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Inorganic Luminescent Materials for Highly Efficient Solid State Light Sources (In,Ga)N LED cool white pcLED
Inorganic Luminescent Materials for Highly
Efficient Solid State Light Sources
(In,Ga)N LED
cool white pcLED
warm white pcLED
Thomas Jüstel
RG Tailored Optical Materials
Institute for Optical Technologies, FH Münster
16 th Austrian Chemistry Days, Innsbruck, Austria
@ September 22 nd , 2015
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany
Slide 1
About 20% of the produced electrical energy is used for lighting (source: NASA) in East
About 20% of the produced electrical energy is used for lighting (source: NASA) in East
About 20% of the produced electrical energy is used for lighting (source: NASA) in East
About 20% of the produced electrical energy is used for lighting (source: NASA) in East
About 20% of the produced electrical energy is used for lighting (source: NASA)
in
East Berlin
 Na lamps
Even 23 years after Germany’s reunification
East and West Berlin can be diminished by lighting
1989
E
n
d
o
f th
e
B
er
li
n
W
a
ll “Th
e w n
i
d
o
f
c ange
h
1990
Germany’s reunification
West Berlin
 Hg lamps
1993
Blue LED
1996
White LED
2014
2015
White LED > 300 lm/W
25 th Anniversaty of Germany’s reunification “The light of change”
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany
Slide 2
1. Inorganic LED Outline 2. Some Basics of Luminescent Materials 3. Tuning Lanthanide Luminescence 4.
1. Inorganic LED Outline 2. Some Basics of Luminescent Materials 3. Tuning Lanthanide Luminescence 4.
1. Inorganic LED Outline 2. Some Basics of Luminescent Materials 3. Tuning Lanthanide Luminescence 4.

1. Inorganic LED

Outline

2. Some Basics of Luminescent Materials

3. Tuning Lanthanide Luminescence

4. Converter Materials for LED

5. Towards Ultimate Efficiency and CRI

6. (New) Applications of LED Light Sources

7. Summary and Outlook

Applications of LED Light Sources 7. Summary and Outlook Prof. Dr. T. Jüstel, Münster Univers ity
Applications of LED Light Sources 7. Summary and Outlook Prof. Dr. T. Jüstel, Münster Univers ity
Applications of LED Light Sources 7. Summary and Outlook Prof. Dr. T. Jüstel, Münster Univers ity
Applications of LED Light Sources 7. Summary and Outlook Prof. Dr. T. Jüstel, Münster Univers ity
Applications of LED Light Sources 7. Summary and Outlook Prof. Dr. T. Jüstel, Münster Univers ity
1 . Inorganic LED - Timeline 1970 1995 2020 Driving forces: Light yield, power dens
1 . Inorganic LED - Timeline 1970 1995 2020 Driving forces: Light yield, power dens
1 . Inorganic LED - Timeline 1970 1995 2020 Driving forces: Light yield, power dens

1

. Inorganic LED - Timeline

1970 1995 2020
1970
1995
2020

Driving forces: Light yield, power density, lifetime, light quality, design

Green to red and NIR LEDs

Green to red and NIR LEDs White inorganic and organic LEDs High performance LED s and
Green to red and NIR LEDs White inorganic and organic LEDs High performance LED s and

White inorganic and organic LEDs

Green to red and NIR LEDs White inorganic and organic LEDs High performance LED s and
Green to red and NIR LEDs White inorganic and organic LEDs High performance LED s and

High performance LEDs and laser diodes

Green to red and NIR LEDs White inorganic and organic LEDs High performance LED s and
Green to red and NIR LEDs White inorganic and organic LEDs High performance LED s and
Green to red and NIR LEDs White inorganic and organic LEDs High performance LED s and

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 4

1 . Inorganic LED - Status Quo 2015 Semiconductor systems (Al 1 - x Ga
1 . Inorganic LED - Status Quo 2015 Semiconductor systems (Al 1 - x Ga
1 . Inorganic LED - Status Quo 2015 Semiconductor systems (Al 1 - x Ga

1. Inorganic LED - Status Quo 2015

1 . Inorganic LED - Status Quo 2015 Semiconductor systems (Al 1 - x Ga x
1 . Inorganic LED - Status Quo 2015 Semiconductor systems (Al 1 - x Ga x

Semiconductor systems

(Al 1-x Ga x )N UV-C/B/A (In 1-x Ga x )N UV-A to cyan green (Al 1-x-y In x Ga y )P red to NIR

(Al 1 - x - y In x Ga y )P red to NIR Technical Data

Technical Data

up to 5 W

up to 8000 lm (CREE) 303 lm/W (CREE)

120 200 °C

to 5 W up to 8000 lm (CREE) 303 lm/W (CREE) 120 200 °C – 100

100 – 200 W/cm 2 2 – 12 K/W

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 5

Emissio n intensity [ a.u.] 1 Inorganic LED - Semiconductors & Spectra . (Al,In,Ga)P 
Emissio n intensity [ a.u.] 1 Inorganic LED - Semiconductors & Spectra . (Al,In,Ga)P 
Emissio n intensity [ a.u.] 1 Inorganic LED - Semiconductors & Spectra . (Al,In,Ga)P 

Emissio n intensity [ a.u.]

1 Inorganic LED - Semiconductors & Spectra

.

(Al,In,Ga)P

580 nm – 700 nm

Yellow Orange Red

(In,Ga)N

370 – 530 nm

UV-A Blue Green

0,35

0,30

0,25

0,20

0 15

,

0,10

0,05

0,00

0,35 0,30 0,25 0,20 0 15 , 0,10 0,05 0,00 400 450 500 550 600 650
400 450 500 550 600 650 700 Wavelength [nm] 650 In 1- x Ga x
400
450
500
550
600
650
700
Wavelength [nm]
650
In 1- x Ga x N
600
550
500
450
400
350
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
InN
GaN
Emission w avelength [n m]

Ga fraction / mol-%

750

(Al,Ga)N

210 370 nm

UV-C UV-A

Today all emission colours and white light is directly accessible by

Multichip LED lamps

Converter materials (phosphors)

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 6

1 Inorganic LED - White Light Sources . Multichip LED Lamps • Narrow band emitter
1 Inorganic LED - White Light Sources . Multichip LED Lamps • Narrow band emitter
1 Inorganic LED - White Light Sources . Multichip LED Lamps • Narrow band emitter

1 Inorganic LED - White Light Sources

.

Multichip LED Lamps

Narrow band emitter e.g. LEDs

½ = 30 nm

Several colored LEDs

Theoretical maximum

430 lm/W for

CCT = 4870 K

CRI = 3 (!)

