PHOSPHOR CONVERTED WHITE LED

PHOSPHOR CONVERTED PHOSPHOR CONVERTED WHITE LEDWHITE LED

1. White LED1. White LED

2. Phosphor Converted White LED2. Phosphor Converted White LED

3. Characteristics of Phosphors for White LED application 3. Characteristics of Phosphors for White LED application

4. Phosphors Claimed, Studied and Used in LED Application4. Phosphors Claimed, Studied and Used in LED Application

5. Phosphor Mounting 5. Phosphor Mounting

A. Fabrication A. Fabrication

B. LED Efficiency B. LED Efficiency

C. Epi GrowthC. Epi Growth

D. Extraction Efficiency D. Extraction Efficiency

E. JunctionE. Junction

F. LED BasicsF. LED Basics

G. LED BusinessG. LED Business

H. LED ApplicationsH. LED Applications

ContentsContents

1. White LED : Introduction 1. White LED : Introduction

LEDLED

형광체형광체

백색(1)

R, G, B LED

single chip(multi color LED)

multi chipmulti chip(single color LED)(single color LED)

B LED + Phosphor

UV LED + Phosphor

R, G PhR, G Ph

* Increased Color

* Mechanical Stability

* Fast switching Time

Advantage (vs. Advantage (vs. CCFL)CCFL)

LEDLED

형광체형광체

백색

LCD BLULCD BLU

color color gamutgamut

color stabilitycolor stabilitychip chip

degradationdegradation

excellent (~100%)

good (~70%)

very good (~90%)

excellent (~100%)

very good

excellent

Advantages vs. DisadvantagesAdvantages vs. Disadvantages

* 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

2G/1B/1R2G/1B/1R

1. White LED : Characteristics1. White LED : Characteristics

1. White LED : Application (Backlight) 1. White LED : Application (Backlight)

LCD Backlight – Lumileds LCD Backlight – Lumileds

Using R, G, B LED Using White LED

What kind of white LED?

LCD Backlight – presented at 2004 FPD (Japan) by HannStar (Taiwan)LCD Backlight – presented at 2004 FPD (Japan) by HannStar (Taiwan)

Mixing & Compensation Area Mixing & Compensation Area

Osram Opto, NichiaOsram Opto, Nichia

Lumileds Lumileds

2 G LED + 1 B LED + 1 R 2 G LED + 1 B LED + 1 R LEDLED

* Efficiency of Green * Efficiency of Green LEDLED B LED * G Phosphor B LED * G Phosphor

(530nm)(530nm)= 60% * 70% * 87% = ~ = 60% * 70% * 87% = ~ 37 %37 %

G LED G LED = ~ 20 %= ~ 20 %>>

Why? difficult to obtain high quality InGaN epi- layer Why? difficult to obtain high quality InGaN epi- layer due to re-evaporation of In from growth surfacedue to re-evaporation of In from growth surface wider FWHM of green LEDwider FWHM of green LED and the subsequent low color purity and the subsequent low color purity

Why? Transition to indirect band-gap material Why? Transition to indirect band-gap material at above 0.53 of Al at above 0.53 of Al

2. Phosphor Converted White LED : Need for Phosphors (I) 2. Phosphor Converted White LED : Need for Phosphors (I)

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* White 를 위해 3.0 lm, 5.7 lm, 0.57 lm 이 필요함 * R LED 의 경우 85%, B LED 의 경우 65 % 만 사용 * current ratio 를 작게 가져가거나 or 2 G LED + 1 B, R LED* HB LED 의 경우 I 와 T 에 따른 보상이 필요함

2. Phosphor Converted White LED : Need for Phosphors (I) 2. Phosphor Converted White LED : Need for Phosphors (I)

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* efficiency vs. temperature* efficiency vs. temperature * efficiency vs. time (life * efficiency vs. time (life time)time)

optical optical feedbackfeedback

- less effect for PC white - less effect for PC white LEDLED

- same effect for PC white - same effect for PC white LEDLED

2. Phosphor Converted White LED : Need for Phosphors (II) 2. Phosphor Converted White LED : Need for Phosphors (II)

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2. Phosphor Converted White LED : Need for Phosphors (II) 2. Phosphor Converted White LED : Need for Phosphors (II)

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3. 3. Characteristics of Characteristics of Phosphors for White LED Application Phosphors for White LED Application

Excitation WLExcitation WL

Absorption efficiency (Reflection)Absorption efficiency (Reflection)

Quantum efficiencyQuantum efficiency

Stock shiftStock shift

Luminance (Peak WL: Eye factor)Luminance (Peak WL: Eye factor)

Emission color (Peak WL, FWHM)Emission color (Peak WL, FWHM)

Temperature dependency (Peak WL, Luminance) Temperature dependency (Peak WL, Luminance)

Particle size Particle size

Scattering ParticleScattering Particle

Surface modification Surface modification

Refractive index (Phosphor, Encapsulation material) Refractive index (Phosphor, Encapsulation material)

Gravity (Phosphor, Encapsulation material) Gravity (Phosphor, Encapsulation material)

