PHD Presentation

A new understanding of luminescence
processes in feldspar using novel

site-selective spectroscopic techniques
Ph.D. defense presentation
Raju Kumar
Supervisor: Dr. Mayank Jain

Co-supervisor: Dr. Myungho Kook
13.02.2020 A new understanding of luminescence processes in feldspar using novel site-selective spectroscopic techniques
What is luminescence?
Absorption of energy
Ultraviolet or X-ray radiation, electron
beams, chemical reactions, and so
on
Spontaneous emission of cold

light
13.02.2020 A new understanding of luminescence processes in feldspar using novel site-selective spectroscopic techniques 2
Optically or thermally stimulated luminescence
Absorbed energy from ionizing radiation
Storage of energy
heat or light stimulation
Emission of light
Band model
Conduction band
Energy
Ionizing radiation
RC
Valence band
T: Trap (electron trapping center), RC: recombination center (hole trapping center)
Band model
Conduction band
Energy
Metastable states OSL or TL
RC
Valence band
T: Trap (electron trapping center), RC= recombination center (hole trapping center)
Applications of luminescence from the metastable states
Personal dosimeters
Luminescence dating
Data storage
Mars
Micro dosimetry
Radiobiology
Luminescence dating: interdisciplinary method
Ra
ics
dia
hys
tio
eP
n
tat
Ph
Lum.
ysi
id S
c
dating
s
Sol
Geo- and archaeo-

Sciences
Luminescence dating principle
Nature Laboratory Measurement
Sample
collection
Trapped charge
Luminescence
Time Measurement time
LUMINESCENCE
AGE
Main research themes in luminescence dating
Developing new applications Extending the age range

> 0.5 million years
Research
Research
Numerical modelling Precision and accuracy
Understanding luminescence processes

and charge transfer
Target minerals in luminescence dating
Quartz Feldspar
 >50% of the Earth’s crust; also available on Moon and Mars
 Quartz  0.1 Ma, Feldspar  0.5 Ma
IRPL, a new powerful tool to explore luminescence processes

Key questions in feldspar luminescence model
CB  Single trap or multiple traps ?
 Trap depth ?
T
 How many excited states ?
RC  Spatial and energy distribution ?

VB
 Electron transport and recombination
T: Principal trap mechanism ?
Feldspar luminescence model
CONDUCTION BAND
E
 Luminescence is a product of
Ec
Excited state
both excitation, transport and
recombination probabilities
Ground state
~7.7 eV
 Not site-specific: multiple traps
can be excited by same energy
r
Band tail states hole distribution
Ev
 Competition effects
DOS VALENCE BAND
*modified from Jain and Ankjægaard, 2011OSL is not ideal to study trap characteristics
Solution: Infrared photoluminescence (IRPL)
Principal trap
CB
NIR IRPL
NIR light IRPL OSL Stokes shift ~0.16 eV

T
Photoluminescence
RC
885nm Laser
Dose
VB
0 *Prasad, 2017
850 900 950 1000 1050 1100 1150
Wavelength(nm)
IRPL characteristics A new understanding of luminescence processes in feldspar
using novel site-selective spectroscopic techniques
CB  IRPL is site specific: only a

function of trapped electron
concentration in the principal
NIR light IRPL OSL trap
T
 High sensitivity
RC
 Non-destructive
VB
Questions addressed
I. Single or multiple principal traps?

Trap depth
How many excited states
Spatial distribution
II. Electron transport and recombination mechanism
III. Testing IRPL for Sediment dating
Instrumentation
COLUR: Risø station for CryOgenic LUminescence Research
 Spectrofluorometer
 Xenon lamp, Halogen

lamp, Lasers
 PMT, CCD, InGaAs detectors
 X-ray irradiator
 Cooling down to 7K
Risø TL/OSL reader: IRPL attachment
Vis-NIR PMT for 880 nm
Liquid light guide

830 nm laser diode
NIR PMT for 955 nm

Detection filters
Cathodoluminescence (CL) system
SEM-CL-EDX system
 Scanning electron microscope Electron beam
 Electron beam induced

luminescence
 Energy dispersive x-ray

spectrometer
5-6 samples K
Na Ca
I. Single or multiple principal traps ?

