak WL, FWHM) ? Temperature dependency (Peak
WL, Luminance) ? Particle size ? Scattering
Particle ? Surface modification ? Refractive
index (Phosphor, Encapsulation material) ?
Gravity (Phosphor, Encapsulation material) ?
Phosphor mixing ratio (CCT, CIE, CRI, Color
Gamut) thickness ? Structure of phosphor
coating layer ? Environment friendly ? Phosphor
degradation ? Radiation damage of encapsulation
(epoxy or silicone)
Illumination vs. backlight
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3. Characteristics of Phosphors for White LED
Application
? Basics of Radiometry and Photometry
1931 CIE X, Y, Z color matching function
555 nm
? Photometry unit lm, cd lm/sr, lux lm/m2,
nit cd/m2
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3. Characteristics of Phosphors for White LED
Application
? Basics of Radiometry and Photometry
Consider one photon at each wavelength,
Br (Y)
cie x
cie y
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3. Characteristics of Phosphors for White LED
Application
? Basics of Radiometry and Photometry CIE (x,y)
chromaticity diagram
all the colors perceivable by human eyes
520 nm
530 nm
540 nm
510 nm
550 nm
560 nm
570 nm
500 nm
580 nm
590 nm
600 nm
610 nm
620 nm
490 nm
480 nm
470 nm
460 nm
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3. Characteristics of Phosphors for White LED
Application
? Basics of Radiometry and Photometry CIE (x,y)
chromaticity diagram
18
3. Characteristics of Phosphors for White LED
Application
? Basics of Radiometry and Photometry CCT
standard light sources (specific emission
spectrum) ? Different body color (R(?) S(?))
? same cct, different (x,y)
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3. Characteristics of Phosphors for White LED
Application
? Basics of Radiometry and Photometry Color
Gamut (Backlight)
current ratio, phosphor ratio for white
NTSC (0.14,0.08), (0.21,0.71), (0.67,0.33)
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3. Characteristics of Phosphors for White LED
Application
? Basics of Radiometry and Photometry CRI
(Illumination)
general color rendering index, Ra
color difference of each sample objects (u,v)
between under standard light source and tested
light source
Ri 100 4.6 ?Ei ?Ei 100 (uk,i
uk)-(uoi-uo)2 (vk,i vk)-(voi-vo)2 1/2 ?
Ra (R1 R5 R8 ) / 8
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3. Characteristics of Phosphors for White LED
Application
? Basics of Radiometry and Photometry Color
Purity
color purity a / (a b)
one of problems
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3. Characteristics of Phosphors for White LED
Application
? Basics of Radiometry and Photometry Color
Mixing (di-chromatic)
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3. Characteristics of Phosphors for White LED
Application
? Basics of Radiometry and Photometry Color
Mixing (tri-chromatic)
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3. Characteristics of Phosphors for White LED
Application
? Basics of Radiometry and Photometry values
from measured spectrum
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3. Characteristics of Phosphors for White LED
Application
? Basics of Radiometry and Photometry values
from simulated spectrum
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3. Characteristics of Phosphors for White LED
Application
? Color Gamut
CCFL
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3. Characteristics of Phosphors for White LED
Application
? Color Gamut
R, G, B LED
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3. Characteristics of Phosphors for White LED
Application
? Color Gamut
B LED Y Ph
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3. Characteristics of Phosphors for White LED
Application
? Color Gamut
B LED R,G Ph
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3. Characteristics of Phosphors for White LED
Application
? Color Gamut
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4. Phosphors Claimed, Studied and Used in LED
Application
What How? - B light converted to
Yellow light by Phosphor
converted to Red and Green (Yellow) light by
Phosphor - UV light converted to Red, Green,
Blue light by Phosphor Key Factor for
Producing White light? - for General Lighting
color rendering index - for BLU color
gamut Who (patent)? Phosphors for PC- White
LED - Nichia - Osram Opto.(Siemens, Osram
Lighting) - Lumileds (Philips) - Gelcore
(GE) - Toyoda - LBG (LWB) - Toshiba
- Matsushita
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4. Phosphors Claimed, Studied and Used in LED
Application

• YAl5O12Ce3,Sm3
• TbAl5O12Ce3
• (Ba,Sr,Ca)2SiO4Eu2

Commercially used Yellow Phosphor for B LED
- Nichia YAGCe - Osram Opto TAGCe
- Lumileds (Philips) YAGCe (Nichia), YAGCe,Pr
- Gelcore (GE) ? - Cree YAGCe
(Nichia) - Toyoda YAGCe (Nichia) -
Rohm, Lite-on, Everlight, Vishay TAGCe
(Osram) - Citizen YAGCe (Nichia) -
Stanley YAGCe (?) - Samsung E.M. TAGCe
(Osram) - Seoul S.C. Ortho-silicateEu
(LWB,Toyoda) - Matsushita ?