Feasible values

~ 350 lm/W for CRI 90, n = 3 - 4

max. 320 lm/W for CRI 99, n = 5

Problems

Thermal stability of the LEDs

LED efficiency

Red and blue

high

Green

moderate

99.5 99 5 LED 98 4 LED 95 3 LED 90 2 LED 80 70
99.5
99
5
LED
98
4
LED
95
3
LED
90
2
LED
80
70
60
Source: Zukauskas, A., et. al ,
50
"Optimization of white polychromatic
40
semiconductor lamps", Applied
Physics Letters 80
(2002) 234-6
30
20
10
5
0
300
350
400
450
Col or render ing inde x

Luminous efficacy [lm/W]

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 7

1. Inorganic LED - White L ight S ources “Phosphor Converted” (pc) LED Phos- phor
1. Inorganic LED - White L ight S ources “Phosphor Converted” (pc) LED Phos- phor
1. Inorganic LED - White L ight S ources “Phosphor Converted” (pc) LED Phos- phor

1. Inorganic LED - White Light Sources

“Phosphor Converted” (pc) LED

- White L ight S ources “Phosphor Converted” (pc) LED Phos- phor Contact Plastic lens Gold

Phos-

phor

Contact Plastic lens Gold wire Heat sink (Cu)
Contact
Plastic
lens
Gold wire
Heat sink (Cu)

(In,Ga)N-

semicon-

ductor

lens Gold wire Heat sink (Cu) (In,Ga)N- semicon- ductor Al I ( G a ) 420

Al I

(

G

a) 420 – 480 nm

d

N S

i

t

L

i

t

LED l

t

, n,

em con uc or

um nescen screen

amp spec rum Cool-white Warm-white Cool & warm-white Cool & warm-white

Blue

Yellow Yellow + red Green + red Blue + green + red

Near UV 370 – 420 nm

1 . Inorganic LED - White L ight Sources Wall Plug Efficiency (WPE) of pcLEDs
1 . Inorganic LED - White L ight Sources Wall Plug Efficiency (WPE) of pcLEDs
1 . Inorganic LED - White L ight Sources Wall Plug Efficiency (WPE) of pcLEDs

1

. Inorganic LED - White Light Sources

Wall Plug Efficiency (WPE) of pcLEDs >> Discharge lamps

InGaN LED (Y,Gd) 3 Al 5 O 12 :Ce 70 1,0 Tc = 5270 K
InGaN LED
(Y,Gd) 3 Al 5 O 12 :Ce
70
1,0
Tc = 5270 K CRI = 82
60
Tc = 4490 K CRI = 79
0,8
50
0,6
40
Tc = 4110 K CRI = 76
Tc = 3860 K CRI = 73
Tc = 3540 K CRI = 70
30
0,4
20
0,2
Gelber
10
Blaue
Leuchtstoff
LED
0,0
0
400
450
500
550
600
650
700
750
800
400
500
600
700
800
Emiss ionsintensitä t [a.u.]
Emiss ion intensi ty

Wellenlänge [nm]

Wavelength [nm]

Status quo cool white phosphor converted LEDs @ 2015

Yellow phosphors

garnets (Y,Gd,Tb) 3 Al 5 O 12 :Ce 3+ ortho-silicates (Ca,Sr,Ba) 2 SiO 4 :Eu 2+ 300 lm/W! (WPE > 80%) 70 - 80 > 5000 K

Luminous efficacy LE

Colour rendering index CRI

Correlated colour temp. CCT

1 . Inorganic LED - White L ight Sources Enhancement of CRI of pcLEDs 1.2
1 . Inorganic LED - White L ight Sources Enhancement of CRI of pcLEDs 1.2
1 . Inorganic LED - White L ight Sources Enhancement of CRI of pcLEDs 1.2

1

. Inorganic LED - White Light Sources

Enhancement of CRI of pcLEDs

1.2 (In,Ga)N LED Y 3 Al 5 O 12 :Ce Red Eu 2+ phosphor JAZZ3300K
1.2 (In,Ga)N LED Y 3 Al 5 O 12 :Ce
Red Eu 2+ phosphor
JAZZ3300K
BB 3300K
1
0.8
0.6
0.4
0.2
400
450
500
550
600
650
700
750
nm
0
400
450
500
550
600
650
700
750
nm
800
Wavelength [nm]
Status quo warm white phosphor converted LEDs @ 2015
black body 3600 K
• Red phosphor Eu 2+ activated
fluorescent, CCT=3600 K
• Luminous efficacy LE
• Colour rendering index CRI
• Correlated colour temp. CCT
80 - 150 lm/W
85 – 95
2500 - 4000 K
R. Mueller-Mach, G.O. Mueller, P.J. Schmidt, T. Jüstel,
400
450
500
550
600
650
700
750
80
nm

Red Deficiency Compensating Phosphor LED, Light Emitting Device, US Patent 20030006702

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 10

y [ lm/ W ] 1 . Inorganic LED - White Light Sources Eu 2
y [ lm/ W ] 1 . Inorganic LED - White Light Sources Eu 2
y [ lm/ W ] 1 . Inorganic LED - White Light Sources Eu 2

y [ lm/ W ]

1

. Inorganic LED - White Light Sources

Eu 2+ Tb 3+ Mn 2+ Ln 3+ Mn 4+

Eu 2 + Tb 3 + Mn 2 + Ln 3 + Mn 4 + 

[ nm ]

LE (lm/W) Red LED Phosphor 257 (Ca,Sr)S:Eu

u

Causes for the reduction in luminous efficacy

1. Spectral interaction due to re-absorption

2. Reduction in lumen equivalent

„Waste “ 90 20 50
„Waste “
90
20
50

Band width [nm]

Position (nm)

- 120

– 30

635

655

620

655

620

C

a,

S

r,

B

a) 2

Si N

5

(

8 :

(Ca,Sr)AlSiN 3 :Eu

E

278

Mg 2 TiO 4 :Mn 4+

320

Ln 3+ activated (Ln = Pr, Sm, Eu) Mn 4+ activated

269

Eu 2+ - activated

300

Eu 2+ - activated

20 – 30

– 60

50 – 60

A. Zukauskas et al., Appl. Phys. Lett. 93 (2008) 051115

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 11

2. Some Basics of Luminescent Materials An (inorganic) luminescent material (phosphor) is a material which
2. Some Basics of Luminescent Materials An (inorganic) luminescent material (phosphor) is a material which
2. Some Basics of Luminescent Materials An (inorganic) luminescent material (phosphor) is a material which

2. Some Basics of Luminescent Materials

An (inorganic) luminescent material (phosphor) is a material which converts absorbed energy into electromagnetic radiation beyond thermal equilibrium

into electromagnetic radiation beyond thermal equilibrium Host Matrix • Cation sites for activator/sensitiser:

Host Matrix

Cation sites for activator/sensitiser:

