Abstract Book Phosphorous Conference

Dirk Poelman
Philippe Smet
Joke Hadermann
Jonas Botterman
Koen Van den Eeckhout

1

2
Persistent luminescence can perfectly be
explained to the layman. Everyone knows the
glow-in-the-dark stars and the tiny glowing
ghosts from several toy companies. The
phenomenon is also associated with glowing
markers on wrist watches and night-glow
pushbuttons. However, it is very often
confused with radioactive materials, and most
people have no clue how and why these
materials are glowing, nor what kinds of
materials are suitable. Unfortunately, this
somewhat relates the layman to us,
researchers in the field. Just like the layman, we
still dont really know how and why bright
persistent luminescence can be obtained:
several models, based on theoretical
considerations, numerical simulations and
extensive experimenting have been proposed,
but there are no final answers yet. On the
experimental side, new and very performing
materials have been developed, but most
probably, these are still far from optimum. In
addition, there are probably countless other
materials both hosts and dopants which are
appropriate.,
Our research group LumiLab at Ghent
University has been working on luminescent
materials for many years, and it is only since a
few years that we started working on persistent
luminescence. It was to our surprise that,
despite the wealth of possible application,
there appeared to be only a relatively small
research community working on persistent
phosphors, and that there were no workshops
or conferences devoted to the topic.
About a year ago triggered by writing an EU-
COST proposal and a review paper on
persistent luminescence we developed the

plan to organize a small-scale meeting focusing
on persistent and storage phosphors. This
would enable a melting pot of ideas pouring
all existing expertise and models together and
strengthen the bonds between researchers in
the field.
We hope that, thanks to your contributions, the
first Phosphoros meeting will achieve this
goal. We trust that you will have the
opportunity to discuss new ideas and
experiments. Also, we would be very glad if
Phosphoros at UGent is not the last meeting on
this exciting topic.
Finally, we want to thank everybody who has
contributed to Phosphoros: the members of
the program committee, our invited speakers,
the contributors of oral and poster
presentations, our co-organizers Koen Van den
Eeckhout, Jonas Botterman and Joke
Hadermann, the entire LumiLab research group
and, last but not least, our sponsors Agfa
Gevaert, Sysmex, FWO-Flanders and Ghent
University.
May the light be with you!
Dirk Poelman and Philippe Smet,
Conference chairs

3

4

5
Committees 6
Program 7
Abstracts: Invited lectures 11
Abstracts: Oral presentations 18
Session I: Eu
2+
-doped persistent phosphors 18
Session II: Applications of persistent phosphors / Energy storage 31
Session III: Thermoluminescence / Persistent luminescence models 42
Session IV: Non Eu
2+
-doped persistent phosphors 55
Abstracts: Poster presentations 64
List of abstracts 95
List of contributing authors 99

6

Local organizing committee
Dirk Poelman
Philippe Smet
Joke Hadermann
Jonas Botterman
Koen Van den Eeckhout

International advisory committee
Marco Bettinelli University of Verona Italy
Philippe Boutinaud University of Clermont-Ferrand France
Pieter Dorenbos Delft University of Technology The Netherlands
Jorma Hls University of Turku Finland
Dariusz Hreniak Inst. of Low Temperature and Structure Research Poland
Stphane Jobic Universit de Nantes France
Thomas Jstel University of Applied Sciences Mnster Germany
Andries Meijerink Utrecht University The Netherlands
Dirk Poelman Ghent University Belgium
Philippe Smet Ghent University Belgium
Wieslaw Strek Inst. of Low Temperature and Structure Research Poland
Bruno Viana Laboratoire de Chimie de la Matire Condense France
Xiaojun Wang Georgia Southern University United States
Eugeniusz Zych University of Wroclaw Poland

7

00 Introduction

Session I: Eu
2+
-doped persistent phosphors

15 Persistent luminescence mechanisms: Human imagination at work
Jorma Hls, University of Turku, Finland
00 Synthesis and characterization of BaAl
2
O
4
:Eu
2+

co-doped with different rare earth ions
Martin Ntwaeaborwa, University of the Free State, South Africa
20 DFT and synchrotron radiation study of the Eu
2+
doped BaAl
2
O
4

Taneli Laamanen, University of Turku, Finland

Coffee break

10 Surface characterization and luminescent properties
of SrAl
2
O
4
:Eu
2+
,Dy
3+
nano thin films
Hendrik C. Swart, University of the Free State, South Africa
30 Fabrication of long-lasting glass-ceramic phosphors
by melt-quenching method and their properties
Setsuhisa Tanabe, Kyoto University, Japan
50 Luminescence studies of a combustion-synthesized
blue-green BaAl
x
O
y
:Eu
2+
,Dy
3+
nanophosphors
Francis B. Dejene, University of the Free State, South Africa
10 Synthesis, persistent luminescence, and thermoluminescence
properties of yellow Sr
3
SiO
5
:Eu
2+
,RE
3+
(RE = Ce,Nd,Dy,Ho,Er,Tm,Yb)
and orange Sr
3-x
Ba
x
SiO
5
:Eu
2+
,Dy
3+
phosphor
Jing Wang, Sun Yat-sen University, China
30 Yellow persistent luminescence in Sr
2
SiO
4
:Eu
2+
,Dy
3+

Thomas Jstel, Fachhochschule Mnster, Germany

Lunch

9
9
10
10
11
11
11
12
12
I 01

O 01

O 02

O 03

O 04

O 05

O 06

O 07

8

Session II: Applications of persistent phosphors / Energy storage

50 Storage and read-out mechanisms in the best
photostimulable phosphor materials
for digital radiography: BaFBr:Eu and CsBr:Eu
Miroslaw Batentschuk, University of Erlangen-Nrnberg, Germany
35 What electron paramagnetic resonance spectroscopy teaches us
about the structure of Eu
2+
centers in CsBr:Eu
2+
X-ray storage phosphors
Henk Vrielinck, Ghent University, Belgium
55 Influences and improvements on the brightness
of industrial luminous afterglow products

Bernhard Walfort, LumiNova AG

Coffee break

40 Elaboration of nanoparticles with persistent luminescence
for in vivo imaging
Cline Rosticher, LCMCP Paris, France
00 Thermoluminescence characteristics of
Lu
2
O
3
:Pr,Hf storage phosphor
Aneta Wiatrowska, University of Wrocaw, Poland
20 Evaluating the brightness of persistent phosphors:
beyond the candela
Dirk Poelman, Ghent University, Belgium
40 Water soluble afterglow nanoparticles for biomedical imaging
and photodynamic therapy
Wei Chen, University of Texas, Arlington, USA

00 Poster session

13
14
14
15
16
16

16
17
I 02

O 08

O 09

O 10

O 11

O 12

O 13

9

Session III: Thermoluminescence / Persistent luminescence models

15 Thermoluminescence as a tool to study
the mechanism of persistent luminescence
Adrie J.J. Bos, Delft University of Technology, The Netherlands
00 Thermoluminescence study of persistent luminescence fading
in Sr
2
MgSi
2
O
7
:Eu
2+
,R
3+
materials
Mika Lastusaari, University of Turku, Finland
20 Thermally stimulated luminescence:
an algorithm for analysing phosphorescence curves

Eduardo Caselli, Universidad Nacional del Centro, Argentina

Coffee break

10 Charging behaviour in persistent phosphors
Koen Van den Eeckhout, Ghent University, Belgium
30 Photoionization of lanthanide defects and how that affects
luminescence and carrier storage
Pieter Dorenbos, Delft University of Technology, The Netherlands
50 Controlling trap depth to enhance persistent luminescence
of silicate nanoparticles for in vivo imaging
Thomas Maldiney, UPCGI Paris, France
10 An x-ray absorption study of SrAl
2
O
4
:Eu,Dy powders
Katleen Korthout, Ghent University, Belgium
30 ZnGa
2
O
4
:Cr
3+
: a new red long-lasting phosphor with high brightness
Aurlie Bessire, LCMCP Paris, France

Lunch

9
10
10
11
11
12
12
11
I 03

O 14

O 15

O 16

O 17

O 18

O 19

O 20

10

Session IV: Non-Eu
2+
-doped and infrared-emitting phosphors

50 Persistent phosphorescence through persistent energy transfer
Xiaojun Wang, Georgia Southern University, USA
35 IR laser stimulated afterglow fluorescence of
Eu(III) doped LaAlO
3
nanocrystals
Pawe Guchowski, Institute of low temperature
and structure research Wrocaw, Poland
55 Synthesis and characterization of Y
2
O
2
S:Eu nanophosphors
using sol-combustion method

Abdub Ali, University of the Free State, South Africa

Coffee break

40 Persistent phosphorescence in Ce
3+
-doped Lu
2
SiO
5

Mitsuo Yamaga, Gifu University, Japan
00 Long-lasting phosphorescence of Ce
3+
-doped garnet crystals
Jumpei Ueda, Kyoto University, Japan
20 Synthesis and characterization of calcium titanium oxide based
pigments with red afterglow
Eugenio Otal, EMPA, Switzerland

40 Closing session

13
14
14
15
16
16

16
I 04

O 21

O 22

O 23

O 24

O 25

11

I 01 Persistent luminescence mechanisms: Human imagination at work 12
I 02 Storage and read-out mechanisms in the best photostimulable 14
phosphor materials for digital radiography: BaFBr:Eu and CsBr:Eu
I 03 Thermoluminescence as a tool to study the mechanism 15
of persistent luminescence
I 04 Persistent phosphorescence through persistent energy transfer 17

12
Persistent luminescence mechanisms: Human imagination at work I 01
Hermi F. Brito
1
, Jorma Hls
1-3,
*, Taneli Laamanen
2,4
, Mika Lastusaari
2,3
, Marja Malkamki
2,4
,
Lucas C.V. Rodrigues
1,2
*Corresponding author: hefbrito@iq.usp.br
1
Universidade de So Paulo, Instituto de Qumica, Departamento de Qumica Fundamental, So Paulo, Brazil
2
University of Turku, Department of Chemistry, FI20014 Turku, Finland
3
Turku University Centre for Materials and Surfaces (MatSurf), Turku, Finland
4
Graduate School of Materials Research (GSMR), Turku, Finland

Keywords: persistent luminescence, mechanisms, europium, terbium
The persistent luminescence will pass its 400
th
anniversary in 2012 though this important
milestone is somewhat uncertain [1]. During its entire lifetime, the origin of persistent
luminescence has certainly stimulated the mental activity of both scientists and laymen alike but
no significant progress in the explanation of the phenomenon was made prior to the 21
st
century.
In fact, in the early times (i.e. the 17
th
century), revolutionary ideas were not particularly greeted
with official recognition (cf. Galileo Galilei spent his life under house arrest since 1632) and thus
taking initiative to explain controversial phenomena may have been dangerous.
The lack of knowledge about the origin of the phenomenon was not, however, preventing the
commercial use of such materials (e.g. copper doped ZnS [2]). The poor performance of ZnS:Cu
paved way to true innovations, e.g. to increase the excitation strength, the only radioactive (and
artificial) rare earth, promethium (Pm
3+
) was used until the effects of radioactivity were realized.
Only the advent of the new Eu
2+
based materials (e.g. aluminates MAl
2
O
4
:Eu
2+
,R
3+
) [3] kicked off a
serious boom in their study first to discover and then to elucidate the mechanism. In the 1990s,
it was thought that sufficient knowledge had been accumulated on the (luminescence) properties
of both the di- and tri- or even the tetravalent rare earths. The harsh reality was soon to prove the
opposite, however, and the details of the persistent luminescence are still under debate.
In one of the first rather schematic mechanisms (Fig. 1), it was suggested quite uncommon
species, e.g. Eu
+
[3]. Of course, under ambient conditions such cannot be found as the simple
chemistry would suggest. In the following years, alternative species as R
2+
and R
IV
(R
4+
) were
introduced as well, though these mechanisms relied on the existence of the Eu
2+
-R
3+
and Eu
3+
-R
2+

(or similar) redox pairs. Unfortunately, it is now clear that persistent luminescence from Eu
2+
can
be observed without R
3+
co-doping [4] though such co-doping frequently enhances even
drastically the original persistent luminescence [5]. Both electron and hole trapping mechanisms
were suggested for Eu
2+
based materials. This proliferation evidently resulted from the lack of
even the basic information of the energetics of the system (i.e. the host band gap and the position
of the Eu
2+
/R
2+
/R
3+
/defect level positions therein). In some cases, if these positions were not
known, they were invented leading to some wild (and false) guesses The ignorance about the
level positions was removed by the invaluable work of P. Dorenbos [6] and thus the door to
master the excitation, emission as well as electron and hole trapping mechanisms was now open.
However, the question on the nature of defects capable of storing the excitation energy, remains.
The persistent luminescence has now been extended from the complete dominance of efficient
Eu
2+
based materials to the Eu
3+
[7] and Tb
3+
[8] based materials as well. Although the

13
mechanisms for these ions are basically an open question, there exist models to predict them.
Despite the persistent luminescence of Ce
3+
and Tb
3+
should follow the well-beaten track of Eu
2+

(electron trapping), the mechanism (Fig. 2) for Eu
3+
may be explained by hole trapping [7].
Following the drastic increase in the price of the rare earth oxides (from 2010 to 2011: up to ten
fold increase!), interest has emerged to use non-rare earth materials (e.g. with Ti
3+
doping).
The experimental work based on trial and error, may be replaced in the future by computational
methods. Considerable progress has been achieved in the reliable and realistic calculation of the
host band gap as well as energy level positions [9]. It might, however, be difficult if not impossible,
to calculate the defect energy levels because of the minute amounts of thermal energy involved.