Commercially used Red, Green Phosphor for B LED
- Strong Candidate CaSEu, STGEu -
Degradation of Sulfide Phosphors ? Luminance ?
Commercially used Phosphors for UV LED -
Toyoda ZnSCu,Al / Halo-phosphateEu / LOSEu
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4. Phosphors Claimed, Studied and Used in LED
Application
Licensing PC - White LED
Rohm
Samsung E.M.
Lumileds
Citizen
Cree
Osram
Nichia
Liteon
Toshiba
Everlight
Toyoda
UV LED Phosphors
Seoul S.C Phosphor from LWG(Toyoda) B LED
chip from Cree
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4. Phosphors Claimed, Studied and Used in LED
Application
Matsushita
1. Publication EP1447853 (2004, 8) 2. Priority
2001, 10 3. 1? UV LED (350410nm) B Ph
(400500nm) G Ph (500550nm) R Ph(600660nm)
Y Ph (550600nm) 28? Y Ph
(Sr1-a1-b1-xBaa1Cab1Eux)2SiO4, 0 ? a1 ? 0.3, 0
? b1 ? 0.6, 0 ? x ? 1 B Ph
(M1-xEux)10(PO4)6Cl2, M Ba, Sr, Ca, Mg
(M1-xEux)(N1-yMny)Al10O17, M
Ba, Sr, Ca N Mg, Zn 0 ? y ? 0.05
G Ph (M1-xEux)(N1-yMny)Al10O17, M Ba,
Sr, Ca N Mg, Zn 0.05 ? y ? 1
(M1-xEux)2SiO4, M Ba, Sr, Ca, Mg
R Ph (Ln1-xEux)O2S, Ln Sc, Y,
La, Gd
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4. Phosphors Claimed, Studied and Used in LED
Application
LBG (LBW)
1. Publication WO 02/054502 (2002, 7) (KR??
2003-74641) 2. Priority 2000, 12 3. 1? UV
or B LED (2-x-y)SrO x(BauCav)O
(1-a-b-c-d)SiO2, aP2O5, bAl2O3, cB2O3, dGeO2
yEu2 ???? ???? 1??? claim B Ph
alkaline earth aluminatesEu2, Mn2 R Ph
Y(V, P, Si)O4Eu2, Y2O2SEu3, Bi3,
alkaline earth magnesium disilicate
(M3-x-yMgSi2O8Eu2, Mn2)
1. Publication WO 02/054503 (2002, 7) with
Toyota Gosei (KR?? 2003-91951) 2. Priority
2000, 12 3. 1? LED Ph? ???? ?????? ????
ortho-silicate 3?(?) ortho-silicate?
???. (2-x-y)SrO x(BauCav)O
(1-a-b-c-d)SiO2, aP2O5, bAl2O3, cB2O3, dGeO2
yEu2 LED Ph? ???? ?????? ?? ?? ??
claim? ?? ??.
36
4. Phosphors Claimed, Studied and Used in LED
Application
Toyoda Gosei
1. Publication KR1997-0030949 (1997, 6) 2.
Priority 1995, 11 3. 1? Phosphor UV
Reject ??? ??
1. Patent US6791116 (2004, 9) with
Matsushita 2. Priority 2002, 4 3. Scattering
material? phosphor? ??? diode ????
1. Publication JP2004-127988 (2004, 4) (WO
04/032251) 2. Priority 2002, 9 3. UV or Blue
LED Y, R, G, B Phosphor Y Ph (2-x-y)BaO
x(SruCav)O (1-a-b-c-d)SiO2, aP2O5, bAl2O3, cB2O3,
dGeO2, Eu2
37
4. Phosphors Claimed, Studied and Used in LED
Application
Toyoda / Toshiba
Near UV LED R, G, B Ph ?
38
4. Phosphors Claimed, Studied and Used in LED
Application
Toshiba
1. Publication JP2004-103443 (2004, 4) 2.
Priority 2002, 9 3. B LED Y, R Phosphors
1. Publication JP2003-318447 (2003, 11) 2.
Priority 2002, 4 3. LED (400500 nm) Ph 1
(500600 nm) Ph 2 (600700 nm)
1. Publication JP1999-246857 (1999, 9) 2.
Priority 1998, 2 3. UV LED R Ph 1?
R Ph (La1xyEuxSmy)2O2S, 0.01 ? x ? 0.15,
0.0001 ? y ? 0.03 ???? ???? 1??? claim
5? La ?? Y or Gd? ?? ??