Coordination number, symmetry, rigidity

Optical band gap

Phonon spectrum

Eu 2+ Eu 2+ Eu 2+ Mn 2+ V O
Eu 2+
Eu 2+
Eu 2+
Mn 2+
V O

Dopants

Type of optical transitions: Line width absorption cross section, decay time

Linearity & Excited state absorption

Impurities and Defects

Concentration quenching

Afterglow and colour center formation

Particle‘s Surface

Surface potential and morphology

Coatings light in- and outcoupling

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 12

2 . Some Basics of Luminescent Materials Relevant optical properties Ph o o um nescence
2
.
Some Basics of Luminescent Materials
Relevant optical properties
Ph
o o um nescence (
t
l
i
PL
)
Photoluminescence spectra
spectra of Mg 2 TiO 4 :Mn
Decay curves of
SrSi 2 N 2 O 2 :Eu
Colour point (stability)
PRO-2009-AB-012 ex307nm
PRO-2009-AB-012 mon656nm
T=100.00 K
1,0
656 nm
T=150.00 K
1000
T=200.00 K
T=250.00 K
0,8
T=300.00 K
T=350 00 K
.
T=400.00 K
Lumen equivalent
T=450.00 K
0,6
100
T=500.00 K
0,4
Reflection spectrum
10
0,2
Quantum efficiency
0,0
1
250
300
350
400
450
500
550
600
650
700
750
800
0
2000
4000
6000
8000
10000
Wavelength [nm]
Time [ns]
Decay curve
T-De endence of inte ral PL
of some typical phosphors
p
g
Linearity of YAG:Ce
and LiEuMo 2 O 8
Thermal quenching
LiEuMo 2 O 8
1,0
Ideal
YAG:Ce U728
Linearity (saturation)
0,8
0,6
Refractive index (dispersion)
0,4
0,2
……
0,0
0
100
200
300
400
500
Exc. density [W/mm 2 ]
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany
Slide 13
intensity [a. uRelative .]
Intensity [counts]
Norm. emission integra ls [a.u]
2 . Some Basics of Luminescent Materials Lanthanide luminescence based on 4f-4f transitions by Dieke
2 . Some Basics of Luminescent Materials Lanthanide luminescence based on 4f-4f transitions by Dieke
2 . Some Basics of Luminescent Materials Lanthanide luminescence based on 4f-4f transitions by Dieke
2 . Some Basics of Luminescent Materials Lanthanide luminescence based on 4f-4f transitions by Dieke
2
.
Some Basics of Luminescent Materials
Lanthanide luminescence based on
4f-4f transitions by Dieke diagram
Shielding of 4f n electrons
by outer filled 5s and 5p shells
 no shift of excited state parabola
and strong zero-phonon lines (ZP)
1) Sharp lines (atomic like spectra),
Stokes shift ~ 0 cm -1
2) Little influence of environment on
energy level scheme of the [Xe]4f n
ground state configuration
3) Parity forbidden transitions
ill
(~ms decay, osc
ator strengt
h f
~
10
-5
)
 Sensitisation necessary!
Ln 3+ ion
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany
Slide 14
2. Some Basics of Luminescent Materials 5d CT CT CT 5d 5d 5d 5d 5d
2. Some Basics of Luminescent Materials 5d CT CT CT 5d 5d 5d 5d 5d
2. Some Basics of Luminescent Materials 5d CT CT CT 5d 5d 5d 5d 5d

2. Some Basics of Luminescent Materials

5d CT CT CT 5d 5d 5d 5d 5d 5d 5d
5d
CT
CT
CT
5d
5d
5d
5d
5d
5d
5d

Typical line emitter

Pr 3+ Scintillators, laser Nd 3+ Lasers Sm 2+/3+ Detectors, storage Eu 3+ Fluorescent lamps Gd 3+ UV lamps Tb 3+ Fluorescent lamps Dy 3+ Security marking Ho 3+ Laser Er 3+ NIR amplifier Tm 3+ Plasma displays Yb

3+

Laser

Typical band emitter

3+

Ce

Pr 3+

Nd 3+

E

2+

2+

u

Yb

LEDs, UV Lamps Detectors, UV lamps UV Lamps s Laser

LED

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 15

En ergy [c m - 1 ] 3 Tuning Lanthanide Luminescence . Photoluminescence of Eu
En ergy [c m - 1 ] 3 Tuning Lanthanide Luminescence . Photoluminescence of Eu
En ergy [c m - 1 ] 3 Tuning Lanthanide Luminescence . Photoluminescence of Eu

En ergy [c m -1 ]

3 Tuning Lanthanide Luminescence

.

Photoluminescence of Eu 2+ : Configuration [Xe]4f 7 isoelectronic to Gd 3+

3.0x10 4

2.0x10

4

1.0x10 4

0.0

isoelectronic to Gd 3 + 3.0x10 4 2. 0x10 4 1.0x10 4 0.0 [Xe]4f 6 [

[Xe]4f 6

[Xe]4f 7

5d 1 2 6 D J I 7/2  c CFS 6 P E 7/2
5d 1
2
6 D J
I 7/2
c
CFS
6
P
E
7/2
 cfs
Centroid
Shift
Stokes
Shift
8
S
7/2
8 S 7/2
8 S 7/2
8 S 7/2
e Eu 2+ IoFre
n ~ 340 00 cm -1

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 16

3. Tuning Lanthanide Luminescence Eu 2 + Doped Luminescent Pigment KMgF 3 :Eu SrB O
3. Tuning Lanthanide Luminescence Eu 2 + Doped Luminescent Pigment KMgF 3 :Eu SrB O
3. Tuning Lanthanide Luminescence Eu 2 + Doped Luminescent Pigment KMgF 3 :Eu SrB O

3. Tuning Lanthanide Luminescence

3. Tuning Lanthanide Luminescence Eu 2 + Doped Luminescent Pigment KMgF 3 :Eu SrB O :Eu

Eu 2+ Doped Luminescent Pigment KMgF 3 :Eu SrB O :Eu BaSO 4 :Eu Sr 2 P 2 O 7 :Eu

BaMgAl 10 SrSiAl 2 O 3

Sr 4 Al 14 O 25 :Eu

BaSi 2 N 2 O 2 :Eu Ba 2 SiO 4 :Eu

Emission Band Maximum [nm] 359 (line)

368

374

420

453

480

490

490

505

520

535

541

575

585

610

615

650

655

700

4

7

O 17 :Eu N:Eu

535 541 575 585 610 615 650 655 700 4 7 O 1 7 :Eu N:Eu

SrAl 2

O 4 :Eu

SrGa

2 S 4 :Eu

SrSi 2

N

2 O 2 :Eu

Sr SiO :Eu Ba 2 Si 5 N 8 :Eu SrS:Eu Sr 2 Si 5 N 8 :Eu CaAlSiN 3 :Eu CaS:Eu SrSiN 2 :Eu

2

4

Rough trend for  E: Fluorides < Oxides < Oxynitrides < Nitrides ~ Sulfides
Rough trend for  E: Fluorides < Oxides < Oxynitrides < Nitrides ~ Sulfides

Rough trend for E: Fluorides < Oxides < Oxynitrides < Nitrides ~ Sulfides

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

17

Slide 17

Emission in tensity [a.u.] 3 Tuning Lanthanide Luminescence . Eu 2 + doped nitrides derived
Emission in tensity [a.u.] 3 Tuning Lanthanide Luminescence . Eu 2 + doped nitrides derived
Emission in tensity [a.u.] 3 Tuning Lanthanide Luminescence . Eu 2 + doped nitrides derived

Emission in tensity [a.u.]

3 Tuning Lanthanide Luminescence

.

Eu 2+ doped nitrides derived from Sr 2 Si 5 N 8 (orthorhombic Pmn21): N [4]

1. Change of CFS: Sr 2 Si 5 N 8 :Eu Ba 2 Si 5 N 8 :Eu

Si 5 N 8 :Eu  Ba 2 Si 5 N 8 :Eu T wo Sr

Two Sr sites with CN = 10

2 Si 5 N 8 :Eu T wo Sr sit es w ith CN = 10
585 nm 625 nm Ba2Si5N8:Eu 1,0 Sr2Si5N8:Eu 0,8 0,6 0,4 0,2 0,0 500 550 600
585 nm
625 nm
Ba2Si5N8:Eu
1,0
Sr2Si5N8:Eu
0,8
0,6
0,4
0,2
0,0
500
550
600
650
700
750
800

Wavelength [nm]

Broad emission bands

Hoppe, H. A.; Lutz, H.; Morys, P.; Schnick, W.S.; Seilmeier, A. J. Phys. Chem. Solids 2000, 61, 2001

3 Tuning Lanthanide Luminescence . Eu 2 + doped nitrides derived from Sr 2 Si
3 Tuning Lanthanide Luminescence . Eu 2 + doped nitrides derived from Sr 2 Si
3 Tuning Lanthanide Luminescence . Eu 2 + doped nitrides derived from Sr 2 Si

3 Tuning Lanthanide Luminescence

.