In conclusion, the importance of imagination and creativity in the explanation of new
luminescence phenomena should not be underestimated at the early stages, at least. However,
the basics of chemistry, physics, spectroscopy and materials science should not be forgotten,
either, since only the successful use of interdisciplinary competence leads to successful
innovations. As the story of persistent luminescence has, hopefully, shown

[1] E. Newton Harvey, A History of Luminescence: From the Earliest Times until 1900, Amer. Phil. Soc.,
Philadelphia, PA, USA (1957) 307.
[2] S. Shionoya et al., Phosphor Handbook, CRC Press, Boca Raton, FL, USA (2007) Ch12.3.
[3] T. Matsuzawa et al., J. Electrochem. Soc. 143 (1996) 2670.
[4] P.F. Smet et al., 16
th
Int. Conf. Lumin. (ICL'11), June 27-July 1, 2011, Ann Arbor, MI, USA.
[5] H.F. Brito et al., J. Therm. Anal. Calorim. 105 (2011) 657.
[6] P. Dorenbos, Phys. Stat. Sol. b 242 (2005) R7 (and many more recent works).
[7] J. Hls et al., 16
th
[8] L.C.V. Rodrigues et al., 16
th
[9] T. Laamanen et al., 16
th

Figure 1: Persistent luminescence mechanism for
SrAl
2
O
4
:Eu
2+
,Dy
3+
[3]. Note the false Eu
+
species!
Figure 2: Persistent luminescence mechanism
for Eu
3+
in Y
2
O
2
S [7].
-2
-1
0
1
2
3
4
5
6
2
3
0
6
, S
2-
2
V
Y
'''
5.8
0
5.2
1
5
D
0-3
O
2-
Band
7
F
0-6
Valence Band
E
n
e
r
g
y

/

e
V
Eu
3+
Conduction Band
Trap Depths
0.6 - 1.0 eV
Irradiation Luminescence
Eu
2+ 8
S
7/2
CT / Eu
3+
S
2-
Band
e
-
h
+
[Eu
3+
]* [Eu
3+
-e
-
]* or [Eu
2+
]*
Y
2
O
2
S:Eu
3+
,Ti
3+
3.4
A
E
[
E
u
3
+
(
7
F
0
)
,

E
u
2
+
(
8
S
7
/
2
)
]
E
g
: 4.8 eV
kT

14
Storage and read-out mechanisms in the best photostimulable I 02
Miroslaw Batentschuk*, Peter Hackenschmied, Andres Osvet, Albrecht Winnacker

*Corresponding author: mirobat@ww.uni-erlangen.de
University of Erlangen-Nrnberg, Germany

Keywords: storage phosphors, BaFBr:Eu, CsBr:Eu, F-center, energy transfer
Since the introduction of X-ray imaging systems based on image plates [1], BaFBr doped with Eu
2+

and related storage phosphors, such as for instance BaSrFBr:Eu [2,3,4] have shown superior
properties among a large number of photostimulable materials. In the last years, the needle image
plates (NIPs) based on CsBr:Eu
2+
storage phosphor are increasingly used for digital X-ray imaging.
These NIPs offer better image quality and allow exposure dose reduction of up to 75 % compared
to the dose required when granular BaFBr:Eu image plates are used.
The operation of the both types of image plates relies on the occurrence of X-ray induced
photostimulated luminescence (PSL). After irradiation, the charge carriers can be stored in traps,
formed by crystal defects. For both materials referred here, the electron trap is F- center, and the
hole trap is v
k
-center (or H-center) stabilised by a neighboring Eu
2+
ion [5,6]. However, the creation
of new F-H-pairs during the irradiation is more pronounced in CsBr:Eu [7] than in BaFBr:Eu [8]. A
detailed analysis of the storage center creation for CsBr:Eu and BaFBr:Eu can be found in [7] and
[9] respectively.
The read-out process is essentially absorption of light in F-centers. It is important that the excited
state of the F-center relaxes after excitation. As a result, a state is built slightly lower than
conduction band which allows a thermal excitation into the conduction band and migration of the
electron to the hole. The next, very interesting process for physics of storage phosphors is the
energy transfer from the electron-hole recombination to the Eu
2+
emitting centers [7] [10].

[1] M. Sonada et al., Radiology 148 (1983) 833-837.
[2] R.J. Klee, J. Phys. D: Appl. Phys. 28 (1995) 2529-2533
[3] A. Meijerink, Mat. Chem. Phys. 44 (1996) 170-177.
[4] M. Batentschuk et al., Radiat. Meas. 29 (1998) 299-305.
[5] M. Thoms et al., Phys. Rev. B 44 (1991) 9240-9247.
[6] P. Hackenschmied et al., Nucl. Instr. Methods Phys. Res. B 191 (2002) 163-167.
[7] M. Weidner et al., J. Appl. Phys. 106 (2009) 063514.
[8] H. H. Rter et al., Phys. Rev. Lett. 65 (1990) 2438-2442.
[9] S. Hesse et al., J. Appl. Phys. 105 (2009) 063505.
[10] P. Hackenschmied et al., Radiat. Meas. 33 (2001) 669-674.

15
Thermoluminescence as a tool to study the mechanism I 03
Adrie J.J. Bos*, Pieter Dorenbos

*Corresponding author: a.j.j.bos@tudelft.nl
Luminescence Materials Research Group, Delft University of Technology, Delft, The Netherlands

Keywords: thermoluminescence, persistent luminescence mechanism, trap depth, TL excitation
Persistent luminescence is the phenomenon that luminescence can last for hours after the
termination of the excitation. At least two kinds of active centres are involved: a luminescence
centre and a trapping centre. The luminescence centre can be studied by emission spectroscopy
and the trapping centre by thermoluminescence. Thermoluminescence (TL) is the thermally
stimulated emission of light of the phosphor following the previous absorption of energy of
radiation. TL is usually observed by measuring the luminescence while the sample is heated at a
constant heating rate. The curve obtained in this way is called a glow curve. In this contribution
we will review how glow curves measured under different circumstances can help us to get insight
how the trapping centres are involved in the mechanism of the persistent luminescence.
In Fig. 1 the glow curves of a well-known persistent luminescence phosphor, SrAl
2
O
4
:Eu
2+
,Dy
3+
, are
shown after excitation with light of different wavelengths. It can be seen that the glow curve
shows a broad, asymmetrical glow peak. Such glow peaks are characteristics for most persistent
luminescent phosphors. Studying the shape and location of the peak can provide insight into the
trap depth or distribution of trap depths responsible of the glow peak. However, the derivation of
these trap depth values is not straightforward. It depends on the model that is used to describe
the TL mechanism. Is there a single trap depth? Is retrapping of the charge possible? To derive
solid information it is necessary to perform a series of experiments. A first series involve the
measurement of TL glow curves with different waiting times between excitation and readout to
investigate whether the decay of the TL glow peak corresponds with the decay of the persistent
luminescence. A second series involve the measurement of TL glow curves as function of the

Figure 1: Glow curves of SrAl
2
O
4
:Eu
2+,
Dy
3+
excited by photons of different wavelengths.
300 350 400 450 500 550 600
0.0
0.2
0.4
0.6
0.8
1.0
T
h
e
r
m
o
l
u
m
i
n
e
s
c
e
n
c
e

(
a
r
b
.

u
n
i
t
s
)
Temperature (K)
425 nm
400 nm
350 nm
Excitation
wavelength
SrAl
2
O
4
:Eu
2+
,Dy
3+
| = 5 K/s

16
period of excitation to see whether the glow peak maximum shifts to lower temperature with
excitation duration. If so this might be an indication for second order kinetics. Another series
involve the measurement of TL glow curves as function of the heating rate. From the shift of the
glow peak maximum the trap depth can be derived. Finally the measured glow curves can be
submitted to glow curve analysis. Only if different methods yield the same trap depth one can
trust the outcome.
From TL glow curves also information can be obtained about the source of the charge carriers
liberated during exposure and about the position of the energy levels. The idea is the following:
monochromatic light is used to excite electrons from impurity states within the band gap into the
conduction band. The thus created free electrons will be captured in available trapping centres of
the sample. The traps are subsequently read out by heating the sample while the
thermoluminescence is recorded. By varying the wavelength, repeating the TL readout, and
displaying the temperature integrated TL yield as function of the wavelengths the TL excitation
spectrum (TLES) will be obtained [1]. In Fig. 2 an example is of such a spectrum is shown together
with the 10 K photoluminescence excitation spectrum (PLES) of Eu
2+
emission. The PL excitation
spectrum of the Eu
2+
5d4f emission starts at around 475 nm, rises steeply to the maximum
around 425 nm, and falls off for lower wavelengths before showing a second maximum at 363 nm.
The TLES starts at the same wavelength but shows a gradual increase in intensity with shorter
wavelengths until a maximum is reached. It is clear that there are differences between the TL and
PL spectra but most important is the observation that the onset of the PL excitation spectrum
coincides with the onset of the TL excitation spectrum. This observation is a strong indication that
excitation of Eu
2+
leads to trap filling, which is the first step in the persistent luminescence
mechanism.

Figure 2: Excitation spectra of SrAl
2
O
4
:Eu
2+,
Dy
3+
. Thermoluminescence excitation
spectrum (TLES) is obtained by integration of the TL glow (see Fig. 1) between 300
and 400 K. Photoluminescence excitation spectrum (PLES) is obtained by
measuring the Eu
2+
5d4f emission at 10 K.

[1] A.J.J. Bos et al., J. Lumin. 131 (2011) 1465-1471.

250 300 350 400 450 500
0.0
0.2
0.4
0.6
0.8
1.0
SrAl
2
O
4
:Eu
2+
,Dy
3+
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
Excitation wavelength (nm)
TLES
PLES

17
Persistent phosphorescence through persistent energy transfer I 04
Xiaojun Wang
1,
*, Jiahuan Zhang
2

*Corresponding author: xwang@georgiasouthern.edu
1
Department of Physics, Georgia Southern University, Statesboro, USA
2
Key Laboratory of Excited State Processes, CIOMP, CAS, Changchun, China

Keywords: persistent energy transfer, phosphors, phosphorescence
Persistent phosphorescence requires the traps for storing the excitation energy that can be slowly
released. The nature of the traps and their mechanisms for capturing energy are complicated and
not totally understood yet, making it difficult to synthesize the persistent phosphors with
designated coloration and/or persistent time. Energy transfer processes in doped insulation
materials, however, are well understood in terms of multipolar interactions between the donor or
sensitizer and acceptors or emitter. If the donor has a high-frequency, efficient persistent
emission, the excitation may persistently transfer to the acceptor, yielding the persistent emission
in the desired wavelength with similar persistent time to that of the donor [1-6]. The process can
also be used to enhance some inefficient phosphorescence and to prepare a single-phase full-color
phosphor material [7].
In this presentation, rare earth and transition metal ions doped aluminates, silicates, germinates,
and titanates samples have been prepared and their optical properties and dynamical processes
investigated. Long persistence phosphorescence has been obtained in different visible and
infrared regions using the mechanism of persistent energy transfer. Both visible and infrared
phosphorescence lasts for more than 10 hours viewed directly by the eyes for visible or through
the G3 detectors for infrared emissions. Optical excitation, emission, thermoluminescence,
photoconductivity, and photo-ionization with resonant microwave absorption have been
employed in studying the mechanism. Most recent developments in persistent energy transfer
research have been discussed.

[1] D. Jia et al., Appl. Phys. Lett. 80 (2002) 1535-1537.
[2] X.J. Wang et al., J. Lumin. 102 (2003) 34-37.
[3] R.X. Zhong et al., Appl. Phys. Lett. 88 (2006) 201916.
[4] S.Ye et al., J. Appl. Phys. 122 (2007) 063545-1-6.
[5] D. Jia et al., Electrochem. Solid-State Lett. 13 (2010) J32-J34.
[6] Y. Teng et al., J. Electrochem. Soc. 158 (2011) K17-K19.
[7] J.S. Kim et al., Appl. Phys. Lett. 84 (2004) 2931-2933.

18

Session I: Eu
2+
-doped persistent phosphors

O 01 Synthesis and characterization of BaAl
2
O
4
:Eu
2+
19
O 02 DFT and synchrotron radiation study of the Eu
2+
doped BaAl
2
O
4
21

O 03 Surface characterization and luminescent properties 23
of SrAl
2
O
4
:Eu
2+
,Dy
3+
nano thin films
O 04 Fabrication of long-lasting glass-ceramic phosphors 25
O 05 Luminescence studies of a combustion-synthesized 26
blue-green BaAl
x
O
y
:Eu
2+
,Dy
3+
nanophosphors
O 06 Synthesis, persistent luminescence, and thermoluminescence 28
3
SiO
5
:Eu
2+
,RE
3+
and orange Sr
3-x
Ba
x
SiO
5
:Eu
2+
,Dy
3+
phosphor
O 07 Yellow persistent luminescence in Sr
2
SiO
4
:Eu
2+
,Dy
3+
30

19
Synthesis and characterization of BaAl
2
O
4
:Eu
2+
O 01
Mantwa A. Lephoto
1
, Shreyas Pitale
1
, Bakang M. Mothudi
1,2
, Hendrik C. Swart
1
, Martin O.
Ntwaeaborwa
1,
*

*Corresponding author: ntwaeab@ufs.ac.za
1
Department of Physics, University of the Free State, Bloemfontein, South Africa
2
Department of Physics, University of South Africa, Pretoria, South Africa

Keywords: combustion method, initiating temperature, photoluminescence, thermoluminescence
Barium aluminate (BaAl
2
O
4
) belongs to a class of materials reperesented by a general formula
MAl
2
O
4
(M= Ba
2+
, Sr
2+
, Ca
2+
, or Mg
2+
). These materials are widely used as host for Eu
2+
and RE
3+
(RE
= rare-earths) to prepare long afterglow (persistent luminescence) phosphors for a variety of
applications in lighting. In this study, blue emitting BaAl
2
O
4
:Eu
2+
,RE
3+
(RE = Dy
3+
, Nd
3+
, Gd
3+
, Sm
3+
,
Ce
3+
, Er
3+
, Pr
3+
and Tb
3+
) phosphors were prepared by a combustion method using initiating
temperature of 600
o
C and urea as a fuel. Photoluminescent (PL) and long afterglow properties of
the blue emitting BaAl
2
O
4
:Eu
2+
,RE
3+
phosphors were investigated for possible application in
luminous paints, emergency vehicle lighting, field emission display technology, sensing and
dosimetry.
Figure 1 shows PL emission spectra of BaAl
2
O
4
:Eu
2+
:RE
3+
(RE = Dy
3+
, Nd
3+
, Gd
3+
, Sm
3+
, Ce
3+
, Er
3+
, Pr
3+

and Tb
3+
) recorded when the phosphors were excited with a 325 nm HeCd laser in air at room
temperature. All the samples exhibit a broad band bluish-green emission with a maximum at ~500
nm. This bluish-green emission is ascribed to the 4f
6
5d
1
4f
7
transitions of Eu
2+
. The highest PL
intensity was observed from the BaAl
2
O
4
:Eu
2+
sample co-doped with Er
3+
and the least intensity
was observed from the Ce
3+
co-doped sample. Note that only the samples co-doped with Nd
3+
and
Dy
3+
exhibited relatively long persistent luminescence compared to other samples.

Figure 1: PL emission spectra of BaAl
2
O
4
:Eu
2+
,RE
3+

(RE = Dy
3+
, Nd
3+
, Gd
3+
, Ce
3+
, Er
3+
) phosphors.

20
Figure 2 shows the (a) decay curves of BaAl
2
O
4
:Eu
2+
,RE
3+
(RE = Dy
3+
, Nd
3+
, Gd
3+
, Ce
3+
, Er
3+
) and (b)
thermoluminescence spectrum of BaAl
2
O
4
:Eu
2+
,Nd
3+
. The longer afterglow was observed from the
BaAl
2
O
4
:Eu
2+
sample co-doped with Nd
3+
. The traps responsible for the long afterglow are
presented in the thermoluminescent glow curve of BaAl
2
O
4
:Eu
2+
,Nd
3+
in figure 2 (b).

Figure 2: (a) Decay curves of BaAl
2
O
4
:Eu
2+
,RE
3+
(RE = Dy
3+
, Nd
3+
, Gd
3+
, Ce
3+
, Er
3+
)
and (b) thermoluminescence spectrum of BaAl
2
O
4
:Eu
2+
,Nd
3+
.

It is well known that the long afterglow is due to trapping and detrapping of charge carriers.
Possible mechanism of the long afterglow of BaAl
2
O
4
:Eu
2+
,RE
3+
phosphors will be discussed.

