Temperature Dependence of

Optical Properties of
K2Ge4O9:Mn4+ and Rb2Ge4O9:Mn4+

Florian Baur
Institute for Optical Technologies

Steinfurt, June 15th, 2016

Introduction Red Emitting Phosphors

pcLEDs comprising a blue-

emitting LED coated with yellow-
emitting YAG:Ce yield cool white
light.

 high luminous efficacy

 low color rendering index
 no suitable replacement for
incandescent lamps
Adding a red-emitting phosphor
yields warm white light.

 decreased luminous efficacy

 increased color rendering index
 can be a suitable replacement
for incandescent lamps

Images: integral-led.com

June 15th, 2016 Florian Baur 2

Introduction Red Emitting Phosphors
Inorganic LEDs - The quest for a narrow band red emitter

Eu2+  Mn4+  QDots: Cd(S,Se), InP, or CuInS2

Ref.: GE, PGS2016, Newport Beach, CA

June 14th, 2016 Florian Baur and Thomas Jüstel 3

Introduction Red Emitting Phosphors
Most commonly employed red emitter is the broad band emitter Eu2+.

Drawback
Partially emits in the deep red to IR spectral region – „wasted photons“

Luminous Efficacy and CRI vs. Emission Wavelength

350 100
Line emitters such as Eu3+ and
Mn4+ offer superior luminous
300 90
efficacy over band emitters
such as Eu2+ while
250
80 maintaining a high CRI.
LE /lm W-1

CRI
200
70 Drawback
Mn4+ requires highly ionic
150
60
hosts to prevent deep red
emission with low luminous
100
efficacy and CRI.
50
620 630 640 650 660 670 680 690 700
Peak Emission Wavelength /nm
Photoluminescence and energy transfer rates and efficiencies in Eu 3+ activated Tb2Mo3O12
F. Baur, F. Glocker, T. Jüstel, J. Mater. Chem. C, 2015, Advance Article

June 15th, 2016 Florian Baur 4

Introduction Red Emitting Phosphors

Phosphor LE /lm W-1 Peak λem /nm • Efficiency decreases strongly while
color point exhibits no significant
K2SiF6:Mn4+ 196 631.0
shift
K2TiF6:Mn4+ 192 631.8
K2GeF6:Mn4+ 191 632.0 • Deep-red emitting Mn4+ phosphors
are not suitable for lighting
Mg14Ge5O24:Mn4+ 80 658
application
K2Ge4O9:Mn4+ 46 663
Rb2Ge4O9:Mn4+ 38 667
Ca2YNbO6:Mn4+ 15 680
Ca2LaSbO6:Mn4+ 7 699
LaScO3:Mn4+ 7 703

• Deep-red emitting Mn4+ phosphors

might be used for display application

June 15th, 2016 Florian Baur 5

Introduction Mn4+ and Racah Parameters
1.0 1.0
The optical properties of Mn4+
depend mainly on three 0.8
2
E( E) ~ B, C, Dq
0.8

Normalized Intensity /counts

Normalized Intensity /counts

4
E( T1) ~ B, Dq
parameters:
0.6 4
E( T2) ~ Dq 0.6
Crystal Field Splitting Dq
• usually 1.9 – 2.3 ∙ 103 cm-1
0.4 0.4

Racah Parameters B & C

• B: usually 600 – 800 cm-1 0.2 0.2

• C: usually 2800 – 3300 cm-1

0.0 0.0
250 300 350 400 450 500 550 600 650 700 750 800
Wavelength /nm

June 15th, 2016 Florian Baur 6

Introduction K2Ge4O9 and Rb2Ge4O9
• K2Ge4O9 and Rb2Ge4O9 are
isostructural
• Ge3O9 rings form layers connected by
GeO6 octahedra
• Two crystallographically distinct GeO6
octahedra:
• Ge(1) has inversion symmetry
• Ge(4) does not have inversion
symmetry

data taken from:

G.J. Redhammer, G. Tippelt, Acta Crystallogr. C 69 (2013) 995.

• The GeO6 octahedra are slightly

more regular in Rb2Ge4O9
• Na and Li analogues crystallize in
a different structure

June 15th, 2016 Florian Baur 7

Synthesis
a) K2(Ge0.999Mn0.001)4O9

Solid state synthesis: *

K2Ge4O9
ICDD 04-007-2836
A2CO3 + GeO2 + MnC2O4∙2H2O
b) Rb2(Ge0.999Mn0.001)4O9

• Calcination: 600 °C / 2 h
*
Rb2Ge4O9
• Addition of 10 mol% excess ICDD 04-008-7436

KF/Rb2CO3
10 20 30 40 50 60
2
• Annealing: 800 °C / 4 h
1.250
1.240
• Washing in demineralized H2O
Volume /nm3
1.230
1.220
1.210
Minor impurity peaks can be observed 1.200
in the XRD, corresponding to 1.190
cristobalite- and rutile-type GeO2. 0.0 0.2 0.4 0.6 0.8 1.0
x