Phosphor mixing ratio (CCT, CIE, CRI, Color Gamut) & thickness Phosphor mixing ratio (CCT, CIE, CRI, Color Gamut) & thickness

Structure of phosphor coating layerStructure of phosphor coating layer

Environment friendlyEnvironment friendly

Phosphor degradationPhosphor degradation

Radiation damage of encapsulation (epoxy or silicone) Radiation damage of encapsulation (epoxy or silicone)

Illumination vs. backlightIllumination vs. backlight

ParametersParameters

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1931 CIE 1931 CIE XX, , YY, , ZZ color matching function color matching function

350 400 450 500 550 600 650 700 750

X = X() P() d

Z = Z() P() d

Y = Y() P() d x = X / (X + Y + Z)y = Y / (X + Y + Z)

u = 4X / (X + 15Y + 3Z)v = 6Y / (X + 15Y + 3Z)

for uniform chromaticity coordinates (color difference between two point)

Br = 680 Y() P() d

lm/W W/nm

555 nm

Photometry unit : lm, cd = lm/sr, lux = lm/mPhotometry unit : lm, cd = lm/sr, lux = lm/m22, nit = cd/m, nit = cd/m22

Basics of Radiometry and Photometry Basics of Radiometry and Photometry

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Consider one photon at each wavelength, Consider one photon at each wavelength,

400 450 500 550 600 650 700

WL(nm)

Br (Y)

Basics of Radiometry and Photometry Basics of Radiometry and Photometry

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cie x, y

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

520 nm530 nm

510 nm540 nm

550 nm

560 nm

570 nm

580 nm

590 nm

600 nm

610 nm620 nm

500 nm

490 nm

480 nm

470 nm460 nm

all the colors perceivable by human eyes

Basics of Radiometry and Photometry : CIE (x,y) chromaticity diagram Basics of Radiometry and Photometry : CIE (x,y) chromaticity diagram

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Basics of Radiometry and Photometry : CIE (x,y) chromaticity diagram Basics of Radiometry and Photometry : CIE (x,y) chromaticity diagram

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same cct

standard light sources (specific emission spectrum)

Different body color (R() S())

same cct, different (x,y)

Basics of Radiometry and Photometry : CCT Basics of Radiometry and Photometry : CCT

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0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

NTSC CCFL + CF B LED + R Ph + G Ph + CF

NTSC : (0.14,0.08), (0.21,0.71), (0.67,0.33)

current ratio, phosphor ratio for white current ratio, phosphor ratio for white

Basics of Radiometry and Photometry : Color Gamut (Backlight) Basics of Radiometry and Photometry : Color Gamut (Backlight)

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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

general color rendering index, Ra

color difference of each sample objects (u,v) between under standard light source and tested light source

Basics of Radiometry and Photometry : CRI (Illumination) Basics of Radiometry and Photometry : CRI (Illumination)

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color purity = a / (a+ b)color purity = a / (a+ b)

one of problemsone of problems

Basics of Radiometry and Photometry : Color Purity Basics of Radiometry and Photometry : Color Purity

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Basics of Radiometry and Photometry : Color Mixing (di-chromatic) Basics of Radiometry and Photometry : Color Mixing (di-chromatic)

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case I 다음값은 입력치 결과치 .입니다

(1) , . , I, V ?단색의 색좌표 휘도 측정치를 입력하시오 그리고 측정시의 값은

x y Br(lm) power(mW) current(A) voltage(V)RED 0.714 0.286 19.52 155.07 0.35 2.90GREEN 0.074 0.656 32.60 93.47 0.35 3.50BLUE 0.135 0.049 9.56 170.82 0.35 3.50

(2) R,G,B .단색의 의 효율은 다음과 같읍니다lm/W WPE(%) EQE(%)

RED => 19.2 15.3GREEN => 26.6 7.6BLUE => 7.8 13.9

(3) White .색좌표 또는 원하는 구현색의 색좌표를 입력하시오

x= 0.310 y= 0.310

(4) 단색 측정치가 삼색혼합시 유지된다면 , White R, G, B current 이때 색좌표 또는 원하는 구현색의 색좌표를 내기 위한 에 대한 값은 .다음과 같읍니다

ratio 1 ratio 2 current (A)RED 0.310 0.074 0.135 RED = 0.382 0.81 0.28

0.310 0.656 0.049 GREEN = 0.471 1.00 0.350.000626 1.000 1.000 1.000 BLUE = 0.147 0.31 0.11

GREEN 0.714 0.310 0.1350.286 0.310 0.049

0.000773 1.000 1.000 1.000

BLUE 0.714 0.074 0.3100.286 0.656 0.310

0.000241 1.000 1.000 1.000

(5) current , R,G,B . 가 위와 같으면 의 휘도는 다음과 같읍니다

lmBr for W = 51.38 W (lm/W) 21.16Br for R = 15.81Br for G = 32.60Br for B = 2.98

(6) x,y coordinate tube (color gamut) .에서 삼색 의 색재현영역 은 다음과 같읍니다 , color purity .그리고 는 다음과 같읍니다