KASEI?
39
4. Phosphors Claimed, Studied and Used in LED
Application
Toshiba
1. Publication JP2000-183408 (2000, 6) 2.
Priority 1998, 12 3. UV LED B Ph O Ph
(excited by B Ph) B Ph M10(PO4)6Cl2Eu2
O Ph (Y,Gd)3Al5O12Ce3
1. Publication JP2002-203991 (2002, 7) 2.
Priority 1997, 9 3. UV LED R, G, B
Phosphors
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4. Phosphors Claimed, Studied and Used in LED
Application
1. Publication JP1996-36835 (1998, 2) 2.
Priority 1996, 7 3. ??? ??? (Y 1-p-q-r
GdpCeqSmr)3(Al1-sGas)5O12, 0 ? p ? 0.8, 0.003 ? q
? 0.2, 0.003 ? r ? 0.08, 0 ? s ? 1
Nichia
1. Patent US5998925 (1999, 12) (Family
US6069440, US6608332, US6614179, JP2927279) 2.
Priority 1996, 7 3. 1?(?) Garnet material,
A3B5O12Ce, A Y, Lu, Sc, La, Gd, Sm B Al,
Ga, In 2? Y? Al? ???? yttrium aluminum
garnet material 3? (Re1-rSmr)3(Al1-sGas)5O
12Ce, 0 ? r ? 1, 0 ? s ? 1, Re Y, Gd
1. Patent US6069440 (2000, 5) 2. Priority
1996, 7 3. 1?(?) Blue light ??? ??? ? ?? ???

1. Patent US6614179 (2003, 9) 2. Priority
1996, 7 3. 1?(?) (Re1-rSmr)3(Al1-sGas)5O12Ce,
0 ? r ? 1, 0 ? s ? 1, Re Y, Gd
41
4. Phosphors Claimed, Studied and Used in LED
Application
Nichia
1. Publication US2004-135504 (2004,7) 2.
Priority 2002, 3 3. ??? ??? 1???, ??? ????
Red ??? ??? ?? ??? ?? LxMyN(2/3x 4/3y)R,
LxMyOzN(2/3x 4/3y 2/3z)R where, L
Mg, Ca, Sr, Ba, Zn M Si (essential), C, Ge
R Eu2 (essential), RE LED below 500
nm Ph 520 780 nm
1. Patent JP3419280 (2003, 4) 2. Priority
1996, 11 3. 365 nm ? LED ? 400 nm, Red Ph
aMgO bLi2O Sb2O3 cMn dMgO eTiO2 fMn
jCaO kMO TiO2 iPr, M Zn, Mg, Sr, Ba
1. Publication JP1998-112557 (1998, 4) 2.
Priority 1996, 10 3. LED (M,Eu,Q)O
n(Al1-m,Bm)2O3, M Mg, Ca, Sr, Ba, Zn 0? m
?0.5 0.5? n ?10
Q (co-activator) Mn, Zr,
Nb, etc.
42
4. Phosphors Claimed, Studied and Used in LED
Application
Nichia
1. Publication JP1999-046019 (1999,2) 2.
Priority 1997, 7 3. Phosphor mounting by Ink
jet method
JP 2998696 (1999), 3036465 (2000), 2900928
(1999), 3065258 (2000) JP Publication
1998-154830, 1998-228249, 1998-233533,
1998-247750, 1999-199781
43
4. Phosphors Claimed, Studied and Used in LED
Application
Nichia
YAG (Y 1-p-q-r GdpCeqSmr)3(Al1-sGas)5O12
?? ?? ??
Gd
Gd
44
4. Phosphors Claimed, Studied and Used in LED
Application
Nichia
YAG (Y 1-p-q GdpCeq)3(Al1-sGas)5O12
45
4. Phosphors Claimed, Studied and Used in LED
Application
Nichia
YAG (Y 1-p-q GdpCeq)3(Al1-sGas)5O12
46
4. Phosphors Claimed, Studied and Used in LED
Application
Nichia
When using YAG, low Ra at low CCT
For High Ra or warm white new red
phosphor ! (655 nm)
47
4. Phosphors Claimed, Studied and Used in LED
Application
Nichia
High CRI daylight white LED, using shorter
YAG and red phosphor
3.2 V / 20 mA 1.8 lm / 28.3 lm/W 4600 K
(0.357/0.355) Ra 76.2
3.3 V / 20 mA 1.67 lm / 28.3 lm/W 4670 K
(0.355/0.361) Ra 87.7
48
4. Phosphors Claimed, Studied and Used in LED
Application
Nichia
High efficacy or CRI warm white LED,
using YAG and red phosphor
3.22 V / 20 mA 1.49 lm / 23.1 lm/W 2810 K
(0.451/0.408) Ra 72.5
3.24 V / 20 mA 1.23 lm / 18.9 lm/W 2830 K
(0.449/0.408) Ra 87.5
49
4. Phosphors Claimed, Studied and Used in LED
Application
Light for 21C Stanley/Mitsubishi/Kasei/Yamaguch
Univ.
