PHOSPHOR CONVERTED WHITE LED 1/219 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 2/219 1. White LED : Introduction LED 형광체 G B (A) multi chip (single color LED) R (1) R, G, B LED (B) single chip (multi color LED) (A) (2) B LED + Phosphor UV LED + Phosphor Advantage (vs. CCFL) * Increased Color Gamut * Mechanical Stability * Fast switching Time B Y B R/G UV R/G/B (B) (3) Y Ph 백색 G B R R, G Ph 3/219 1. White LED : Characteristics LCD BLU (1-A) LED 형광체 color gamut color stability chip degradation G B 2G/1B/1R excellent (~100%) good R 백색 (1-B) G B R excellent (~100%) (2-A) (2-B) good B Y good (~70%) very good B R/G very good (~90%) very good UV R/G/B (3) excellent ? (~100%) excellent Advantages 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 4/219 1. White LED : Application (Backlight) LCD Backlight – Lumileds 5/219 1. White LED : Application (Backlight) LCD Backlight – Lumileds 6/219 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? 7/219 1. White LED : Application (Backlight) Mixing & Compensation Area Osram Opto, Nichia G B R Lumileds G B R 8/219 2. Phosphor Converted White LED : Need for Phosphors (I) * Efficiency of Green LED 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 9/219 2. Phosphor Converted White LED : Need for Phosphors (I) * * * * White를 위해 3.0 lm, 5.7 lm, 0.57 lm 이 필요함 R LED의 경우 85%, B LED의 경우 65 %만 사용 current ratio를 작게 가져가거나 or 2 G LED + 1 B, R LED HB LED의 경우 I와 T에 따른 보상이 필요함 10/219 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 11/219 2. Phosphor Converted White LED : Need for Phosphors (II) 12/219 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 Illumination vs. backlight 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) 13/219 3. Characteristics of Phosphors for White LED Application Basics of Radiometry and Photometry 2.0 1931 CIE X, Y, Z color matching function 1.8 1.6 1.4 1.2 555 nm 1.0 0.8 0.6 0.4 0.2 0.0 350 400 X = X() P() d Y = Y() P() d 450 500 550 600 x = X / (X + Y + Z) y = Y / (X + Y + Z) Z = Z() P() d lm/W W/nm 650 700 750 u = 4X / (X + 15Y + 3Z) v = 6Y / (X + 15Y + 3Z) for uniform chromaticity coordinates (color difference between two point) Br = 680 Y() P() d Photometry unit : lm, cd = lm/sr, lux = lm/m2, nit = cd/m2 14/219 3. Characteristics of Phosphors for White LED Application Basics of Radiometry and Photometry Consider one photon at each wavelength, 1.0 Br (Y) 0.9 0.8 cie x 0.7 cie x, cie y 0.6 0.5 0.4 cie y 0.3 0.2 0.1 0.0 400 450 500 550 600 650 700 WL(nm) 15/219 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 cie x, y 0.9 520 nm 530 nm 0.8 540 nm 510 nm 550 nm 0.7 560 nm 0.6 570 nm 500 nm 580 nm 0.5 y 590 nm 0.4 600 nm 610 nm 620 nm 0.3 490 nm 0.2 480 nm 0.1 470 nm 460 nm 0.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 x 16/219 3. Characteristics of Phosphors for White LED Application Basics of Radiometry and Photometry : CIE (x,y) chromaticity diagram 17/219 3. Characteristics of Phosphors for White LED Application Basics of Radiometry and Photometry : CCT same cct v u y standard light sources (specific emission spectrum) Different body color (R() S()) x same cct, different (x,y) 18/219 3. Characteristics of Phosphors for White LED Application Basics of Radiometry and Photometry : Color Gamut (Backlight) current ratio, phosphor ratio for white 0.8 0.7 0.6 cie y 0.5 0.4 0.3 0.2 0.1 NTSC : (0.14,0.08), (0.21,0.71), (0.67,0.33) 0.