NTSCcolor gamut = 0.183 116 % R 0.67 0.33

G 0.21 0.71B 0.14 0.08

Basics of Radiometry and Photometry : Color Mixing (tri-chromatic) Basics of Radiometry and Photometry : Color Mixing (tri-chromatic)

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5000.0

10000.0

15000.0

20000.0

25000.0

30000.0

35000.0

40000.0

45000.0

50000.0

350 400 450 500 550 600 650 700 750 800

WL(nm)

B G R B G R

Basics of Radiometry and Photometry : values from measured spectrum Basics of Radiometry and Photometry : values from measured spectrum

case I corrected F 2.93E+11 1.12E+11 2.97E+11 x y mW lm peak (nm)peak center 460 510 640 B 0.138 0.055 122.0 7.6 460# 2.86E+17 1.50E+17 3.01E+17 G 0.106 0.624 58.1 20.4 510WL(nm) B G R R 0.703 0.295 94.0 14.5 640

lmx= 0.310 y= 0.310 lm/W WPE(%) EQE(%) ratio 2 current (A) Br for W = 32.50 CG= 0.164

B 6.2 10.0 13.1 0.28 0.10 Br for R = 2.13current(A) voltage(V) G 16.7 4.7 6.9 1.00 0.35 Br for G = 20.40

B 0.35 3.50 R 14.3 9.3 13.8 0.69 0.24 Br for B = 9.97G 0.35 3.50R 0.35 2.90 W(lm/W) = 14.35 NTSC % = 104.1

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350 400 450 500 550 600 650 700 750 800

WL(nm)

B G R B G R

Basics of Radiometry and Photometry : values from simulated spectrum Basics of Radiometry and Photometry : values from simulated spectrum

case I std. Dev. 12 15 9 x y mW lm peak (nm)peak center 460 510 640 B 0.143 0.036 172.7 7.8 460intensity 200 120 250 G 0.074 0.656 93.5 32.6 510WL(nm) B G R R 0.714 0.286 155.1 19.5 640

case II std. Dev. 12 20 9 x y mW lm peak (nm)peak center 460 545 630 B 0.143 0.036 172.7 7.8 460intensity 200 120 250 G 0.298 0.676 87.5 52.7 545WL(nm) B G R R 0.702 0.298 157.5 29.6 630

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White by CCFL

400 450 500 550 600 650 700

WL(nm)

White by CCFL + CF

400 450 500 550 600 650 700

WL(nm)

W CCFL + R CF W CCFL + G CF W CCFL + B CF CCFL + CF

Color Gamut Color Gamut CCFLCCFL

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White by R, G, B LED

400 450 500 550 600 650 700

WL(nm)

R LED G LED B LED White by RGB LED

White by R, G, B LED + CF

400 450 500 550 600 650 700

WL(nm)

W LED + R CF W LED + G CF W LED + B CF RGB LED + CF

Color Gamut Color Gamut R, G, B LEDR, G, B LED

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White LED

400 450 500 550 600 650 700

WL(nm)

White LED + CF

400 450 500 550 600 650 700

WL(nm)

W LED + R CF W LED + G CF W LED + B CF W LED + CF

Color Gamut Color Gamut B LED + Y PhB LED + Y Ph

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White by B LED + R, G Ph

400 450 500 550 600 650 700 750 800

WL(nm)

CaS SrGa2S4 B LED

White by B LED + R, G Ph

400 450 500 550 600 650 700 750 800

WL(nm)

W + R CF W + G CF W + R/ G/ B CF W + B CF

Color Gamut Color Gamut B LED + R,G PhB LED + R,G Ph

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0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

RGB LED NTSC RGB LED + CFCCFL + CF B LED + Y Ph + CF B LED + R Ph + G Ph + CF

BLU system x y CCT (K) color gamut NTSC %NTSC - - - 0.158 1.00RGB LED 0.2505 0.2874 14500 0.164 1.04RGB LED + CF 0.2617 0.3063 11000 0.151 0.96B LED + Y Ph + CF 0.3234 0.3146 6000 0.113 0.71CCFL + CF 0.3026 0.2705 8400 0.111 0.70B LED + R,G Ph + CF 0.3062 0.2863 7541 0.145 0.91

Color Gamut Color Gamut

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4. Phosphors Claimed, Studied and Used in LED Application 4. Phosphors Claimed, Studied and Used in LED Application

* What & How?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?Key Factor for Producing White light? - for General Lighting : color rendering indexcolor rendering index - for BLU : color gamutcolor gamut * Who (patent)? Phosphors for PC- White LEDWho (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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* Commercially used Commercially used Yellow Yellow PhosphorPhosphor for B LEDfor B LED - Nichia : YAG:Ce - Osram Opto : TAG:Ce - Lumileds (Philips) : YAG:Ce (Nichia), YAG:Ce,Pr - Gelcore (GE) : ? - Cree : YAG:Ce (Nichia) - Toyoda : YAG:Ce (Nichia) - Rohm, Lite-on, Everlight, Vishay : TAG:Ce (Osram) - Citizen : YAG:Ce (Nichia) - Stanley : YAG:Ce (?) - Samsung E.M. : TAG:Ce (Osram) - Seoul S.C. : Ortho-silicate:Eu (LWB,Toyoda) - Matsushita : ?