-Trap depth
-How many excited states
-Spatial distribution
IRPL emission spectrum (7K)
1127 1033 954 886 nm
1.0
-- 925nm LP filter
T* 0.8
IRPL(a.u.)
0.6
1.30 eV (955 nm) 0.4

1.40 eV (885 nm)
T
0.2
0.0
1.1 1.2 1.3 1.4
Emission energy (eV)
1127 1033 954 886 nm

-- 850nm LP filter
1.0
-- 925nm LP filter
T* 0.8
IRPL(a.u.)
1.41 eV (880 nm) 0.6
1.30 eV (955 nm) 0.4

1.49 eV (830 nm)
T
0.2
0.0
1.1 1.2 1.3 1.4
Emission energy (eV)
1127 1033 954 886 nm

-- 850nm LP filter
1.0
-- 925nm LP filter
E 0.8
IRPL(a.u.)
0.6
0.4
0.2
0.0
1.1 1.2 1.3 1.4
What do the two emission peaks represent ? Emission energy (eV)
 Two excited energy levels of a single trap ?

 Two different traps?
Excitation spectra (7K)
Emission spectrum Excitation spectra
1127 1033 954 886 827 nm 1240 827 620 496 413 354 310 276 nm
60 1240 827 620 496 413 354 310 276 nm
955 nm emission
1.0
100
955 nm emission
?
IRPL (a.u.)
0.8
IRPL (a.u.)
IRPL (a.u.)
40
0.6 10 ?
0.4 20 ? 880 nm emission
1
0.2
0.0
1.0 1.01.51.5 2.0
2.0 2.5
2.5 3.0
3.0 3.5
3.5 4.0
4.0 4.5
4.5
1.1 1.2 1.3 1.4 1.5
Emission energy (eV) Excitation energy
Excitation energy(eV)
(eV)
The two emissions do not arise from the same trap

Dose dependent excitation spectra (7K)
Normalized integrated counts (a.u.)

827 620 496 413 354 310 nm
8
1.0 Em. at 955 nm
6 0.8
IRPL (a.u.)
Dose 0.6
4
0.4
Peak 1
Peak 2
2 0.2 Exc. at 2.95 eV (Peak 3)
Exc. at 3.44 eV (Peak 3)
0.0 Exc. at 4.13 eV (Peak 3)
0 0 50 100 150 200
1.5 2.0 2.5 3.0 3.5 4.0
Excitation energy (eV) X-ray irradiation time (min)
IRPL and OSL excitation spectra (7K)
886 775 689 620 564 517 477 nm
1.0
Normalized intensity (a.u.)
0.8
OSL Optical trap depth: 1.9-2.5 eV
0.6 IRPL (955 nm) (OSL technique)
0.4
0.2
0.0
1.4 1.6 1.8 2.0 2.2 2.4 2.6
Excitation energy (eV)
Second peak represents conduction band transition

Dose dependent excitation spectra (7K)
827 620 496 413 354 310 nm

8 CB
Excited state
First excited state In conduction band
6
IRPL (a.u.)
Conduction band T
4 transition
2 RC
VB
0
1.5 2.0 2.5 3.0 3.5 4.0
Optical trap depth in different samples
Sample Trap depth (eV)

IRPL 955 IRPL 880
R48 ~ 2.07 ~ 2.40
R47 ~ 2.05 ~ 2.20
R45 ~ 1.90 ~ 2.30
K8 ~ 2.09 ~ 2.18
R28 ~ 2.15 ~ 2.31
K9 ~ 2.21 ~ 2.25
Trap depth for 880 nm traps is greater than 955 nm Traps
Thermal stability
1.2
1.0
880 nm
↓ Dose (Beta particles) 0.8
Lx/Tx
↓ Preheat at T °C 0.6
↓ IRPL (880 nm) 0.4 955 nm
↓ IRPL (955 nm) 0.2
0.0
0 100 200 300 400 500 600
Preheat(°C)
Optical bleachability at RT
1.0 IR bleaching
1.0
880 nm
0.8
Residual IRPL
↓ Dose (Beta particles) 0.8
Ubleached
880 nm
(a.u.)
0.6
↓ Bleaching (IR, Blue, UV) 0.6
955 nm
955 nm
IRPL
↓ IRPL (880 nm) 0.4
0.4
IR
↓ IRPL (955 nm) 0.2
0.2
UV
Blue
0.00.0 1.5 2.0
0 1000 2000 30002.5 4000 3.05000
Bleachng energy (eV)
Time(s)
Spatial distribution of the two IRPL emissions
Carried out using spectrally resolved Cathodoluminescence (CL) mapping
Conduction band
e-beam
RC
Valence band
*from Wikipedia
Spatial Resolution 4 m for 20 keV electrons
Spatial distribution of NIR emissions: Barycenter
Barycenter
4
CL (a.u.)
2
0
800 900 1000
Wavelength (nm)
Spatial distribution of NIR emissions
Barycenter
Peak position
Spatial distribution of NIR emissions
Conclusion on Spatial distribution
R43 R50 K13
The two traps vary spatially and compositionally
Conclusion on single vs multiple trap
Dissimilarities (880 vs. 955nm)