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 cie x NTSC CCFL + CF B LED + R Ph + G Ph + CF 19/219 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 20/219 3. Characteristics of Phosphors for White LED Application Basics of Radiometry and Photometry : Color Purity color purity = a / (a+ b) one of problems 21/219 3. Characteristics of Phosphors for White LED Application Basics of Radiometry and Photometry : Color Mixing (di-chromatic) 22/219 3. Characteristics of Phosphors for White LED Application Basics of Radiometry and Photometry : Color Mixing (tri-chromatic) case I 다음값은 입력치 결과치 입니다. (1) 단색의 색좌표, 휘도 측정치를 입력하시오. 그리고, 측정시의 I, V 값은? x RED GREEN BLUE y 0.714 0.074 0.135 0.286 0.656 0.049 Br(lm) power(mW) 19.52 155.07 32.60 93.47 9.56 170.82 current(A) voltage(V) 0.35 2.90 0.35 3.50 0.35 3.50 (2) 단색의 R,G,B의 효율은 다음과 같읍니다. lm/W WPE(%) EQE(%) RED => 19.2 15.3 GREEN => 26.6 7.6 BLUE => 7.8 13.9 (3) White 색좌표 또는 원하는 구현색의 색좌표를 입력하시오. x= 0.310 y= 0.310 (4) 단색 측정치가 삼색혼합시 유지된다면 이때, White 색좌표 또는 원하는 구현색의 색좌표를 내기 위한 R, G, B에 대한 current 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 0.35 0.000626 1.000 1.000 1.000 BLUE = 0.147 0.31 0.11 GREEN 0.000773 BLUE 0.000241 0.714 0.286 1.000 0.310 0.310 1.000 0.135 0.049 1.000 0.714 0.286 1.000 0.074 0.656 1.000 0.310 0.310 1.000 (5) current가 위와 같으면, R,G,B의 휘도는 다음과 같읍니다. lm Br for W = Br for R = Br for G = Br for B = 51.38 15.81 32.60 2.98 W (lm/W) 21.16 (6) x,y coordinate에서 삼색tube의 색재현영역(color gamut)은 다음과 같읍니다. 그리고, color purity는 다음과 같읍니다. NTSC color gamut = 0.183 116 % R G B 0.67 0.21 0.14 0.33 0.71 0.08 23/219 3. Characteristics of Phosphors for White LED Application Basics of Radiometry and Photometry : values from measured spectrum ca se I corrected F peak center # WL(nm) 2.93E+11 1.12E+11 2.97E+11 460 510 640 2.86E+17 1.50E+17 3.01E+17 B G R x= y 0.055 0.624 0.295 mW 122.0 58.1 94.0 lm 7.6 20.4 14.5 peak (nm) 460 510 640 lm WPE(%) EQE(%) ratio 2 current (A) Br for 6.2 10.0 13.1 0.28 0.10 Br for 16.7 4.7 6.9 1.00 0.35 Br for 14.3 9.3 13.8 0.69 0.24 Br for 0.310 lm/W B G R current(A) voltage(V) 0.35 3.50 0.35 3.50 0.35 2.90 W= R= G= B= W(lm/W) = 32.50 CG= 2.13 20.40 9.97 14.35 NTSC % = 0.164 104.1 50000.0 45000.0 40000.0 35000.0 30000.0 Int e nsi t y B G R 0.310 y= x 0.138 0.106 0.703 B G R 25000.0 20000.0 15000.0 10000.0 5000.0 0.0 350 400 450 500 550 600 650 700 750 800 WL ( nm) B G R B G R 24/219 3. Characteristics of Phosphors for White LED Application Basics of Radiometry and Photometry : values from simulated spectrum ca se I std. Dev. peak center intensity WL(nm) 12 460 200 B x= B G R ca se II G 9 640 250 R 0.310 y= std. Dev. peak center intensity WL(nm) y 0.036 0.656 0.286 mW 172.7 93.5 155.1 lm 7.8 32.6 19.5 peak (nm) 460 510 640 lm WPE(%) EQE(%) ratio 2 current (A) Br for 6.4 14.1 18.3 0.27 0.10 Br for 26.6 7.6 11.0 1.00 0.35 Br for 19.2 15.3 22.9 0.78 0.27 Br for lm/W B G R W= R= G= B= W(lm/W) = 12 460 200 B x 0.143 0.074 0.714 B G R 0.310 current(A) voltage(V) 0.35 3.50 0.35 3.50 0.35 2.90 x= 20 545 120 G 9 630 250 R 0.310 y= x 0.143 0.298 0.702 B G R y 0.036 0.676 0.298 mW 172.7 87.5 157.5 lm 7.8 52.7 29.6 lm/W B G R 49.89 CG= 2.12 32.60 15.18 21.26 NTSC % = 0.186 117.6 peak (nm) 460 545 630 lm WPE(%) EQE(%) ratio 2 current (A) Br for 6.4 14.1 18.3 0.44 0.15 Br for 43.0 7.1 11.0 1.00 0.35 Br for 29.1 15.5 22.9 0.83 0.29 Br for 0.310 current(A) voltage(V) 0.35 3.50 0.35 3.50 0.35 2.90 W= R= G= B= W(lm/W) = 80.63 CG= 3.42 52.68 24.53 30.95 NTSC % = 0.158 100.3 12.0 10.0 8.0 Int e nsi t y B G R 15 510 120 6.0 4.0 2.0 0.0 350 400 450 500 550 600 650 700 750 800 WL ( nm) B G R B G R 25/219 3. Characteristics of Phosphors for White LED Application Color Gamut CCFL White by CCFL + CF Intensity (count) Intensity (count) White by CCFL 400 400 450 500 550 WL(nm) 600 650 450 700 500 550 600 650 700 WL(nm) W CCFL + R CF W CCFL + G CF W CCFL + B CF CCFL + CF 26/219 3. Characteristics of Phosphors for White LED Application Color Gamut R, G, B LED White by R, G, B LED + CF Intensity (count) Intensity (count) White by R, G, B LED 400 450 500 550 600 650 700 400 450 R LED G LED B LED 500 550 600 650 700 WL(nm) WL(nm) White by RGB LED W LED + R CF W LED + G CF W LED + B CF RGB LED + CF 27/219 3. Characteristics of Phosphors for White LED Application Color Gamut B LED + Y Ph White LED + CF Intensity (count) Intensity (count) White LED 400 400 450 500 550 WL(nm) 600 650 450 700 500 550 600 650 700 WL(nm) W LED + R CF W LED + G CF W LED + B CF W LED + CF 28/219 3. Characteristics of Phosphors for White LED Application Color Gamut B LED + R,G Ph White by B LED + R, G Ph Intensity (count) Intensity (count) White by B LED + R, G Ph 400 450 500 550 600 650 700 750 800 400 450 500 CaS SrGa2S4 550 600 650 700 750 800 WL(nm) WL(nm) B LED W + R CF W + G CF W + R/ G/ B CF W + B CF 29/219 3. Characteristics of Phosphors for White LED Application Color Gamut 0.8 0.7 0.6 cie y 0.5 0.4 0.3 0.2 0.1 0.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 cie x RGB LED CCFL + CF BLU system NTSC RGB LED RGB LED + CF B LED + Y Ph + CF CCFL + CF B LED + R,G Ph + CF NTSC B LED + Y Ph + CF x 0.2505 0.2617 0.3234 0.3026 0.3062 y 0.2874 0.3063 0.3146 0.2705 0.2863 RGB LED + CF B LED + R Ph + G Ph + CF CCT (K) color gamut 0.158 14500 0.164 11000 0.151 6000 0.113 8400 0.111 7541 0.145 NTSC % 1.00 1.04 0.96 0.71 0.70 0.91 30/219 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 31/219 4. Phosphors Claimed, Studied and Used in LED Application YAl5O12:Ce3+,Sm3+ * Commercially used Yellow Phosphor for B LED - Nichia : YAG:Ce TbAl5O12:Ce3+ - Osram Opto : TAG:Ce (Ba,Sr,Ca)2SiO4:Eu2+ - 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 Red, Green Phosphor for B LED - Strong Candidate : CaS:Eu, STG:Eu - Degradation of Sulfide Phosphors ? Luminance ? * Commercially used Phosphors for UV LED - Toyoda : ZnS:Cu,Al / Halo-phosphate:Eu / LOS:Eu 32/219 4. Phosphors Claimed, Studied and Used in LED Application Licensing : PC - White LED Samsung E.M. Rohm Citizen Osram Everlight Lumileds Cree Nichia Liteon Toyoda Toshiba UV LED + Phosphors * Seoul S.C : Phosphor from LWG(Toyoda) + B LED chip from Cree 33/219 4. Phosphors Claimed, Studied and Used in LED Application Matsushita 1. Publication : EP1447853 (2004, 8) 2. Priority : 2001, 10 3. * 1항 : UV LED (350~410nm) + B Ph (400~500nm) + G Ph (500~550nm) + R Ph(600~660nm) + Y Ph (550~600nm) * 2~8항 : 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 34/219 4. Phosphors Claimed, Studied and Used in LED Application LBG (LBW) 1. Publication : WO 02/054502 (2002, 7) (KR공개 2003-74641) 2. Priority : 2000, 12 3. * 1항 : UV or B LED + (2-x-y)SrO x(BauCav)O (1-a-b-c-d)SiO2, aP2O5, bAl2O3, cB2O3, dGeO2 : yEu2+ * 형광체를 강조하여 1항에서 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+) 1. Publication : WO 02/054503 (2002, 7) with Toyota Gosei (KR공개 2003-91951) 2. Priority : 2000, 12 3. * 1항 : LED + Ph로 이루어진 발광장치에서 형광체는 