* Commercially used Commercially used RedRed, , GreenGreen Phosphor for B LED Phosphor for B LED - Strong Candidate : CaS:Eu, STG:Eu - Degradation of Sulfide Phosphors ? Luminance ? * Commercially used Phosphors for UV LEDCommercially used Phosphors for UV LED - Toyoda : ZnS:Cu,Al / Halo-phosphate:Eu / LOS:Eu

YAl5O12:Ce3+,Sm3+

TbAl5O12:Ce3+

(Ba,Sr,Ca)2SiO4:Eu2+

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Osram Nichia

Samsung E.M.

Everlight Liteon Toyoda Toshiba

LumiledsCitizen

UV LED + Phosphors

Licensing : PC - White Licensing : PC - White LEDLED

* Seoul S.C : Phosphor from LWG(Toyoda) + B LED chip from Cree* Seoul S.C : Phosphor from LWG(Toyoda) + B LED chip from Cree

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1. Publication : EP1447853 (2004, 8)2. Priority : 2001, 103. * 1 항 : UV LED (350~410nm) + B Ph (400~500nm) + G Ph (500~550nm) + R Ph(600~660nm) + Y Ph (550~600nm)

* 2~8 항 : 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

MatsushitaMatsushita

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1. Publication : WO 02/054502 (2002, 7) (KR 공개 2003-74641)2. Priority : 2000, 123. * 1 항 : UV or B LED +

(2-x-y)SrO x(BauCav)O (1-a-b-c-d)SiO2, aP2O5, bAl2O3, cB2O3, dGeO2 : yEu2+

* 형광체를 강조하여 1 항에서 claim * B Ph : alkaline earth aluminates:Eu2+, Mn2+

R Ph : Y(V, P, Si)O4:Eu2+, Y2O2S:Eu3+, Bi3+,

alkaline earth magnesium disilicate (M3-x-yMgSi2O8:Eu2+, Mn2+)

LBG (LBW)LBG (LBW)

1. Publication : WO 02/054503 (2002, 7) with Toyota Gosei (KR 공개 2003-91951)2. Priority : 2000, 123. * 1 항 : LED + Ph 로 이루어진 발광장치에서 형광체는 ortho-silicate * 3 항 ( 종 ) : ortho-silicate 를 규정함 .

(2-x-y)SrO x(BauCav)O (1-a-b-c-d)SiO2, aP2O5, bAl2O3, cB2O3, dGeO2 : yEu2+

* LED + Ph” 로 이루어진 발광장치상의 구조 등에 대한 claim 이 주를 이룸 .

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1. Publication : KR1997-0030949 (1997, 6)

2. Priority : 1995, 11

3. * 1 항 : Phosphor + UV

* Reject : 재심사 청구

Toyoda GoseiToyoda Gosei

1. Patent : US6791116 (2004, 9) with Matsushita

2. Priority : 2002, 4

3. * Scattering material 과 phosphor 를 함유한 diode 발광장치

1. Publication : JP2004-127988 (2004, 4) (WO 04/032251)2. Priority : 2002, 93. * 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+

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Toyoda / ToshibaToyoda / Toshiba* Near UV LED + R, G, B Ph ?

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1. Publication : JP2004-103443 (2004, 4)

2. Priority : 2002, 9

3. * B LED + Y, R Phosphors

ToshibaToshiba

1. Publication : JP2003-318447 (2003, 11)

2. Priority : 2002, 4

3. * LED (400~500 nm) + Ph 1 (500~600 nm) + Ph 2 (600~700

1. Publication : JP1999-246857 (1999, 9)2. Priority : 1998, 23. * UV LED + R Ph

* 1 항 : R Ph = (La1–x–yEuxSmy)2O2S, 0.01 x 0.15, 0.0001 y 0.03

* 형광체를 강조하여 1 항에서 claim * 5 항 : La 대신 Y or Gd 를 일부 함유

KASEI?

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ToshibaToshiba

1. Publication : JP2000-183408 (2000, 6)2. Priority : 1998, 123. * UV LED + B Ph + O Ph (excited by B Ph)

* B Ph = M10(PO4)6Cl2:Eu2+

* O Ph = (Y,Gd)3Al5O12:Ce3+

1. Publication : JP2002-203991 (2002, 7)

2. Priority : 1997, 9

3. * UV LED + R, G, B Phosphors

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1. Publication : JP1996-36835 (1998, 2)2. Priority : 1996, 73. * 형광체 특허임

* (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

NichiaNichia

1. Patent : US5998925 (1999, 12) (Family : US6069440, US6608332, US6614179, JP2927279)2. Priority : 1996, 7

3. * 1 항 ( 독 ) : Garnet material, A3B5O12:Ce, A = Y, Lu, Sc, La, Gd, Sm & B = Al, Ga, In

