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
p Technologies,
g , FH Münster

16th Austrian Chemistry Days, Innsbruck, Austria

@SSeptember
b 22ndd, 2015
201
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 Berlin
 Na lamps
Even 23 years after Germany’s reunification
East and West Berlin can be diminished by lighting
1989 End of the Berlin Wall “The
The wind of change”
change West Berlin
1990 Germany’s reunification  Hg lamps
1993 Blue LED
1996 White LED
2014 White LED > 300 lm/W
2015 25th Anniversaty of Germany’s reunification “The light of change”
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 2
 Outline
1. Inorganic LED

2. Some Basics of Luminescent Materials

3. Tuning Lanthanide Luminescence

4 Converter Materials for LED

4.

5. Towards Ultimate Efficiency and CRI

6. (New) Applications of LED Light Sources

7. Summary and Outlook

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 3

 1. Inorganic LED - Timeline
1970 1995 2020

Driving forces: Light yield, power density, lifetime, light quality, design
Green to red and NIR LEDs White inorganic and organic LEDs High performance
LED and
LEDs d laser
l di d
diodes

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 4

 1. Inorganic LED - Status Quo 2015

Semiconductor systems Technical Data

(Al1-xGa
G x)N UV-C/B/A
UV C/B/A up to 5 W
(In1-xGax)N UV-A to cyan green up to 8000 lm (CREE)
(Al1-x-yInxGay)P red to NIR 303 lm/W (CREE)
120 – 200 °C
C
100 – 200 W/cm2
2 – 12 K/W

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 5

 1. Inorganic LED - Semiconductors & Spectra
0,35

(Al,In,Ga)P

a.u.]
0,30

on intensity [a
 580 nm – 700 nm 0,25

 Yellow  Orange  Red 0,20

0 15
0,15

Emissio
(In,Ga)N 0,10

 370 – 530 nm 0,05

 UV-A  Blue  Green 0,00

400 450 500 550 600 650 700 750

650
Wavelength [nm]
(Al,Ga)N In1-xGaxN

m]
avelength [nm
600
 210 – 370 nm
 UV-C  UV-A
550

500

Emission wa
Today all emission colours and white light 450

is directly accessible by 400

 Multichip p LED lamps

p 350
0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
 Converter materials (phosphors) InN
Ga fraction / mol-%
GaN

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 6

 1. Inorganic LED - White Light Sources
Multichip LED Lamps
• Narrow band emitter e.g.
g LEDs
– ½ = 30 nm 99.5
– Several colored LEDs 99 5 LED
98 4 LED
95

Color renderring index

x
• Theoretical
Th ti l maximum
i 3 LED
– 430 lm/W for 90 2 LED
– CCT = 4870 K 80
– CRI = 3 (!) 70
60 Source: Zukauskas, A., et. al..,
50 "Optimization of white polychromatic

• Feasible values 40 semiconductor lamps", Applied

Physics Letters 80 (2002) 234-6
30
– ~ 350 lm/W
l /W for
f CRI 90
90, n = 3 - 4
20
– max. 320 lm/W for CRI 99, n = 5
10
• Problems 5
– Thermal stability of the LEDs 0
300 350 400 450
– LED efficiency
Luminous efficacy [lm/W]
• Red and blue high
• Green moderate
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 7
 1. Inorganic LED - White Light Sources
“Phosphor Converted” (pc) LED

Phos-
phor

Contact
Plastic
lens
((In,Ga)N-
, )
semicon-
Gold wire ductor

Heat sink (Cu)

(Al,In,Ga)N
(Al In Ga)N Semiconductor Luminescent screen LED lamp spectrum
Blue 420 – 480 nm Yellow Cool-white
Yellow + red Warm-white
Green + red Cool & warm-white
Near UV 370 – 420 nm Blue + green + red Cool & warm-white
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 8
 1. Inorganic LED - White Light Sources
Wall Plug Efficiency (WPE) of pcLEDs >> Discharge lamps
I G N LED
InGaN (Y Gd)3Al5O12:Ce
(Y,Gd) C 70
1,0

60 Tc = 5270 K CRI = 82
sionsintensitätt [a.u.]

0,8 Tc = 4490 K CRI = 79

Emissiion intensiity
50
T = 4110 K CRI = 76
Tc
0,6 40 Tc = 3860 K CRI = 73
30
Tc = 3540 K CRI = 70
0,4
Emiss

20
0,2
Blaue Gelber 10

LED Leuchtstoff
0,0 0
400 450 500 550 600 650 700 750 800
400 500 600 700 800
Wellenlänge [nm] Wavelength [nm]
Status quo cool white phosphor converted LEDs @ 2015
• Yellow pphosphors
p garnets ((Y,Gd,Tb))3Al5O12:Ce3+
g
ortho-silicates (Ca,Sr,Ba)2SiO4:Eu2+
• Luminous efficacy LE 300 lm/W! (WPE > 80%)
• Colour rendering index CRI 70 - 80
• Correlated colour temp. CCT > 5000 K
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 9
 1. Inorganic LED - White Light Sources
Enhancement of CRI of pcLEDs
4

1.2
(In,Ga)N LED Y3Al5O12:Ce Red Eu2+ phosphor 4
JAZZ 3300K
4
BB 3300K
4
1
4

0.8 4

4
0.6
4

0.4 5

0
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 Eu2+ activated fluorescent, CCT=3600 K

• Luminous efficacy LE 80 - 150 lm/W

• Colour rendering index CRI 85 – 95
• Correlated colour temp. CCT 2500 - 4000 K
R. M
R Mueller-Mach,
ll M h G.O.G O Mueller,
M ll P.J.P J Schmidt,
S h idt T.
T Jüstel,
Jü t l 400 450 500 550 600 650 700 750
nm
800

Red Deficiency Compensating Phosphor LED, Light Emitting Device, US Patent 20030006702
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 10
 1. Inorganic LED - White Light Sources Eu2+ Tb3+ Mn2+ Ln3+ Mn4+