Eu 2+ doped nitrides derived from Sr 2 Si 5 N 8 (orthorhombic Pmn21): N [4]

2. Change of centroid shift: Sr 2 Si 5 N 8 :Eu Sr 2 Si 5-x Al x N 8-x O x :Eu

Sr 2 Si 5 N 8 :Eu,Al,O

1,0 Emission spectrum Excitation spectrum Reflection spectrum 0,8 0,6 254 nm exc. QE = 83.6%
1,0
Emission spectrum
Excitation spectrum
Reflection spectrum
0,8
0,6
254 nm exc.
QE = 83.6%
RQ = 4.4%
LO = 0.754
450 nm exc.
90.2%
11.5%
0.798
0,4
LE = 199 lm/W 213 lm/W
x = 0.628
0.633
y = 0.365
0.366
0,2
 max = 623 nm
623 nm
0,0
100
200
300
400
500
600
700
800
Rela tive intensity

Wavelength [nm]

q

Excitation spectra Emission spectra 1,0 1,0 Si,N ---> Al,O r 0,5 0,5 0,0 0,0 300
Excitation spectra
Emission spectra
1,0
1,0
Si,N ---> Al,O
r
0,5
0,5
0,0
0,0
300
400
500
600
700
800

Wavelength [nm]

T. Jüstel, W. Mayr, P.J. Schmidt, H. Höppe, W.S. Schnick, European Patent EP02102752.9

R eflectance [%] Intensity [a.u ] 3 Tuning Lanthanide Luminescence . Eu 2 + doped
R eflectance [%] Intensity [a.u ] 3 Tuning Lanthanide Luminescence . Eu 2 + doped
R eflectance [%] Intensity [a.u ] 3 Tuning Lanthanide Luminescence . Eu 2 + doped

R eflectance [%]

Intensity [a.u]

3 Tuning Lanthanide Luminescence

.

Eu 2+ doped nitrides derived from Sr 2 Si 5 N 8 (orthorhombic Pmn21): N [4]

3. Change of centroid shift Sr 2 Si 5 N 8 :Eu SrSi 2 O 2 N 2 :Eu (triclinic P1)

1,0

0,8

0,6

0,4

2 O 2 N 2 :Eu (triclinic P1) 1,0 0,8 0,6 0,4 0,2 0,0 Emission spectra
2 O 2 N 2 :Eu (triclinic P1) 1,0 0,8 0,6 0,4 0,2 0,0 Emission spectra

0,2

0,0

Emission spectra Excitation spectra Reflection spectra  max = 542 nm  centroid = 536
Emission spectra
Excitation spectra
Reflection spectra
 max = 542 nm
 centroid = 536 nm
x = 0.352, y = 0.614
LE = 553 lm/W
R 450 nm = 32%
QE = 81%
250
300
350
400
450
500
550
600
650
700
750
800

80

60

40

20

0

Wavelength [nm]

V. Bachmann, T. Jüstel, A. Meijerink, , J. Luminescence 121 (2006) 441

C R Ronda P J Schmidt

.

.

.

.

,

100

121 (2006) 441 C R Ronda P J Schmidt . . . . , 100 Four

Four Sr sites with CN = 6 (+1)

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 20

3 Tuning Lanthanide Luminescence . First all nitride LED demonstrated in 2005 (QE > 0.9,
3 Tuning Lanthanide Luminescence . First all nitride LED demonstrated in 2005 (QE > 0.9,
3 Tuning Lanthanide Luminescence . First all nitride LED demonstrated in 2005 (QE > 0.9,

3 Tuning Lanthanide Luminescence

.

First all nitride LED demonstrated in 2005 (QE > 0.9, QE rel (200 °C) > 0.95)

(In,Ga)N LED + SrSi 2 N 2 O 2 :Eu + Sr 2 Si 5
(In,Ga)N LED + SrSi 2 N 2 O 2 :Eu + Sr 2 Si 5 N 8 :Eu
3.00E-06
Drive
at 25 °C
2.50E-06
1.11E-01
4.75E-01
2.00E-06
1.30E+00
1.92E+00
1.50E-06
2.78E+00
4.09E+00
1.00E-06
5.01E-07
1.00E-09
380
430
480
530
580
630
680
730
780

Colour rendering index > 88 Excellent colour point stability with drive is achieved

5000 99 4500 4000 97 3500 95 3000 93 2500 2000 91 1500 89 1000
5000
99
4500
4000
97
3500
95
3000
93
2500
2000
91
1500
89
1000
87
500
0
85
012345
Current , A (pulsed)
CCT_25C
CCT_125C
Ra_25C
Ra_125C
CCT, K
Ra

R. Mueller-Mach, G.O. Mueller, M.R. Krames, H.A. Höppe, F. Stadler, W.S. Schnick, T. Jüstel, P.J. Schmidt, All Nitride White Light Emitting Diodes, Phys. Stat. Sol. A 202 (2005) 1727

4. Converter Materials for LED Inorganic Phosphors Simplified energy level scheme of Eu 2 +
4. Converter Materials for LED Inorganic Phosphors Simplified energy level scheme of Eu 2 +
4. Converter Materials for LED Inorganic Phosphors Simplified energy level scheme of Eu 2 +

4. Converter Materials for LED

Inorganic Phosphors

Simplified energy level scheme of Eu 2+

Garnets  Ce 3+ (Y,Gd,Tb) 3 Al 5 O 12 :Ce T yp ca spec
Garnets  Ce 3+
(Y,Gd,Tb) 3 Al 5 O 12 :Ce
T
yp ca spec ra o
i
l
t
f E
u
2+
p
h
osp ors
h
1,0
Lu 3
Al 5 O 12 :Ce
0,8
Lu 3
(Ga,Al) 5 O 12 :Ce
(Lu,Y) 3 Sc 2 Al 3 O 12
(Y,Lu) 3 (Al,Mg,Si)
:Ce
5 O 12 :Ce
0,6
Ca(Y,Lu) 2 Al 4 SiO 12 :Ce
0,4
0,2
Ortho-Silicates  Eu 2+
(Ca,Sr,Ba)
SiO
4 :Eu
0,0
2
300
400
500
600
700
800
(Ca,Sr,Ba)
SiO
:Eu
Wavelength [nm]
3
5
(Oxy)Nitrides  Eu 2+ or Ce 3+
(Sr,Ca,Ba) 2 Si 5 N 8 :Eu „2-5-8“
(Sr,Ca,Ba)Si N O :Eu
(Ca,Sr)AlSiN 3 :Eu,O
1-2-2-2“
2
2
2
„1-1-1-3“
(Ca,Sr,Ba)SiN 2 :Eu „1-1-2“
La 3 Si 6 N 11 :Ce „3-6-11“
Ba 3 Si 6 O 12 N 2 :Eu
,ß-SiAlONes:Eu
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany
Slide 22
No rmalised emissio n intensity
4 Converter Materials for LED . Narrow band red emitter M I I [Mg 3
4 Converter Materials for LED . Narrow band red emitter M I I [Mg 3
4 Converter Materials for LED . Narrow band red emitter M I I [Mg 3

4 Converter Materials for LED

.