* 2 항 :Y 와 Al 을 함유하는 yttrium aluminum garnet material

* 3 항 : (Re1-rSmr)3(Al1-sGas)5O12:Ce, 0 r 1, 0 s 1, Re = Y, Gd

1. Patent : US6069440 (2000, 5)

2. Priority : 1996, 7

3. * 1 항 ( 독 ) : Blue light 일부를 흡수할 수 있는 형광체

1. Patent : US6614179 (2003, 9) 2. Priority : 1996, 7

3. * 1 항 ( 독 ) : (Re1-rSmr)3(Al1-sGas)5O12:Ce, 0 r 1, 0 s 1, Re = Y, Gd

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1. Publication : US2004-135504 (2004,7)2. Priority : 2002, 33. * 형광체 자체가 1 항이며 , 연색성 증가위해 Red 성분의 보충을 갖는 형광체 조성

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

NichiaNichia

1. Patent : JP3419280 (2003, 4)2. Priority : 1996, 113. * 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.

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NichiaNichia

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

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NichiaNichia

* YAG : (Y 1-p-q-r GdpCeqSmr)3(Al1-sGas)5O12

온도 특성 향상

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NichiaNichia

* YAG : (Y 1-p-q GdpCeq)3(Al1-sGas)5O12

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NichiaNichia

* YAG : (Y 1-p-q GdpCeq)3(Al1-sGas)5O12

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NichiaNichia

When using YAG, low Ra at low CCT

For “High Ra” or “warm white” : new red phosphor ! (655 nm)

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NichiaNichia

High CRI – daylight white LED, using shorter YAG and red phosphor

3.2 V / 20 mA1.8 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

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NichiaNichia

High efficacy or CRI – warm white LED, using YAG and red phosphor

3.22 V / 20 mA1.49 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

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Light for 21C : Stanley/Mitsubishi/Kasei/Yamaguch Univ.Light for 21C : Stanley/Mitsubishi/Kasei/Yamaguch Univ.

* Near UV LED + R, G, B Ph

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Light for 21C : Stanley/Mitsubishi/Kasei/Yamaguch Univ.Light for 21C : Stanley/Mitsubishi/Kasei/Yamaguch Univ.

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SharpSharp

CG : ~ 74 % of NTSC450 mcd at 4 V /40 mA

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1. Patent : US6351069 (2002,2) (family : US6680569)2. Priority : 1999, 23. * wavelength conversion : primary FL material, supplementary FL material (red)

* Y3Al5O12:Ce3+ + Y3Al5O12:Ce3+, Pr3+

* Y3Al5O12:Ce3+ + SrS:Eu2+

LumiledsLumileds

1. Patent : US6686691(2004,3)2. Priority : 1999, 93. * 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

* SrGa2S4:Eu2+ + SrS:Eu2+ + CaS:Eu2+

SrGa2S4:Ce3+ + SrS:Ce3+ + CaS:Ce3+

1. Patent : US6642618 (2003, 11)2. Priority : 2000, 12

3. * 5 항 : white light by sol-gel glass (SiO2) layer containing (Sr,Ba,Ca)Ga2S4:Eu2+ + SrS:Eu2+

1. Patent : US 6603258 (2003, 8)2. Priority : 2001, 43. * white light by LED (485 ~ 515nm) + (Sr,Ba,Ca)S:Eu2+ (600 ~ 620nm), 특히 SrS:Eu2+

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1. Patent : US6084250 (2000,7) by Philips (Family : US6051925, JP 공개 2000-509912)2. Priority : 1997, 33. * 1 항 : UV (300 ~ 370 nm) + B Ph (430~490 nm) + G Ph ( 520~570 nm) + R Ph (590~630 nm)

* 6 항 : B Ph = BaMgAl10O17: Eu2+, G Ph = ZnS:Cu, R Ph = Y2O2S:Eu3+

* 7 항 : Organic phosphor (dye)

LumiledsLumileds

3. * 1 항 : white light by LED (380 ~ 500nm) + (Sr,Mg,Ba,Ca)(Ga,Al,In)2S4:Eu2+ (490 ~ 610 nm)

* LED/Phosphor structure (encapsulation, mounting)

1. Patent : US6717353 (2004, 4)2. Priority : 2002, 103. * 1 항 : 1st WL converting material comprising Sr-SiON:Eu2+ (or YAG:Ce) emitting 2nd WL light * 2 항 : UV and Blue light = 1st WL light * 3 항 : Green = 2nd WL light * 4, 8 항 : Red Ph = 2nd WL converting material (using 2nd WL lght),

(Sr1–a–b–cBabCac)2Si5N8:aEu2+

Blue Ph = 3rd WL converting material (using 1st WL light),

(Sr1–a–xBax)3MgSi2O8:aEu2+

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1. Patent : US6501102 (2002, 12)2. Priority : 2002, 1 3. * 1 항 : LED (below 460 nm)