ortho-silicate * 3항(종) : ortho-silicate를 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 claim이 주를 이룸. 35/219 4. Phosphors Claimed, Studied and Used in LED Application Toyoda Gosei 1. Publication : KR1997-0030949 (1997, 6) 2. Priority : 1995, 11 3. * 1항 : Phosphor + UV * Reject : 재심사 청구 1. Patent : US6791116 (2004, 9) with Matsushita 2. Priority : 2002, 4 3. * Scattering material과 phosphor를 함유한 diode 발광장치 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+ 36/219 4. Phosphors Claimed, Studied and Used in LED Application Toyoda / Toshiba * Near UV LED + R, G, B Ph ? 37/219 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 (400~500 nm) + Ph 1 (500~600 nm) + Ph 2 (600~700 nm) 1. Publication : JP1999-246857 (1999, 9) 2. Priority : 1998, 2 3. * UV LED + R Ph KASEI? * 1항 : R Ph = (La1–x–yEuxSmy)2O2S, 0.01 x 0.15, 0.0001 y 0.03 * 형광체를 강조하여 1항에서 claim * 5항 : La 대신 Y or Gd를 일부 함유 38/219 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)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 39/219 4. Phosphors Claimed, Studied and Used in LED Application 1. Publication : JP1996-36835 (1998, 2) Nichia 2. Priority : 1996, 7 3. * 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 1. Patent : US5998925 (1999, 12) (Family : US6069440, US6608332, US6614179, JP2927279) 2. Priority : 1996, 7 3. * 1항(독) : Garnet material, A3B5O12:Ce, A = Y, Lu, Sc, La, Gd, Sm & B = Al, Ga, In * 2항 :Y와 Al을 함유하는 yttrium aluminum garnet material * 3항 : (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. * 1항(독) : Blue light 일부를 흡수할 수 있는 형광체 1. Patent : US6614179 (2003, 9) 2. Priority : 1996, 7 3. * 1항(독) : (Re1-rSmr)3(Al1-sGas)5O12:Ce, 0 r 1, 0 s 1, Re = Y, Gd 40/219 4. Phosphors Claimed, Studied and Used in LED Application 1. Publication : US2004-135504 (2004,7) Nichia 2. Priority : 2002, 3 3. * 형광체 자체가 1항이며, 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 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. 41/219 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 42/219 4. Phosphors Claimed, Studied and Used in LED Application Nichia * YAG : (Y sGas)5O12 1-p-q-r GdpCeqSmr)3(Al1온도 특성 향상 Gd Gd 43/219 4. Phosphors Claimed, Studied and Used in LED Application Nichia * YAG : (Y 1-p-q GdpCeq)3(Al1-sGas)5O12 44/219 4. Phosphors Claimed, Studied and Used in LED Application Nichia * YAG : (Y 1-p-q GdpCeq)3(Al1-sGas)5O12 45/219 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) 46/219 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 47/219 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 48/219 4. Phosphors Claimed, Studied and Used in LED Application Light for 21C : Stanley/Mitsubishi/Kasei/Yamaguch Univ. * Near UV LED + R, G, B Ph 49/219 4. Phosphors Claimed, Studied and Used in LED Application Light for 21C : Stanley/Mitsubishi/Kasei/Yamaguch Univ. * Near UV LED + R, G, B Ph 50/219 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 51/219 4. Phosphors Claimed, Studied and Used in LED Application 1. Patent : US6351069 (2002,2) (family : US6680569) 2. Priority : 1999, 2 Lumileds 3. * wavelength conversion : primary FL material, supplementary FL material (red) * Y3Al5O12:Ce3+ + Y3Al5O12:Ce3+, Pr3+ * Y3Al5O12:Ce3+ + SrS:Eu2+ 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 * SrGa2S4:Eu2+ + SrS:Eu2+ + CaS:Eu2+ SrGa2S4:Ce3+ + SrS:Ce3+ + CaS:Ce3+ 1. Patent : US6642618 (2003, 11) 2. Priority : 2000, 12 3. * 5항 : 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, 