Narrow band red emitter M II [Mg 3 SiN 4 ]:Eu 2+

Novel siliconitrides: Ca[Mg 3 SiN 4 ]:Ce 3+ , Sr[Mg 3 SiN 4 ]:Eu 2+ , and Eu[Mg 3 SiN 4 ]“ Problem: Stability towards hydrolysis and thermal quenching

Problem: Stability towards hydrolysis and thermal quenching W.S. Schnick et al., Chem. Mater. 26 (2014) 2712

W.S. Schnick et al., Chem. Mater. 26 (2014) 27122719

4 Converter Materials for LED . Narrow band red emitter Sr[LiAl 3 N 4 ]:Eu
4 Converter Materials for LED . Narrow band red emitter Sr[LiAl 3 N 4 ]:Eu
4 Converter Materials for LED . Narrow band red emitter Sr[LiAl 3 N 4 ]:Eu

4 Converter Materials for LED

.

4 Converter Materials for LED . Narrow band red emitter Sr[LiAl 3 N 4 ]:Eu 2

Narrow band red emitter Sr[LiAl 3 N 4 ]:Eu 2+

Claimed as next generation LED-phosphor material”

Synthesis LiAlH 4 + (1-x) SrH 2 + x EuF 3 + 2 AlN + N 2 (Sr 1-x Eu x )[LiAl 3 N 4 ] + 3x HF + (3-x) H 2 RF-Furnace, 1000 °C

3 N 4 ] + 3x HF + (3-x) H 2 RF-Furnace, 1000 °C Optical Properties

Optical Properties

= 651 nm for 5% Eu 2+

max

FWHM = 1180 cm -1 QE(200 °C) > 95%rel. to QE(RT) Decay time of Eu 2+ ~ 1.1 µs

Problems: Excitation @ 410 nm photo ionisation and strong re-absorption of YAG:Ce/LuAG:Ce PL

W.S. Schnick et al., Nature Materials (2014) 1-6

PL W.S. Schnick et al., Nature Materials (2014) 1-6 Prof. Dr. T. Jüstel, Münster Univers ity

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 24

4. Converter Materials for LED Red-emitting line emitter K MF :Mn (M = Si ,
4. Converter Materials for LED Red-emitting line emitter K MF :Mn (M = Si ,
4. Converter Materials for LED Red-emitting line emitter K MF :Mn (M = Si ,

4. Converter Materials for LED

Red-emitting line emitter

K MF :Mn (M = Si , Ge , Ti) 2 6 Emission spectrum 1,0
K MF :Mn (M = Si
, Ge
, Ti)
2
6
Emission spectrum
1,0
Excitation spectrum
631 nm
0,8
0,6
0,4
0,2
0,0
250
300
350
400
450
500
550
600
650
700
750
800
Relative inte nsity

Wavelength [nm]

Relative intensit y [a.u.]
Relative intensit y [a.u.]

Warm white pcLED

1,0 CCT = 3000 K Blue chip + YAG:Ce + K 2 SiF 6 :Mn
1,0
CCT = 3000 K
Blue chip + YAG:Ce + K 2 SiF 6 :Mn
0,8
0,6
0,4
0,2
0,0
400
500
600
700
800

Wavelength (nm)

LED Chip Converter

Blue

420 – 480 nm

Yellow (Y,Gd,Tb,Lu)Al 5 O 12 :Ce

Red

3

Mn 4+ - phosphors :3%Ce + K [MF ]:Mn 4+

2

6

Typical yellow/red blend Tb Al O

Problems

5

12

Absorption strength, linearity, and stability of Mn 4+

MnF 4 MnF 2 + F 2

A. Srivastava et al., GE, US Patent US2006/0169998

4 Converter Materials for LED . Requirements to the „ideal“ red phosphor • Emission wavelen
4 Converter Materials for LED . Requirements to the „ideal“ red phosphor • Emission wavelen
4 Converter Materials for LED . Requirements to the „ideal“ red phosphor • Emission wavelen

4 Converter Materials for LED

.

Requirements to the „ideal“ red phosphor

Emission wavelength ~ 610 – 630 nm

QE(RT) > 90% and QE(150 °C) > 80%

Strong absorption at 410 nm and 450 nm

T 1/2 > 200 °C

V(λ) weighed brightness value > 60% relative to (Ca,Sr)AlSiN 3 :Eu,O

Narrow FWHM

Decay time < 10 ms

No saturation to 100 W/mm 2

• High (photo)chemical and thermal stability Activator Spectral range [nm] Lumen equivalent [lm/W opt ]
• High (photo)chemical and thermal stability
Activator
Spectral range
[nm]
Lumen equivalent
[lm/W opt ]
Decay
Efficiency
time 
Absorption
at 450 nm exc.
RE-Ions
Eu
2+
Eu 3+
Sm 3+
360 - 700
590 - 710
560 - 710
590 - 680
50 – 550
200 – 360
240 – 260
100 – 220
~ 1 µs
~ 1 ms
0.5 ms
0.1 ms
high
high
moderate
moderate - high
strong
weak
weak
Pr 3+
weak
TM-Ions
Mn
2+
500 - 650
620 - 680
100 - 550
80 – 230
5-15 ms
hi
g
h
weak
Mn
4+
1-10 ms
high
moderate

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 26

4 Converter Materials for LED . Remaining Challenges • Red narrow band or line emitter
4 Converter Materials for LED . Remaining Challenges • Red narrow band or line emitter
4 Converter Materials for LED . Remaining Challenges • Red narrow band or line emitter

4 Converter Materials for LED

.

Remaining Challenges

Red narrow band or line emitter

to increase lumen equivalent

Reduced re-absorption

 t o ncrease pac age ga n i k i Red emitting ion Eu
 t
o ncrease pac age ga n
i
k
i
Red emitting ion
Eu 2+
LE [lm/W]
80 - 200
Eu 3+
220 – 360
Sm 3+
240 – 260
P r
3+
200
220

CaAlSiN 3 :Eu (Mitsubishi Chemicals)

1,0 [Xe]4f 6 5d 1 - [Xe]4f 7 0,8 0,6 0,4 0,2 Emission spectrum Excitation
1,0
[Xe]4f 6 5d 1
- [Xe]4f 7
0,8
0,6
0,4
0,2
Emission spectrum
Excitation spectrum
0,0
300
400
500
600
700
800
Normali sed intensity [a.u .]

Wavelength [nm]

NaGdW 2 O 8 :Eu 3+ (60%)

Emission spectrum QE 465 = 48.1% 1,0 Excitation spectrum RQ 465 = 75.8% QE 394
Emission spectrum
QE 465 = 48.1%
1,0
Excitation spectrum
RQ 465 = 75.8%
QE 394 = 54.8%
0,8
RQ 394 = 63.5%
x = 0.668
y = 0.331
0,6
LE = 268 lm/W
 max = 616 nm
0,4
 centroid = 627 nm
0,2
0,0
300
400
500
600
700
800
Normalised
intensity [a.u.]