Solid solution series (RbxK1-x)2Ge4O9

June 15th, 2016 Florian Baur 8

Optical Properties Reflectance
Wavelength /nm
800 700 600 500 400 300 800 700 600 500 400 300
100 100
a) 300 K b) 300 K
90 350 K 350 K 90
400 K 400 K
80 450 K 80
450 K
70 70
Reflectance /%

60 60

Reflectance /%
50 50

40 40

30 30

20 20

10 10

0 0
15 20 25 30 35 40 15 20 25 30 35 40
Wavenumber /103 cm-1

Temperature-dependent reflectance spectra reveal changes in the position of

various absorption bands in both a) K2Ge4O9:Mn4+ and b) Rb2Ge4O9:Mn4+

Strongly overlapping bands prevent detailed analysis  excitation spectra required

June 15th, 2016 Florian Baur 9

Optical Properties Excitation
• 4T
2 band shifts to lower energy with increasing temperature
• Crystal field splitting (CFS) decreases
• Dq(77K) = 2207 cm-1; Dq(375K) = 2140 cm-1

• 4T
1 band exhibits a less pronounced shift to lower energies
• Racah parameter B increases
• B(77K) = 770 cm-1; B(375K) = 805 cm-1

• Charge transfer (CT) band does not shift with temperature

Wavelength /nm
600 550 500 450 400 350 300 250 600 550 500 450 400 350 300 250

1.0 1.0
77 K a) CT
77 K b) CT
175 K 150 K
Normalized Intensity (a.u.)

Normalized Intensity (a.u.)

0.8 300 K 300 K 0.8
350 K 4
A2 4
T1 350 K 4 4
A2 T1
0.6 0.6
4 4
A2 T2
4 4
0.4 A2 T2 0.4

0.2 0.2

0.0 0.0
20 25 30 35 40 20 25 30 35 40
Wavenumber /103 cm-1

June 15th, 2016 Florian Baur 10

 Optical Properties Site Selective Emission

• Low-temperature band is likely another 4T2

band at lower energy
additional band
below 100 K
 This indicates a lager Mn-O distance:
Ge(1)-O distance is larger than Ge(4)-O

1,0
ex= 520 nm
• Excitation via the low-temperature band
ex= 310 nm
results in a less pronounced ZPL
0,8
Emission Intensity (a.u.)

 This indicates a more centrosymmetric

0,6 Mn4+ environment: Ge(1)O6 has 3
symmetry
0,4

• The additional band likely stems from Mn4+

0,2
ions located on Ge(1) site
0,0
640 650 660 670 680 690 700 710

Wavelength /nm

June 15th, 2016 Florian Baur 11

Optical Properties Thermal Quenching
1,0

Normalized Emission Integral [a.u.]

• A bi-sigmoidal thermal quenching curve 0,8

was observed:
0,6

K2Ge4O9:Mn4+ Rb2Ge4O9:Mn4+
0,4

T1/2,a = 160 K T1/2,a = 162 K K2Ge4O9:Mn4+

Rb2Ge4O9:Mn4+
T1/2,b = 379 K T1/2,b = 346 K 0,2
Double Fermi-Dirac Fit
Double Fermi-Dirac Fit
0,0
100 150 200 250 300 350 400 450 500

Temperature /K

T1/2,a does not vary between T1/2,b does vary between

K2Ge4O9 and Rb2Ge4O9 
Ge(1)-O distance does not
vary strongly
K2Ge4O9 and Rb2Ge4O9 and T1/2,a corresponds
is larger in K2Ge4O9  to Mn(1) ions
Ge(4)-O does vary and is T1/2,a corresponds
larger in Rb2Ge4O9 to Mn(4) ions

June 15th, 2016 Florian Baur 12

Optical Properties Thermal Quenching
2 2
(a) (b)

00
50

15
17
00
Time /µs

Time /µs
15

00
Logarithmic Intensity (a.u.)

10
50
12

0
00

50
10 100 200 300 100 200 300
Temperature /K Temperature /K
77 K
77 K 100 K
100 K 125 K
125 K 150 K
150 K 175 K
175 K 200 K
200 K 225 K
225 K 250 K
250 K 275 K
275 K 300 K
300 K 325 K
325 K 350 K
350 K

2 4 6 8 10 12 14 16 2 4 6 8 10 12 14 16
Time /ms

Decay constants decrease with increasing

temperature:

• The linear decrease implies that this is not

caused by quenching but increasing Not applicable in this
probability of the 2E4A2 transition material!

June 15th, 2016 Florian Baur 13

Optical Properties Racah Parameters
• Dq decreases with increasing
temperature

CFS is proportional to R-5 where R is

the mean Mn-O distance.

n ≈ 4.8
Mn-O distance
increases by 0.5%
between 77 and
375 K

• B increases with increasing

temperature

Large B indicates a less covalent

nature of the Mn-O bond as expected
from increasing Mn-O distance.