Causes for the reduction in luminous efficacy

W]
y [ lm/W
1. Spectral interaction due to re-absorption
2. Reduction in lumen equivalent

„Waste“  [ nm ]
Band width [nm] Position (nm) LE (lm/W) Red LED Phosphor
90 - 120 635 257 (Ca,Sr)S:Eu
(Ca Sr Ba)2Si5N8:Eu
(Ca,Sr,Ba)
(Ca,Sr)AlSiN3:Eu

20 – 30 655 278 Mg2TiO4:Mn4+

20 – 30 620 320 Ln3+ activated

(Ln = Pr, Sm, Eu)
Mn4+ activated

50 – 60 655 269 Eu2+- activated

50 – 60 620 300 Eu2+- activated

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 converts
absorbed energy into electromagnetic radiation beyond thermal equilibrium

Host Matrix
• Cation sites for activator/sensitiser:
y
Coordination number, symmetry, y rigidity
g y
• Optical band gap
• Phonon spectrum
Eu2+
Dopants
• Type of optical transitions: Line width Eu2+
absorption cross section, decay time Eu2+
• Linearity
y & Excited state absorption
p Mn2+
VO
Impurities and Defects
• Concentration quenching
• Afterglow and colour center formation

Particle‘s Surface
• Surface p potential and morphology
p gy
• 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
Photoluminescence spectra Photoluminescence (PL) Decay curves of
spectra of Mg2TiO4:Mn SrSi2N2O2:Eu
1,0 PRO-2009-AB-012 ex307nm T=100.00 K

Colour point (stability)

Intensity [counts]
PRO-2009-AB-012 mon656nm 656 nm T=150.00 K
1000 T=200.00 K
T=250.00 K
0,8 T=300.00 K

u.]
T=350 00 K
T=350.00

Relative intensity [a.u

T=400.00 K
Lumen equivalent 0,6 100
T=450.00 K
T=500.00 K

Reflection spectrum
0,4

10
02
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-Dependence of integral PL Linearity of YAG:Ce
Thermal quenching of some typical phosphors and LiEuMo2O8
1,0 LiEuMo2O8
Ideal

als [a.u]
YAG:Ce U728
y ((saturation))
Linearity 0,8

Norm. emission integra

0,6

Refractive index (dispersion) 0,4

0,2

……
0,0
0 100 200 300 400 500

Exc. density [W/mm2]

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 13

 2. Some Basics of Luminescent Materials
Lanthanide luminescence based on
4f-4f transitions by
y Dieke diagram
g
Shielding of 4fn electrons
by outer filled 5s and 5p shells
 no shift of excited state parabola
and strong zero-phonon lines (ZP)

1) Sharp
Sh li
lines (atomic
( t i like
lik spectra),
t )
Stokes shift ~ 0 cm-1
2) Little influence of environment on
energy level scheme of the [Xe]4fn
ground state configuration
3) Parity forbidden transitions
(~ms decay
decay, oscillator strength f ~10-55)
 Sensitisation necessary! Ln3+ ion
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 14
 2. Some Basics of Luminescent Materials
5d
Typical line emitter
CT CT
5d CT
5d
Pr3+ Scintillators, laser
5d
Nd3+ Lasers
5d Sm2+/3+ Detectors, storage
5d 5d
Eu3+ Fluorescent lamps
5d
Gd3+ UV lamps
Tb3+ Fluorescent lamps
Dy3+ Security marking
H 3+
Ho L
Laser
Er3+ NIR amplifier
Tm3+ Plasma displays
Yb3+ Laser

Typical band emitter

Ce3+ LEDs, UV Lamps
LEDs
Pr3+ Detectors, UV lamps
Nd3+ UV Lamps
Eu22+ LEDs
Yb2+ Laser
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 15
 3. Tuning Lanthanide Luminescence
Photoluminescence of Eu2+: Configuration [Xe]4f7 isoelectronic to Gd3+
[Xe]4f65d1 2D
J
6I
7/2
3.0x104
c
CFS
000 cm-1 6P
7/2 E
E
cfs
m-1]

Centroid
nergy [cm

0x104
2.0x10
2
Shift
on ~ 340

Stokes
Shift
e Eu2+ Io
En

1.0x104
Free

0.0 [Xe]4f7 8S
7/2
8S
7/2
8S
7/2
8S
7/2
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 16
 3. Tuning Lanthanide Luminescence
Eu2+ Doped Luminescent Pigment Emission Band Maximum [nm]
KMgF3:Eu 359 (line)
SrB4O7:Eu 368
BaSO4:Eu 374
Sr2P2O7:Eu 420
BaMgAl10O17:Eu 453
SrSiAl2O3N:Eu 480
Sr4Al14O25:Eu 490
BaSi2N2O2:Eu 490
Ba2SiO4:Eu 505
SrAl2O4:Eu 520
SrGa2S4:Eu 535
SrSi2N2O2:Eu 541
Sr2SiO4:Eu 575
Ba2Si5N8:Eu 585
SrS:Eu 610
Sr2Si5N8:Eu 615
CaAlSiN3:Eu 650
CaS:Eu 655
SrSiN2:Eu 700

Rough trend for E: Fluorides < Oxides < Oxynitrides < Nitrides ~ Sulfides
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 17
17
 3. Tuning Lanthanide Luminescence
Eu2+ doped nitrides derived from Sr2Si5N8 (orthorhombic Pmn21): N[4]

1. Change of CFS: Sr2Si5N8:Eu  Ba2Si5N8:Eu

585 nm 625 nm Ba2Si5N8:Eu
1,0
,
Sr2Si5N8:Eu
S 2Si5N8 E

Emission intensity [a.u.]