+ 2nd, 3rd WL light from YAG, (Y,Ln)AG, (Y,Ln)(Al,Ga)G, SrS, SrGa2S4, NitridoSilicate

* 2 항 : Ce3+, Eu2+ etc. * Phosphor powder layer, Phosphor thin film, Substrate for light emitting structure

LumiledsLumileds

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

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1. Patent : US6590235 (2003, 7) (Family : US6204523)

2. Priority : 1998, 11

3. * Encapsulating material (silicone) for UV LED

LumiledsLumileds

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

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Lumileds - PhilipsLumileds - Philips

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LumiledsLumileds* Blue LED + Y Ph (YAG:Ce, YAG:Ce,Pr)

* Blue LED + G Ph (SrGa2S4:Eu2+) + R Ph (SrS:Eu2+)

Resistance to humidity ?Preventing coating ?LCD BLU ?

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LumiledsLumileds

* Blue LED + Y Ph (YAG:Ce, YAG:Ce,Pr) + R Ph (CaS:Eu2+)

For Illumination ?

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Lumileds - PhilipsLumileds - Philips*

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LumiledsLumileds

* UV LED + R, G, B Phosphors

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LumiledsLumileds

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LumiledsLumileds

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SarnoffSarnoff* SrCaS:Eu2+

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SarnoffSarnoff* SrCaS:Eu2+

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1. Patent : US6066861 (2000, 5) (Family : US6245259, 6277301, 6576930, 6592780, 6613247)2. Priority : 1996, 93. * 1 항 : WL (from UV, Blue, Green) converting casting composition Resin (epoxy)

A3B5X12:M3+, 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 항 : YAG:Ce

* 10 항 : Lighting emitting S.C. component = S.C. body (UV, Blue, green) + A3B5X12:M

Osram Opto.Osram Opto.

1. Patent : US6245259 (2001, 6)2. Priority : 1996, 93. * 1 항 : WL (from UV, Blue, Green) converting casting composition Resin (epoxy) Ce doped phosphors size 20 m (d 5 m) * 7 항 : YAG:Ce * 10 항 : Lighting emitting S.C. component = S.C. body (UV, Blue, green) + Ce doped phosphors * 15 항 : Yellow by Blue LED * 16 항 : Green, Red by Blue LED

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1. Patent : US6277301 (2001, 8)2. Priority : 1996, 93. * 1 항 : 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 항 : size 20 m (d 5 m) * 11 항 ( 독 ) : White lighting emitting S.C. component = S.C. body (UV, Blue, green) + Ce doped phosphors(blue to yellow) with epoxy * 12 항 ( 독 ) : 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

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1. Patent : US6613247 (2003, 9)2. Priority : 1996, 93. * 1 항 : 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 항 : YAG:Ce3+ phosphor * 12 항 ( 독 ) : 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 항 : White = Blue LED + yellow light by Ce doped phosphor * 18 항 : White = Blue LED + green and red light

1. Patent : US6669866 (2003, 12) (Family : US6552487)2. Priority : 1999, 7

3. * 1 항 ( 독 ) : light source comprising emission from 420 to 490 nm and phosphor A3B5O12:Ce3+

A = Tb or one of Y, Gd, La, Lu & B = Al, Ga * 2 항 : Tb solely or predominantly (TAG)

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1. Patent : US6504179 (2003, 1)2. Priority : 2000, 53. * 1 항 : LED (300 ~ 470nm) + Eu activated calcium magnesium chlorosilicate (green phosphor) Ce activated rare earth garnet (yellow phosphor)

* 2 항 : Green (Ca8-x–yEuxMnyMg(SiO4)4Cl2)

* 3 항 : Yellow ((Re)3(Al,Ga)5O12:Ce, 특히 YAG:Ce or TAG:Ce)

* 4 항 : 특히 , LED (330~370 nm) + phosphors (430~470, 490~525, 545~590 nm) * 5 항 : 특히 , LED (430~470 nm) + phosphors (545~590, 490~525 nm)

1. Patent : US 6649946 (2003, 11) (Family : US 6682663)2. Priority : 1999, 113. * 1 항 ( 독 ) : “Yellow to Red” emitting phosphor

MxSiyNz:Eu2+, M = La, Sr, Ba, Zn

* 8 항 : LED + phosphors * 9 항 : LED = 420~470nm

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1. Patent : US6695982 (2004, 2)2. Priority : 2000, 63. * 1 항 : 형광체 제조 방법

AB2S4: D, A = Mg, Ca, Sr & B = Al, Ga, Y & D = Ce3+, Eu2+

1. Publication : US2004-0124758 (2004, 7)2. Priority : 2000, 73. * 1 항 ( 독 ) : UV (370~420 nm) or Blue (420~480 nm) + MS:Eu2+ (M = Ba, Mg, Zn, Ca, Sr) containing one of Ba, Mg, Zn

+ MN2S4:Eu2+ or Ce3+ (M = Ba, Mg, Zn, Ca, Sr & N = Al, Ga, In, Y, La, Gd)