• Excitation spectra
(Higher energy electronic states) Do these two traps
• Thermal stability
Different
arise from the same
(trap depth)
trap defect or different
• Optical bleachability
(photoionization cross-section)
defects?
• 0.1 eV (75 nm) difference
Excited state lifetime
1.0
Conduction Band
0.4 tIRPL880 = 21 ± 1 ms
ln(I)
880 nm Trap
Ec
0.1
0.0
1.0 S1
0.4 tIRPL955 = 20 ± 2 ms
ln(I)
0.1
955 nm Trap S0
0.0
50 60 70 80 90 100
TCSPC off time (ms)
Electron capture probability
1.0
Conduction Band
0.8 Ec
Normalised PL
0.6
S1
0.4
0.2 880 nm
955 nm S0
0.0
0 200 400 600 800 1000 1200 1400
Dose(Gy)
Conclusion on single vs multiple trap
880 and 955 nm emissions
Dissimilarities Similarities
• Excitation spectra • Dose response curve

(Higher energy electronic states) (e- capture cross section)
• Optical bleachability • IRPL Lifetime

(photoionization cross-section) (excited state relaxation)
• Thermal stability
Different
(trap depth)
trap Same defect
• 0.1 eV (75 nm) difference
General conclusion: same defect in two different crystal fields/sites

7 samples K
Na Ca
II. Electron transport and recombination

mechanism
A coupled PL/OSL system
Interpretation of OSL is often ambiguous
CONDUCTION BAND
e-, h+ detrapping by light Ec
transport (localized or delocalized)
hole distribution r
e-h recombination Ev
VALENCE BAND
A coupled PL/OSL system
CB
NIR light IRPL −

+¿ ( 𝑥 ) ∙ 𝑒 ( 𝑥 )
𝐼𝑅𝑆𝐿 ( 𝑥) h
T = ¿
𝐼𝑅𝑃𝐿 ( 𝑥) 𝑒 − ( 𝑥)
RC
VB
Coupled PL/OSL system: a powerful tool to investigate

luminescence processes
Fraction of electron population participating in IRSL
IRPL
IRPL (after 100s pause)
1.5x105 IRPL /after 100s IRSL50)
1. IRPL for 5s
IRPL counts (per 0.5s)
1.0x105 2. Pause = 100s IRSL50 for 100s
5.0x104
3. IRPL for 5s
0.0
0 2 4
Time (s)
6 8 10 ΔIRPL  IRSL50
Fraction of electron population participating in IRSL
8
25
20 6
DIRPL955 x 103
DIRPL880 x 103 15
4
10
2
5
880 nm
0 955 nm 0
0 10 20 30
IRSL x 105
7 samples: 21 aliquots
IRPL for 5s
Fraction of electron population participating in IRSL IRSL at T ° C for 40s (T=50,
100, 150, 200)
IRPL for 5s
Laboratory dose Laboratory dose

pIR-200 pIR-200
IRPL955 IRPL880
IRSL (T)
pIR-150 pIR-150
IRSL (T)
pIR-100 pIR-100 072255(K)

981009(K)
981010(K)
981013(K)
IR50 IR50 092202(K)
092204(N)
H22553(K)
0 20 40 60 80 100 20 40 60 80 100
DIRPL % DIRPL (%)
IRSL (RT): 35-60% of 955 nm traps IRSL (RT): 20-30% of 880 nm traps
Pulse annealing: thermal decay of IRPL and IRSL
2.0
Normalized signal
1.5
1.0
IRPL mh=
mh
0.5 IRSL
0.0
100 200 300 400 500 600
Anneal temperature (°C)
Thermal depletion of IRSL is governed by holes availability and not electrons

Conclusion on transport and recombination
• Coupled PL/OSL system, powerful tool to understand the

dynamics of the metastable states.
– Both principal traps participate in OSL/IRSL but

contribution from 955 nm trap is dominant.
– Thermal depletion of IRSL is caused by the depletion

of holes.
8 samples K
(20-128 ka)
Na Ca
III. Testing IRPL for Sediment dating
IRSL-IRPL integrated SAR protocol
Preheat 320° C, 60 s
IR stimulated luminescence – 50°C IRSL50
IR stimulated luminescence – 90° C IRSL90
-----
IRSL-IRPL integrated SAR protocol
Preheat 320° C, 60 s
IRPL (880 nm) APh-IRPL
IRPL (955 nm)
IR stimulated luminescence – 50°C IRSL50
IRPL (880 nm) pIR50-IRPL
IRPL (955 nm)
IRPL (880 nm) pIR50,90-IRPL
IRPL (955 nm)
IR stimulated luminescence – 290° C Bleaching
IRPL (885 nm) IRPLbkg
IRPL (955 nm)
-----
Conclusion on IRPL dating (8 samples)
880 nm emission 955 nm emission