21
DFT and synchrotron radiation study of the Eu
2+
doped BaAl
2
O
4

O 02
Hermi F. Brito
1
, Maria C.F.C. Felinto
2
, Jorma Hls
1,3,4
, Taneli Laamanen
3,5,
*, Mika Lastusaari
3,4
,
Marja Malkamki
3,5
, Pavel Novk
6
, Lucas C.V. Rodrigues
1,3
, Roberval Stefani
1

*Corresponding author: taanla@utu.fi
1
2
Instituto de Pesquisas Energticas e Nucleares, Centro de Qumica e Meio Ambiente, So Paulo, Brazil
3
University of Turku, Department of Chemistry, Turku, Finland
4
5
6
Academy of Sciences of the Czech Republic, Institute of Physics, Prague, Czech Republic

Keywords: DFT calculations, electronic structure, persistent luminescence, barium aluminate
Persistent luminescence materials release stored energy as light gradually at room temperature.
The alkaline earth aluminates doped with Eu
2+
and R
3+
(MAl
2
O
4
:Eu
2+
,R
3+
; M: Ca/Sr/Ba; R: e.g.
Nd/Dy [1]) are among the most efficient ones. The development of even more efficient materials
is hindered by the lack of knowledge on the effect of charge compensation defects and structural
distortions resulting from the charge/size mismatch between the R
3+
and M
2+
ions. The defects
may play either a desired or unwanted role as energy storage or luminescence quenching centers,
respectively. Neither it is clear the exact electronic structure (band gap, valence (VB) and
conduction band (CB) composition, Eu
2+
/R
3+
4f
7
and 4f
6
5d
1
level positions) of MAl
2
O
4
:Eu
2+
,R
3+
.
In this work, the ab initio density functional theory (DFT) calculations using the WIEN2k program
package [2] were employed together with experimental methods to study the Eu
2+
doped BaAl
2
O
4
.
Every eighth of the hosts Ba
2+
ions was replaced with Eu
2+
and the different energy schemes were
calculated. Selected luminescence properties were studied experimentally by using the
synchrotron radiation (SR) VUV-UV-vis spectroscopy.
The BaAl
2
O
4
structure was found less distorted with Eu
2+
substituting Ba1 than Ba2 as witnessed
by the three-fold average decrease in the Eu-O distances for the latter. In addition, the difference
(40 eV) in the total energies suggests that Eu
2+
prefers the Ba1 site which may result in only one
emission band, at least at low (e.g. 1 mole-%) doping levels. The VB is mainly of the O 2p
character, whilst the CB consists mostly of the Ba (5.3 to 13 eV) and Al (13+ eV) levels.

Figure 1: Calculated (GGA+U method) band
structure of MAl
2
O
4
:Eu
2+
(M: Ca/Sr/Ba).
-5 0 5 10 15
0
50
100
150
200
Constant U (7.62 eV)
BaAl
2
O
4
:Eu
2+
CaAl
2
O
4
:Eu
2+

D
O
S

/

A
r
b
.

U
n
i
t
Energy / eV
SrAl
2
O
4
:Eu
2+
Eu 4f
7
Total

22
Only fair agreement was found between the calculated (5.7) and experimental (6.5 eV) band gap
energy. This may be due to the covalent character in BaAl
2
O
4
. The increasing lattice covalency in
the MAl
2
O
4
(CaSrBa) series moves the Eu
2+
4f
7
ground level towards VB (Figure 1). After the
optimization of the crystal structure, the 4f
6
5d
1
-4f
7
energy difference was 4.3 eV for both Ba sites.
This suggests that the emission energy is the same irrespective of the Ba site occupied by Eu
2+
.
The experimental band gap energy decreased slightly (with 0.1 eV from 10 to 300 K) with
increasing temperature. This is in agreement with the conventional behaviour found for the
semiconducting materials [3]. The SR emission spectrum consists of two bands (2.4 and 2.8 eV)
which may be due to the 4f
6
5d
1
4f
7
emission of Eu
2+
in both Ba sites (Figure 2). However, this is
not directly indicated by the electronic structure calculations (see above). The weak additional
luminescence band may thus also originate from the possible creation of a new Ba
2+
site due to
the effect of water exposure on BaAl
2
O
4
:Eu
2+
[4].

Figure 2: The synchrotron radiation
excited (
exc
: 92 nm) emission spectra
of BaAl
2
O
4
:Eu
2+
,Dy
3+
at selected
temperatures between 10 and 300 K
(SUPERLUMI, HASYLAB).
The DFT results show that the calculations are an excellent tool to probe the crystal and electronic
structure of the Eu
2+
doped persistent luminescence materials especially when difficult or
impossible to study experimentally. Trap states induced by the isolated defects and defect
aggregates present in the BaAl
2
O
4
:Eu
2+
,R
3+
materials should still be studied in detail since they are
expected to have a crucial effect on the persistent luminescence efficiency of these materials.
Acknowledgments: Financial support is acknowledged from the Turku University Foundation, Jenny and
Antti Wihuri Foundation (Finland) and the Academy of Finland (contracts #123976/2006, #134459/2009
and #137333/2010). The DFT calculations were carried out using the supercomputing resources of the CSC
IT Center for Science (Espoo, Finland).

[1] T. Matsuzawa et al., J. Electrochem. Soc. 143 (1996) 2670-2673.
[2] P. Blaha et al., In: Schwarz, K. (Ed.), WIEN2k, An Augmented Plane Wave + Local Orbitals Program for
Calculating Crystal Properties, Users Guide, Vienna University of Technology, Austria, 2001.
[3] Y.P. Varshni, Physica 34 (1967) 149-154.
[4] H.F. Brito et al., Academy of Finland Seminar: Materials in Photonics, Helsinki, February 15, 2011
(Poster).

400 450 500 550 600
0
50k
100k
150k
200k
250k
300k
220
BaAl
2
O
4
:Eu
2+
,Dy
3+
Combustion
synthesis, 500
o
C
exc
: 92 nm

I
n
t
e
n
s
i
t
y

/

A
r
b
.

U
n
i
t
Wavelength / nm
300
100
T: 190 K
10
3.2 2.8 2.4 2
4
F
9/2
6
H
13/2
Energy / eV
Dy
3+

23
Surface characterization and luminescent properties of O 03
SrAl
2
O
4
:Eu
3+
,Dy
3+
nano thin films
Hendrik C. Swart, Martin O. Ntwaeaborwa, P.D. Nsimama, R.E. (Ted) Kroon, Francis B. Dejene, J.J.
(Koos) Terblans

*Corresponding author: swarthc@ufs.ac.za

Keywords: SrAl
2
O
4
:Eu
2+
, Dy
3+
, phosphor thin films, PLD, photoluminescence, diffusion
The afterglow property of SrAl
2
O
4
:Eu
2+
,Dy
3+
makes it a potential candidate for luminous paints on
highway poles, house numbering, rural lighting, etc. For industrial applications, thin films are
preferred due to better thermal stability, less out gassing and better adhesion to solid. Among the
popular thin-film preparation techniques, the pulsed laser deposition (PLD) technique has become
increasingly important because of its use of small targets, high deposition rate and capability of
forming thin films with proper stoichiometry [2]. Photoluminescence (PL) and
cathodoluminescence (CL) properties of amorphous SrAl
2
O
4
:Eu
3+
,Dy
3+
thin films prepared by
pulsed laser deposition in vacuum, oxygen (O
2
) and argon (Ar) atmospheres were investigated.
Atomic Force Microscopy (AFM) was used to determine the topographical images of the films and
the PHI 700 Scanning Auger Nanoprobe was used to determine the elemental composition of the
different thin films. Auger electron spectroscopy and CL were used simultaneously to monitor
surface degradation under prolonged electron bombardment.
Long afterglow SrAl
2
O
4
:Eu
2+
,Dy
3+
thin film phosphors were successfully ablated on Si (100) substrates by the
pulsed laser deposition technique. AFM data (Figure 1 a and b) showed that the deposited thin films
were packed with a uniform layer of nano grains. Better PL intensities were obtained from the
unannealed nano structured films prepared in Ar and O
2
atmospheres with respect to the smooth
layers prepared in vacuum. Stable green emission at 515-520 nm, attributed to 4f
6
5d
1
4f
7
Eu
2+

transitions, was obtained. After annealing the thin films at 800C, the CL intensity of the green
emission of the vacuum thin film increased considerably. The CL intensity of the Ar and O
2
thin
films were almost completely quenched after annealing. The amorphous thin films were also
crystalline after the annealing process. The desegregation of adventitious C on the surface of the
smooth vacuum layer and the nanostructures Ar and O
2
layers was responsible for the intensity
quenching. C was uniformly distributed throughout the Ar and O
2
thin films, Figure 1 (d), while
only the top few nanometers of the vacuum films, Figure 1(c), contained C.
In the APPH ratios versus electron dose results, there were a decrease in C/O and an increase in
Sr/O and Al/O ratios with an increase in the electron dose. The C was removed from the film as
volatile species as a result of the Electron stimulated surface chemical reaction process. The CL
intensity of the annealed film was very stable on further electron bombardment. The
SrAl
2
O
4
:Eu
2+
,Dy
3+
material can be considered to be one of the potential candidates for electron
beam operating device application based on its high stability to the electron bombardment.

24

[1] H. Chander et al., J. Cryst. Growth 271 (2004) 307.
[2] K. B. Han et al., Thin Solid Films 437 (2003) 285.

0 25 50 75 100 125
0
20
40
60
80
100
O
Al
Sr
C
Si
A
t
o
m
i
c

c
o
n
c
e
n
t
r
a
t
i
o
n

(
%
)
Sputter time (min)
0 10 20 30 40 50 60 70 80
0
15
30
45
60
75
90
A
t
o
m
i
c

c
o
n
c
e
n
t
r
a
t
i
o
n

(
%
)
Sputter time (min)
O
Al
Sr
C
Si
Figure 1: The AFM images and the AES depth profiles of SrAl
2
O
4
:Eu
2+
,Dy
3+
thin
films deposited in (a) and (c) vacuum and (b) and (d) Argon atmospheres,
respectively, after annealing at 800 C for 2 hours.
(a) (b)
(c)
(d)

25
Figure 3: Pictures of glass ceramic samples :
(a) light emission observed under UV lamp
excitation. After stopping UV irradiation, the
afterglows of No. 5-1 were recorded at (b) 0s
and, (c)10 s, 1 min, 3 min, 5 min, 7 min and 9
min.

Fabrication of long-lasting glass-ceramic phosphors O 04
Setsuhisa Tanabe
1,
*, Takayuki Nakanishi
1,2
, Yumiko Katayama
1
, Jumpei Ueda
1
*Corresponding author: stanabe@gls.mbox.media.kyoto-u.ac.jp
1
Kyoto University, Graduate School of Human and Environmental Studies, Kyoto, Japan
2
Hokkaido University, Graduate School of Engineering, Sapporo, Japan

Keywords: glass-ceramics, SrAl
2
O
4
, europium, white LED
Glass-ceramic-based long-lasting phosphor was fabricated by quenching a melt of SrO-Al
2
O
3
-B
2
O
3

system doped with Eu and Dy. The SrAl
2
O
4
was the main and only crystalline phase and borate
glass containing Sr and less amount of Al was the surrounding phase in the glass ceramics. The
glass ceramics showed long-lasting phosphorescence comparable to the LumiNova by Nemoto Co.
Moreover, the glass ceramics showed excellent
excitation efficiency by 460nm excitation compared
with the phosphos prepared by solid-state reaction.
From the lattice constant, it is suggested that the Al
3+
-
sites in SrAl
2
O
4
crystals are partially substituted by B
3+

ions with smaller size. Thus the ligand field of Eu
2+
ions
was possibly modified by partial coordination of BO
4-

tetrahedron in addition to the AlO
4-
tetrahedron. The
present study proposes that the glass ceramics
fabricated have potential as new SrAl
2
O
4
-based
phosphors for white LED excitation (~460 nm).
Figure 1: Compositional mapping images for main
component atoms: Sr, Al, O, Eu, by electron probe
microanalyzer (EPMA).

Figure 2: XRD patterns (27 31) of SrAl
2
O
4
crystals with different compositions. (a) Pure (no-
doped) (b) Eu
2
O
3
-doped (2 mol%), and (c) Eu
2
O
3
(2
mol%) and B
2
O
3
(1wt%)-doped. The data of the glass
ceramics are also shown as (d).

26
Luminescence studies of a combustion-synthesized O 05
blue-green BaAl
x
O
y
:Eu
2+
,Dy
3+
nanophosphors
Francis B. Dejene

Corresponding author: dejenebf@qwa.uovs.ac.za
Department of Physics, University of the Free State (Qwa-Qwa campus), Phuthaditjhaba, South Africa

Keywords: BaAl
x
O
y
:Eu
2+
,Dy
3+
, nanophosphors, solution-combustion, structure, luminescence
Blue-green luminescent BaAl
2
O
4
:Eu
2+
,Dy
3+
phosphor powders were synthesized using the solution
combustion method. The effects of preparation conditions such the variation of amount of urea
and addition of boric acid as flux on the structural and luminescence properties of the powders
were investigated. The phosphors were characterized by X-ray diffraction (XRD), scanning electron
microscopy (SEM) and fluorescence spectrophotometer. In the combustion reaction process, the
contents of urea determine the adiabatic temperature of combustion and the reaction
sustainability which both influence the formation of BaAl
2
O
4
phase and photoluminescence
properties. So, we investigated the effect of urea and boric acid content on the host phase, and
prepared some samples with poor-fuel, stoichiometric, rich fuel and with or without boric acid.
The representative SEM results of samples prepared without boric acid revealed nano sized
particles (Fig. 1) and that the surface of the powder samples showed lots of voids and pores. EDS
(electron diffraction spectroscopy) confirm the presence of the Ba, Al, O, Eu and Dy.

Figure 1: SEM micrographs of as-synthesized BaAl
x
O
y
:Eu
2+
,Dy
3+
without boric acid
depict mixture of rod like and granular nanostructure.
The XRD results revealed changes in structure from BaAl
12
O
19
to a BaAl
2
O
4
single hexagonal phase.
The dominant diffraction peaks index well with the card file (JCPDS:17-0306) in agreement with
other reports [1].

27
400 450 500 550 600 650 700
0
100
200
300
400
500
600
700
Boric Axid mole %
15 %
10 %
7 %
5 %
2 %
0 %

I
n
t
e
n
s
i
t
y

(
a
.

u
.
)
Wavelength (nm)

Figure 2: PL emission spectra (
exc
= 325 nm) of BaAl
x
O
y
:Eu
2+
,Dy
3+
phosphor for
different content of boric acid
The excitation spectrum of phosphors generally shows a broad-band spectrum extending from 250
to 400 nm. The PL results, which are in good agreement with the XRD data, revealed a main peak
at 496 nm and a shoulder peak at 580 for sample prepared without boric acid. The peaks are due
to the transitions from the lowest 2D level of the excited 4f
6
5d
1
configuration to the ground
8
S
7/2

level of the 4f
7
configuration of the Eu
2+
ion. It has been reported the emission spectrum of the
BaAl
2
O
4
:Eu
2+
,Dy
3+
samples obtained by solid state method presented a main peak at 500 nm, and
a shoulder peak at 435 nm. Compared to our results, it clearly exhibited a slight blue shift of the
broad band which might be caused by the quantum size effect [2]. Sample with boric acid show
peaks at 480, 580, 615 and 656 nm. It was observed that it also significantly reduces the intensity
of blue emission while enhancing the red emissions. The decay characteristics show that the
afterglow property was enhanced by the addition of B
2
O
3
[3]. The B
2
O
3
acts as an inert high
temperature solvent (flux) to facilitate the grain growth of barium aluminates. These increase the
penetration of trap centers in the ceramics and therefore achieve improvements in persistence
luminescence.