Near UV LED R, G, B Ph
50
4. Phosphors Claimed, Studied and Used in LED
Application
Light for 21C Stanley/Mitsubishi/Kasei/Yamaguch
Univ.
Near UV LED R, G, B Ph
51
4. Phosphors Claimed, Studied and Used in LED
Application
Sharp
Near UV LED R, G, B Ph
CG 74 of NTSC 450 mcd at 4 V /40 mA
52
4. Phosphors Claimed, Studied and Used in LED
Application
1. Patent US6351069 (2002,2) (family
US6680569) 2. Priority 1999, 2 3. wavelength
conversion primary FL material, supplementary
FL material (red) Y3Al5O12Ce3
Y3Al5O12Ce3, Pr3 Y3Al5O12Ce3
SrSEu2
Lumileds
1. Patent US6686691(2004,3) 2. Priority 1999,
9 3. composition comprising a mixture of a 1st
and a 2nd phosphor, each phosphor
comprising a host sulfide material and rare earth
dopant Especially, Blue LED
SrGa2S4Eu2 SrSEu2 CaSEu2
SrGa2S4Ce3 SrSCe3 CaSCe3
1. Patent US6642618 (2003, 11) 2. Priority
2000, 12 3. 5? white light by sol-gel glass
(SiO2) layer containing (Sr,Ba,Ca)Ga2S4Eu2
SrSEu2
1. Patent US 6603258 (2003, 8) 2. Priority
2001, 4 3. white light by LED (485 515nm)
(Sr,Ba,Ca)SEu2 (600 620nm), ?? SrSEu2
53
4. Phosphors Claimed, Studied and Used in LED
Application
1. Patent US6084250 (2000,7) by Philips (Family
US6051925, JP??2000-509912) 2. Priority 1997,
3 3. 1? UV (300 370 nm) B Ph (430490 nm)
G Ph ( 520570 nm) R Ph (590630 nm) 6?
B Ph BaMgAl10O17 Eu2, G Ph ZnSCu, R Ph
Y2O2SEu3 7? Organic phosphor (dye)
Lumileds
1. Patent US6717353 (2004, 4) 2. Priority
2002, 10 3. 1? 1st WL converting material
comprising Sr-SiONEu2 (or YAGCe) emitting 2nd
WL light 2? UV and Blue light 1st WL
light 3? Green 2nd WL light 4,
8? Red Ph 2nd WL converting material (using
2nd WL lght),
(Sr1abcBabCac)2Si5N8aEu2
Blue Ph 3rd WL converting material (using 1st
WL light),
(Sr1axBax)3MgSi2O8aEu2
1. Patent US6417019 (2002, 7) 2. Priority
2001, 4 3. 1? white light by LED (380
500nm) (Sr,Mg,Ba,Ca)(Ga,Al,In)2S4Eu2 (490
610 nm) LED/Phosphor structure
(encapsulation, mounting)
54
4. Phosphors Claimed, Studied and Used in LED
Application
Lumileds
1. Patent US6501102 (2002, 12) 2. Priority
2002, 1 3. 1? LED (below 460 nm)
2nd, 3rd WL light from YAG, (Y,Ln)AG,
(Y,Ln)(Al,Ga)G, SrS, SrGa2S4, NitridoSilicate
2? Ce3, Eu2 etc. Phosphor powder
layer, Phosphor thin film, Substrate for light
emitting structure
1. Patent US6650044 (2003, 11) 2. Priority
2000, 10 3. Stencing method for phosphor layer
1. Patent US6576488 (2003, 6) 2. Priority
2001, 6 3. Electrophoretic method for
conformal coating
1. Patent US6645652 (2003, 11) 2. Priority
2001, 6 3. Stencing, Electrophoresis method
for phosphor layer
55
4. Phosphors Claimed, Studied and Used in LED
Application
Lumileds
1. Patent US6590235 (2003, 7) (Family
US6204523) 2. Priority 1998, 11 3.