350 +10% 350 +10%
APh-IRPL pIR50IRPL
Measured D e (Gy)
Measured De (Gy)
300 -10% 300 +10%
250 250
200 200
150 150
100 100
50 50
0 0
0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350
Expected De (Gy) Expected De (Gy)
Accurate dose up to 300 Gy can be obtained without fading correction
Conclusions
1. The validity of the feldspar phenomenological model based on localized
recombination is confirmed. However, it is demonstrated that IRSL/OSL
signals arises from two different traps (880 and 955 nm centers) instead of
one trap. These traps have:
– Different ground and excited-state energies
– Different spatial distribution
– Different correlation with K-Na%
The two traps consist of the same defect in different crystal fields.
Conclusions
1. The validity of the feldspar phenomenological model based on localized
recombination is confirmed. However, it is demonstrated that IRSL/OSL
signals arises from two different traps (880 and 955 nm centers) instead of
one trap. These traps have:
– Different ground and excited-state energies
– Different spatial distribution
– Different correlation with K-Na%
The two traps consist of the same defect in different crystal fields.
2. Accurate doses up to 300 Gy (128 ka) can be obtained using IRPL without
fading correction.
Impact
Techniques
- A novel method to map energy levels of metastable states
- A unique coupled PL/OSL physical system to understand the
dynamics of the metastable states
Luminescence dating
- A new luminescence dating technique based on IRPL
- Measurement of trapping of charge at a high resolution (6-22 μm)
paves the way for studying micro-dosimetry and for developing next
generation dating techniques at the sub-single-grain level
Publications
1. Kumar, R., Kook, M., Murray, A. S., & Jain, M. (2018). Towards direct measurement of electrons in metastable
states in K-feldspar: Do infrared-photoluminescence and radioluminescence probe the same trap? Radiation
Measurements, 120(December 2017), 7–13.
2. Kumar, R., Martin, L.I.D.J., Poelman, D., Vandenberghe, V., Grave, J.De., Kook, M., & Jain, M. (Submitted). Site-
selective mapping of metastable states using electron-beam induced luminescence microscopy.
3. Kumar, R., Kook, M., & Jain, M. (Submitted). Sediment dating using Infrared photoluminescence (IRPL).
4. Kumar, R., Kook, M., & Jain, M. (To be submitted). Characterization of electron-trapping centers in feldspar by
low-temperature photoluminescence excitation-emission spectroscopy.
Kook, M., Kumar, R., Murray, A. S., Thomsen, K. J., & Jain, M. (2018). Instrumentation for the non-destructive
5.
optical measurement of trapped electrons in feldspar. Radiation Measurements, 120, 247-252.
6. Jain, M., Kumar, R., Kook, M., (To be submitted: Available at arXiv). A coupled PL-OSL system to probe
dynamics of the metastable states.
Thank you !
• Center for nuclear technologies (DTU Nutech) for funding my Ph.D.
• People for their support and encouragement:

• Karsten Bracht Nielsen • Jeppe
• Mayank Jain • Mark Baily
• Søren Vig Dalsgaard • Martin
• Myungho Kook • Dirk Poelmann
• Bent Lauritzen • Nicolo
• Jens-Peter Lynov • Lisa Martin
• Jørgen Hesselbjerg • Ashkhen
• Bent Lauritzen • Dimitri Vandenberghe
• Lars Peter Pirtzel • Claire
• Jan-Pieter Buylaert • Amit Kumar Prasad
• Per Günther Sørensen • Frederik
• Andrew Murray • Marine Frouin
• Bo Dalbjerg • Warren
• Kristina Thomsen • Reza Sohbati
• Louise Maria Helsted • Oscar
• Claus Andersen • Eike F. Rades
• Vicki Hansen • Elaine
• Lars Lindvold • Svenja Riedesel
• Henrik Olesen • Trine
• Erik Nonbøl • Pia Elhauge
• Nina Jensen • Magdalena
• Arne Miller • Merete Holmegaard Larsen
• Linda Bohn • Tim
• Per roos • Xiao Xiao
• Nicolas Stenger • And everybody at DTU
Supplementary material
IRPL and OSL excitation spectra (7K)
886 775 689 620 564 517 477 nm
1.0
Normalized intensity (a.u.)
( 𝐸 − 𝐸 𝑡 ) 3/ 2
 ( 𝐸 , 𝐸𝑡) 
[ )]
2
0.8 IRPL (880 nm) 𝐸 𝐸 − 𝐸 𝑡 1− ( 𝑚𝑜