[1] X.Y. Chen et al., J. Phys. Chem. C, 113 (2009) 2685.
[2] R. Stefani et al., J. Opt. Mater. 31 (2009) 1815.
[3] A. Nag et al., Mater. Res. Bull. 39 (2004) 331.

28
Synthesis, persistent luminescence, and thermoluminescence O 06
3
SiO
5
:Eu
2+
,RE
3+
(RE= Ce, Nd, Dy, Ho, Er, Tm, Yb)
and orange Sr
3-x
Ba
x
SiO
5
:Eu
2+
, Dy
3+
phosphor
Jing Wang*, Baohong Li, Ye Li , Qiang Su

*Corresponding author: ceswj@mail.sysu.edu.cn
Ministry of Education Key Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of
Optoelectronic Materials and Technologies, School of Chemistry and Chemical Engineering, Sun Yat-sen University,
Guangzhou, PR China

Keywords: rare earth, silicates, orange persistent phosphor
In the last decades, persistent luminescent materials have attracted much attention because they
have significant practical and potential applications in many fields, e.g., emergent lighting, display,
detection of high-energy rays such as UV, X-ray, -ray etc, and multidimensional optical memory
and imaging storage. Up to nowasday, the research interests worldwide have been mainly focused
on blue and green persistent luminescent materials based on Eu
2+
doped aluminates, silicates,
aluminosilicates and oxides. Comparatively, the yellow, orange and especially red persistent
luminescent materials with good chemical stability and excellent persistent luminescent
performance such as high brightness and long duration are in great scarcity.
In the present case, we develop a yellow Sr
3
SiO
5
: Eu
2+
,RE
3+
(RE= Ce, Nd, Dy, Ho, Er, Tm, Yb) and an
orange Sr
3-x
Ba
x
SiO
5
: Eu
2+
, Dy
3+
persistent luminescent phosphor and systematically characterized
them using XRD, photoluminescent excitation and emission spectra, persistent decay curve and
emission spectra, and thermoluminescence spectra. The XRD results show that the structure of all
Sr
3
SiO
5
: Eu
2+
,RE
3+
samples was mainly coincident with Sr
3
SiO
5
and a solid solution of Sr
2.94-
x
Ba
x
Eu
0.03
Dy
0.03
SiO
5
were formed in the range of x=1-0.6. The photoluminescence properties show
that all phosphors can be efficiently excited by UV-visible light from 250 to 500 nm, and exhibit
intense tunable emission from yellow-orange region toward orange-red region (570-591 nm). They

29

Figure 1: The persistent emission spectra (
ex
=370nm) of Sr
3
SiO
5
:
0.03Eu
2+
,0.03RE
3+
(RE= Ce, Nd, Dy, Ho, Er, Tm, Yb) and Sr
3-x
Ba
x
SiO
5
:
0.03Eu
2+
,0.03Dy
3+
(x=0,0.05,0.1,0.2,0.4,0.6).

are due to 4f5d and 5d4f allowed transitions of Eu
2+
ion. The yellow persistent luminescence
strongly depends on co-doped rare earth ion and its performance decreases in the order: Nd>Ho>
Dy>Er>Tm>Ce> Yb and the persistent luminescence color can be finely tuned from yellow region
toward orange-red region (557-591 nm) simply by modify the composition ratio of Sr
1-x
/Ba
x
. The
thermoluminescence properties show that one peak is dominating at 367.5 K in Sr
3
SiO
5
: Eu
2+
,Dy
3+

and is prominent at 351.5 K in Sr
2.74
Ba
0.2
Eu
0.03
Dy
0.03
SiO
5
, which are associated with the foreign
defects due to the aliovalent substitution of rare earth ions.

[1] P.F. Smet et al., J. Electrochem. Soc. 156 (2009) H243-H248.
[2] J. Wang et al., J. Mater. Chem. 14 (2004) 2569-2574.
[3] X. Sun et al., J. Phys.D: Appl. Phys. 41 (2008) 195414-195417.

30
Yellow persistent luminescence in Sr
2
SiO
4
:Eu
2+
,Dy
3+
O 07
Danuta Dutczak, Alexander Milbrat, Thomas Jstel*
*Corresponding author: tj@fh-muenster.de
Mnster University of Applied Sciences, Steinfurt, Germany

Keywords: ortho-silicates, persistent phosphors
During the last decade, afterglow phosphors have attracted considerable attention due to their
potential applications in various fields, including safety indication, light sources, graphic arts or
optical data storage. After the discovery of SrAl
2
O
4
:Eu
2+
,Dy
3+
in the middle of the 1990ties
extensive research on different afterglow materials were conducted to tune their emission color
and to prolong their persistent luminescence properties. To this end, different synthesis methods,
various co-dopants, and fluxes were investigated. However, these studies did not deliver efficient
afterglow phosphors for the yellow to red spectral range.
Until now, the only efficient afterglow phosphors are blue to green emitting Eu
2+
doped silicates or
aluminates. Therefore, the development of an efficient yellow and red emitting afterglow
phosphor is an ongoing challenge for solid state chemists. There are only few publications dealing
with yellow or red emitting afterglow phosphors and most of them show weak and rather short
persistent luminescence.
This contribution deals with the Sr
2
SiO
4
:Eu
2+
,Dy
3+
yellow emitting afterglow phosphor and aims at
the improvement of its optical properties and the extension of its persistent luminescence.
Sr
2
SiO
4
:Eu
2+
,Dy
3+
samples were prepared via a solid state and sol- gel method. The calcination was
performed in a strongly reducing atmosphere comprising 30% N
2
and 70% H
2
at 1350 C.
Sr
2
SiO
4
:Eu
2+
exists in a monoclinic and an orthorhombic phase. The preparation via solid state
method yields the orthorhombic phase, while the preparation by means of sol-gel method yields
the monoclinic phase. The UV and VUV excited luminescence at room and liquid nitrogen
temperature, as well as, the decay times were recorded to characterize the synthesized samples.
The most persistent luminescence has been observed for Sr
2
SiO
4
:1%Eu
2+
,0.5%Dy
3+
crystallising in
the orthorhombic phase.

[1] N. Lakshminarasimhan et al., Mater. Res. Bull. 43 (2008) 29462953.
[2] Z. Pan et al., J. Lumin. 129 (2009) 11051108.
[3] J.H. Lee et al., Mater. Sci. Eng. B 146 (2008) 99102.

31

Session II: Applications of persistent phosphors / Energy storage

O 08 What electron paramagnetic resonance spectroscopy teaches us 32
2+
centers in CsBr:Eu
2+
O 09 Influences and improvements on the brightness 34

O 10 Elaboration of nanoparticles with persistent luminescence 35
for in vivo imaging
O 11 Thermoluminescence characteristics of 37
Lu
2
O
3
Aneta Wiatrowska, University of Wroclaw, Poland
O 12 Evaluating the brightness of persistent phosphors: 39
beyond the candela
O 13 Water soluble afterglow nanoparticles for biomedical imaging 41

32
What electron paramagnetic resonance spectroscopy teaches us O 08
2+
centers in CsBr:Eu
2+
Henk Vrielinck
1,
*
,#
, Dmitry Zverev
1
, Paul Leblans
2
, Jean-Pierre Tahon
2
, Paul Matthys
1
, Freddy
Callens
1

*Corresponding author: henk.vrielinck@ugent.be
#
Postdoctoral Fellow of the Flemish Research Foundation (FWO)
1
Ghent University, Department of Solid State Sciences, Gent, Belgium
2
Agfa Healthcare NV, Mortsel, Belgium

Keywords: storage phosphors, photostimulated luminescence, CsBr, Eu
2+
, EPR
Since the late 1990s Agfa has directed research efforts towards the development of a CsBr:Eu
2+

based X-ray storage phosphor for medical image plates (IPs) in computer radiography, that would
solve the resolution problems of the BaFBr:Eu
2+
powder IPs, while maintaining high sensitivity [1].
It was found that thermal evaporation of CsBr:Eu
2+
on an Al substrate may result in oriented
needle growth (needle image plate, NIP), only a few m in diameter and up to several 100 m in
length (see Fig. 1), matching resolution and sensitivity requirements. This in itself is very
remarkable, as melt-grown Eu
2+
doped single crystals perform rather poor as photostimulated
luminescence (PSL) phosphor. It was further shown that a post-synthesis anneal at moderate
temperatures (180-200C), preferably in a humid atmosphere, improves the PSL sensitivity of the
plates [2]. With the aim of understanding the PSL properties of CsBr:Eu
2+
NIPs and explaining the
differences with large single crystals, we investigated these systems with electron paramagnetic
resonance (EPR) and electron nuclear double resonance (ENDOR). We focused attention on the
structure of incorporated Eu
2+
centers. In this contribution, we review the results of these studies.

Figure 1: CsBr:Eu NIP : side (left) and top (right) view SEM image
In literature the decay of the Eu
2+
-related EPR spectrum in CsBr at room temperature had been
attributed to the aggregation of <110> oriented Eu
2+
-V
Cs
(Cs vacancy) dipoles with the formation of
trimers as an initial step [3]. Hackenschmied et al. [4] observed the XRD signature of additional
Cs
x
Eu
y
Br
z
phases in CsBr:Eu
2+
powders after annealing to 200C and a correlated increase of the
sensitivity of the PSL phosphor. Later studies further recognized the significance of oxygen and/or
water in the annealing process, from which a hypothesis on the formation of Eu
2+
-O
2-
self-
compensating defect pairs emerged [5]. Eu
2+
trimer or Cs
x
Eu
y
Br
z
phase formation in CsBr,
however, remain popular models for explaining the high PSL sensitivity of NIPs. Our EPR and
ENDOR study yielded two conclusions that put these literature hypotheses in another perspective.

33
Our first conclusion concerns the Eu
2+
related centers in NIPs, which prove to differ substantially in
structure from those in single crystals (both in aggregated and in isolated form), as is already clear
from the comparison of their EPR spectra in Fig. 2. The intensity of the EPR spectrum of the NIPs
was shown to be correlated with the plate sensitivity [5]. A detailed study of the temperature
dependence of the EPR spectrum, in combination with ENDOR at 3 K, enabled us to propose a
model for the centers, in which a Eu
2+
ion substitutes for Cs
+
and is accompanied by a H
2
O
molecule and a V
Cs
at two of the nearest neighbor cation sites [6].

Figure 2: Q-band (34 GHz) EPR spectra of (a) CsBr:Eu
2+
NIPs at RT, (b) single
crystals at RT with Eu
2+
in aggregated state, (c) NIPs at 20 K (B // <100>) and (d)
single crystals heated to 820 K and quenched to 77 K at 20 K (B // <100>). Note
the difference in scale between left and right panels.
The second conclusion is about the Eu
2+
centers in CsBr single crystals. In agreement with
literature we find that isolated Eu
2+
centers, obtained after heating crystals to 820 K and rapid
quenching to 77 K, aggregate at room temperature (RT). In contrast with earlier reports, however,
the analysis of the angular dependence of the spectra clearly shows that these isolated Eu
2+

centers have cubic symmetry at temperatures down to 20 K. This either means that a charge
compensating V
Cs
near the Eu
2+
ion remains highly mobile at very low temperatures and produces
an effective cubic field via fast hopping, or perhaps more likely that a dominant fraction of
isolated Eu
2+
ions in CsBr have no V
Cs
in their vicinity.
The consequences of our findings on future research towards understanding and/or optimizing
CsBr:Eu
2+
NIPs will be discussed.

[1] P. Leblans et al., Physica Medica, XV (1999) 301304.
[2] M. Weidner et al., Radiat. Meas. 42 (2007) 661-664, and PhD thesis M. Weidner (2009).
[3] V. P. Savelev et al., Fizika Tverdogo Tela 16 (1974) 1090-1093.
[4] P. Hackenschmied et al., J. Appl. Phys. 93 (2003) 5109-5112.
[5] S. Hesse et al., Radiat. Meas. 42 (2007) 638-643.
[6] F. Loncke et al., Appl. Phys. Lett. 92 (2008) 204102.
[7] H. Vrielinck et al., Phys. Rev. B 83 (2011) 054102.

34
Influences and improvements on the brightness O 09
Bernhard Walfort

Corresponding author: walfort@rctritec.com
LumiNova AG, Teufen, Switzerland

Keywords: luminous products, improvement
Afterglow pigments are nowadays used in many products. Typical applications are in traffic- or
safety signs, instrument illumination or toy industry. Each of these applications have their special
requirements to the pigment characteristics (excitability, decay behaviour, particle size, emission
colour, body colour, etc.). The development and manufacturing of a very good glowing product is
not only possible by the use of a phosphorescent pigment with highest brightness, it is always also
an interaction between the design of the product, the pigment characteristics and the processing
parameters.
The main design and processing parameters are:
- type of chosen binder-matrix (varnish, binder, powder coating, plastic or pure powder)
- application process used (filling, printing, extrusion, spraying, etc.)
- design & layout (luminous area, layer thickness, mass of applied pigment, background
colour, etc.)
We will give an overview about:
- typical requirements asked from industry and a demonstration on selected examples how
these requirements can be fulfilled by adjustment of the pigment characteristics and
processing parameters.
- products showing a satisfying performance
- products and applications which are not suited for use of luminous afterglow pigments

35
Elaboration of nanoparticles with persistent luminescence O 10
for in vivo imaging
Cline Rosticher
1,
*, Corinne Chanac
1
, Bruno Viana
2
, Aurlie Bessire
2

*Corresponding author: celine.rosticher@etu.upmc.fr
1
Laboratoire Chimie de la Matire Condense de Paris - Universit Pierre et Marie Curie - UMR CNRS 7574 - Collge
de France, Paris, France
2
Laboratoire Chimie de la Matire Condense de Paris - Universit Pierre et Marie Curie - UMR CNRS 7574 Ecole
Nationale Suprieure de Chimie de Paris, France

Keywords: persistent luminescence, in vivo imaging, nanotracers , silicate, oxisulfide
In the past decades, there has been a great improvement in the domain of the imaging systems
and new imaging tools have been developed. Optical imaging, in which photons are the
information source, is a rapidly expanding field.
We aim at developing nanoparticles with persistent luminescence emitting in the red to near-
infrared range for small animal imaging. The nanoparticles are first excited by a UV light for a
couple of minutes outside the animal body, then injected to the animal, where they emit visible
light for hours after the injection (figure 1). Autofluorescence, resulting from external illumination
during signal acquisition, is therefore avoided.