Wavelength [nm]

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 27

4. Converter Materials for LED Known RE activators able to show red PL with line
4. Converter Materials for LED Known RE activators able to show red PL with line
4. Converter Materials for LED Known RE activators able to show red PL with line

4. Converter Materials for LED

Known RE activators able to show red PL with line emission

Pr 3+ Sm 3+ Eu 3+ 30 30 30 Near UV LED Blue LED 5
Pr 3+
Sm 3+
Eu 3+
30
30
30
Near UV LED
Blue LED
5
D
3
5
D
2
5
20
3 P 1
20
20
D
4
1
G
5
1
D
D
5/2
0
2
6
F
1
10
G
10
11/2
10
4
1 F 4 3 F 2
7
6
3 H
F
6
6
H 11/2
3
H
5
6
0
0
0
7 F
3 H 4
H 5/2
0
3
Energy / 10
cm -1
3
Energy / 10
cm -1
3
Energy / 10
cm -1

Pr (III)

Sm (III)

Eu (III)

Problems concerning the application in pcLEDs

Position of the charge-transfer and 4f5d transitions E >> 30000 cm -1

4f-4f transitions of Eu 3+ are spin- and parity forbidden < 100 cm -1

Strategies to enhance absorption strength in the near UV or blue spectral range

Activator concentration

Organic sensitisers

Inorganic sensitisers VO 4 3- , MoO 6 6- , WO 6 6- (CT),Sm 2+ , Eu 2+ (4f5d), Tb 3+ (4f4f)

Covalent interaction

Enhance spectral width

Increase interaction length

Increase to 100% if no conc. quenching occur Polycyclic aromatics (-* transitions)

Eu 3+ coordinated by polarisable anions Multiple activator sites, cation disorder Ceramics, crystals

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 28

4 Converter Materials for LED . Molybdates/tungstates as host materials for Eu 3 + Pb(Mo,W)O
4 Converter Materials for LED . Molybdates/tungstates as host materials for Eu 3 + Pb(Mo,W)O
4 Converter Materials for LED . Molybdates/tungstates as host materials for Eu 3 + Pb(Mo,W)O

4 Converter Materials for LED

.

Molybdates/tungstates as host materials for Eu 3+

Pb(Mo,W)O

4

Wulfenite (yellowish)

materials for Eu 3 + Pb(Mo,W)O 4 Wulfenite (yellowish) Ca (M o, W)O 4 = Ca

Ca(Mo,W)O 4 = Ca 2 (Mo,W) 2 O 8

Scheelite

(M o, W)O 4 = Ca 2 (M o, W) 2 O 8 Sch ee lite
(M o, W)O 4 = Ca 2 (M o, W) 2 O 8 Sch ee lite

ALn(Mo,W) 2 O 8 1 site (8)

A 4 Ln 4 (Mo,W) 2 sites (8,10)

8 O 32

Ln 2

Ln 2 (Mo,W) 2 O 9

Ln 2 (Mo,W) 3 O 12 1 site (8)

(Mo,W)O 6

3 sites (8,8,8) 2 sites (8,9)

1 site (8) (M o, W)O 6 3 sit es (8 ,8, 8) 2 sites (8,9)

Ln 2 Mo 3 O 12

1 st example LiGd 1-x Mo 2 O

8

:Eu x

2 nd example Li 3 Ba 2 Gd 3-x Mo

8

O 32 :Eu 3x

3 rd example (Gd 1-x Tb x ) 2 Mo 3 O 12 :Eu

4 Converter Materials for LED . Eu 3 + doped Molybdates - LiEuMo 2 O
4 Converter Materials for LED . Eu 3 + doped Molybdates - LiEuMo 2 O
4 Converter Materials for LED . Eu 3 + doped Molybdates - LiEuMo 2 O

4 Converter Materials for LED

.

Eu 3+ doped Molybdates - LiEuMo 2 O 8 a phosphor with cation disorder

Luminescence spectra 1,0 Emission spectrum Excitation spectrum 0,8 0,6 0,4 0,2 0,0 250 300 350
Luminescence spectra
1,0
Emission spectrum
Excitation spectrum
0,8
0,6
0,4
0,2
0,0
250
300
350
400
450
500
550
600
650
700
750
Normalised i ntensity

5% Eu 3+

Wavelength [nm] 1,0 0,5 0,0 250 300 350 400 450 500 550 600 N ormalized
Wavelength [nm]
1,0
0,5
0,0
250
300
350
400
450
500
550
600
N ormalized Intensity

Wavelength[nm]

100% Eu 3+

T-dependent integral emission intensity 6 5x10 Integral intensity 6 4x10 6 3x10 6 2x10 6
T-dependent integral emission intensity
6
5x10
Integral intensity
6
4x10
6
3x10
6
2x10
6
1x10
0
Emissio n maxima [Coun ts]

100

200

300

400

Temperature [K]

500

QE 465 ~ 100% R 465 = 75% R 395 = 60% CIE x =
QE 465 ~ 100%
R 465 = 75%
R 395 = 60%
CIE x = 0.665
CIE y = 0.333
LE = 269 lm/W opt
 max = 614 nm
 centroid = 623 nm
 1/e = 0.39 ms (0.2 x Y 2 O 3 :Eu)
d 50 = 4.2 µm

US Patent US2007/0090327, “Novel red fluorescent powder”, Industrial Technology Research Institute, Taiwan M. Rico, U. Giebner, et.al, “Growth, spectr. and tunable laser oper. of disord. crystal LiGd(MoO 4 ) 2 doped with Yb”, J. Opt. Soc. Am. B 22 (2006) 1083

4 Converter Materials for LED . Eu 3 + doped Molybdates - LiEuMo 2 O
4 Converter Materials for LED . Eu 3 + doped Molybdates - LiEuMo 2 O
4 Converter Materials for LED . Eu 3 + doped Molybdates - LiEuMo 2 O

4 Converter Materials for LED

.

Eu 3+ doped Molybdates - LiEuMo 2 O 8 a phosphor with cation disorder

Conversion of the powders into ceramics to reduce scattering and to enhance interaction length (5 µm 500 µm)

Lumiramic or c 2 -ceramics ~ 200 – 300 µm

395 nm 465 nm LED LED 1 0 , LiEuMo 2 O 8 LED 
395 nm
465 nm
LED
LED
1 0
,
LiEuMo 2 O 8
LED  Max = 394 nm
LED  Max = 464 nm
0,8
0,6
0,4
0,2
0,0
250
300
350
400
450
500
550
Intensity [a. u.]

Wavelength [nm]

350 400 450 500 550 Intensity [a. u.] Wavelength [nm] Prof. Dr. T. Jüstel, Münster Univers
350 400 450 500 550 Intensity [a. u.] Wavelength [nm] Prof. Dr. T. Jüstel, Münster Univers
350 400 450 500 550 Intensity [a. u.] Wavelength [nm] Prof. Dr. T. Jüstel, Münster Univers
350 400 450 500 550 Intensity [a. u.] Wavelength [nm] Prof. Dr. T. Jüstel, Münster Univers
4 Converter Materials for LED . Eu 3 + doped Molybdates - LiEuMo 2 O
4 Converter Materials for LED . Eu 3 + doped Molybdates - LiEuMo 2 O
4 Converter Materials for LED . Eu 3 + doped Molybdates - LiEuMo 2 O

4 Converter Materials for LED

.