0,8

0,6

0,4

0,2

0,0
500 550 600 650 700 750 800

Wavelength [nm]

T
Two S sites
Sr it with
ith CN = 10  Broad
B d emission
i i bands
b d

Hoppe, H. A.; Lutz, H.; Morys, P.; Schnick, W.S.; Seilmeier, A. J. Phys. Chem. Solids 2000, 61, 2001
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 18
 3. Tuning Lanthanide Luminescence
Eu2+ doped nitrides derived from Sr2Si5N8 (orthorhombic Pmn21): N[4]

2. Change of centroid shift: Sr2Si5N8:Eu  Sr2Si5-xAlxN8-xOx:Eu

Sr2Si5N8:Eu,Al,O
1,0 Emission spectrum Excitation spectra Emission spectra
Excitation spectrum 1,0 1,0
Reflection spectrum
08
0,8
ative intensity

254 nm exc. 450 nm exc. Si,N ---> Al,O

0,6 QE = 83.6% 90.2%
RQ = 4.4% 11.5%
LO = 0.754 0.798
qr 0,5 0,5 
Rela

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 0,0 0,0

100 200 300 400 500 600 700 800 300 400 500 600 700 800
Wavelength [nm] Wavelength [nm]

T. Jüstel, W. Mayr, P.J. Schmidt, H. Höppe, W.S. Schnick, European Patent EP02102752.9
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 19
 3. Tuning Lanthanide Luminescence
Eu2+ doped nitrides derived from Sr2Si5N8 (orthorhombic Pmn21): N[4]

3. Change of centroid shift

Sr2Si5N8:Eu  SrSi2O2N2:Eu (triclinic P1) 1,0 100

Emission spectra
0,8 Excitation spectra 80
Reflection spectra
max= 542 nm
centroid= 536 nm

Reflectance [%]
R
Intensity [a.u]]
0,6 x = 0.352, y = 0.614 60
LE = 553 lm/W
R450 nm= 32%
QE = 81%
0,4 40

0,2 20

0,0 0
250 300 350 400 450 500 550 600 650 700 750 800

Four Sr sites with CN = 6 (+1) Wavelength [nm]

V. Bachmann, T. Jüstel, A. Meijerink,

C R Ronda,
C.R. Ronda P
P.J.
J Schmidt
Schmidt,
J. Luminescence 121 (2006) 441
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, QErel(200 °C) > 0.95)
(In,Ga)N LED + SrSi2N2O2:Eu + Sr2Si5N8:Eu
Colour rendering index > 88
Excellent colour p
point stability
y
3.00E-06 with drive is achieved
Drive
at 25 °C
2.50E-06 5000
1.11E-01
4500 99
4.75E-01 4000 97
2.00E-06
1.30E+00 3500 95
1.92E+00 3000

CCT, K
1.50E-06 2500 93

Ra
2.78E+00
2000 91
4 09E+00
4.09E+00
1.00E-06 1500 89
1000
500 87
5.01E-07
0 85
0 1 2 3 4 5
1.00E-09 Current , A (pulsed)
380 430 480 530 580 630 680 730 780
CCT_25C CCT_125C Ra_25C Ra_125C

R Mueller
R. Mueller-Mach,
Mach G.O.
G O Mueller,
Mueller M
M.R.
R Krames
Krames, HH.A.
A Höppe
Höppe, F.
F Stadler,
Stadler WW.S.
S Schnick
Schnick, T
T. Jüstel
Jüstel, P
P.J.
J Schmidt
Schmidt,
All Nitride White Light Emitting Diodes, Phys. Stat. Sol. A 202 (2005) 1727
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 21
 4. Converter Materials for LED
Inorganic Phosphors Simplified energy
level scheme of Eu2+
Garnets  Ce3+ Typical spectra of Eu22+ phosphors
(Y,Gd,Tb)3Al5O12:Ce 1,0

Lu3Al5O12:Ce

n intensity
Lu3(Ga,Al)5O12:Ce 0,8

ormalised emission
(Lu,Y)3Sc2Al3O12:Ce 0,6

(Y,Lu)3(Al,Mg,Si)5O12:Ce
Ca(Y,Lu)2Al4SiO12:Ce 0,4

No
0,2
Ortho-Silicates  Eu2+
(Ca,Sr,Ba)2SiO4:Eu 0,0
300 400 500 600 700 800
(Ca,Sr,Ba)3SiO5:Eu Wavelength [nm]

(Oxy)Nitrides  Eu2+ or Ce3+

(Sr,Ca,Ba)2Si5N8:Eu „2-5-8“
(Sr,Ca,Ba)Si2N2O2:Eu „1-2-2-2“
„1 222
(Ca,Sr)AlSiN3:Eu,O „1-1-1-3“
(Ca,Sr,Ba)SiN2:Eu „1-1-2“
La3Si6N11:Ce „3-6-11“
B 3Si6O12N2:Eu
Ba E
,ß-SiAlONes:Eu
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 22
 4. Converter Materials for LED
Narrow band red emitter MII[Mg3SiN4]:Eu2+

Novel siliconitrides: Ca[Mg3SiN4]:Ce3+, Sr[Mg3SiN4]:Eu2+, and Eu[Mg3SiN4]“

Problem: Stability towards hydrolysis and thermal quenching

W.S. Schnick et al., Chem. Mater. 26 (2014) 2712−2719

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 23
 4. Converter Materials for LED
Narrow band red emitter Sr[LiAl3N4]:Eu2+

Claimed as next generation LED-phosphor material”

Synthesis
LiAlH4 + (1-x) SrH2 + x EuF3 + 2 AlN + N2
 (Sr1-xEux)[LiAl3N4] + 3x HF + (3-x) H2
RF-Furnace, 1000 °C

Optical Properties
max = 651 nm for 5% Eu2+
FWHM = 1180 cm-1
QE(200 °C) > 95%rel. to QE(RT)
Decay y time of Eu2+ ~ 1.1 µ
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

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 24
 4. Converter Materials for LED
Red-emitting line emitter
K2MF6:Mn (M = Si, Ge, Ti) Warm white pcLED
1,0 Emission spectrum 1,0 CCT = 3000 K
Excitation spectrum Blue chip + YAG:Ce + K2SiF6:Mn
631 nm
0,8 0,8

y [a.u.]
nsity
Relative inten

Relative intensity
06
0,6 0,6

0,4 0,4

0,2 0,2

0,0 0,0
250 300 350 400 450 500 550 600 650 700 750 800
400 500 600 700 800
Wavelength [nm]
Wavelength (nm)