Encapsulating material (silicone) for UV LED
1. Patent US5813752, US5813753 (1998,9) 2.
Priority 1997, 5 3. Enhanced efficiency by
short wave pass filter between LEDs and phosphor
layer (reflecting visible light from
phosphor layer)
1. Patent US5959316 (1999,9) (by HP) 2.
Priority 1998, 9 3. Uniform phosphor layer
on the hemisphere transparent spacer
56
4. Phosphors Claimed, Studied and Used in LED
Application
Lumileds - Philips
57
4. Phosphors Claimed, Studied and Used in LED
Application
Lumileds - Philips
58
4. Phosphors Claimed, Studied and Used in LED
Application
Lumileds
Blue LED Y Ph (YAGCe, YAGCe,Pr) Blue LED
G Ph (SrGa2S4Eu2) R Ph (SrSEu2)
Resistance to humidity ? Preventing coating ? LCD
BLU ?
59
4. Phosphors Claimed, Studied and Used in LED
Application
Lumileds
Blue LED Y Ph (YAGCe, YAGCe,Pr) R Ph
(CaSEu2)
For Illumination ?
60
4. Phosphors Claimed, Studied and Used in LED
Application
Lumileds - Philips

61
4. Phosphors Claimed, Studied and Used in LED
Application
Lumileds - Philips

62
4. Phosphors Claimed, Studied and Used in LED
Application
Lumileds
UV LED R, G, B Phosphors
63
4. Phosphors Claimed, Studied and Used in LED
Application
Lumileds
64
4. Phosphors Claimed, Studied and Used in LED
Application
Lumileds
65
4. Phosphors Claimed, Studied and Used in LED
Application
Sarnoff
SrCaSEu2
66
4. Phosphors Claimed, Studied and Used in LED
Application
Sarnoff
SrCaSEu2
67
4. Phosphors Claimed, Studied and Used in LED
Application
Osram Opto.
1. Patent US6066861 (2000, 5) (Family
US6245259, 6277301, 6576930, 6592780, 6613247) 2.
Priority 1996, 9 3. 1? WL (from UV, Blue,
Green) converting casting composition
Resin (epoxy) A3B5X12M3, A
Y, Ca, Sr B Al, Ga, Si X O, S M Ce,
Tb (YAG, Thiogallate,
Orthosilicate) (not, Eu) size ? 20
?m (d ? 5 ?m) 7? YAGCe 10?
Lighting emitting S.C. component S.C. body (UV,
Blue, green) A3B5X12M
1. Patent US6245259 (2001, 6) 2. Priority
1996, 9 3. 1? WL (from UV, Blue, Green)
converting casting composition
Resin (epoxy) Ce doped phosphors
size ? 20 ?m (d ? 5 ?m) 7?
YAGCe 10? Lighting emitting S.C.
component S.C. body (UV, Blue, green) Ce
doped phosphors 15? Yellow by Blue LED
16? Green, Red by Blue LED
68
4. Phosphors Claimed, Studied and Used in LED
Application
Osram Opto.
1. Patent US6277301 (2001, 8) 2. Priority
1996, 9 3. 1? WL (from UV, Blue, Green)
converting casting composition
Resin (epoxy) Ce doped phosphors,
garnet doped with rare earth, thiogallates doped
with rare earth, Aluminates doped
rare earth, orthosilicates doped with rare earth
tempering above 200 oC 2?
size ? 20 ?m (d ? 5 ?m) 11?(?) White
lighting emitting S.C. component
S.C. body (UV, Blue, green) Ce doped
phosphors(blue to yellow) with epoxy 12?(?)
White lighting emitting S.C. component S.C.
body (UV, Blue, green)
garnet doped with rare earth, thiogallates doped
with rare earth,
aluminates doped rare earth,
orthosilicates doped with rare earth (blue
to green and red) with epoxy
69
4. Phosphors Claimed, Studied and Used in LED
Application
Osram Opto.
1. Patent US6613247 (2003, 9) 2. Priority
1996, 9 3. 1? WL (from UV, Blue, Green)
converting casting composition
Resin (epoxy) garnet doped with
rare earth, thiogallates doped with rare earth
aluminates doped rare earth,
orthosilicates doped with rare earth
size ? 20 ?m (d ? 5 ?m) 7? YAGCe3
phosphor 12?(?) White lighting emitting
S.C. component S.C. body (UV, Blue, green)
garnet doped with rare earth,
thiogallates doped with rare earth,
aluminates doped rare earth,
orthosilicates doped with rare earth 17?
White Blue LED yellow light by Ce doped
phosphor 18? White Blue LED green and
red light
1. Patent US6669866 (2003, 12) (Family
US6552487) 2. Priority 1999, 7 3. 1?(?)
light source comprising emission from 420 to 490
nm and phosphor A3B5O12Ce3 A
Tb or one of Y, Gd, La, Lu B Al, Ga
2? Tb solely or predominantly (TAG)
70
4. Phosphors Claimed, Studied and Used in LED
Application
Osram Opto.