Figure 1: a) particles in suspension are excited by UV light. b) The required
quantity of liquid is taken then c) injected in an anaesthetized animal.
d) Acquisition of the signal coming from the animal can begin
without any external illumination.
Different families of materials have been considered as host lattices for doping with transition
metal and lanthanide ions: silicates and oxysulfides. Our starting material composition for the
silicate compounds was Ca
0.2
Zn
0.9
Mg
0.9
Si
2
O
6
[1]
and to improve the emission in the infrared we now
develop Ca
x
Mg
y
Si
2
O
6
(with x and y smaller than 1) compounds which were doped with the same
luminescent ions (Eu
2+
, Dy
3+
, Mn
2+
). Those are synthesized by a sol gel method. We are also
interested in gadolinium oxysulfides doped by some luminescent ions such as Eu
2+
, Ti
4+
, Mg
2+
. They
are obtained by hydrothermal method and microwave route. All these compounds were
characterized by Transmission Electronic Microscopy, X-Ray Diffraction, and their luminescent
properties were studied with a ICCD camera (photon-imager from Biospace).

36
The final objective of this work is to obtain biocompatible and/or biodegradable nanoparticles
with the highest luminescence intensity and time.
In the end, we want to develop nanoparticles of doped calcium phosphates, which are the most
important inorganic constituents of biological hard tissues.

[1] Q. le Masne de Chermont et al., Proc. Natl. Acad. Sci. USA 104 (2007) 92669271.

37
Thermoluminescence characteristics of Lu
2
O
3
:Pr,Hf storage phosphor O 11
Aneta Wiatrowska
1
, Eugeniusz Zych
1,2,
*

*Corresponding author: zych@wchuwr.pl
1
Faculty of Chemistry, University of Wrocaw, Poland
2
Wroclaw Research Centre EIT+, Wrocaw, Poland

Keywords: Lu
2
O
3
:Pr,Hf, storage phosphors, thermoluminescence
Thermoluminescence (TSL) is a thermally stimulated emission of light following a previous
irradiation with visible, ultraviolet or yet more energetic photons [1]. The results obtained from
glow curves offer very usefull information about the possible interactions between the impurities
and other defects enganed in the process. Lu
2
O
3
possesses a high density (~9.42 g/cm
3
) and high
effective atomic number (Z
eff
= 67.3) which makes it an attractive host for scintillators, X-ray and X-
ray storage phosphors as it efficiently absorbs the high energy radiation.
The investigated materials, Lu
2
O
3
:Pr,Hf were fabricated by the Pechini method using Lu
2
O
3
, HNO
3
,
Pr
6
O
11
, HfCl
4
, citric acid and ethylene glycol. Raw powders were prepared at 700 C. These were
subsequently heat-treated at different temperatures up to 1700 C in different atmospheres for 5
hours. Structural measurements proved that lutetium oxide activated with Pr
3+
ion and co-doped
with Hf
IV
ion crystallized in cubic structure.

Figure 1: 3D graph of TSL of Lu
2
O
3
:0.05%Pr,0.1%Hf after exposure to X-Rays for 10
minutes at room temperature. The heating rate was 4.8 C/s.

Figure 1 shows a 3D graph of TSL of Lu
2
O
3
:Pr,Hf irradiated with X-Rays for 10 minutes. The
thermally stimulated luminescence (TSL) covers the range of 575 - 700 nm and corresponds to the
1
D
2
-
3
H
4,5
transitions within the Pr
3+
. Radioluminescence, photoluminescence, thermoluminescence
and optically stimulated luminescence spectra of Lu
2
O
3
:Pr,Hf do not differ, practically.

38
As seen in Fig. 1 at least three glow bands appear indicating that at least three different traps are
active in storing energy in Lu
2
O
3
:Pr,Hf. The trap parameters: depth trap (E) and frequency factor
(s) were calculated by fitting the glow curves with the general order kinetics model [2]. Analysis of
the data will be presented. TSL intensity is strongly dependent on the synthesis conditions, while
the shape of the glow curves is not. The highest intensity of thermoluminescence was observed
for materials prepared in reducing atmosphere at 1700 C. It was proved that this is Hf addition
which is crucial for the efficient permanent energy trapping in Lu
2
O
3
:Pr.
Changes in thermoluminescence glow curves due to IR irradiation (980 nm and 780 nm) are given
in Fig. 2. Carriers from traps giving TSL at 110 C and 220 C were freed upon stimulation with 980
nm radiation. 780 nm radiation removed additionally energy from the trap giving TSL around 245
C. Yet, the trap producing TSL around 325 C was not affected by such radiation. More details will
be given in the presentation. Analysis of TSL properties of these materials will be shown and
effects of technological conditions will also be presented.

Figure 2: TSL glow curves of Lu
2
O
3
:Pr,Hf registered after exposure to UV radiation,
and additionally stimulated with 980 nm (30 or 60 min)
or 780 nm (30 min) radiation. The heating rate was 4.8 C/s.

[1] S. W. S. McKeever, Thermoluminescence of solids, Cambridge Solid State Science Series, 1985
[2] G. Kitis et al., Nucl. Instr. Meth. Phys. Res. B 262 (2007) 313-322.

39
Evaluating the brightness of persistent phosphors: O 12
beyond the candela
Katrien Meert, Philippe F. Smet, Dirk Poelman*

*Corresponding author: dirk.poelman@ugent.be
Lumilab, Department of Solid State Sciences, Ghent University, Belgium

Keywords: persistent phosphors, photometry, photopic, scotopic, mesopic, vision
Product specifications of persistent luminescent materials are based on their luminance at specific
times after excitation or on the time until the luminance has dropped to a certain level (typically, a
value of 0.32 mcd/m
2
is used). However, this only allows a useful comparison of different
materials when they have a similar emission spectrum. Indeed, due to the shift of the human eye
sensitivity towards lower wavelengths upon decreasing light intensity (the so-called Purkinje
effect), a red-emitting material having the same luminance as a blue- or green-emitting material
will look much weaker under low level background illumination [1]. The aim of the present work is
to gain a better understanding of the relation between measured luminance and perceived
brightness of persistent luminescent materials and to find alternative variables to describe such
materials.
The human eye is a highly complicated instrument in which physical, photochemical and
neurological effects influence the actual observation of brightness and colour. Under daylight
conditions, cones are used for high spatial resolution and colour vision (the photopic regime),
while at low-level light conditions, the much more light sensitive rods take over (the scotopic
regime). During twilight, in the so-called mesopic region, both rods and cones are active. Many
efforts are being made to describe human response in this intermediate region, since it is of major
interest for optimizing illumination conditions in outdoor environments, like street lighting. Apart
from having a different absolute sensitivity, spectral response and distribution over the retina of
the eye, rods and cones sensitize or dark adapt in a different way and on a different time scale. In
view of all these elements, it is highly unlikely that the human eye response under all illumination
conditions can be modelled realistically with a limited number of parameters. Therefore, we have
limited ourselves to trying to describe the visibility of a persistent luminescent material in a simple
but realistic case: a person is light-adapted in a well lit room, when the electricity fails and the
person is left in complete darkness, except for a persistent luminescent sign [2].
Starting from these assumptions, we have developed a simple visibility model, accounting for the
different spectral response of rods and cones and the shift from cone to rod vision upon
decreasing luminance. In addition, the model takes into account the dark adaptation of the eye:
when a test person is suddenly left in the dark, both rods and cones are still light adapted and the
person is virtually blind. During the first few minutes, the cones remain more sensitive than the
rods, and the visibility threshold is determined by the increasing cone sensitivity. After about 8
minutes, the rod sensitivity surpasses that of the cones; this is called the rod-cone breakdown. The
present model explicitly uses the relative sensitivity of rods and cones at any time during the dark
adaptation process to define a visibility index, which is assumed to give a better description of
the observed brightness of persistent luminescent materials. Figure 1 shows both the measured

40
luminance of a number of differently coloured benchmark persistent phosphors (GloTech Int.)
and the predicted visibility index. Lab experiments using a number of test persons confirm the
almost constant apparent brightness during a long period of time and the observed brightness
ratio of the materials, totally different from the ratios one would expect from the measured
luminance values.

Figure 1: Measured luminance (left) and predicted visibility (right) of a number of
persistent phosphors as a function of time. The visibility index is calculated for a
test person who is fully light adapted at time zero.

[1] D. Poelman et al., Opt. Expr. 17 (2009) 358-364.
[2] D. Poelman et al., Opt. Expr. 18 (2010) 26293-26299.

41
Water soluble afterglow nanoparticles for biomedical imaging O 13
Wei Chen
Corresponding author: weichen@uta.edu
Nano-Bio Physics, Department of Physics, University of Texas at Arlington, Texas

Cancer is a class of diseases in which a group of cells display uncontrolled growth. Every year,
about 562,340 Americans are expected to die of cancer, more than 1,500 people a day. Cancer is
the second most common cause of death in the US, exceeded only by heart disease. In the US,
cancer accounts for nearly 1 of every 4 deaths. Early detection and effective treatment are the
best hope for cancer patients. Photodynamic therapy (PDT) is a promising recipe for cancer
treatment. However, the difficulty of light penetration into deep tissue has hitherto prevented the
application of photodynamic therapy for deep cancer treatment. The three components that are
required for PDT are oxygen, photosensitizers, and light. It is commonly accepted that singlet
oxygen is the predominant cytotoxic agent produced during PDT. Therefore, PDT efficiency is
largely determined by the yield of singlet oxygen, which is a product of photosensitizer structure,
light absorption characteristics (intensity and wavelength), and oxygen concentration. Light must
be delivered to the photosensitizers to activate them. Light in the near infrared range of 700-900
nm, provides best tissue penetration. All current porphyrin-derived PDT compounds, such as
Photofrin, have a strong absorption band near 400 nm called the Soret band.

The Soret band
absorption is more than 10 times stronger in intensity than the absorption at 630 nm.
Unfortunately, attempting to activate porphyrins through absorption at the Soret band is not
practical because blue light has minimal penetration into tissue; thus, direct photodynamic
therapy is not efficient for deep cancer treatment.
To solve the problem of light penetration and to enhance the PDT treatment for deep cancers, I
have proposed a new PDT system in which the light is provided by afterglow nanoparticles with
attached photosensitizers. When the nanoparticle-photosensitizer conjugates are targeted to
tumor and stimulated by X-ray during radiotherapy, the particles will generate light to activate the
photosensitizers for photodynamic therapy. Therefore, the radiation and photodynamic therapies
are combined and occur simultaneously, and the tumor destruction will be more efficient. More
importantly, it can be used for deep tumor treatment as X-ray can penetrate deep into the tissue
such as Breast and prostate cancers. This novel modality is called nanoparticle self-lighting
photodynamic therapy (NSLPDT). In this presentation, I will report the progress of the research in
my group on the design, synthesis and evaluation of nanoparticle conjugates for photodynamic
therapy.

42

Session III: Thermoluminescence / Persistent luminescence models

O 14 Thermoluminescence study of persistent luminescence fading 43
in Sr
2
MgSi
2
O
7
:Eu
2+
,R
3+
materials
O 15 Thermally stimulated luminescence: 45
an algorithm for analyzing phosphorescence curves

O 16 Charging behaviour in persistent phosphors 46
O 17 Photoionization of lanthanide defects and how that affects 47
O 18 Controlling trap depth to enhance persistent luminescence 49
O 19 An x-ray absorption study of SrAl
2
O
4
:Eu,Dy powders 51
O 20 ZnGa
2
O
4
:Cr
3+
: a new red long-lasting phosphor with high brightness 53

43
Thermoluminescence study of persistent luminescence fading O 14
in Sr
2
MgSi
2
O
7
:Eu
2+
,R
3+
materials
Hermi F. Brito
1
, Jorma Hls
1,2,3
, Hgne Jungner
4
, Taneli Laamanen
2,5
, Mika Lastusaari
2,3,
*,
Marja Malkamki
2,5
1,2
*Corresponding author: miklas@utu.fi
1
2
3
4
University of Helsinki, Dating Laboratory, Helsinki, Finland
5

Keywords: thermoluminescence, persistent luminescence, trapping, europium, disilicate
Sr
2
MgSi
2
O
7
:Eu
2+
,Dy
3+
[1] with the blue persistent emission at 475 nm lasting for 24+ hours is one of
the most efficient persistent luminescence materials. Previous thermoluminescence (TL) results
have shown that the shallowest, and simultaneously the main trap for each Sr
2
MgSi
2
O
7
:Eu
2+
,R
3+

material above room temperature is at ca. 0.7 eV below the conduction band corresponding to a
strong TL maximum at ca. 90
o
C [e.g. 2]. The combined results for the trap level energies, obtained
from the experimental data and density functional theory (DFT) calculations, suggested that the
main trap responsible for the persistent luminescence of Sr
2
MgSi
2
O
7
:Eu
2+
,R
3+
is created by charge
compensation lattice defects induced by the R
3+
co-dopants. The defects were tentatively
identified as oxygen vacancies [2]. In this work, the fading of persistent luminescence from
Sr
2
MgSi
2
O
7
:Eu
2+
,R
3+
(R: Y, La-Nd, Sm-Lu) was studied based on the TL and room temperature
luminescence measurements to gain more information on the persistent luminescence
mechanism. The analysis of the TL glow curves was carried out by deconvolution with the program
TLanal v.1.0.3 [3].
The glow curve analysis (Fig. 1) suggested second order kinetics for all the TL signals of these
materials. For e.g. Sr
2
MgSi
2
O
7
:Eu
2+
,Dy
3+
, the main TL peak consists of two traps at 0.63 and
0.97 eV. The glow curves measured at different times after the irradiation show that the shallower
trap is emptied practically completely before the deeper one starts to be bleached to any extent.
The persistent luminescence fading was calculated with the second order decay model [4] using
the single trap depth (E
t
), effective pre-exponential factor (s) and initial trap density (n
0
) values
obtained from the TL glow curve deconvolutions. For e.g. Sr
2
MgSi
2
O
7
:Eu
2+
,Dy
3+
, the calculated
persistent luminescence decay for the shallower trap follows the experimental curve very well
until ca. 60 min (Fig. 2). Beyond this point, which seems to coincide with the total bleaching of this
shallower trap, the experimental decay becomes faster than the calculated one. Contrary to this, it
would be expected that once the deeper trap starts to dominate, the fading would become
slower. The results thus suggest that the decharging is then no longer controlled by isolated traps,
but rather takes place via multiple interacting traps.
The results presented above together further data was used to discuss the details of the
mechanism of persistent luminescence for the Sr
2
MgSi
2
O
7
:Eu
2+
,R
3+
materials.

44

Figure 1: The deconvolution of the TL
glow curve for Sr
2
MgSi
2
O
7
:Eu
2+
,Dy
3+
after
30 s UV irradiation. Inset: effect of fading
(delay: 5 min 10 h) on the glow curve.

Figure 2: Persistent luminescence fading
for Sr
2
MgSi
2
O
7
:Eu
2+
,Dy
3+
(at room
temperature) and that calculated from
the TL data for the 0.63 eV trap based on
second order kinetics.

Acknowledgments: Financial support is acknowledged from the Turku University Foundation, Jenny and
Antti Wihuri Foundation (Finland) and the Academy of Finland (contracts #117057/2000, #123976/2006,
#134459/2009 and #137333/2010). Dr. Kari O. Eskola (University of Helsinki), Dr. Janne Niittykoski
(University of Turku, currently at OMG Kokkola Chemicals Ltd., Kokkola, Finland) and MSc Jukka Hassinen
(University of Turku) are gratefully acknowledged for their help with the thermoluminescence
measurements.