Eu 3+ doped Molybdates - LiEuMo 2 O 8 a phosphor with cation disorder Conversion of the powders into “single crystals” to reduce scattering and to enhance interaction length (5 µm mm)

Crystals grown by Czrochalski

long-term

„violet“

short-term „bright “

l ong- t erm „violet“ s h or t-t erm „bright “ 1,0 0,8 PL 5
1,0 0,8 PL 5 D 0 - 7 F 2 bright sample 0,6 violett sample
1,0
0,8
PL
5 D 0 - 7 F 2
bright
sample
0,6
violett sample
5 D 0 - 7 F 4
0,10
0,05
5 D 0 - 7 F 1
5 D 0 - 7 F 3
0,00
580
600
620
640
660
680
700
720
Intensity [normiert]

Wavelength [nm]

151 Eu Mößbauer
151 Eu Mößbauer
SQUID
SQUID

g-factor

10,0 6,0 4,0 3,0 2,5 2,0 1,5 bright sample 2,0 violet sample 1,5 1,0 0,5
10,0
6,0
4,0
3,0
2,5
2,0
1,5
bright sample
2,0
violet sample
1,5
1,0
0,5
0,0
-0,5
-1 0
,
X-band EPR
-1,5
100
200
300
400
500
dX"/dB

B-field [mT]

Conclusion: Formation of Mo V due to Oxygen loss

S. Schwung, D. Rytz, A. Gross, U. Ch. Rodewald, R.-D. Hoffmann, B. Gerke, B. Heying, S. Schwickert, R. Poettgen, T. Jüstel, LiEuMo 2 O 8 - Crystal Growth, Structure, and Optical Properties, Opt. Mater. 35 (2014)

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 32

4 Converter Materials for LED . Eu 3 + doped Molybdates - LiEuMo 2 O
4 Converter Materials for LED . Eu 3 + doped Molybdates - LiEuMo 2 O
4 Converter Materials for LED . Eu 3 + doped Molybdates - LiEuMo 2 O

4 Converter Materials for LED

.

Eu 3+ doped Molybdates - LiEuMo 2 O 8 a phosphor with cation disorder

Sat ration at hi h excitation densit ?

u

g

y

Emission spectra (HEL-2006-DU292) LiEuMo 2 O 8

Type

YAG:Ce

LiEuMo 2 O 8

615 nm 375 nm 390 µs 5 W/mm 2

em

exc

1/e

P in

545 nm 445 nm 65 ns 30 kW/mm 2

(saturation expected)

P

Out

nm 445 nm 65 ns 30 kW/mm 2 (saturation expected) P Out E n e r

Energy [eV]

2,3 2,2 2,1 2 1,9 1,8 1,7 Exc. 375 nm diode laser Exc. spot diameter
2,3
2,2
2,1
2
1,9
1,8
1,7
Exc. 375 nm diode laser
Exc. spot diameter 11µm
10
W//mm 2
1,0x10 6
20
W//mm 2
30
W//mm 2
40
W//mm 2
8,0x10 5
50
W//mm 2
100
W//mm 2
150
W//mm 2
200
W//mm 2
6,0x10 5
250
W//mm 2
300
W//mm 2
350
W//mm 2
4,0x10 5
400
W//mm 2
450
W//mm 2
500
W//mm 2
5
2,0x10
0,0
600
650
700
N orm. emission integ rals [a.u]

Wavelength [nm]

Observations

No saturation up to 500 W/mm 2

No s ectral chan e

p

g

For comparison Osram Ostar ~ 50 W/mm

2

P In Norm. emission integrals [a.u]
P
In
Norm. emission
integrals [a.u]

1,0

0,8

0,6

0,4

0,2

0,0

LiE Mo O u 2 8 Ideal YAG:Ce U728 0 100 200 300 400 500
LiE Mo O
u
2
8
Ideal
YAG:Ce U728
0
100
200
300
400
500

Laser

Exc. density [W/mm 2 ]

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 33

4 Converter Materials for LED . Eu 3 + doped Molybdates - Li 3 Ba
4 Converter Materials for LED . Eu 3 + doped Molybdates - Li 3 Ba
4 Converter Materials for LED . Eu 3 + doped Molybdates - Li 3 Ba

4 Converter Materials for LED

.

Eu 3+ doped Molybdates - Li 3 Ba 2 (Gd,Eu) 3 Mo 2 O 8 with cation disorder

Ba 2 (Gd,Eu) 3 Mo 2 O 8 with cation disorder Site a CN = 10
Ba 2 (Gd,Eu) 3 Mo 2 O 8 with cation disorder Site a CN = 10
Ba 2 (Gd,Eu) 3 Mo 2 O 8 with cation disorder Site a CN = 10

Site a CN = 10 (Ba, Gd) “bicapped square antiprism”

Site b CN = 8

(Ba, Li, Gd)

“ distorted

cubic”

Unit cell of Li 3 Ba 2 Gd 3 (MoO 4 ) 8 typical for Ln = La - Gd Crystal system: Monoclinic Space group C2/c, Z = 2 Density = 5.14 g/cm 3

Unit cell parameter for Ln = Gd

a = 5.238 Å

b = 12.758 Å

c = 19.151 Å

ß = 91.13°

4 Converter Materials for LED . Eu 3 + doped Molybdates - Li 3 Ba
4 Converter Materials for LED . Eu 3 + doped Molybdates - Li 3 Ba
4 Converter Materials for LED . Eu 3 + doped Molybdates - Li 3 Ba

4 Converter Materials for LED

.

Eu 3+ doped Molybdates - Li 3 Ba 2 (Gd,Eu) 3 Mo 2 O 8 with cation disorder

Ba 2 (Gd,Eu) 3 Mo 2 O 8 with cation disorder Both photographs taken upon 395

Both photographs taken upon 395 nm excitation

Material

Optical band gap [eV]

Source

Li 3

Ba 2 La 3 (MoO 4 ) 8

3.7

From own Tauc-Plot Phys. Rev. B 57 (1998)

Ca 8 (MoO 4 ) 8 = CaMoO 4

3.4

y 4 Converter Materials for LED . Eu 3 + doped Molybdates - Li 3
y 4 Converter Materials for LED . Eu 3 + doped Molybdates - Li 3
y 4 Converter Materials for LED . Eu 3 + doped Molybdates - Li 3

y

4 Converter Materials for LED

.

Eu 3+ doped Molybdates - Li 3 Ba 2 (Gd,Eu) 3 Mo 2 O 8 with cation disorder

CIE 1931 Colour Points

Quantum efficiency upon 395 nm exc.

0,9

0 8

,

0,7

0,6

0,5

0,4

0,3

0,2

0,1

0,0

2000 K 100 K Li 3 Ba 2 La 3-x Eu x (MoO 4 )
2000 K
100
K
Li 3 Ba 2 La 3-x Eu x (MoO 4 ) 8
Li 3 Ba 2 La 3-x Eu x (MoO 4 ) 8
520
530
90
K 3000
4000
K
540
0
80
6000
550
560
70
10 000 K
LuAG:Ce
570
60
YAG C
:
e
580
(Sr,Ca) 2 SiO 4 :Eu
50
590
600
x
40
630
490
6
CaS:Eu
30
20
480
10
470
460
420
0
Q uantum efficie ncy [%]
x
= 0.3
x
= 0.6
x
= 0.9
x
= 1.2
x
= 1.5
x
= 1.8
x
= 2.1
x
= 2.4
x
= 2.7
x
= 3.0

0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

10

20

30

40

50

60

70

80

90

100

x

Eu 3+ concentration [%]

A. Katelnikovas, A. Kareiva, T. Jüstel, J. Mater. Chem. 22 (2012) 22126

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 36

4 Converter Materials for LED . Phosphor converted LED comprising a Li 3 Ba 2
4 Converter Materials for LED . Phosphor converted LED comprising a Li 3 Ba 2
4 Converter Materials for LED . Phosphor converted LED comprising a Li 3 Ba 2

4 Converter Materials for LED

.

Phosphor converted LED comprising a Li 3 Ba 2 Eu 3 (MoO 4 ) 8 ceramic

a Li 3 Ba 2 Eu 3 (MoO 4 ) 8 ceramic 455 nm InGaN LED

455 nm InGaN LED

2 Eu 3 (MoO 4 ) 8 ceramic 455 nm InGaN LED 380 nm InGaN LED

380 nm InGaN LED Full conversion LED

nm InGaN LED 380 nm InGaN LED  Full co nv ersion LED Prof. Dr. T.