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Osram Opto.Osram Opto.* Blue LED + Y Ph (TAG:Ce)

* Blue LED + Y,G Ph (Y(Al,Ga)G:Ce or TAG:Ce) + R Ph ((AE)2Si5N8:Eu2+)

Shorter YAG

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Osram Opto.Osram Opto.* Near UV LED + R, G, B Ph

Sr4Al14O25:Eu2+ (~490 nm)SrAl12O19:Eu2+ (~520 nm)SrAl2O4:Eu2+ (~400 nm)

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Osram Opto : SiemensOsram Opto : Siemens* YAG : (Y 1-p-q GdpCeq)3(Al1-sGas)5O12

GdGdGaGa

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Osram Opto : SiemensOsram Opto : Siemens* YAG : (Y 1-p-q GdpCeq)3(Al1-sGas)5O12

* f-d absorption or CT absorption

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Osram Opto : SiemensOsram Opto : Siemens* Potential R, G, B, Y Ph

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3. * 1 항 : 380~420nm LED + Blue Ph (BaMg2Al16O27:Eu2+) + Y Ph ((Tb1–x–yAxREy)3DzO12)

A = Y, La, Gd, Sm & RE = Ce etc & D = Al, Ga, In

* 15 항 : B Ph = (Sr,Ba,Ca,Mg)5(PO4)3Cl:Eu2+

GE or GelcoreGE or Gelcore

1. Patent : US6501100 (2002, 12)2. Priority : 2000, 5 3. * 1 항 : UV LED (370~405 nm) + Ph 1 (570~620 nm) + Ph 2 (480~520 nm)

* Ph 1 = APO:Eu2+,Mn2+, A2P2O7:Eu2+,Mn2+, A = Sr, Ca, Ba, Mg

Ph 2 = A4D14O25:Eu2+, (AD)8O13:Eu2+, A10(PO4)6Cl2:Eu2+, A2Si3O8 ACl2:Eu2+

A = Sr, Ca, Ba, Mg & D = Al, Ga

1. Patent : US6580097 (2003, 6) (Family : US6252254, US6469322)2. Priority : 1998, 23. * 1 항 : Blue LED + Ph 1 + Ph 2

* G Ph 1 = YBO3:Ce3+,Tb3+, BaMgAl10O17:Eu2+,Mn2+, (Sr,Ca,Ba)(Al,Ga)2s4:Eu2+,Y3Al5O12:Ce3+

* R Ph 2 = Y2O2S:Eu3+,Bi3+, YVO4:Eu3+,Bi3+, SrS:Eu2+, SrY2S4:Eu2+, CaLa2S4:Ce3+, (Ca,Sr)S:Eu2+

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3. * 1 항 : UV, Blue LED + Green Ph (LnBO3:Ce3+,Tb3+, Ln = Sc, Y, La, Gd, Lu)

* 9 항 : Blue Ph ((Ba,Sr,Ca)5(PO4)3Cl: Eu2+,Mn2+) 함유

* 10 항 : Red Ph 함유

1. Patent : US6685852 (2004, 2)2. Priority : 2001, 43. * 1 항 : UV LED (315~480nm, 바람직하게는 350~410nm) + 아래 Phosphor 가운데 2 종

(1) Sr2P2O7:Eu2+,Mn2+

(2) (Ba,Sr,Ca)5(PO4)3(F,Cl,OH): Eu2+,Mn2+

(3) 3.5 MgO – 0.5 MgF2 – GeO2:Mn4+

(4) (Ba,Sr,Ca)5(PO4)3(Cl,OH): Eu2+

(5) (Ba,Sr,Ca)2MgAl16O27:Eu2+, (Ba,Sr,Ca)MgAl10O17:Eu2+, (Ba,Sr,Ca)Mg3Al14O25:Eu2+

(6) (5) 에서 Mn2+ 를 co-activator 로 사용

1. Patent : US6791259 (2004, 9)

2. Priority : 2000, 8

3. * Scattering material 사용 (between LED & Phosphor

material)

* size 는 /3~ /2

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1. Patent : US6621211 (2003, 9)2. Priority : 2000, 53. * 1 항 : UV LED (360~420 nm)

(1) Ph = 575~620 nm : (Sr,Ca,Ba,Mg)PO:Eu2+,Mn2+, (Sr,Ca,Ba,Mg)2P2O7:Eu2+,Mn2+

(2) Ph = 495~550 nm : ASiO4:Eu2+, A2DSi2O7:Eu2+, AAl2O4:Eu2+, A = Sr, Ba, Ca & D = Mg, Zn

(3) Ph = 420~480 nm : Mg2Al16O27:Eu2+, (Sr,Ba,Ca)5(PO4)3Cl:Eu2+, Zn(Ba,Eu)O-6Al2O3,

BaAl12O19:Eu2+, KAl11O11:Eu2+

(4) Ph = 620~670 nm (optional): 3.5 MgO – 0.5 MgF2 – GeO2:Mn4+

1. Patent : US6616862 (2003, 9)2. Priority : 2001, 53. * Mn2+ 첨가로 red shift * UV LED (350~420 nm)

* 1 항 : (Ba,Sr,Ca,Mg)5(PO4)3(F,Cl,OH):Eu2+,Mn2+ (orange color) Optionally, add blue phosphors