[1] T. Lin et al., J. Mater. Sci. Lett. 20 (2001) 1505-1506.
[2] H.F. Brito et al., J. Therm. Anal. Calorim. (2011), online: March 3, 2011.
[3] K.S. Chung, TL Glow Curve Analyzer v. 1.0.3., Korea Atomic Energy Research Institute and Gyeongsang
National University, Korea, 2008.
[4] R. Chen et al., Theory of Thermoluminescence and Related Phenomena, World Scientific, Singapore,
1997.

100 200 300
0
1M
2M
3M
4M
100 200
0.0
0.5M
1.0M
1.5M
UV irradiation 30 s
Heating rate: 5
o
Cs
-1

I
n
t
e
n
s
i
t
y

/

C
o
u
n
t
s
Temperature /
o
C
Sr
2
MgSi
2
O
7
:Eu
2+
,Dy
3+
Delay
5 min
25
2 h
5
10
0.63 eV
0.97

0 100 200 300
1k
10k
100k
Observed (UV Irradiation 1 min)
Calculated (2
nd
order kinetics)
Sr
2
MgSi
2
O
7
:Eu
2+
,Dy
3+

P
e
r
s
i
s
t
e
n
t

L
u
m
i
n
e
s
c
e
n
c
e

I
n
t
e
n
s
i
t
y

/

A
r
b
.

U
n
i
t
s
Time / min

45
Thermally stimulated luminescence: an algorithm O 15
for analysing phosphorescence curves
Pablo Molina
1,2
, Julin Marcazz
1,2
, Marcelo Lester
1,2
, Martin Santiago
1,
2, Eduardo Caselli
1,3,
*

*Corresponding author: ecaselli@exa.unicen.edu.ar
1
Universidad Nacional del Centro de la Provincia de Buenos Aires, Tandil, Argentina
2
Concejo Nacional de Investigaciones Cientficas y Tcnicas (CONICET), Buenos Aires, Argentina
3
Comisin de Investigaciones Cientficas de la Provincia de Buenos Aires, La Plata, Argentina

Keywords: phosphorescence, curve analysis
Deconvolution of glow and thermally stimulated phosphorescence curves is a widely used
procedure to find the parameters characterising luminescence mechanisms. Most of the employed
models are derived from the set of coupled differential equations describing the adopted model
by resorting to the quasi-equilibrium approximation (QE approximation) and considering only a
trap and a recombination centre (OTOR model) [1]. This model has been extended to a model
having a thermally disconnected trap, i.e., a trap from which electrons cannot escape for the
temperatures a sample is subjected to (Mixed Order kinetics) [1]. A phenomenological model,
dubbed General Order kinetics (GO), is frequently employed, but this model is not physically
meaningful. Since most materials have two or more traps interaction among traps should be
considered when it comes to understand the physics involved in the emission of light.
An algorithm is put forward which does not resort to the QE approximation and takes into account
interactions among traps. The algorithm is based on a model consisting of several active traps, one
recombination centre a thermally disconnected trap. It is a generalization of the interactive multi-
trap system [2, 3]. The analysis of phosphorescence curves by fitting the model to experimental
data requires the integration of the set of coupled differential equations describing the traffic of
carriers among the different centres (recombination and trap centres). Algorithms for fitting a
theoretical model to experimental data, such as the Levenberg-Marquardt method, requires that
the set of equations be integrated a large number of times, what renders the method unsuitable
because of huge computational times. Further, on occasions, the solutions of the differential
equations can be unstable unless the step size of integration is taken to be extremely small
(stiffness). The reported algorithm overcomes these difficulties.

[1] R. Chen et al., Theory of Thermoluminescence and Related Phenomena, World Scientific, Singapore,
1997.
[2] V. Pagonis et al., Numerical and Practical Exercises in Thermoluminescence, Springer, 2006.
[3] http://www2.mcdaniel.edu/Physics/TLwebsite/mathematicafiles.html

46
Charging behaviour in persistent phosphors O 16
Koen Van den Eeckhout*, Philippe F. Smet, Dirk Poelman

*Corresponding author: koen.vandeneeckhout@ugent.be
LumiLab, Department of Solid State Sciences, Ghent University, Belgium

Keywords: charging, mechanism, MAl
2
O
4
:Eu
During the excitation of a persistent phosphor, the intensity of the luminescence does not
immediately jump to a constant value. Instead, it rises gradually during several seconds or minutes
before reaching its final value. This phenomenon is caused by the competition between trap filling
on one hand, and luminescence on the other hand. The more the excited electrons are being
trapped, the less they are available for luminescence. Hence, in the beginning of the excitation
process, when nearly all traps are empty, the trapping process dominates the luminescence, and
the intensity of the emitted light will be low. Clearly, the charging behaviour is closely related to
the traps present in the material.
It is, therefore, surprising that so little investigations on charging behaviour have been reported
[1-3]. These charging curves can learn us more about the amount and density of the traps, the rate
at which electrons (or holes) are being caught, the trap depth, and possibly even their nature and
origin. In fact, the luminescence during charging is closely related to the afterglow of the
phosphor, the only difference being the presence of an external excitation source. Hence, we can
expect to learn at least as much from charging behaviour as there is to learn from afterglow
intensity.
We investigated the charging behaviour in the well-known SrAl
2
O
4
:Eu,Dy and CaAl
2
O
4
:Eu,Nd
phosphors, as a function of the excitation source, duration, and intensity. These measurements
were combined with afterglow and thermoluminescence measurements to study the amount of
traps being filled. The charging curves under intense laser radiation, where the luminescence is
practically saturated, were also measured, to investigate the concentrations of traps and
activators present in the material.
We will present some simple models for the involved processes, with greatly simplified
assumptions, in order to explain some of the observed charging features.

[1] D. Jia, Optical Materials 22 (2003) 65.
[2] Z. He et al., J. Lumin. 119-120 (2006) 309.
[3] X. Zhang et al., J. Lumin. 128 (2008) 818.

47
Photoionization of lanthanide defects O 17
and how that affects luminescence and carrier storage
Pieter Dorenbos*, Adrie J.J. Bos

*Corresponding author: p.dorenbos@tudelft.nl
Luminescence Materials Research Group, Delft University of Technology, The Netherlands

Keywords: photoionization, lanthanides, tunneling
The mechanism active in persistent luminescence phopshors comprises the transport of charge
carriers through the lattice from a donor defect state to an acceptor defect state. In the case of
transport via the conduction band, an electron needs first to be exicted by daylight to energy
levels within the conduction band, next the electron has to delocalize from its parent defect, and
finally it needs to be trapped by the electron accepting defect. This is the charge carrier storing
phase. A reversed process by transport through the conduction band can be active in the
persistent luminescence phase. Alternatively when acceptor and donor defects are close
neighbors, charge carriers may be transferred between them if their final and initial states show
significant orbital overlap, or otherwise a tunneling recombination pathways are thinkable.
From our recent investigations on the YPO
4
:Ce
3+
;Ln
3+
system we managed to study those charge
carrier delocalization phenomena [1,2]. This is illustrated in Fig. 1 for YPO
4
:Ce
3+
;Sm
3+
. After the
storage phase Ce
4+
and Sm
2+
are created. In Fig. 1 the Ce
3+
5d-4f emission is monitored under
optical stimulation of Sm
2+
. From the temperature and excitation wavelength dependence
valuable and unique information is obtained on the thermally activated release of electrons from
Sm
2+
excited states that are located inside the conduction band. Also evidence for tunneling
recombination in close pairs of Ce
4+
-Sm
2+
was obtained.
1.6 1.8 2.0 2.2 2.4 2.6 2.8
0.1
1
10
100
4f
5
5d
1
d
b
SmB

I
n
t
e
n
s
i
t
y

[
a
r
b
.
u
n
i
t
s
]
Energy (eV)
SmA
4f
5
5d
2
a
c
e
f
g
h
i
7
F
0
-
5
D
0

Figure 1: OSL excitation spectra of Sm
2+
in YPO
4
:Ce
3+
;Sm
3+
as function of
temperature. Spectrum a) is at 10K and spectra b) through i)
are from 160 K to 300 K with 20 K interval.

48
In this presentation the different charge carrier transport pathways and how they can be revealed
by experiment will be reviewed. Possible relationships between electron delocalization. and
luminescence excitation efficiency in ordinary phosphors are also addressed.

[1] P. Dorenbos et al., Phys. Rev. B. 82 (2010) 195127.
[2] A.J.J. Bos et al., Radiat. Meas. 43 (2008) 222-226.

49
Controlling trap depth to enhance persistent luminescence O 18
Thomas Maldiney
1
, Aurlie Lecointre
2
, Bruno Viana
2,
*, Aurlie Bessire
2
,

Michel Bessodes
1
, Didier
Gourier
2
,Cyrille Richard
1
, Daniel Scherman
1

*Corresponding author: bruno-viana@chimie-paristech.fr
1
Unit de Pharmacologie Chimique et Gntique et d'Imagerie; CNRS, UMR 8151, Inserm, U1022, Universit Paris
Descartes, Facult des Sciences Pharmaceutiques et Biologiques, Chimie Paristech, Paris, France.
2
Laboratoire de Chimie de la Matire Condense de Paris; Chimie-ParisTech, UPMC, Collge de France, CNRS UMR
7574, Paris, France

Keywords: diopside, lanthanide, electron traps, nanoparticles, in vivo imaging
In vivo optical imaging, using photons as primary information, has witnessed several major
improvements in the last decades. In this field, we previously reported the synthesis of persistent
luminescence nanoparticles (PLNP) with formula Ca
0.2
Zn
0.9
Mg
0.9
Si
2
O
6
:Eu
2+
,Mn
2+
,Dy
3+
[1] and
sharing the same crystalline structure as diopside CaMgSi
2
O
6
Such material possesses the ability to
be excited under UV-light before intravenous injection in mice, and to emit in the near-infrared
window without further irradiation, circumventing autofluorescence from animal tissues. It was
demonstrated that PLNP could be used as sensitive optical probe for in vivo imaging, and that their
biodistribution was highly dependent on both core diameter and global surface charge [2].
However, luminescence from these PLNP was not intense enough to provide long-term monitoring
of in vivo probes accumulation, unveiling the need to work on new nanomaterials with improved
optical characteristics.
To better understand the origin of such phenomenon, we suggested a mechanism of persistent
luminescence in diopside host, with Mn
2+
acting both as the hole trap and the recombination
center. We then hypothesized that trivalent lanthanide ions could act as an efficient electron trap
for persistent luminescence [6, 7].
Starting from the hypothesis that controlling electrons trap depth could help to enhance the
optical properties of PLNP, we presently report the synthesis of several Mn
2+
doped diopside
nanoparticles, either co-doped with trivalent lanthanide ions CaMgSi
2
O
6
:Mn
2+
,Ln
3+
(Ln = Dy, Pr, Ce,
Nd), only excitable with X-rays, or tri-doped with divalent europium and trivalent lanthanide ions
CaMgSi
2
O
6
:Mn
2+
,Eu
2+
,Ln
3+
, to enable UV excitation. These nanomaterials were compared to hybrid
enstatite-diopside Ca
0.2
Zn
0.9
Mg
0.9
Si
2
O
6
already used for in vivo imaging. Divalent manganese,
present in all the compounds, is at the origin of the red emission. In this work, we identify Pr
3+
as
the optimal electron trap in diopside host, which led to an improved nanomaterial, excitable with
UV light, and displaying the most intense afterglow in the near-infrared region (see Fig. 1). We
finally managed to extract nanoparticles with narrow distribution from the initial polydisperse
powder, and report their application for highly sensitive real-time in vivo bio-imaging in mice (see
Fig. 2).

50

Figure 1: Decay of the Mn
2+
luminescence intensity
at 685 nm of Mn and rare-earth co-doped
CaMgSi
2
O
6
:Mn,Ln compounds, recorded after
10 minutes X-ray irradiation. Insert: LLP spectrum,
6 seconds after X-ray irradiation, due to the
4
T
1
6
A
1
transition of Mn
2+
ions in Mg
2+
sites.
Figure 2: In vivo imaging of different diopsides
NPs (size <150nm) following injection of
100 g (A) Ca
0.2
Zn
0.9
Mg
0.9
Si
2
O
6
:Eu,Mn,Dy;
(B) CaMgSi
2
O
6
:Eu,Mn,Pr. Signal recorded
for 15 minutes following systemic injection
after UV-excitation of the probes (100 g).

[1] Q. le Masne de Chermont et al., Proc. Natl. Acad. Sci. USA 104 (2007) 9266-9271.
[2] T. Maldiney et al., ACS Nano 5 (2011) 854-862.
[3] A. Lecointre et al., J. Lumin.129 (2009) 1527-1530.
[4] A. Lecointre et al., Radiat. Meas. 45 (2010) 497-499.
X 10
0 600 1200 1800 2400 3000
10
100
1000
10000
I
n
t
e
n
s
i
t
y
(
a
.
u
.
)
Time (s)
CMSO
CMSO:Pr
CMSO:Dy
CMSO:Nd
CMSO:Ce
X 10
0 600 1200 1800 2400 3000
10
100
1000
10000
I
n
t
e
n
s
i
t
y
(
a
.
u
.
)
Time (s)
CMSO
CMSO:Pr
CMSO:Dy
CMSO:Nd
CMSO:Ce
500 600 700 800
Wavelengths (nm)
500 600 700 800
Wavelengths (nm)

51
An x-ray absorption study of SrAl
2
O
4
:Eu,Dy powders O 19
Katleen Korthout*, Koen Van den Eeckhout, Philippe F. Smet, Dirk Poelman

*Corresponding author: katleen.korthout@ugent.be
LumiLab, Department of Solid State Sciences, Gent, Belgium

Keywords: persistent phosphors, XAS, rare earths
Exactly fifteen years before this conference, Matsuzawa et al. reported on the very bright and
long-lasting afterglow of SrAl
2
O
4
:Eu,Dy [1]. This discovery launched the research into other
persistent materials and to the mechanism behind it. Nevertheless, fifteen years later, the
understanding of the persistent luminescence mechanisme is still limited [2].
We combined radioluminescence (RL) and x-ray absorption spectroscopy (XAS) measurements on
the Eu and Dy L
III
-edges of the phosphor. XAS can be used to investigate the valence state of the
rare earth dopants, while RL gives information about the charging behaviour of the phosphor upon
x-ray irradiation.

