Recent Progress in Phosphors for

White LEDs

Takayuki Hisamune

Phosphor Technical Group

LED Materials Department
Information and Electronics Division
Mitsubishi Chemical Corporation
Outline

1.Mitsubishi Chemical Corporation (MCC) Introduction

2. MCC Phosphor Business Introduction
3. Basics of Phosphors & White LEDs
4. MCC Phosphors for LEDs
5. Nitride Red Phosphor Improvement
6. Nitride Yellow Phosphor Improvement
7. MCC Remote Phosphor
8. MCC VxRGB Solution
9. Conclusion
MCC Introduction
 MCC Phosphor Business Introduction
History
 1936 Started research on phosphor and fluorescent screen
 1945 Started research on X-Ray intensifying screens
 1959 Started mass production of phosphors for CRTs
 1965 Started operation at Odawara plant (Phosphor for CRTs & X-ray
Screens)
 1972 Started research on phosphors for PDPs
 1984 Started research on phosphors for Tri-color FLs
 1984 Started mass production of phosphors for Tri-color FLs
 1994 Started mass production of phosphors for PDPs

Year: Dai Nippon Toryo

Year: Kasei Optonix
 2001 Started research on LED phosphor
 2003 Increase in mass production of Phosphors for CCFLs
 2004 Invention of nitride red phosphor
 2005 Release of phosphors for WCG CCFLs
 2006 Started production of LED phosphors
 2009 Started mass production of LED phosphors in Odawara
 2011 Released nitride yellow and green phosphors
 2012 Released remote phosphor

Year: Kasei Optonix

Year: Mitsubishi Chemical
MCC’s Phosphor Manufacturing and R&D Bases
Odawara Techno Center

Yokohama Research Center

Alliance
Beijing Nakamura Yuji
Science & Technology (Xian)
Basics of Phosphors & White LEDs
Functions of phosphors
Materials taht transform eneriy into light
α-ray

X-ray
Visible light

cathode ray

Vacuum ultra violet ray

Ultra violet ray

visible light
(Blue, Violet)

infrared light

Y3Al5O12:Ce
Host lattice: Activator
Several types of white LEDs

Pseudo-white In early stages . . .

1. Blue LED Chip & Yellow Phosphor
phosphors Low Color Rendering Index: Ra<80
Blue-LED (General lighting)
Poor Color Reproducibility (LCD BLU)
White Improved types . . .
phosphors
2.Blue LED Chip & Green (Yellow)
Blue-LED & Red Phosphors Ra>80
3. Violet LED Chip (ca. 400 nm)
White & Blue & Green & Red Phosphors

phosphors High Color Rendering Index: Ra90

nUV-LED
Good Color Reproducibility
 Emission spectra & thermal quenching properties of S(C)ASN

1.2
BR-101A

1.0 BR-101B 1.2

BR-101D 1.0

Peak Intensity
0.8 BR-102C
0.8
0.6 CASN
Intensity

BR-102D
0.6 0.4 YAG
BR-102E
0.2
0.0
0.4
0 50 100 150 200
Temperature [ºC]
0.2

0.0
500 550 600 650 700 750

Wavelength [nm]
CASN = BR-101:CaAlSiN3:Eu
SCASN = BR-102:(Sr,Ca)AlSiN3:Eu
MCC Phosphors for LEDs
Lineup
0.900
520nm VG-401A (GBAM)
BG-201B (BSS)
0.800
540

BG-601B (β-SiAlON)
0.700
560
BG-301B (CSO)
0.600
BG-801 (LuAG)
500
580
0.500 BG-701 (GYAG)
CIE (y)

0.400 600
BY-201,202series (LSN)
BY-102 series (YAG)
620
0.300
700nm
490 BR-103A (CASON)
0.200 BR-102 series (SCASN)
BR-101 series (CASN)
480
0.100
VB-101A (BAM)
470

0.000 VB-201A (SCA)

460
0.000 0.100 0.200 0.300 0.400 0.500 0.600 0.700 0.800

CIE (x)
Important Properties of Phosphors

Emission
Emission Properties
Properties Powder
Powder Properties
Properties
Luminance Particle Size

Color Size Distribution

Temperature Dependence
Dispersion
Reliability

Decay Time
Phosphor Manufacturing Process

Ｂｌｅｎｄｉｎｇ Ｆｉｒｉｎｇ

Ｄｒｙｉｎｇ Ｄｉｓｐｅｒｓion
(Classification) Ｗａｓｈｉｎｇ
＆Ｓｉｅｖｉｎｇ
(Ｃｏａｔｉｎｇ)

Ｐａｃｋｉｎｇ Ｉｎｓｐｅｃｔｉｏｎ Sｈｉｐｐｉｎｇ

 Control Factors for Phosphor Properties
Process Factor
Blending
Blending
Raw Purity
Purity
RawMaterials
Materials
Particle
ParticleSize
Size Emission
EmissionProperties
Properties
Firing
Firing Temperature
Temperature
Atmosphere
Atmosphere
Pressure
Pressure Powder
PowderProperties
Properties
Flux
Flux
After
AfterFiring
Firing Dispersion
Dispersion
Classification
Classification
Coating
Coating
Nitride Phosphor Manufacturing Process