4 3. * white light by LED (485 ~ 515nm) + (Sr,Ba,Ca)S:Eu2+ (600 ~ 620nm), 특히 SrS:Eu2+ 52/219 4. Phosphors Claimed, Studied and Used in LED Application 1. Patent : US6084250 (2000,7) by Philips (Family : US6051925, JP공개2000-509912) 2. Priority : 1997, 3 Lumileds 3. * 1항 : UV (300 ~ 370 nm) + B Ph (430~490 nm) + G Ph ( 520~570 nm) + R Ph (590~630 nm) * 6항 : B Ph = BaMgAl10O17: Eu2+, G Ph = ZnS:Cu, R Ph = Y2O2S:Eu3+ * 7항 : Organic phosphor (dye) 1. Patent : US6717353 (2004, 4) 2. Priority : 2002, 10 3. * 1항 : 1st WL converting material comprising Sr-SiON:Eu2+ (or YAG:Ce) emitting 2nd WL light * 2항 : UV and Blue light = 1st WL light * 3항 : Green = 2nd WL light * 4, 8항 : 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+ 1. Patent : US6417019 (2002, 7) 2. Priority : 2001, 4 3. * 1항 : white light by LED (380 ~ 500nm) + (Sr,Mg,Ba,Ca)(Ga,Al,In)2S4:Eu2+ (490 ~ 610 nm) * LED/Phosphor structure (encapsulation, mounting) 53/219 4. Phosphors Claimed, Studied and Used in LED Application 1. Patent : US6501102 (2002, 12) Lumileds 2. Priority : 2002, 1 3. * 1항 : LED (below 460 nm) + 2nd, 3rd WL light from YAG, (Y,Ln)AG, (Y,Ln)(Al,Ga)G, SrS, SrGa2S4, NitridoSilicate * 2항 : 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 54/219 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 55/219 4. Phosphors Claimed, Studied and Used in LED Application Lumileds - Philips 56/219 4. Phosphors Claimed, Studied and Used in LED Application Lumileds - Philips 57/219 4. Phosphors Claimed, Studied and Used in LED Application Lumileds * 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 ? 58/219 4. Phosphors Claimed, Studied and Used in LED Application Lumileds * Blue LED + Y Ph (YAG:Ce, YAG:Ce,Pr) + R Ph (CaS:Eu2+) For Illumination ? 59/219 4. Phosphors Claimed, Studied and Used in LED Application Lumileds - Philips * 60/219 4. Phosphors Claimed, Studied and Used in LED Application * Lumileds - Philips 61/219 4. Phosphors Claimed, Studied and Used in LED Application Lumileds * UV LED + R, G, B Phosphors 62/219 4. Phosphors Claimed, Studied and Used in LED Application Lumileds 63/219 4. Phosphors Claimed, Studied and Used in LED Application Lumileds 64/219 4. Phosphors Claimed, Studied and Used in LED Application * SrCaS:Eu2+ Sarnoff 65/219 4. Phosphors Claimed, Studied and Used in LED Application * SrCaS:Eu2+ Sarnoff 66/219 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. * 1항 : 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) * 7항 : YAG:Ce * 10항 : Lighting emitting S.C. component = S.C. body (UV, Blue, green) + A3B5X12:M 1. Patent : US6245259 (2001, 6) 2. Priority : 1996, 9 3. * 1항 : WL (from UV, Blue, Green) converting casting composition Resin (epoxy) Ce doped phosphors size 20 m (d 5 m) * 7항 : YAG:Ce * 10항 : Lighting emitting S.C. component = S.C. body (UV, Blue, green) + Ce doped phosphors * 15항 : Yellow by Blue LED * 16항 : Green, Red by Blue LED 67/219 4. Phosphors Claimed, Studied and Used in LED Application Osram Opto. 1. Patent : US6277301 (2001, 8) 2. Priority : 1996, 9 3. * 1항 : 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 * 2항 : size 20 m (d 5 m) * 11항(독) : White lighting emitting S.C. component = S.C. body (UV, Blue, green) + Ce doped phosphors(blue to yellow) with epoxy * 12항(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 68/219 4. Phosphors Claimed, Studied and Used in LED Application 1. Patent : US6613247 (2003, 9) Osram Opto. 2. Priority : 