LED Chip
p Blue 420 – 480 nm
Converter Yellow (Y,Gd,Tb,Lu)Al5O12:Ce
Red Mn4+- phosphors
Typical yellow/red blend Tb3Al5O12:3%Ce + K2[MF6]:Mn4+
Problems Absorption strength, linearity, and stability of Mn4+
MnF4  MnF2 + F2

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

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 25
 4. Converter Materials for LED
Requirements to the „ideal“ red phosphor
• Emission wavelength
g ~ 610 – 630 nm
• QE(RT) > 90% and QE(150 °C) > 80%
• Strong absorption at 410 nm and 450 nm
• T1/2 > 200 °C
• V(λ) weighed brightness value > 60% relative to (Ca,Sr)AlSiN3:Eu,O
• Narrow FWHM
• Decay time < 10 ms
• No saturation to 100 W/mm2
• High (photo)chemical and thermal stability
Activator Spectral range Lumen equivalent Decay Efficiency Absorption
[nm] [lm/Wopt] time  at 450 nm exc.
RE-Ions
Eu2+ 360 - 700 50 – 550 ~ 1 µs high strong
Eu 3+ 590 - 710 200 – 360 ~ 1 ms high weak
Sm3+ 560 - 710 240 – 260 0.5 ms moderate weak
Pr 3+ 590 - 680 100 – 220 0.1 ms moderate - high weak
TM-Ions
Mn2+ 500 - 650 100 - 550 5-15 ms high weak
Mn 4+ 620 - 680 80 – 230 1-10 ms high moderate
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 26
 4. Converter Materials for LED
CaAlSiN3:Eu (Mitsubishi Chemicals)
Remaining Challenges 1,0
6
[Xe]4f 5d
1

7
- [Xe]4f

Normalised intensity [a.u..]

0,8

• Red narrow band or line emitter 0,6

 to increase lumen equivalent 0,4

,

0,2

• Reduced re-absorption Emission spectrum

Excitation spectrum

 to increase package gain

0,0
300 400 500 600 700 800

Wavelength [nm]
3+
NaGdW2O8:Eu (60%)

Red emitting ion LE [lm/W] 1,0 Emission spectrum

Excitation spectrum
QE465 = 48.1%
RQ465 = 75.8%

E 2+
Eu 80 - 200 QE394 = 54.8%

d intensity [a.u.]
0,8
RQ394 = 63.5%
x = 0.668

Eu3+ 220 – 360 0,6

y = 0.331
LE = 268 lm/W
max = 616 nm

Normalised
0,4 centroid= 627 nm

Sm3+ 240 – 260

0,2

Pr33+ 200 – 220 0,0

300 400 500 600 700 800
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 emission
Pr3+ Sm3+ Eu3+
30 30 30

Near UV LED 5
D3
03 cm-1

03 cm-1

03 cm-1
3
Blue LED 5
D2
20 P1 20 20 5
4
D
G5/2 5 1
D0
Energy / 10

Energy / 10

Energy / 10
1
D2

6
1 F11/2
10 G4 10 10
1
F4 3
F2
3 6 7
H6 H11/2 F6
3
H5
3 6 7
0 H4 0 H5/2 0 F0
Pr (III) Sm (III) Eu (III)

Problems concerning the application in pcLEDs

• Position of the charge-transfer
g and 4f5d transitions E >> 30000 cm-1
• 4f-4f transitions of Eu3+ are spin- and parity forbidden  < 100 cm-1
Strategies to enhance absorption strength in the near UV or blue spectral range
• Activator concentration Increase to 100% if no conc. quenching occur
• Organic sensitisers Polycyclic aromatics (-* transitions)
• Inorganic sensitisers VO43-, MoO66-, WO66- (CT),Sm2+, Eu2+ (4f5d), Tb3+ (4f4f)
• Covalent interaction Eu3+ coordinated by polarisable anions
• E h
Enhance spectral
t l width
idth M lti l activator
Multiple ti t sites,
it cation
ti di
disorder
d
• Increase interaction length 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 Eu3+

Pb(Mo,W)O4 Wulfenite (yellowish)

C (M W)O4 = Ca
Ca(Mo,W)O C 2(Mo,W)
(M W)2O8 S h lit
Scheelite Ln2(Mo,W)O
L (M W)O6 3 sites
it (8,8,8)
(8 8 8)
Ln2(Mo,W)2O9 2 sites (8,9)
Ln2((Mo,W)
, )3O12 1 site ((8))

ALn(Mo,W)2O8 A4Ln4(Mo,W)8O32 Ln2Mo3O12

1 site
it (8) 2 sites
it (8(8,10)
10)

1st example
p 2nd example
p 3rd example
p
LiGd1-xMo2O8:Eux Li3Ba2Gd3-xMo8O32:Eu3x (Gd1-xTbx)2Mo3O12:Eu
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 29
 4. Converter Materials for LED
Eu3+ doped Molybdates - LiEuMo2O8 a phosphor with cation disorder
1,0
Luminescence spectra T dependent integral emission intensity
T-dependent 6
Emission spectrum 5x10
Excitation spectrum
5% Eu3+ Integral intensity
0,8
ntensity

6
4x10

nts]
0,6
Normalised in

on maxima [Coun
6
0,4 3x10

0,2
6
2x10

Emissio
0,0
250 300 350 400 450 500 550 600 650 700 750

1,0
Wavelength [nm] 6
1x10

100% Eu3+
0
Normalized Intensity

100 200 300 400 500

Temperature [K]

QE465 ~ 100% LE = 269 lm/Wopt

0,5

R465 = 75% max = 614 nm

R395 = 60% centroid = 623 nm
CIE x = 0.665 1/e = 0.39 ms (0.2 x Y2O3:Eu)
0,0
250 300 350 400 450 500 550 600 CIE y = 0.333 d50 = 4.2 µm
• Wavelength [nm]