1. Patent US6504179 (2003, 1) 2. Priority
2000, 5 3. 1? LED (300 470nm) Eu
activated calcium magnesium chlorosilicate (green
phosphor)
Ce activated rare earth garnet (yellow
phosphor) 2? Green (Ca8-xyEuxMnyMg(SiO4)4
Cl2) 3? Yellow ((Re)3(Al,Ga)5O12Ce, ??
YAGCe or TAGCe) 4? ??, LED (330370
nm) phosphors (430470, 490525, 545590 nm)
5? ??, LED (430470 nm) phosphors
(545590, 490525 nm)
1. Patent US 6649946 (2003, 11) (Family US
6682663) 2. Priority 1999, 11 3. 1?(?)
Yellow to Red emitting phosphor
MxSiyNzEu2, M La, Sr, Ba, Zn 8?
LED phosphors 9? LED 420470nm

71
4. Phosphors Claimed, Studied and Used in LED
Application
Osram Opto.
1. Patent US6695982 (2004, 2) 2. Priority
2000, 6 3. 1? ??? ?? ?? AB2S4
D, A Mg, Ca, Sr B Al, Ga, Y D Ce3,
Eu2

1. Publication US2004-0124758 (2004, 7) 2.
Priority 2000, 7 3. 1?(?) UV (370420 nm)
or Blue (420480 nm)
MSEu2 (M Ba, Mg, Zn, Ca, Sr) containing one
of Ba, Mg, Zn MN2S4Eu2 or
Ce3 (M Ba, Mg, Zn, Ca, Sr N Al, Ga, In, Y,
La, Gd)
72
4. Phosphors Claimed, Studied and Used in LED
Application
Osram Opto.
Shorter YAG
Blue LED Y Ph (TAGCe) Blue LED Y,G Ph
(Y(Al,Ga)GCe or TAGCe) R Ph ((AE)2Si5N8Eu2)
73
4. Phosphors Claimed, Studied and Used in LED
Application
Near UV LED R, G, B Ph
Osram Opto.
Sr4Al14O25Eu2 (490 nm) SrAl12O19Eu2 (520
nm) SrAl2O4Eu2 (400 nm)
74
4. Phosphors Claimed, Studied and Used in LED
Application
Osram Opto.
75
4. Phosphors Claimed, Studied and Used in LED
Application
Osram Opto Siemens
YAG (Y 1-p-q GdpCeq)3(Al1-sGas)5O12
Gd
Ga
76
4. Phosphors Claimed, Studied and Used in LED
Application
Osram Opto Siemens
YAG (Y 1-p-q GdpCeq)3(Al1-sGas)5O12
f-d absorption or CT absorption
77
4. Phosphors Claimed, Studied and Used in LED
Application
Potential R, G, B, Y Ph
Osram Opto Siemens
78
4. Phosphors Claimed, Studied and Used in LED
Application
GE or Gelcore
1. Patent US6765237 (2004, 7) 2. Priority
2003, 1 3. 1? 380420nm LED Blue Ph
(BaMg2Al16O27Eu2) Y Ph ((Tb1xyAxREy)3DzO12)
A Y, La, Gd, Sm RE Ce etc
D Al, Ga, In 15? B Ph
(Sr,Ba,Ca,Mg)5(PO4)3ClEu2
1. Patent US6501100 (2002, 12) 2. Priority
2000, 5 3. 1? UV LED (370405 nm) Ph 1
(570620 nm) Ph 2 (480520 nm) Ph 1
APOEu2,Mn2, A2P2O7Eu2,Mn2, A Sr, Ca, Ba,
Mg Ph 2 A4D14O25Eu2, (AD)8O13Eu2,
A10(PO4)6Cl2Eu2, A2Si3O8 ACl2Eu2
A Sr, Ca, Ba, Mg D Al, Ga
1. Patent US6580097 (2003, 6) (Family
US6252254, US6469322) 2. Priority 1998, 2 3.
1? Blue LED Ph 1 Ph 2 G Ph 1
YBO3Ce3,Tb3, BaMgAl10O17Eu2,Mn2,
(Sr,Ca,Ba)(Al,Ga)2s4Eu2,Y3Al5O12Ce3 R
Ph 2 Y2O2SEu3,Bi3, YVO4Eu3,Bi3, SrSEu2,
SrY2S4Eu2, CaLa2S4Ce3, (Ca,Sr)SEu2
79
4. Phosphors Claimed, Studied and Used in LED
Application
1. Patent US6469322 (2002, 10) 2. Priority
1998, 2 3. 1? UV, Blue LED Green Ph
(LnBO3Ce3,Tb3, Ln Sc, Y, La, Gd, Lu)
9? Blue Ph ((Ba,Sr,Ca)5(PO4)3Cl Eu2,Mn2) ??