June 15th, 2016 Florian Baur 14

Optical Properties Emission
Wavelength /nm
725 700 675 650 625 725 700 675 650 625

1.0 a) b) 1.0

77 K 77 K
100 K 100 K
Normalized Intensity (a.u.)

0.8 150 K 0.8

Normalized Intensity (a.u.)

150 K
175 K 200 K
200 K 250 K
0.6 250 K 300 K 0.6
300 K 350 K
350 K 400 K
0.4 15225 15250 15275 15300 15325 15350
375 K 15200 15225 15250 15275 15300
450 K 0.4
Wavenumber /cm-1 400 K Wavenumber /cm-1 500 K
450 K
0.2
500 K 0.2

0.0 0.0
14000 14500 15000 15500 16000 14000 14500 15000 15500 16000
Wavenumber /cm-1

From strongly increasing B (+5%) a shift of the emission 2E4A2

to higher energies would be expected  shift to lower energies
observed!

Racah parameter C has to decrease!

June 15th, 2016 Florian Baur 15

Optical Properties Racah Parameters
3225
a) b)
22000 3200
3175
• B increases with increasing
21800
3150
temperature
Wavenumber /cm-1

3125

Wavenumber /cm-1
21600
3100
21400 3075

800
• C decreases with increasing
15275

15250
790 temperature
780
15225
770
10 Dq
• Dq decreases with increasing
15200 Racah parameter B
Energy 2E Racah parameter C 760

50 100 150 200 250 300 350 400 50

Temperature /K
100 150 200 250 300 350 400
temperature

Both B and C are a measure

for electron repulsion in the
d-orbitals

Why do B and C exhibit an

opposing trend?

June 15th, 2016 Florian Baur 16

Optical Properties Racah Parameters

Opposing trends of B and C can be

observed between other Mn4+-
phosphors as well: The Racah parameters are linear
combinations of Slater-Condon
Phosphor B /cm-1 C /cm-1 parameters:

CaZrO3:Mn4+ 650 ~ 3300 B = F2 – 5F4

SrTiO3:Mn4+ 719 ~ 2800 C = 35F4

• F2 reflects the electron environment

GdAlO3 :Mn4+ 600 ~ 3200 at the outer regions of the ion
LaAlO3:Mn4+ 700 ~ 2900
Z. Bryknar, V.A.Trepakov, Z.Potucek, L.Jastrabik, J.Lumin. 87–89 (2000) 605
• F4 concerns the inner regions
G. Blasse, P.H.M. De Korte, J. Inorg. Nucl. Chem. 43 (1981) 1505
M.A. Noginov, G.B. Loutts, J. Opt. Soc. Am. B 16 (1999) 3
M.E. van Ipenburg, G.J. Dirksen, G. Blasse, Mater. Chem. Phys. 39 (1995) 236.

June 15th, 2016 Florian Baur 17

Optical Properties Racah Parameters
A concept introduced by Brik, Carmadello
and Srivastava can help in understanding
this observation:

A M-O-Mn bond angle close to 180° often

results in high covalent nature of the bond
and low energy of emission.

M.G. Brik, S.J. Camardello, A.M. Srivastava, ECS J. Solid

State Sci. Technol. 4 (2015) R39

June 15th, 2016 Florian Baur 18

Optical Properties Racah Parameters
Apparently the bond angle has a strong
influence on Racah parameter C:

Phosphor B /cm-1 C /cm-1 M-O-Mn angle

CaZrO3:Mn4+ 650 3173 146.50 °
SrTiO3:Mn4+ 719 2812 180.00 °

GdAlO3:Mn4+ 600 ~ 3200 156.65 °

LaAlO3:Mn4+ 700 ~ 2900 171.90 °

With increasing temperature the Thermal expansion of the material

bond angles in K2Ge4O9 and results in larger Mn-O distances
Rb2Ge4O9 appear to get closer to
180 °  B increases.

 C decreases.
F. Baur and T. Jüstel, J Lumin 177 (2016) 354–360

June 15th, 2016 Florian Baur 19

Conclusions and Outlook
• Racah parameter B and C do not necessarily follow the same trend

• Parameter C seems to be strongly influenced by the M-O-Mn bond

angle
• angles close to 180 ° result in low value of C

• In some materials an increase in Mn-O bond length results in an

increase in value of B

• Small Mn-O distance results in a higher thermal quenching

temperature

• Investigation on the (Rb,K)2Ge4O9:Mn4+ will yield additional insight

into the relation of B and C to structural properties

June 15th, 2016 Florian Baur 20

Acknowledgement

Thank you for your kind attention!

The authors are grateful to

Merck KGaA, Germany for
financial support.

June 15th, 2016 Florian Baur 21