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(MoO4)2 doped with Yb”, J. Opt. Soc. Am. B 22 (2006) 1083

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 30

 4. Converter Materials for LED
Eu3+ doped Molybdates - LiEuMo2O8 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 c2-ceramics ~ 200 – 300 µm

395 nm 465 nm
LED LED
1,0
LiEuMo2O8
LED Max = 394 nm
0,8 LED Max= 464 nm
u.]
Intensity [a.u

0,6

0,4

0,2

0,0
250 300 350 400 450 500 550
Wavelength [nm]

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 31

 4. Converter Materials for LED
Eu3+ doped Molybdates - LiEuMo2O8 a phosphor with cation disorder
CConversion of the ppowders into “single
g crystals”
y to reduce
scattering and to enhance interaction length (5 µm mm)
1,0

Crystals grown by Czrochalski

0,8

0,6
PL 5 7
D0- F2
bright sample SQUID
violett sample

l
long-term
t short-term
h tt

Intensity [normiert]
5 7
D0- F4

0,10

„violet“ „bright “
5 7
0,05 D0- F1 5 7
D0- F3

0,00
580 600 620 640 660 680 700 720
Wavelength [nm]

g-factor
151Eu Mößbauer 10,0 6,0 4,0 3,0 2,5 2,0 1,5

bright sample
2,0
violet sample
1,5

1,0

dX"/dB
0,5

0,0

-0,5

-1
1,0
0

-1,5 X-band EPR

100 200 300 400 500

B-field [mT]

Conclusion: Formation of MoV 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, LiEuMo2O8 - 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
Eu3+ doped Molybdates - LiEuMo2O8 a phosphor with cation disorder
 Saturation at high excitation density? Emission spectra (HEL-2006-DU292) LiEuMo O Energy
gy [[eV]]
2,3 2,2 2,1 2 1,9
2 8
1,8 1,7

Exc. 375 nm diode laser

1,0x106 10 W//mm2
Exc. spot diameter 11µm 20 W//mm2

N o rm . em ission in te g ra ls [a .u]
30 W//mm2

Type YAG:Ce LiEuMo2O8 8,0x105

40 W//mm2
50 W//mm2
100 W//mm2

em 545 nm 615 nm 6,0x105

150 W//mm2
200 W//mm2
250 W//mm2

exc 445 nm 375 nm

300 W//mm2

POut 4,0x105
350 W//mm2
400 W//mm2

1/e 65 ns 390 µs
450 W//mm2
500 W//mm2
/e 0 105
22,0x10

Pin 30 kW/mm2 5 W/mm2

(saturation expected)
0,0
600 650 700
Wavelength [nm]

10
1,0 LiEuMo2O8

Observations Ideal

N o rm . e m iss io n in te g ra ls [a .u ]
YAG:Ce U728
0,8

No saturation up to 500 W/mm2

No spectral change
0,6

0,4

For comparison PIn 0,2

Osram Ostar ~ 50 W/mm2 0,0

0 100 200 300 400 500

Laser Exc. density [W/mm2]

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 33
 4. Converter Materials for LED
Eu3+ doped Molybdates - Li3Ba2(Gd,Eu)3Mo2O8 with cation disorder
Site a
CN = 10
(Ba, Gd)
“bicapped
square
antiprism”

Site b
CN = 8
(Ba, Li, Gd)
“di t t d
“distorted
cubic”
Unit cell of Li3Ba2Gd3((MoO4)8 Unit cell p
parameter for Ln = Gd
typical for Ln = La - Gd a = 5.238 Å
Crystal system: Monoclinic b = 12.758 Å
Space group C2/c, Z = 2 c = 19.151 Å
Density = 5.14 g/cm3 ß = 91.13°
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 34
 4. Converter Materials for LED
Eu3+ doped Molybdates - Li3Ba2(Gd,Eu)3Mo2O8 with cation disorder

Both photographs
taken upon
395 nm excitation

Material Optical band gap [eV] Source

Li3Ba2La3(MoO4)8 3.7 From own Tauc-Plot
Ca8(MoO4)8 = CaMoO4 34
3.4 Phys Rev.
Phys. Rev B 57 (1998)
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 35
 4. Converter Materials for LED
Eu3+ doped Molybdates - Li3Ba2(Gd,Eu)3Mo2O8 with cation disorder

CIE 1931 Colour Points Quantum efficiency upon 395 nm exc.

0,9 100
520 Li3Ba2La3-xEux(MoO4)8 Li3Ba2La3-xEux(MoO4)8
530
0,8
08 90
540
0
0,7 550 80

ency [%]
560 70
0,6 LuAG:Ce 570
0
YAG:Ce 60

uantum efficie
0,5 580
(Sr,Ca)2SiO4:Eu
y

590 50
0,4 30 20 600 x
40 00 00 40
00 K K
0,3 490 60 K 630
00 6
10 K CaS:Eu 30

Qu
00
0
0,2 K
20

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
480
0,1 10
470
460
0,0 420 0
00
0,0 01
0,1 02
0,2 03
0,3 04
0,4 05
0,5 06
0,6 07
0,7 10 20 30 40 50 60 70 80 90 100
x 3+
Eu 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 Li3Ba2Eu3(MoO4)8 ceramic

455 nm InGaN LED

380 nm InGaN LED

 Full
u co
conversion
e s o LED

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 37

 4. Converter Materials for LED
Synthesis of (Tb1-xEux)2Mo3O12  Sensitisation of Eu3+ by Tb3+ at 487 nm
Tb4O7
1st firing
fi i step
t
+ Eu2O3 Milling Regrinding
900 °C / 10 h air
+ MoO3