𝑚
∗
0.6 OSL
IRPL (955 nm)
0.4 Optical trap depth: 1.9-2.5 eV (OSL technique)
0.2
0.0
1.4 1.6 1.8 2.0 2.2 2.4 2.6
Second peak represents conduction band transition

IRPL and IRRL at 7 K
1033 9541.0 886 827 nm

IRPL 1033 954 886 nm
1.4
--- 850nm LP filter
0 Gy
2.0
1.2 216 Gy 0.8 D0=644.99±15.99
Intensity (a.u)
432 Gy
702 Gy
1.0 918 Gy 1.5
IRRL(a.u.)
IRPL(a.u.)
1134 Gy
1350 Gy 0.6
0.8 D0=-602.78±35.2
1.0
0.6 0.4
Excitation @830nm
IRRL
0.4 0.5
0.2
0.2
0.0
0.0 1.2 1.3 1.4
1.2 1.3 0.0 1.4 1.5
0 200 400 600 Emission energy(eV)
800 1000 1200 1400
Emission energy(eV)
Dose (Gy)
Deconvolution
886 827 775 729 689 620 564 517 443 388 344 310nm
25 (a) 120 min
20
IRPL 1.30 (a.u.)

15
10
0
1.4 1.5 1.6 1.7 1.8 2.0 2.2 2.4 2.8 3.2 3.6 4.0
886 827 775 729 689 620 564 517 443 388 344 310 nm
6
(a.u.) 1.41
4
IRPL
2
(b)
0
1.4 1.5 1.6 1.7 1.8 2.0 2.2 2.4 2.8 3.2 3.6 4.0
Deconvolution
Dec. of First peak Dec. of Second peak Dec. of Third peak

1.30 1.34 1.44 1.51 1.97 2.04 2.12 2.24 3.02 3.36 3.64
eV
1.41 - - - 2.03 2.13 2.16 2.49 3.38 3.60 3.79
eV

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A new understanding of luminescence

processes in feldspar using novel

Supervisor: Dr. Mayank Jain

Spontaneous emission of cold

Absorbed energy from ionizing radiation

heat or light stimulation

Metastable states OSL or TL

Geo- and archaeo-

Developing new applications Extending the age range

Understanding luminescence processes

 >50% of the Earth’s crust; also available on Moon and Mars

 Quartz  0.1 Ma, Feldspar  0.5 Ma

IRPL, a new powerful tool to explore luminescence processes

CB  Single trap or multiple traps ?

RC  Spatial and energy distribution ?

NIR light IRPL OSL Stokes shift ~0.16 eV

CB  IRPL is site specific: only a

I. Single or multiple principal traps?

II. Electron transport and recombination mechanism

III. Testing IRPL for Sediment dating

 Xenon lamp, Halogen

 PMT, CCD, InGaAs detectors

Vis-NIR PMT for 880 nm

Liquid light guide

NIR PMT for 955 nm

 Scanning electron microscope Electron beam

 Electron beam induced

 Energy dispersive x-ray

I. Single or multiple principal traps ?

1127 1033 954 886 nm

1.30 eV (955 nm) 0.4

1127 1033 954 886 nm

1.30 eV (955 nm) 0.4

1127 1033 954 886 nm

 Two excited energy levels of a single trap ?

The two emissions do not arise from the same trap

Normalized integrated counts (a.u.)

886 775 689 620 564 517 477 nm

Second peak represents conduction band transition

827 620 496 413 354 310 nm

Sample Trap depth (eV)

Trap depth for 880 nm traps is greater than 955 nm Traps

↓ Dose (Beta particles) 0.8

↓ IRPL (880 nm) 0.4 955 nm

↓ IRPL (955 nm) 0.2

R43 R50 K13

The two traps vary spatially and compositionally

Dissimilarities (880 vs. 955nm)

TCSPC off time (ms)

• Excitation spectra • Dose response curve

• Optical bleachability • IRPL Lifetime

General conclusion: same defect in two different crystal fields/sites

II. Electron transport and recombination

e-, h+ detrapping by light Ec

transport (localized or delocalized)

NIR light IRPL −

Coupled PL/OSL system: a powerful tool to investigate

1.0x105 2. Pause = 100s IRSL50 for 100s

Laboratory dose Laboratory dose

pIR-100 pIR-100 072255(K)

DIRPL % DIRPL (%)

Thermal depletion of IRSL is governed by holes availability and not electrons