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 37

4 Converter Materials for LED . Synthesis of (Tb 1 - x Eu x )
4 Converter Materials for LED . Synthesis of (Tb 1 - x Eu x )
4 Converter Materials for LED . Synthesis of (Tb 1 - x Eu x )

4 Converter Materials for LED

.

Synthesis of (Tb 1-x Eu x ) 2 Mo 3 O 12 Sensitisation of Eu 3+ by Tb 3+ at 487 nm

Tb O

4

7

+ Eu 2 O 3

+ MoO 3

by Tb 3 + at 487 nm Tb O 4 7 + Eu 2 O 3

Milling

3 + at 487 nm Tb O 4 7 + Eu 2 O 3 + MoO

1 st firing step

7 + Eu 2 O 3 + MoO 3 Milling 1 s t fi ring st

900 °C / 10 h

air

Reduction: Tb 4 O 7 + MoO 3 2 Tb 2 Mo 3 O 12 + ½ O 2

Regrinding

→ 2 Tb 2 Mo 3 O 1 2 + ½ O 2 Regrinding 2 n
→ 2 Tb 2 Mo 3 O 1 2 + ½ O 2 Regrinding 2 n
→ 2 Tb 2 Mo 3 O 1 2 + ½ O 2 Regrinding 2 n

2 nd firing step 900 °C / 10 h air

O 2 Regrinding 2 n d firing step 900 °C / 10 h air (Tb 1

(Tb 1-x Eu x ) 2 Mo 3 O 12

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 38

4 Converter Materials for LED . Phase analysis of (Tb 1 - x Eu x
4 Converter Materials for LED . Phase analysis of (Tb 1 - x Eu x
4 Converter Materials for LED . Phase analysis of (Tb 1 - x Eu x

4 Converter Materials for LED

.

Phase analysis of (Tb 1-x Eu x ) 2 Mo 3 O 12 samples (x = 0.0 – 1.0)

Tb 2 Mo 3 O 12 (Tb 0.4 Eu 0.6 ) Mo 3 O 12
Tb 2 Mo 3 O 12
(Tb 0.4 Eu 0.6 )
Mo 3 O 12
2
1,165
(Tb 0.9 Eu 0.1 )
Mo 3 O 12
(Tb 0.2 Eu 0.8 )
Mo 3 O 12
2
2
1,160
1,155
Eu 2 Mo 3 O 12
(Tb 0.6 Eu 0.4 )
Mo 3 O 12
2
1,150
1,145
Tb 2 Mo 3 O 12
ICDD 04-009-6395
Eu 2 Mo 3 O 12
Mater. Res. Bull. (1971) 6, 545
0
20
40
60
80
100
Eu 2 Mo 3 O 12
Tb 2 Mo 3 O 12
Eu 3+ concentration (mol-%)
10
20
30
40
50
60
10
20
30
40
50
60
2
2
cell volu mUnit
e (nm 3 )

Tb 2 Mo 3 O 12 and Eu 2 Mo 3 O 12 form a solid solution with no miscibility gap

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 39

4 Converter Materials for LED . Excitation spectra of (Tb 1 - x Eu x
4 Converter Materials for LED . Excitation spectra of (Tb 1 - x Eu x
4 Converter Materials for LED . Excitation spectra of (Tb 1 - x Eu x

4 Converter Materials for LED

.

Excitation spectra of (Tb 1-x Eu x ) 2 Mo 3 O 12 samples (x = 0.0 – 1.0)

Tb 2 Mo 3 O 12 4 3 2 1 5  = 541 5
Tb 2 Mo 3 O 12
4
3
2
1
5
= 541 5 nm
.
6
em
7
9
8
(a)
(Tb
0.8 Eu 0.2 ) 2 Mo 3 O 12
 em = 615 nm
(b)
27
25
24
Eu 2 Mo 3 O 12
18
26
14
23
 em = 615 nm
29
28
21
22
10
17
13
11
19
16
15
(c)
20
12
250
300
350
400
450
500
550
600
Wavelength (nm)
3+
Excitation Tb 2 Mo 3 O 12 :20% Eu
( em = 615nm)
Intensity (a.u.)
1,4 7 F 0  5 D 2 (Eu 3+ ) 20 %Eu 3+ LED
1,4
7 F 0 5 D 2 (Eu 3+ )
20 %Eu 3+
LED 485 nm
LED 480 nm
1,2
1,0
7 F 6 5 D 4 (Tb 3+ )
0 8
,
0,6
0,4
0,2
0,0
450
460
470
480
490
500
510
520
Normalized Inte nsity [a.u.]

Optimal spectral overlap for 20% Eu and a 480 nm (In,Ga)N c

hi p

3+

Tb 3+ and Eu 3+ levels and transitions

34 5 D 5 F j + 5 I j 5 0 D 32 1
34
5
D
5 F j + 5 I j
5
0
D
32
1
5
G
32
5
2
G
5
3
L
5
6
L
5 H j
30
7
5
G
30
4
5
L
8
5
D
2
5
5 D 4
28
G
28
5
5
5 L
L
10
9
5
G
6
5
5 L 9
L
5
26
10
G
5
26
j
D 3
5 L
8
5 L
7
24
24
5 L 6
5 D 3
22
22
5 D 2
5
D
20
4
20
5 D 1
18
18
5 D 0
16
16
14
14
12
12
10
10
8
8
6
7
6
F
0
7
F
1
7
7 F 6
F
2
4
7
F
4
7 F 5
3
7
F
4
7 F 4
2
7
2
F
7 F 3
5
7 F 2
7 F
1
0
0
7
F 6
7
F 0
Tb 3+
Eu 3+
Wavenu mber x10 -3 [cm -1 ]
1
:
4
8
7
n
m
2
:
3
7
8
n
m
3
:
3
7
1
.
5
n
m
4
:
3
6
3
-
3
6
9
n
m
5
:
3
5
9
.
5
n
m
6
:
3
4
8
-
3
5
5
n
m
7
:
3
3
6
-
3
4
5
n
m
8
:
~
3
2
6
n
m
9
:
3
1
9
n
m
1
Waven umber x10 -3 [cm -
]
1
1
:
5
8
0
n
m
,
1
4
:
5
2
6
.
5
n
m
,
1
8
:
4
6
5
n
m
,
2
2
:
4
1
5
.
5
n
m
2
3
:
3
9
8
-
4
0
2
n
m
,
2
4
:
3
9
4
n
m
,
2
5
:
3
7
1
-
3
9
0
n
m
,
2
7
:
3
6
2
.
5
n
m
2
8
:
3
1
5
-
3
3
2
n
m
,
2
9
:
2
9
7
-
3
0
6
n
m
1
0
:
5
9
0
.
5
n
m
,
1
3
:
5
3
5
n
m
,
1
7
:
4
7
3
n
m
,
2
1
:
4
1
9
n
m
,
2
6
:
3
6
6
.
5
n
m
1
2
:
5
5
3
n
m
,
1
6
:
4
8
7
n
m
,
2
0
:
4
2
7
n
m
1
5
:
5
1
2
.
5
n
m
,
1
9
:
4
4
7
.
5
n
m

Wavelength [nm]

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany

Slide 40

4 Converter Materials for LED . Luminescence decay of (Tb 1 - x Eu x