Reduction: Tb4O7 + MoO3 → 2 Tb2Mo3O12 + ½ O2

2nd firing step

900 °C / 10 h air

(Tb1-xEux)2Mo3O12
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 38
 4. Converter Materials for LED
Phase analysis of (Tb1-xEux)2Mo3O12 samples (x = 0.0 – 1.0)

Tb2Mo3O12 (Tb0.4Eu0.6)2Mo3O12

1,165

(Tb0.9Eu0.1)2Mo3O12 (Tb0.2Eu0.8)2Mo3O12

me (nm3)
1,160

Unit cell volum

1,155

(Tb0.6Eu0.4)2Mo3O12 Eu2Mo3O12

1,150

1,145
Tb2Mo3O12 Eu2Mo3O12
ICDD 04-009-6395 Mater. Res. Bull. (1971) 6, 545 0 20 40 60 80 100
Tb2Mo3O12 Eu2Mo3O12
Eu3+ concentration (mol-%)

10 20 30 40 50 60 10 20 30 40 50 60
2 2

Tb2Mo3O12 and Eu2Mo3O12 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 (Tb1-xEux)2Mo3O12 samples (x = 0.0 – 1.0)
Tb3+ and Eu3+ levels and transitions
Tb2Mo3O12 4 3 2 1
5
em= 541.5
541 5 nm 6
34
5
9 8 7
5
5
D0 F j + 5I j
D
32 5 1
G 32
(a) 5 2
G
5 3
L
5 6
5
Hj
L
30 5 7
G 30
(Tb0.8Eu0.2)2Mo3O12
Intensity ((a.u.)

5 4
L
5 8 5
D D4
em= 615 nm 28 5 2
G5
5
L9
28 5
L10
5 5
G
5 6
L9
26 L 5
Gj
(b) 5 10
D3 26 5
L8
5
L
5 7
27 25 24 24 24 L6
Eu2Mo3O12 18
26 23 14 5
em= 615 nm 29 28 D3
22 21 10 22
17 13 22 5
19 11 D2
15

number x10-3 [cm-11]

(c) 16
20 12 5
D4
20 20

mber x10-3 [cm-1]

5
D1
250 300 350 400 450 500 550 600 18 18
5
D0
Wavelength (nm) 16 16 m
n
5
Excitation Tb2Mo3O12:20% Eu (em= 615nm)
3+ .
m 6
n 6
5 3

Wavenum
14 :

Optimal
O ti l
14 .
2 6

Waven
3+ 6 2
1,4 7 5
F0  D2 (Eu )
3+ 20 %Eu m
n 3
:
,
m
LED 485 nm 5 7 n
m mm .
5 2 9
12 n nn 12 1 , 1

spectral
LED 480 nm 9m55m 4 m 4
m6 n
1,2 54
mmn3n33nm :
2 0
:
1
nn.5-. 5--6n 2 9 2
ensity [a.u.]

781398629 , 3 ,
10 877654331 m -
1 m
4333333~3 10 n 7 n m

overlap for
7 5 3+
1,0 F6  D4 (Tb ) :2
1 :3
:4:5:6
:7:8
:9: 5
6
3
: m
3
7
n
7
4 5 n 4 2
: 2 : 4
8 , 6 7 :
8 8 1 m 0 1 0 m
, n 3
- , 2 n

20% Eu3+
0,8 m 4 7 m ,
n 9 9 n m 5
.
Normalized Inte

5 3 2 5 n 7
.
6 : : 3 7 4
4 9 5 8 4
6 7
F 6 2
5 2 2
, :
3 4 :
9
, :
0,6 7 0 :

and a 480
F 7
4 m m 1 6 1
7 1
F6 1 n n , 1 ,
F2 , 2 2 m , m
7 m 0 3 n m n
4 7
F3 4 F5 n 4
-
3
- 5
. n 5
.
0 8 5 0 3 2
0,4 8 9 1 9 5 1

nm (In,Ga)N
7 7
F4 F4 5 3 3 5 5 5
: : :
8 : :
2 :
5
1 3 2 0
7
F3 1 2 1 1 1
2 7
F5 2
0,2 7
F2

0,0
chip 0
7
0
7
7
F1

F6 F0
450 460 470 480 490 500 510 520
3+
Wavelength [nm] Tb Eu3+
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 40
 4. Converter Materials for LED
Luminescence decay of (Tb1-xEux)2Mo3O12 upon 487 nm excitation
(Tb0.999Eu0.001)2Mo3O12
(Tb0.95Eu0.05)2Mo3O12
a)) L
Low Eu
E 3+ concentration
t ti
ensity [counts]

(Tb0.6Eu0.4)2Mo3O12
3
10
Energy migration over Tb3+ sublattice results
in observation of distinct rise time
102
Emission Inte

b) High Eu3+ concentration

101
No energy migration over Tb3+ sublattice
yields very short rise time & pure Eu3+ PL
100 800 Rate of Tb3+ Eu3+ Energy Transfer
0 1 2 3 4 5 6 ET Linear Fit Curve
700
Time [ms] Eu 150

(Tb0.999Eu0.001)2Mo3O12 600

Transfer Rate [ms-1]

Exponential Fit Curve
µs]
500
s]

Decay Time [µ
Emission Intensity [counts

3 100
10 400

300

200 50
2
10 100

0
0
0 10 20 30 40 50 60
0 10 20 30 40 50 60
101 ET = 287 µs Eu3+ concentration [%]
Eu3+ concentration
Eu = 769 µs

ex = 487 nm, em = 615 nm

Decay curve fitting by
I(t) = A*exp(-t/2) - (B*exp(-t/1) / (1/1-1/2))
0
10
0 1 2 3 4 5 6
Time [ms]

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 41

 4. Converter Materials for LED
Temperature dependence of (Tb1-xEux)2Mo3O12 upon 487 nm excitation
1,0
100 K 100 K
0,9 150 K 300 K
200 K
ensity [a.u.]