1996, 9 3. * 1항 : 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) * 7항 : YAG:Ce3+ phosphor * 12항(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 * 17항 : White = Blue LED + yellow light by Ce doped phosphor * 18항 : White = Blue LED + green and red light 1. Patent : US6669866 (2003, 12) (Family : US6552487) 2. Priority : 1999, 7 3. * 1항(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 * 2항 : Tb solely or predominantly (TAG) 69/219 4. Phosphors Claimed, Studied and Used in LED Application Osram Opto. 1. Patent : US6504179 (2003, 1) 2. Priority : 2000, 5 3. * 1항 : LED (300 ~ 470nm) + Eu activated calcium magnesium chlorosilicate (green phosphor) Ce activated rare earth garnet (yellow phosphor) * 2항 : Green (Ca8-x–yEuxMnyMg(SiO4)4Cl2) * 3항 : Yellow ((Re)3(Al,Ga)5O12:Ce, 특히 YAG:Ce or TAG:Ce) * 4항 : 특히, LED (330~370 nm) + phosphors (430~470, 490~525, 545~590 nm) * 5항 : 특히, LED (430~470 nm) + phosphors (545~590, 490~525 nm) 1. Patent : US 6649946 (2003, 11) (Family : US 6682663) 2. Priority : 1999, 11 3. * 1항(독) : “Yellow to Red” emitting phosphor MxSiyNz:Eu2+, M = La, Sr, Ba, Zn * 8항 : LED + phosphors * 9항 : LED = 420~470nm 70/219 4. Phosphors Claimed, Studied and Used in LED Application Osram Opto. 1. Patent : US6695982 (2004, 2) 2. Priority : 2000, 6 3. * 1항 : 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, 7 3. * 1항(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) 71/219 4. Phosphors Claimed, Studied and Used in LED Application * Blue LED + Y Ph (TAG:Ce) Shorter YAG Osram Opto. * Blue LED + Y,G Ph (Y(Al,Ga)G:Ce or TAG:Ce) + R Ph ((AE)2Si5N8:Eu2+) 72/219 4. Phosphors Claimed, Studied and Used in LED Application * Near UV LED + R, G, B Ph Osram Opto. Sr4Al14O25:Eu2+ (~490 nm) SrAl12O19:Eu2+ (~520 nm) SrAl2O4:Eu2+ (~400 nm) 73/219 4. Phosphors Claimed, Studied and Used in LED Application Osram Opto. 74/219 4. Phosphors Claimed, Studied and Used in LED Application * YAG : (Y 1-p-q GdpCeq)3(Al1-sGas)5O12 Osram Opto : Siemens Ga Gd 75/219 4. Phosphors Claimed, Studied and Used in LED Application * YAG : (Y 1-p-q GdpCeq)3(Al1-sGas)5O12 Osram Opto : Siemens * f-d absorption or CT absorption 76/219 4. Phosphors Claimed, Studied and Used in LED Application * Potential R, G, B, Y Ph Osram Opto : Siemens 77/219 4. Phosphors Claimed, Studied and Used in LED Application 1. Patent : US6765237 (2004, 7) GE or Gelcore 2. Priority : 2003, 1 3. * 1항 : 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 * 15항 : B Ph = (Sr,Ba,Ca,Mg)5(PO4)3Cl:Eu2+ 1. Patent : US6501100 (2002, 12) 2. Priority : 2000, 5 3. * 1항 : 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, 2 3. * 1항 : 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+ 78/219 4. Phosphors Claimed, Studied and Used in LED Application 1. Patent : US6469322 (2002, 10) GE or Gelcore 2. Priority : 1998, 2 3. * 1항 : UV, Blue LED + Green Ph (LnBO3:Ce3+,Tb3+, Ln = Sc, Y, La, Gd, Lu) * 9항 : Blue Ph ((Ba,Sr,Ca)5(PO4)3Cl: Eu2+,Mn2+) 함유 * 10항 : Red Ph 함유 1. Patent : US6791259 (2004, 9) 2. Priority : 2000, 8 3. * Scattering material 사용 (between LED & Phosphor material) * size는 /3~ /2 1. Patent : US6685852 (2004, 2) 2. Priority : 2001, 4 3. * 1항 : UV LED (315~480nm, 바람직하게는 350~410nm) + 아래 Phosphor 가운데 2종 (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-activator로 사용 79/219 4. Phosphors Claimed, Studied and Used in LED Application 1. Patent : US6621211 (2003, 9) GE or Gelcore 2. Priority : 2000, 5 3. * 1항 : 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, 5 3. * Mn2+ 첨가로 red shift * UV LED (350~420 nm) * 1항 : (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. * 1항(독) : 형광체를 claim, TAG, (Tb1–x–yAxREy)aDzO12, A = Y, La, Gd, Sm & D = Al,Ga * 38항(독) : LED + phosphor * 40항(독) : LED = 400~480 nm + phosphor 80/219 4. Phosphors Claimed, Studied and Used in LED Application 1. Patent : US6538371 (2003, 5) 2. Priority : 2000, 3 GE or Gelcore 3. * Blue LED + YAG:Ce3+ * 1항 : System color output을 향상시키는 방법 (CIE coord.에서 BBL과 line의 상관관계 이용) 1. Patent : US6522065 (2003, 2) 2. Priority : 2000, 3 3. * 1항 : 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. * 1항 : Ca8Mg(SiO4)4Cl2:Eu2+,Mn2+를 포함하는 조성 * 2항 : 상기 G Ph와 R, B Ph를 포함하는 조성 * 3항 : UV LED (330 ~420 nm, 특히 355~365 nm) * 6항 : G = Ca8Mg(SiO4)4Cl2:Eu2+,Mn2+, R = Y2O3:Eu3+,Bi3+, B = (Sr,Ba,Ca)5(PO4)3Cl:Eu2+ or BaMg2Al16O27:Eu2+ 81/219 4. Phosphors Claimed, Studied and Used in LED Application GE or Gelcore {C}3[A]2(D)3O12 Y3Al5O12 tetrahedral site octahedral site dodecahedral 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. * Replacement to Ga brings about decrease of emission intensity. 82/219 4. Phosphors Claimed, Studied and Used in LED Application GE or Gelcore Al5 Al4Ga1 Al3Ga2 Al2Ga3 Al1Ga4 similar thermal quenching No emission at RT crossover bet. d and f level Photo-ionization 83/219 4. Phosphors Claimed, Studied and Used in LED Application GE or Gelcore Y3Al5O12 (garnet) REAlO3 replacement to Large RE3+ (perovskite) 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. 84/219 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 85/219 4. Phosphors Claimed, Studied and Used in LED Application * Blue or Near UV LED + Phosphors For BLU ? GE or Gelcore For Illumination ? 86/219 4. Phosphors Claimed, Studied and Used in LED Application * Near UV LED + Phosphors GE or Gelcore Replace into B2O3? or ? What phosphor ? 87/219 4. Phosphors Claimed, Studied and Used in LED Application * Near UV LED + R, G, B Ph GE or Gelcore 88/219 4. Phosphors Claimed, Studied and Used in LED Application GE or Gelcore * LED + white phosphor Activator ? ? 89/219 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) 90/219 4. Phosphors Claimed, Studied and Used in LED Application * Blue LED + Phosphors Phosphortech CRI? 91/219 4. Phosphors Claimed, Studied and Used in LED Application * UV LED + Phosphors Phosphortech 92/219 4. Phosphors Claimed, Studied and Used in LED Application Review by C. Summers * 254 Hg emission AC no sulfide phosphor * LED CW : decay time (fast – recycling) ground state depletion high order effect (quenching) sulfide phosphor? GIT, Phosphortech * 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 N-UV or B LED? Peak WL? * 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 93/219 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 > 90 94/219 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? 95/219 4. Phosphors Claimed, Studied and Used in LED Application NIMS (Japan) * Blue LED + Y Ph (Ca--SiAlON:Eu2+) APL, V84, P5405, 2004 USP 6,776,927 (NIMS), USP 6657379 (Elektrische Gmbh) 96/219 4. Phosphors Claimed, Studied and Used in LED Application * UV LED + Nano phosphors Sandia 97/219 4. Phosphors Claimed, Studied and Used in LED Application Temperature Dependence B LED Due to I increase : band filling Phosphor : more sensitive upon T 98/219 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. 99/219