Figure 1: The experimental set-up, combining XANES and RL measurements.
In this work we establish XAS as an appealing technique to study the valence states of rare earths
in persistent phosphors. Furthermore we demonstrate that a valence state change upon x-ray
irradiation occurs for the Eu ions, but not for the Dy ions [3].
Upon x-ray irradiation at 120K, SrAl
2
O
4
:Eu,Dy emits the typical bluish green light. However, the
radioluminescence intensity is not constant, as it monotonically increases until reaching a
stationary value. We will show that the RL intensity can be empirically described by introducing
two time constants. From the changes in the RL intensity, the filling process of the traps relevant
for the persistent luminescence can be modeled.
The Eu L
III
XANES spectra of SrAl
2
O
4
:Eu,Dy consist of two well resolved edge resonances, indicating
the existence of two valence states for the Eu ions. The dynamics of the valence state changes was
studied by calculating the peak area ratio between Eu
3+
and Eu
2+
as a function of x-ray exposure.
The results show a relative increase in peak area ratio of the Eu
3+
ions upon irradiation. This
observation proves the ionization of Eu
2+
to Eu
3+
, as suggested by several models of persistent

52
luminescence [4-7]. The time evolution of this valence state change is proportional to the number
of filled traps, as derived from the RL intensity profile.

Figure 2: . XANES peak area ratio between Eu
3+
and Eu
2+

as a function of x-ray irradiation time at 120K (blue dots).
The red line shows the modeled peak area ratio
based on the radioluminescence intensity profile.
Summarizing, we have combined radioluminescence and x-ray absorption spectroscopy to study
the valence states of europium and dysprosium ions in the persistent luminescent material
SrAl
2
O
4
:Eu,Dy. Part of the europium ions ionize from Eu
2+
to Eu
3+
during the trapping process.
However, no reduction of the Dy
3+
ions could be detected, indicating that the released electrons
are not captured by the codopant ions. These observations should be included in future models
for the mechanism of persistent luminescence.
EXAFS was employed to study the local structure around the rare earth dopants. Preliminary
results on the EXAFS analysis on europium-doped persistent phosphors will be presented.

[1] T. Matsuzawa et al., J. Electrochem. Soc. 143 (1996) 2670-2673.
[2] K. Van den Eeckhout et al., Materials 3 (2010) 2536-2566.
[3] K. Korthout et al., Phys. Rev. B, in press.
[4] P. Dorenbos, J. Electrochem. Soc. 152 (2005) H107-H110.
[5] F. Clabau et al., Chem. Mater. 17 (2005) 3904-3912.
[6] T. Aitasalo et al., J. Phys. Chem. B 110 (2006) 4589-4598.
[7] J. Hls et al., J. Luminesc. 129 (2009) 1606-1609.

53
ZnGa
2
O
4
:Cr
3+
: a new red long-lasting phosphor with high brightness O 20
Aurlie Bessire
1,2,
*, Sylvaine Jacquart
1,2
, Kaustubh Priolkar
2
, Aurlie Lecointre
1
, Bruno Viana
1
,
Didier Gourier
1
*Corresponding author: aurelie-bessiere@chimie-paristech.fr
1
Chimie Paristech, Laboratoire de Chimie de la Matire Condense de Paris, UPMC, Collge de France, UMR-CNRS
7574, Paris, France
2
Department of Physics, Goa University, Taleigao Plateau, Goa, India

Keywords: red, persistent phosphor, gallate, chrome, spinel, bioimaging
It was recently shown that in vivo optical imaging of a small animal can be carried out by using a
persistent phosphor emitting in the red/near-infrared part of the spectrum as the luminescent
probe [1]. A red/near-infrared emission is necessary for luminescence to pass through the animal
tissues which strongly absorb ultraviolet (UV)-blue-green and far-infrared parts of the spectrum
(see Figure 1). By using persistent luminescence particles, the illumination of the animal is
unnecessary and autofluorescence of the tissues is avoided. Furthermore UV excitation of the
particle is carried out before its injection and therefore is not attenuated by the tissues. Therefore
a highly improved quality of imaging can be obtained relative to more common fluorescent
probes. The technique was first demonstrated in 2007 with Ca
0.2
Zn
0.9
Mg
0.9
Si
2
O
6
:Eu
2+
,Dy
3+
,Mn
2+

(CZMSO) nanoparticles, from which red persistent luminescence was detected in a small animal
vasculature for up to one hour after their injection [1].

Figure 1: Absorbance curves of the main biological components
of animal tissues, adapted from [2].

We report here on a new red long-lasting phosphorescence (LLP) material potentially suitable for
in vivo imaging. ZnGa
2
O
4
is a wide band gap semiconductor which allows doping by luminescent
ions such as transition metal ions and shows red luminescence with Cr
3+
doping [3]. It crystallizes
in the normal spinel structure with Zn
2+
ions occupying tetrahedral sites and Ga
3+
ions occupying
octahedral sites. When excited, Cr
3+
emits via its
2
E
4
A
2
transition which gives rise to a far red
CZMSO
(cf. text)
ZnGa
2
O
4
:Cr
3+
Optical window
CZMSO
(cf. text)
ZnGa
2
O
4
:Cr
3+
Optical window

54
luminescence with a maximum at 696 nm in the zinc gallate host [3].

This wavelength range is
totally suitable for in vivo imaging as it corresponds to an absorption minimum for the biological
tissues (see Figure 1).
In this presentation we will show that ZnGa
2
O
4
:Cr
3+
compares better than CZMSO used up to now
for in vivo imaging with UV excitation [4]. Furthermore the mechanism of LLP has been
investigated by varying the nominal Zn/Ga stoichiometry and by using UV and X-ray excitation to
record wavelength-resolved persistent luminescence and thermally stimulated luminescence
(TSL). ZnGa
2
O
4
:Cr
3+
revealed new elements in the field of LLP. The use of Cr
3+
as both luminescent
centre and probe of the local environment appeared as of uttermost use in the investigation of
the mechanisms. The very narrow emission lines of Cr
3+
ions in Ga
3+
sites are so sensitive to
chromium environment that the coordination sphere of the luminescent centre Cr
3+
can be
elucidated (see Figure 2). Hence we showed that antisite defects Ga
Zn
of the ZnGa
2
O
4
spinel
structure were likely to be involved in the charge trapping and recombination processes
responsible for LLP in ZnGa
2
O
4
:Cr
3+
. The LLP intensity was singularly improved by decreasing the
nominal Zn/Ga ratio, i.e. by creating more Zn vacancies that constitute the thermally emptied
traps in the LLP process.

Figure 2: Immediate and persistent luminescence spectra
of ZnGa
2
O
4
:Cr
3+
after X-ray irradiation.

[2] M. R. Hamblin et al., Proc. SPIE 6140 (2006) 614001-12.
[3] H. M. Kahan et al., J. Chem. Phys. 54 (1971) 5197-5205.
[4] A. Bessire et al., Opt. Exp. 19 (2011) 10131-10137.

55

Session IV: Non-Eu
2+
-doped and infrared-emitting phosphors

O 21 IR laser stimulated afterglow fluorescence of 56
Eu(III) doped LaAlO
3
nanocrystals
O 22 Synthesis and characterization of Y
2
O
2
S:Eu nanophosphors 58

O 23 Persistent phosphorescence in Ce
3+
-doped Lu
2
SiO
5
59
O 24 Long-lasting phosphorescence in Ce
3+
-doped garnet crystals 60
O 25 Synthesis and characterization of calcium titanium oxide based 62

56
IR laser stimulated afterglow fluorescence of O 21
Eu(III) doped LaAlO
3
nanocrystals
Pawe Guchowski, Wiesaw Strk*

*Corresponding author: W.Strek@int.pan.wroc.pl
Institute of Low Temperature and Structure Research, Wrocaw, Poland

Keywords: perovskite, photostimulated luminescence, persistent phosphors
The afterglow luminescence was observed in Eu
3+
doped LaAlO
3
nanocrystalline powders (their
synthesis and morphology are presented) under photo-, cathode- and X-Ray irradiation. The
measurements were performed at room and liquid nitrogen temperatures (Fig.1). It was found
that afterglow luminescence of Eu
3+
ion may be drastically amplified (by order) after illumination
with IR laser diode (Fig.2). An increase of afterglow luminescence intensity increased linearly with
incident laser power (Fig.3). It can be noted that the CT band in excitation spectra decreases with
increasing of stimulation power (Fig.4).

Figure 1: The luminescence spectra of Eu:LaAlO
3
measured
under 266nm excitation wavelength (a) and the observed
persistent luminescence after stimulation by IR diode
exc.
= 975 nm (b)

Figure 2: The power dependence of IR LD stimulated persistent luminescence intensity

57
400 600 800 1000 1200 1400 1600 1800
2200
2400
2600
2800
3000
3200

i
n
t
e
n
s
i
t
y

(
a
.
u
.
)
pump laser power (mW)

Figure 3: Dependence of persistent luminescence intensity on incident laser power.

Figure 4: The power dependence of excitation spectra of Eu:LaAlO
3

measured with simultaneous stimulation by IR laser diode
(inset shows the dependence of CT band intensity on IR LD power)

58
Synthesis and characterization of Y
2
O
2
S:Eu nanophosphors O 22
Abdub G. Ali
1
, Francis B. Dejene
1,
*, Hendrik C. Swart
2

*Corresponding author: aliag@ufs.ac.za
1
Department of Physics, University of the Free State (Qwaqwa Campus), Phuthaditjhaba, South Africa
2

Rare earth oxysulfide materials exhibit high luminescence efficiency as well as excellent chemical
stability. These materials are widely used as luminescent host materials of several commercially
available red emitting phosphors. However, there still remain issues affecting the operational
parameters such as luminescence efficiency, stability against temperature, high color purity and
long afterglow. Y
2
O
2
SEu nano powders were prepared by low-temperature synthesis method
using sulfur-contained organic fuel in an ethanol-aqueous solution. The prepared nano powders
were characterized by Scanning electron microscope, X-ray diffraction, photoluminescence spectra
and X-ray photoelectron spectroscopy. It is shown that the assistant fuel ethanol has the effect of
decreasing the water needed, simplifying the experiment procedure by dissolving rare earth
nitrate and sulfur-contained organic fuel into an even solution, and prompting the formation of
rare earth oxysulfide by igniting first during heating that leads to combustion decomposition
reaction. Y
2
O
2
SEu nano crystallines with strong photoluminescence and X-ray luminescence are
obtained using thiourea as organic fuel. Mixtures of Y
2
O
3
Eu and Y
2
O
2
SEu are acquired using
thiourea as fuel, and the content of Y
2
O
2
SEu increases until reaches to about half of the Y
2
O
3
Eu
with the increasing amount of thiourea. Y
2
O
2
SO
4
Eu emerges when S/Y=6 and increases with
increasing thiourea content.

59
Persistent phosphorescence in Ce
3+
-doped Lu
2
SiO
5
O 23
Mitsuo Yamaga
1,
*, Yusuke Ohsumi
1
, Tomomi Nakayama
1
, Thomas P. J. Han
2

*Corresponding author: yamaga@gifu-u.ac.jp
1
Department of Mathematical and Design Engineering, Gifu University, Japan
2
Department of Physics, University of Strathclyde, Glasgow, UK

Keywords: Ce
3+
, oxide crystals, scintillators, persistent phosphors
Ce
3+
-doped oxide crystals are in general not useful in laser operation because of the excited state
absorption. However, they have advantages as scintillators, such as high light-yield and fast
fluorescence decay time. Recently, Ce
3+
-doped

Lu
2
SiO
5
(LSO) crystals have been developed as new
scintillators [1]. Phosphorescence from the crystals with degraded quality was observable
persistently over a day [2]. Such phosphorescence is undesirable as scintillators, but is still useful
in passive optical sources.
A model has been developed to explain the mechanism of persistent phosphorescence observed
in the detail studies of Ce
3+
-doped Ca
2
Al
2
SiO
7
[3] and Eu
2+
-doped barium silicates [4]. Electron-hole
pairs are produced in these crystals through UV (visible) excitation of Ce
3+
(Eu
2+
). Electrons are
trapped at O
2-
vacancies as F
+
centres, whereas holes are self-trapped at Al
3+
(Si
4+
) tetrahedral
sites. The trapped electrons and holes move back to Ce
3+
(Eu
2+
) in the crystals through hopping
and tunnelling, and recombine radiatively at Ce
3+
(Eu
2+
).
In this paper, we discuss similarities and differences between scintillator materials and persistent
phosphors using the optical data of the Ce
3+
-doped LSO crystal. The Ce
3+
fluorescence spectrum in
the Ce:LSO crystal consists of the broad band with the double peaks at 400 and 430 nm. The decay
curve of the fluorescence observed below 300 K in the range from 1 to 500 ns fits well to a single
exponential function with a decay time of 40 ns. The decay time decreases rapidly with increasing
temperatures above 300 K. Although the line shape of the persistent phosphorescence observed
in the Ce:LSO crystal is the same as that of the fluorescence, the decay time has a distribution in
the wide range from 1 to 10
4
s. The ratio of the decay time of the phosphorescence to that of the
fluorescence is 10
8
to 10
12
.
The temperature dependence of the decay curves of the phosphorescence in the Ce:LSO crystal
was observed in the range from 300 to 500 K. The decay curves at 300 and 500 K fit well to power
functions of t
-0.2
and t
-1
, respectively. The function of t
-1
is derived from the radiative
recombination process of trapped electron and hole through tunnelling [5]. On the other hand,
the function of t
-0.2
is derived from the radiative recombination process of trapped electron and
hole through both hopping and tunnelling [4]. The temperature dependence of the decay curves
between 300 and 500 K suggests three different recombination processes of trapped electrons
and holes with different thermal activation energies.