0,8 500 K
250 K
0,7
300 K
0,6 350 K

s]
400 K

ensity [~counts
Normalized Inte

0,5
450 K
0,4 500 K
0,3
0,2
580 582 584 586 588 590 592 594
01
0,1 Wavelength [nm]

Inte
0,0
2,3 2,2 2,1 2,0 1,9 1,8 1,7 1,6
(Tb0.6Eu0.4)2Mo3O12
Energy [eV]
1,0
09
0,9
0,8
ntegral [a.u.]

250 300 350 400 450 500 550 600

0,7
Wavelength [nm]
0,6
0,5
Emission In

0,4
Heating to 500 K
0,3
0,2 ex = 487 nm • Less than 40% PL quenching
0,1
TQ½= 596 K ± 29 K • Thermal population of 7F1 and 7F2 levels
0,0
100 150 200 250 300 350 400 450 500 • Red-shift of CT level
Temperature [K]
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 42
 4. Converter Materials for LED
Phosphor converted LED comprising Tb2Mo3O12:Eu(40%)
1,0 465 nm LED 465 nm LED
1,0

s]

Normalized Inten
N
ntensity [~counts
+ Tb2Mo3O12:Eu3+ (40%) ceramic

0,5 0,5

nsity [~counts]
Tb3+
3

Normalized In

465 nm InGaN LED 0,0

400 450 500 550 400 450 500 550 600 650 700 750 800
0,0

Wavelength [nm]
1,0 380 nm LED
1,0
380 nm LED
zed Intensity [~counts]

Norma
+ Tb2Mo3O12:Eu3+ (40%) ceramic

alized Intensity [[~counts]

0,5 0,5
Normaliz

380 nm InGaN LED

 Full conversion 0,0 0,0
360 380 400 420 350 400 450 500 550 600 650 700 750 800
LED poss
possible
be Wavelength [nm]

F. Baur, F. Glocker, T. Jüstel, J. Mater. Chem. C3 (2015) 2054

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 43
 4. Converter Materials for LED
LE and CRI calculations of warm-white phosphor converted LEDs

Phosphors used for calculations

465 nm blue LED (22 nm FWHM) with YAG:Ce and one of

CaAlSiN3:Eu2+ (CAS:Eu2+)
Sr2Si5N8:Eu2+ (Sr258:Eu2+)
SrLiAl3N4:Eu2+
Tb2Mo3O12:Eu3+ (TMO:Eu3+)
Tb2Mo
M 3O12:Sm
S 3+ (TMO:Sm
(TMO S 3+)
Mg14Ge5O24:Mn4+ (MGMn4+)
K2SiF6:Mn4+ (KSF:Mn4+)

All spectra
p set to 2700 K  Luminous efficacy
y ((LE)) & CRI

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 44

 4. Converter Materials for LED
LE and CRI calculations of warm-white phosphor converted LEDs

Tb2Mo3O12:Eu(40%)
gives 20% higher
LE compared
to SrLiAl3N4:Eu

The reduced re-

absorption in Eu3+
phosphor
comprising LEDs
yields a higher
package gain as
well

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 45

 5. Application Areas of LED Light Sources
Signal lighting and traffic lights

• 85 - 90% energy saving by replacing incandescent lamps

• Life time > 5 years

• Longer maintenance intervals

• Lower maintenance costs

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 46

 5. Application Areas of LED Light Sources
Indoor and outdoor lighting
Standard white

LED AArray for

f dynamic
d i
colour lighting optional

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 47

 5. New Applications of LED Light Sources

Eye receptors
• Rods B/W-contrast
• Cones colour perception
• Blue light (pRGC) hormonal control

Visible (blue LED) light influences

• concentration of sleep hormone melatonin
• concentration of stress hormone cortisol
 Attention,
Att ti b
body
d temperature
t t etc.
t
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 48
 5. New Applications of LED Light Sources
Melatonin suppression Light source Luminous efficacy Ratio
Jü
Jüngere Leute
L t Ph t t i h Wirkung
Phototopische Wi k
100
lumin. efficacy
430 nm
80
555 nm photopic circadian and
photopic
g [%]
Relative Wirkung

60 Daylight 6500 K 100 lm/W 2,78

460 nm FL 3000 K 90 lm/W 1,00
40
FL 4100 K 90 lm/W 1,85
Ält
Ältere
20 Leute LED 5500 K >100 lm/W 2,91
(linsen-
korrigiert)
0

 Melanopic lighting by LED lamps

400 450 500 550 600 650 700
Wellenlänge [nm]

Body temperature
Melatonin (sleep hormone)
Cortisol (stress hormone)
Uhrzeit
Awareness

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 49

 5. New Applications of LED Light Sources
New trend: Lighting for healthcare and well-being
Photo therapy
• Vitamin D build up 310 nm
• Acne, eczema, psoriasis, vitiligo treatment 415 nm
• Melatonin suppression 430 nm
• Bilirubin reduction 450 nm
• Pain therapy 453 nm
• Photo dynamic therapy Red/NIR
• Rheumatism treatment NIR
Cosmetic
• Tanning UV-A + UV-B
• Epilation 755 nm
• Wrinkle reduction / Collagen production NIR
• Macule and tattoo removal 694, 1064 nm
Diagnostics
• Endoscopy VIS
• In-vitro and in-vivo fluorescence marker VIS
• Optical imaging NIR
• Photoplethysmography NIR
Surgery
• Laser scalpel 1.06, 10.6 µm
• Eye correction 193, 800 nm
• Caries removal 2.94, 10.6 µm

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 50

 6. Summary and Outlook
White light emitting phosphor converted LEDs in 2015

Many manufacturer Citizen, CREE, Epistar, GE, GLI, Nichia, Osram

Opto, Panasonic, Philips Lumileds, Seoul
Semiconductors, Soraa, Toyoda Gosei, …..
& High efficiency Cool-white: > 200 lm/W
Warm-white > 100 lm/W
Color rendering index 70 – 95
Life time L70 > 10000 h
Design Retrofits for TL, CFL and GLS