10? Red Ph ??
GE or Gelcore
1. Patent US6791259 (2004, 9) 2. Priority
2000, 8 3. Scattering material ?? (between LED
Phosphor material) size? ?/3 ?/2
1. Patent US6685852 (2004, 2) 2. Priority
2001, 4 3. 1? UV LED (315480nm, ??????
350410nm) ?? Phosphor ??? 2? (1)
Sr2P2O7Eu2,Mn2 (2)
(Ba,Sr,Ca)5(PO4)3(F,Cl,OH) Eu2,Mn2
(3) 3.5 MgO 0.5 MgF2 GeO2Mn4
(4) (Ba,Sr,Ca)5(PO4)3(Cl,OH) Eu2 (5)
(Ba,Sr,Ca)2MgAl16O27Eu2, (Ba,Sr,Ca)MgAl10O17Eu2
, (Ba,Sr,Ca)Mg3Al14O25Eu2 (6) (5)??
Mn2? co-activator? ??
80
4. Phosphors Claimed, Studied and Used in LED
Application
GE or Gelcore
1. Patent US6621211 (2003, 9) 2. Priority
2000, 5 3. 1? UV LED (360420 nm) (1)
Ph 575620 nm (Sr,Ca,Ba,Mg)POEu2,Mn2,
(Sr,Ca,Ba,Mg)2P2O7Eu2,Mn2 (2) Ph
495550 nm ASiO4Eu2, A2DSi2O7Eu2,
AAl2O4Eu2, A Sr, Ba, Ca D Mg, Zn
(3) Ph 420480 nm Mg2Al16O27Eu2,
(Sr,Ba,Ca)5(PO4)3ClEu2, Zn(Ba,Eu)O-6Al2O3,

BaAl12O19Eu2, KAl11O11Eu2 (4) Ph
620670 nm (optional) 3.5 MgO 0.5 MgF2
GeO2Mn4
1. Patent US6616862 (2003, 9) 2. Priority
2001, 5 3. Mn2 ??? red shift UV LED
(350420 nm) 1? (Ba,Sr,Ca,Mg)5(PO4)3(F,Cl,
OH)Eu2,Mn2 (orange color)
Optionally, add blue phosphors
1. Patent US6596195 (2003, 7) 2. Priority
2001, 6 3. 1?(?) ???? claim, TAG,
(Tb1xyAxREy)aDzO12, A Y, La, Gd, Sm D
Al,Ga 38?(?) LED phosphor
40?(?) LED 400480 nm phosphor
81
4. Phosphors Claimed, Studied and Used in LED
Application
1. Patent US6538371 (2003, 5) 2. Priority
2000, 3 3. Blue LED YAGCe3 1?
System color output? ????? ?? (CIE coord.?? BBL?
line? ???? ??)
GE or Gelcore
1. Patent US6522065 (2003, 2) 2. Priority
2000, 3 3. 1? UV LED white phosphor
A22xNa1xExD2V3O12, A Ca, Ba, Sr, D
Mg, Zn, E Eu3, Sm3 (e.g.) 370 nm LED
Ca22xNa1xEuxMg2V3O12
1. Patent US6294800 (2001, 9) (Family
US6255670) 2. Priority 1998, 12 3. 1?
Ca8Mg(SiO4)4Cl2Eu2,Mn2? ???? ?? 2? ??
G Ph? R, B Ph? ???? ?? 3? UV LED (330
420 nm, ?? 355365 nm) 6? G
Ca8Mg(SiO4)4Cl2Eu2,Mn2, R
Y2O3Eu3,Bi3, B
(Sr,Ba,Ca)5(PO4)3ClEu2 or BaMg2Al16O27Eu2
82
4. Phosphors Claimed, Studied and Used in LED
Application
GE or Gelcore
C3A2(D)3O12
Y3Al5O12
tetrahedral site
Ga prefers tetrahedral site to larger octahedral
site. Expansion of structure. Replacement to Ga
provides longer Ce3 - O distance. Less crystal
field. (centropoid shift, covalency ?) Blue
shift of Em. Ex. spectrum.
octahedral site
dodecahedral site
Replacement to Ga brings about decrease of
emission intensity.