3. * 1 항 ( 독 ) : 형광체를 claim, TAG, (Tb1–x–yAxREy)aDzO12, A = Y, La, Gd, Sm & D = Al,Ga * 38 항 ( 독 ) : LED + phosphor * 40 항 ( 독 ) : LED = 400~480 nm + phosphor

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1. Patent : US6538371 (2003, 5)2. Priority : 2000, 33. * Blue LED + YAG:Ce3+

* 1 항 : System color output 을 향상시키는 방법 (CIE coord. 에서 BBL 과 line 의 상관관계 이용 )

1. Patent : US6522065 (2003, 2)2. Priority : 2000, 33. * 1 항 : UV LED + white phosphor

A2–2xNa1+xExD2V3O12, A = Ca, Ba, Sr, & D = Mg, Zn, & E = Eu3+, Sm3+

* (e.g.) 370 nm LED + Ca2–2xNa1+xEuxMg2V3O12

1. Patent : US6294800 (2001, 9) (Family: US6255670)2. Priority : 1998, 12

3. * 1 항 : Ca8Mg(SiO4)4Cl2:Eu2+,Mn2+ 를 포함하는 조성

* 2 항 : 상기 G Ph 와 R, B Ph 를 포함하는 조성 * 3 항 : UV LED (330 ~420 nm, 특히 355~365 nm)

* 6 항 : G = Ca8Mg(SiO4)4Cl2:Eu2+,Mn2+,

R = Y2O3:Eu3+,Bi3+,

B = (Sr,Ba,Ca)5(PO4)3Cl:Eu2+ or BaMg2Al16O27:Eu2+

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{C}3[A]2(D)3

dodecahedral site

octahedral site

tetrahedral site

Y3Al5O12

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.

* Replacement to Ga brings about decrease of emission intensity.

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similar thermal quenching No emission at RT

crossover bet. d and f level

Photo-ionization

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Y3Al5O12(garnet)

Secondary phase due to solubility Quenching by energy transfer from Ce3+ to RE3+ Mainly, replacement to Gd (red shift) or Lu (blue shift).

replacement to Large RE3+

REAlO3(perovskite)

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.

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Overlap with 5D4 level of Tb3+

Energy transfer from Ce3+ to Tb3+ (i.e., back transfer)

TAG : no change of Q.E. at RT significant change at high T

Patent : US6596195 (2003, 7)

Using TAG phosphors

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GE or GelcoreGE or Gelcore* Blue or Near UV LED + Phosphors

For Illumination ? For BLU ?

87/219

GE or GelcoreGE or Gelcore* Near UV LED + Phosphors

What phosphor ?

Replace into B2O3?

88/219

GE or GelcoreGE or Gelcore* Near UV LED + R, G, B Ph

89/219

* LED + white phosphor

?Activator ?

90/219

PhosphortechPhosphortech* Blue or UV LED + Phosphors

* Eg for ZnS : 3.7 eV (~335nm) for ZnSe : 2.7 eV (~460nm)

* Excitation (absorption) : bandgap absorption or absorption by activators (Cu,A)

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PhosphortechPhosphortech* Blue LED + Phosphors

92/219

PhosphortechPhosphortech* UV LED + Phosphors

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* 254 Hg emission AC no sulfide phosphor * LED CW : decay time (fast – recycling) ground state depletion high order effect (quenching) sulfide phosphor?

* 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

* For UV LED Sr2SiO4:Eu2+ : 3.2 lm/W, Ra=68 vs. 2 lm/W, Ra=80 for YAG – APL 82, 683, 2003 Ca10(PO4)6Cl2:Eu2+ : 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

GIT, PhosphortechGIT, Phosphortech

Review by C. Summers Review by C. Summers

N-UV or B LED?Peak WL?

94/219

* Lumileds : for Blue LED, STG and SS from 2000 (two phosphor) combinations

Ra > 90

GIT, PhosphortechGIT, PhosphortechReview by C. Summers Review by C. Summers

95/219

* for Blue LED, YAG was broadly used.

Q. When Ce was excess,

efficiency or peak shift?

GIT, PhosphortechGIT, PhosphortechReview by C. Summers Review by C. Summers

96/219

NIMS (Japan)NIMS (Japan)* Blue LED + Y Ph (Ca--SiAlON:Eu2+)

APL, V84, P5405, 2004

USP 6,776,927 (NIMS), USP 6657379 (Elektrische Gmbh)

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SandiaSandia* UV LED + Nano phosphors

98/219

Temperature Temperature DependenceDependence

B LED Due to I increase : band filling

Phosphor : more sensitive upon T

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Temperature Temperature DependenceDependence

Phosphor : more sensitive upon T The reason for this behavior ? several factors should be considered.

PHOSPHOR CONVERTED WHITE LED

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