Alloy Method Hybrid Method Nitride Method

Component Metals Component Metals

Firing (Nitriding)

Alloy Mixing Component Nitrides

Mixing

Firing (Nitridiing) Firing Firing

After firing process

Phosphor
Improvement of Nitride Red Phosphor
Emission Spectra of Various Generation of SCASN

3rd
2nd
1st
Relationship between Peak Wavelength & Luminance of Various
Generations of SCASN

180

160
1st
140
2nd
Luminance　[%]

120 3rd

100

80

60

40

20
610 620 630 640 650 660 670
Peak wavelength /nm
Reliability Test Data of 1st and 3rd Generation of SCASN

Time
0 250 500 750 1000

１ｓｔ
３ｒｄ
0
⊿ｘ

Blue chip + “LuAG(BG-801/A2) + BR-102series *CCT: 3000K

Conditions: 85℃ 85 % RH, 1 W pkg
Improvement of Nitride Yellow Phosphor
Emission Spectra of LSN & β-SiAlON
1.2
LSN: Peak 535 nm
1.0 SiAlON: Peak 543 nm

0.8
Intensity

0.6

0.4

0.2

0.0
380 480 580 680 780
Wavelength / nm
 Emission Spectra of Various Yttrium Containing LSN
1.2 CIE(x) Ymol%
Normalized PL Intensity +Y ex. 455 nm
1.0 x = 0.423 (Y 0.00)
x = 0.430 (Y 0.03)
0.8 x = 0.450 (Y 0.12)
x = 0.458 (Y 0.16)
0.6 x = 0.475 (Y 0.32)

0.4

0.2

0.0
480 580 680 780
Wavelength / nm

Peak at 535 nm Peak at 555 nm

*The Ce concentration was fixed.

 Thermal Quenching Properties of Yellow Phosphors
Maintenance ratio of peak intensity /%

105
ex. 455 nm
LSN-n x = 0.422
100 LSN-Y x = 0.456
BOSE x = 0.427
95
YAG x = 0.452
90

85 LSN

80
YAG
75
0 50 100 150 200 250
Temperature / ℃
Color Range of LED with Various LSN

LSN-n (x=0.42) LSN-Y (x=0.47)

0.50
3000K

K
00
K
0.45

40
5000
60 00K
0.40

K
9000
0.35
00K
y

150

0.30

0.25
uv
00
0.
±

0.20
0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55
x
Production List of Nitride Yellow
Peak
Luminance
Type Composition x y Wavelength d50 /μm
(%)
/ nm
BY-201A La3Si6N11:Ce 127 0.420 0.558 535 22
BY-201/B La3Si6N11:Ce 138 0.418 0.559 535 16
BY-202/A (La,Y)3Si6N11:Ce 132 0.456 0.533 549 16

BY-201A
BY-201/B
Intensity a.u.

BY-202/A

400 500 600 700 800

Wavelength /nm
MCC Remote Phosphor
Remote Phosphor Lighting on the Market
Bulb Down light

Philips

Philips

Toshiba Xicato
Remote Phosphor Materials of MCC

3 Dimensions 2 Dimensions
Base Material CCT CRI
Phosphor compound

Poly- various
plate min. 2700 K 70～90
carbonate shape

various plate
Silicone min. 2700 K 70～90
shape film

“One stop service and customized”

MCC VxRGB White LED
High Color Quality

１.
１.Similar
Similarspectrum
spectrumas
assunlight.
sunlight.
２.
２.High
Highcolor
colorrendering
renderingindex
index
Ra
Ra==Typ. 95 ((R1
Typ.95 R1--15
15))≧
≧90
90

MCC VxRGB LED B+Y White LED

Excellent color Poor color fidelity
fidelity due to true especially in red region
color white

* VxRGB is registered trademark by Mitsubishi Chemical Corporation.

 Color Separation
* No color separation when using VxRGB technology
* VxRGB leads to high quality lights

MCC VxRGB Blue-Base White LED

* VxRGB is registered trademark by Mitsubishi Chemical Corporation.

Color VxRGB Lighting Application image
Application Image
* VxRGB is registered trademark by Mitsubishi Chemical Corporation.
Table lamp

Dining lamp
Powder room

Museum lighting
Retail shop
Fitting room

Food
Vegetables, Bread

Food
Fresh meat & fishe
Conclusion
MCC Phosphor Business

Long history and extensive experience in display, lighting and

medical applications

Produce wide variety of LED phosphors

Invented new materials and continue to improve them

High luminance, superior thermal quenching, and reliability

Provide not only phosphors but also solutions like remote

phosphors & VxRGB LEDs