83
4. Phosphors Claimed, Studied and Used in LED
Application
GE or Gelcore
Al4Ga1
Al1Ga4
Al2Ga3
Al3Ga2
Al5
similar thermal quenching
No emission at RT
crossover bet. d and f level
Photo-ionization
84
4. Phosphors Claimed, Studied and Used in LED
Application
GE or Gelcore
Y3Al5O12 (garnet)
REAlO3 (perovskite)
replacement to Large RE3
Secondary phase due to solubility Quenching by
energy transfer from Ce3 to RE3 Mainly,
replacement to Gd (red shift) or Lu (blue shift).
When replacement to Tb, f-d absorption of
Tb3 at 275 nm. (checking by excitation
spectrum of Ce3) Energy transfer from Tb3
to Ce3 (phonon assisted?) i.e., no
quenching Red shift of both Em. And Ex.
spectrum.
85
4. Phosphors Claimed, Studied and Used in LED
Application
GE or Gelcore
TAG no change of Q.E. at RT
significant change at high T
Overlap with 5D4 level of Tb3 Energy transfer
from Ce3 to Tb3 (i.e., back transfer)
Patent US6596195 (2003, 7) Using TAG phosphors
86
4. Phosphors Claimed, Studied and Used in LED
Application
Blue or Near UV LED Phosphors
GE or Gelcore
For Illumination ?
For BLU ?
87
4. Phosphors Claimed, Studied and Used in LED
Application
Near UV LED Phosphors
GE or Gelcore
Replace into B2O3?
or
?
What phosphor ?
88
4. Phosphors Claimed, Studied and Used in LED
Application
Near UV LED R, G, B Ph
GE or Gelcore
89
4. Phosphors Claimed, Studied and Used in LED
Application
GE or Gelcore
LED white phosphor
Activator ?
?
90
4. Phosphors Claimed, Studied and Used in LED
Application
Blue or UV LED Phosphors
Phosphortech
Excitation (absorption) bandgap absorption or
absorption by activators (Cu,A)
Eg for ZnS 3.7 eV (335nm) for ZnSe
2.7 eV (460nm)
91
4. Phosphors Claimed, Studied and Used in LED
Application
Blue LED Phosphors
Phosphortech
CRI?
92
4. Phosphors Claimed, Studied and Used in LED
Application
UV LED Phosphors
Phosphortech
93
4. Phosphors Claimed, Studied and Used in LED
Application
GIT, Phosphortech
Review by C. Summers
B LED ? ? high I high T color change of
pump ? change of excitation for
ph (WL) change of emission
from ph (Intensity) UV LED ? ? better for
phosphor development ?
patent for phosphor better
pump efficiency (n-UV) tri
color phosphor (emulation)
no involving in color mixing
254 Hg emission ? ? AC
? no sulfide phosphor LED ? ? CW
decay time (fast recycling)
ground state depletion
high order effect (quenching)
? sulfide phosphor?
N-UV or B LED? Peak WL?
For UV LED ? Sr2SiO4Eu2 3.2 lm/W, Ra68
vs. 2 lm/W, Ra80 for YAG APL 82, 683,
2003 ? Ca10(PO4)6Cl2Eu2 UV to Ph, Blue
from Ph, Blue to YAG Jpn. JAP 41, L371,
2002 ? 30 lm/W, Ra 93 from B,Y,O phosphors
IDW 817, 2000 ? AE silicon-nitride
material for life time small stoke shift due to
rigid lattice - Acta Cryst. C53, 1751, 1997
? RE silicon-nitride, silicon oxy nitride
? coating for sulfide phosphor life time
94
4. Phosphors Claimed, Studied and Used in LED
Application
GIT, Phosphortech
Review by C. Summers
Lumileds for Blue LED, STG and SS from 2000
(two phosphor) combinations
Ra gt 90
95
4. Phosphors Claimed, Studied and Used in LED
Application
GIT, Phosphortech
Review by C. Summers
for Blue LED, YAG was broadly used.
Q. When Ce was excess, efficiency or peak
shift?
96
4. Phosphors Claimed, Studied and Used in LED
Application
Blue LED Y Ph (Ca-?-SiAlONEu2)
NIMS (Japan)
APL, V84, P5405, 2004
USP 6,776,927 (NIMS), USP 6657379 (Elektrische
Gmbh)
97
4. Phosphors Claimed, Studied and Used in LED
Application
UV LED Nano phosphors
Sandia
98
4. Phosphors Claimed, Studied and Used in LED
Application
Temperature Dependence
B LED Due to I increase band filling
Phosphor more sensitive upon T
99
4. Phosphors Claimed, Studied and Used in LED
Application
Temperature Dependence
? Phosphor more sensitive upon T ? The reason
for this behavior ? several factors should be
considered.