Advantage of inorganic LEDs over

Incandescent- and halogen
g lampsp Discharge
g & fluorescent lamps
p
Longer life time Easier to dim
Higher efficacy Better colour rendering
Higher robustness Higher robustness
No IR radiation No UV radiation
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 51
 6. Summary and Outlook
Trend: Increase of colour purity (LCDs) & luminous efficacy (lamps)
10
1,0
RbGd(Si(CN2)4]:Eu3+
 Narrow band or line emitting LED phosphors
1. Little thermal quenching 0,8

2. Reduced photochemical aging 0,6

3. Superior linearity 0,4

ensity [a.u.]
4. Reduced sensitivity towards photoionisation
0,2
Emission (Ex: 375 nm)
Excitation (Em: 618 nm)
 Rigid
Ri id host
h t materials
t i l with
ith high
hi h

Inte
0,0
250 300 350 400 450 500 550 600 650 700 750
thermal conductivity and low defect density Wavelength [nm]

suitable for Eu2+ (narrow band) or Eu3+ (red line) RbGd(Ge(CN ) ]:Eu3+
MK152b RbGd[Ge(CN2)4]:Eu 2 (5%)
4 3+
Energy [eV]
4,5
,5 4 3,5 3 2,5
,5 2
1,0

 Hosts with rigid and defined cation positions 0,8

• Carbonitrides  Sr2Si5N8-[(4x/3)+z]CxO3z/2
• Borosilicates  borophosphates or -germanates
germanates 0,6
,

• Carbodiimides: MILnIII(MIV(CN2)4]:Eu3+ 0,4

sity [a.u.]
0,2

Intens
J M
J. Meyer, T
T. Jüstel,
Jü t l ett al.
l Inorg.
I Ch
Chem. 48 (2010) 2954 Emission (E
(Ex: 373 nm)
Excitation (monitored at 618 nm)

0,0
250 300 350 400 450 500 550 600 650 700 750 800

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Wavelength [nm]
Slide 52
 6. Summary and Outlook
Trend: Increase of power density of (In,Ga)N LEDs and laser diodes

 Laser diodes (LD) take over LED-applications (>40% WPE of LED!)

1. Automotive front lighting (Audi, BMW, Daimler)
2. Laser-TV (LG)
( )
3. Laser-Projectors (Casio, Sony, Texas Instruments)
4. High-power light sources, e.g. spotlights or „Light engines“ with
fibre bundles

 LED: 0.2 - 2 W/mm2 (Luxeon)

 LD: 25 - 40 kW/mm2 (Nichia)

Measures:
• Increase
I off photochemical
h t h i l and d thermal
th l stability
t bilit
• Reduction of ESA and photo ionisation processes
• Increase of thermal conductivity
• Reduction of thermal expansion coefficient (cf. UHP!)
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 53
 6. Summary and Outlook
Trend: Increase of user benefit of light sources!
Lifestyle
Lif t l &
Communication

H lth
Health
User benefitt

Ambience

Environmental compatability
Energy
gy efficiencyy + cost reduction Geometric,, spectral,
p , and
Lighting Life time temporal
Recycling modulation

F th application
Further li ti areas Time

• Agricultural / Biochemical / Medicinal / Photobiology, -chemistry, -technology

• Disinfection or p
purification of water / air / surfaces
• Automotive and communication technology (THz W-LAN)
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 54
 6. Summary and Outlook
Trend: (In,Ga)N LEDs and laser diodes with expanded functionality
3+
Gd3Ga
G 5O12:Cr
C

1. Physiological effects
Emission spectrum (Exc. @ 560 nm)
1,0 Excitation spectrum (Emission monitored @ 726 nm)

Stimulating blood circulation: 700–1000 nm 0,8

Melatonin suppression:
pp 420 nm

normalised Intensity [a.u.]

0,6

Wound healing: ~ 800 nm

0,4

0,2

2. Spectroscopic/sensory function 0,0

250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000

IR spectroscopy Wavelength [nm]

NIR emission + up-conversion of reflected radiation

0,08

sität [a.u.]
3. Data transfer 0,06

L
Locall NIR network
t k

Emissionsintens
0,04

ns-phosphors
700 – 3000 nm
0,02

0,00
300 400 500 600 700 800 900 1000
Wellenlänge [nm]

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 55

 6. Summary and Outlook
Parameters LEDs Laser diodes (LDs)
- Luminous flux > 100 lm > 1000 lm
- Luminous efficacy > 100 lm/W > 100 lm/W
- Colour quality (with converter!) > 80 > 80
- Life time > 20000 h > 10000 h
- Applications Lighting Projection
Medical field Medical field
Signalling equipment Material processing
Photochemistry Communication
Agriculture Automotive
Cosmetics Spectroscopy

C Hurni et al
C. al., Applied Physics Letters
106, 031101 (2015)
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 56
 6. Summary and Outlook ???
Development of light sources is driven by chemistry! Ceramics
Material
Nitrides
control
(In,Ga)N
(Al,In,Ga)P
Garnets
GaAs
Halogen cycle
Rare Earth
MgWO4 & Ph
Phosphors
h
Zn2SiO4:Mn
C, Os, W

1895 1905 1915 1925 1935 1945 1955 1965 1975 1985 1995 2005 2015
Year
Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 57
 Acknowledgement
• Research Group “Tailored Optical Materials“
for synthesis, photographs, spectroscopy, etc.
• University of Tübingen, Germany
Prof. H.-J. Meyer for fruitful discussions
• Vilnius
Vilni s University,
Uni ersit Lith
Lithuania
ania
Prof. A. Kareiva for exchange of students
• Universiteit Utrecht, The Netherlands
Prof A
Prof. A. Meijerink for fruitful discussions
• FEE Idar-Oberstein for FGK Höhr-Grenzhausen
for ceramics and crystals
• BMBF, Merck KGaA Darmstadt,
Philips Lighting Eindhoven, Merz Frankfurt,
Schott Mainz, and DPL Emmerthal for
generous financial support

Prof. Dr. T. Jüstel, Münster University of Applied Sciences, Germany Slide 58