[1] L. A. Kappers et al., J. Lumin. 102-103 (2003) 162.
[2] D. W. Cooke et al., J. Lumin. 92 (2001) 83.
[3] M. Yamaga et al., Phys. Rev. B 65 (2002) 235108.
[4] M. Yamaga et al., Phys. Rev. B 71 (2005) 205102.
[5] S. W. S. Mckeever, Thermoluminescence of Solids, Cambridge University Press, Cambridge (1985)

60
Long-lasting phosphorescence of Ce
3+
-doped garnet crystals O 24
Jumpei Ueda
1,
*, Kotaro Aishima
1
, Setsuhisa Tanabe
1,2

*Corresponding author: j.ueda@at3.ecs.kyoto-u.ac.jp
1
Graduate School of Human and Environmental Studies, Kyoto University, Kyoto, Japan
2
Japan Science and Technology Agency - Precursory Research for Embryonic Science and Technology, Tokyo, Japan

Keywords: long-lasting phosphorescence, afterglow luminescence, Ce
3+
, garnet, blue LED
Long-lasting phosphorescent materials doped with rare earth ions are of practical interest as
luminous paints for safety indication and emergency lighting. So far, there have been a number of
reports of the long-lasting phophorescence in materials doped with rare earth ions, such as Eu
2+

and Ce
3+
. Most of the long-lasting phosphors show the best performance in the persistent time
and brighteness after UV excitation, such as a fluorescent lamp. Recently, however, white light
emitting diodes (LEDs) generally consisting of blue LEDs and yellow phosphors have started to be
widely used as indoor illumination in place of fluorescent lamps because of their high luminous
efficiency, long lifetime, and energy saving ability. Therefore, blue-light induced long-lasting
phosphorescent materials have been the subject of considerable development.
The Ce
3+
-doped garnet crystals used as yellow phosphors for the conventional white LEDs have
many advantages such as strong absorption at the blue LED wavelength (~450 nm), broad yellow
emission, and high quantum efficiency. If the long-lasiting phosphorescence by blue excitation is
realized in the Ce
3+
-doped garnet ceramics, this material can be a good candidate for long-lasting
phosphors by white-LED excitation. However, very few studies of the afterglow luminescence of
Ce
3+
in garnet crystals have been reported. In a previous paper by Holloway and Kestigian in 1969,
they only mentioned observation of the afterglow luminescence in Ce
3+
:Y
3
Al
2
Ga
3
O
12
and
Ce
3+
:Y
3
Al
1.5
Ga
3.5
O
12
by UV excitation.[1] To the best of our knowledge, long-lasting
phosphorescence properties and mechanism in garnet phosphors by blue excitation have never
been investigated. In this study, we present an afterglow mechanism and propose a new
persistent phosphor under white light emitting diode (LED) illumination.[2]
Ce
3+
-doped yittrium scandium galium garnet (YSGG) crystals with (Y
0.995
Ce
0.005
)
3
Sc
2
Ga
3
O
12

compositions were synthesized by solid-state reaction. Commercial powders of Y
2
O
3
(99.99%),
Sc
2
O
3
(99.9%), Ga
2
O
3
(99.99%), and CeO
2
(99.99 %) were used as starting materials. The powders
mixed by a planetary ball milling were pressed into pellets with a 20 mm-diameter and sintered at
1600C for 20 h in vacuum. The as-made pellets were heat-treated under O
2
atmosphere for 20 h.
Photoluminescence (PL), photoluminesence excitation (PLE), photocurrent excitation (PCE)
spectra, afterglow curves and thermoluminescence (TL) were measured for investigation of long-
lasting phosphorescent properties.
Figure 1 shows photographs of the as-made and O
2
-annealed Ce:YSGG ceramics under no
excitation, UV excitation, and after excitation. The green luminescence and afterglow
luminescence were observed at around 500 nm in both Ce:YSGG ceramics by the UV excitation
and after excitation. The luminescence band is ascribed to the 5d - 4f transition of Ce
3+
in the YSGG
crystals. In addition, two broad PLE bands were observed at around 440 and 350 nm in both
Ce:YSGG ceramics by monitoring at 500 nm. The PLE bands at 440 and 350 nm are attributed to

61
the transitions from the ground 4f level to the 5d
1
and 5d
2
levels, which are the lowest and the
2nd lowest 5d levels, respectively. The afterglow luminescence was observed for 1 hour after the
440 nm excitation in the Ce:YSGG ceramic prepared under vacuum. This result indicates that the
present YSGG ceramics can be used as a green afterglow phosphor under indoor illumination
environments utilizing white LEDs composed of a blue LED, instead of fluorescent tubes, which
contains higher energy photons.
The green afterglow decay time by blue excitation decreased after O
2
annealing. Therefore, one of
the potential traps can be oxygen vacancies. In addition, TL peaks were observed at around 75 and
245 K. The depth of trap levels at 75 and 245 K were estimated by using the Hoogenstraaten plot
to be 0.22 and 0.46 eV. From the PCE spectra, two broad bands were observed around 410 and
350 nm. These bands at 410 and 350 nm are ascribed to the transitions from the ground 4f level to
the 5d
1
and 5d
2
levels, respectively. Judging from the activation energy of photocurrent that is
estimated by the temperature dependence of PCE spectra, the 5d
1
and 5d
2
level are located just
below the bottom of the conduction band and within conduction band, respectively, as shown in
Figure 2. This situation is not the case in other garnets such as Y
3
Al
5
O
12
whose band gap is wider
than 6eV.[3] Therefore, the excitation to the 5d
1
level can easily promote the carriers to the
conduction band due to the lower threshold for photoionization. The photoinduced electrons in
the conduction band can be captured by some electron traps. The electrons at the traps (0.22 and
0.46 eV) were moderately released by a thermally stimulated process at room temperature, and
could then be transferred back to the 5d states. Therefore, the green afterglow luminescence in
the Ce:YSGG ceramic was observed by the blue excitation at room temperature.

[1] J.W.W. Holloway et al., J. Opt. Soc. Am. 59 (1969) 60-63.
[2] J. Ueda et al., Appl. Phys. Express 4, (2011) 042602.
[3] F. T. You et al., J. Phys. Condens. Matter 23 (2011) 6.

Figure 1: Images of the as-made and O
2
-annealed
Ce:YSGG ceramics under no excitation, UV excitation,
and after UV excitation.
Figure 2: Energy level scheme of Ce
3+
in
Y
3
Sc
2
Ga
3
O
12
crystal and electron traps

62
Synthesis and characterization of calcium titanium oxide based O 25
pigments with red afterglow.
Eugenio H. Otal
1,
*, Bernhard Walfort
2
, Alexandra Maegli
1
, Songhak Yoon
1
, Angelika Veziridis
1
, Anke
Weidenkaff
1
, Hans Hagemann
3
*Corresponding author: eugenio.otal@empa.ch
1
Empa, Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Solid State Chemistry and
Catalysis, Dbendorf, Switzerland.
2
LumiNova AG, Teufen, Switzerland
3
Dpartement de Chimie Physique, Univ. de Genve, Switzerland.

Keywords: red afterglow, CaTiO
3
, defects
Long lasting afterglow pigments are an interesting field of research for solid state chemists due to
the complex structure-composition-property dependence. The main applications of these
pigments are in the area of safety illumination and emergency signage, where the use of
SrAl
2
O
4
:Eu,Dy [1] fulfill the main requirements: afterglow of more than 12 hours, activation with
daylight (190 nm 470 nm) and emission around the maximum sensibility of the human eye, 520
nm.
The performance of afterglow materials is mainly related to the position of the lanthanides energy
levels in the band gap and the presence of defects in the lattice. While the first depends on the
host lattice and the lanthanides introduced as doping elements, the second mainly depends on the
preparation method and slight modifications in the composition of the host material. Defects act
as electron traps increasing the afterglow time [2].
The development of novel high performance red emitting phosphors by using alternative host
materials is an active field of research. Perovskite-type materials are interesting for this
application because the stable crystal structure enables substitutions on cationic and anionic
positions to modify the attractive physical properties of the compounds [3].
A suitable host material candidate is Pr doped CaTiO
3
[4], which exhibits a red emission around
610 nm but with short afterglow time of less than 2 hours. The origin of defects in this material
can be caused/controlled by inducing an excess of Ca and Ti vacancies in the crystal lattice during
the synthesis. The formation and stability of the resulting defects in the CaTiO
3
lattice can be
controlled by adjusting the excess of Ca atoms in the precursors as well as the thermal treatment
procedure during the synthesis [5].
Besides the production of the solids with excess of Ca in the precursor, the defects can also be
introduced in the by other ways, e.g. partial anionic substitution, replacement of O by N and/or F
[6].
According to this, we present a systematic approach to the study of afterglow properties of
complex titanium oxides, oxynitrides, oxyfluorides and fluorooxynitrides as a function of the
synthesis parameter and thermal treatment. The results are systematically related to the observed
afterglow time to conclude on structure-composition-property relations.


63
[2] W. Jia et al., J. Lumin. 119-120 (2006) 13-18.
[3] S.G. Ebbinghaus et al., Prog. Solid State Chem.37 (2009) 173-205.
[4] Y. Pan et al., J. Solid State Chem.174 (2003) 69-73.
[5] M. eh et al., J. Mater. Sci. 29 (1994) 6295-6300.
[6] G. Tobas et al., Inorg. Chem.43 (2004) 8010-8017.

64

P 01 Energy transfer by ZnO to SiO
2
:Ce
3+
matrix 66
P 02 Improvement on CaAl
2
O
4
:Eu
2+
,Nd
3+
: 67
lower temperature synthesis, longer afterglow duration
Nursen Avci, Ghent University, Belgium
P 03 Red persistent luminescence in biocompatible Ca
3
(PO
4
)
2
69
P 04 Persistent luminescence and mechanoluminescence 71
in MSi
2
O
2
N
2
:Eu
2+
(M = Ca,Sr,Ba)
Jonas Botterman, Ghent University, Belgium
P 05 Influence of titanium and lutetium on 73
the persistent luminescence of ZrO
2

Hermi Brito, Universidade de So Paulo, Brazil
P 06 The effects of Eu ions and Eu:Dy ratio on the structural, 75
morphological and luminescence properties
of blue-green BaAl
x
O
y
:Eu
2+
,Dy
3+
nano phosphors
P 07 Solution-combustion synthesis and photoluminescence property 77
of Gd,YBO
3
:Tb
3+
phosphor powders
P 08 Ca and Hf co-dopants as properties designing constituents 79
of Lu
2
O
3
:Tb-based storage phosphors
Dagmara Kulesza, University of Wrocaw, Poland
P 09 Effects of co-dopants in long lasting phosphorescence phosphors 81
Chengyu Li, Changchun Institute of Applied Chemistry, China
P 10 Luminescent properties of CaAl
2
O
4
:Eu
2+
,Dy
3+
,Nd
3+
phosphors 82
prepared by combustion method
Bakang M. Mothudi, University of South Africa, South Africa
P 11 Persistent luminescence behavior of materials 84
doped with Eu
2+
and Tb
3+
ions
Lucas Rodrigues, Universidade de So Paulo, Brazil
P 12 Persistent luminescence in rare-earth doped nitrido-silicates 86

65
P 13 Preparation and persistent luminescence in 87
rare-earth doped Ca
2
Si
5
N
8
nanoparticles
Bruno Viana, LCMCP Paris, France
P 14 Properties of blue emitting CaAl
2
O
4
:Eu
2+
,Dy
3+
phosphors 89
by optimizing the amount of flux and fuel
Ali Wako, University of the Free State, South Africa
P 15 Effect of Eu
2+
and Nd
3+
on the properties of blue CaAl
2
O
4
:Eu
2+
,Nd
3+
91
long afterglow phosphor
P 16 Controlling storage properties of Lu
2
O
3
:Tb, and Lu
2
O
3
:Pr phosphors 93
by means of aliovalent co-dopants and preparation conditions
Eugeniusz Zych, University of Wrocaw, Poland

66
Energy transfer by ZnO to SiO
2
:Ce
3+
matrix P 01
Abdub G. Ali
1
, Francis B. Dejene
1,
*, Hendrik C. Swart
2

*Corresponding author: aliag@ufs.ac.za
1
2

High quality luminescent ZnO powder with different sizes was prepared by wet chemical synthesis
through a sol gel process just by adjusting the molar ratio of sodium hydroxide to zinc acetate. The
prepared nano powders were characterized by Scanning electron microscope, X-ray diffraction,
photoluminescence spectra and X-ray photoelectron spectroscopy. XRD confirmed the wurtzite
structure of ZnO. All elements expected in the nanoparticles were observed through EDX. SEM
showed agglomerated particles albeit with nanosized agglomerates on the surface and which were
interpreted as the building particles of the bigger ones. A further indication to nanosized particles
of the ZnO powder was revealed by the TEM image and blue shifted luminescence of both UV-vis
and PL measurements. The deep level defect emission luminescence is predominant for the
prepared ZnO nanoparticles by sol-gel, while the intensity of the green emission luminescence is
optimum for OH
-
/Zn
+
molar ratio of 4.4. This enhanced luminescence was attributed to quantum
confinement caused by the nano sized ZnO nanoparticles. The choice of appropriate molar ratio of
the precursor is paramount in the size control of ZnO nanoparticles as no catalyst is employed. At
low concentration of NaOH the incorporation of ZnO into SiO
2
: Ce resulted in quenching of green
emission from ZnO nanopartcles while enhancing blue photoluminescence from the Ce
3+
activator.
This enhanced luminescence was attributed to an energy transfer from the ZnO nanoparticles to
the Ce
3+
activator. In contrast it was noted that at higher NaOH concentrations both the green
emission peak of ZnO and blue emission of the activator were enhanced.

67
Improvement on CaAl
2
O
4
:Eu
2+
, Nd
3+
: P 02
Nursen Avci*, Philippe F. Smet, Dirk Poelman

*Corresponding author: nursen.avci@ugent.be

Keywords: CaAl
2
O
4
: Eu
2+
, Nd
3+
, non-aqueous sol-gel synthesis, persistent luminescence
Persistent luminescence materials are not only used in self-lit signalization in daily life but also for
in vivo optical imaging [1]. In addition radiation detection, structural damage and temperature
sensing [2] and luminescent photocatalysis [3] are promising application areas for persistent
luminescence materials. This diverseness in the usage makes them valuable luminescent
materials. The alkaline earth aluminates doped with Eu
2+
and R
3+
(R: rare earth) MAl
2
O
4
: Eu
2+
, R
3+

(M: Ca, Sr, Ba) are among the best known persistent luminescent materials [4].
In this study we investigate the persistent luminescence properties of CaAl
2
O
4
: Eu
2+
, Nd
3+

synthesized by non-aqueous sol-gel technique. In order to find the optimum concentration ratio
between Eu and Nd, different Eu and Nd concentrations are used. After the preparation, samples
are annealed at different temperatures (from 800 to 1200
o
C) for 1 h in air to obtain monoclinic
calcium aluminate. Subsequently Eu
3+
was reduced to Eu
2+
using different methods. To evaluate
the persistent luminescence of our CaAl
2
O
4
: Eu
2+
, Nd
3+
powders, they were compared with a
commercial product purchased from Glotech [5].
Previous investigations revealed the strongest luminescence in this material is obtained for the
monoclinic phase and the minimum reported temperature to obtain monoclinic CaAl
2
O
4
is around
1200
o
C. In our study, by changing the preparation technique we achieve to synthesize the
monoclinic phase at 900
o
C. Additionally doping with rare earths did not affect this temperature.
Although the monoclinic phase formation begins at 900
o
C, photoluminescence (PL) measurements
indicate that the optimum temperature was 1000
o
C.
In our synthesis technique it is necessary to use an additional annealing step to reduce Eu
3+
to Eu
2+

after annealing at 1000
o
C in air. Depending on the temperature and atmosphere for reduction, a
gray powder (which is not desirable for a luminescent material) or a powder with a white body
color can be achieved, the latter indicating a lower number of deep defects.
Figure 1a shows the PL emission spectra recorded at an excitation wavelength of 330 nm of
CaAl
2
O
4
doped with 1% Eu and CaAl
2
O
4
doped with 0.5% Eu 0.5% Nd. Only Eu
2+
emission can be
observed: there is no Eu
3+
emission and codoping with Nd
3+

ion does not affect the emission
wavelength or the shape of the emission spectrum. Preliminary results on the persistent
luminescence properties of CaAl
2
O
4
: Eu
2+
, Nd
3+
prepared by non-aqueous sol-gel technique show
that 0.5% Eu and 0.5% Nd are the optimum doping concentrations. Comparison between decay
profiles for commercial CaAl
2
O
4
: Eu
2+
, Nd
3+
and CaAl
2
O
4
: Eu
2+
(0.5%), Nd
3+
(0.5%) is presented in
figure 1b. As seen in the figure, for CaAl
2
O
4
: Eu
2+
(0.5%), Nd
3+
(0.5%) an overall increase in afterglow
intensity of about 206% is achieved using the new preparation technique.

68

Figure 1: (a) PL emission spectra recorded at an excitation wavelength of 330 nm
of (solid line) CaAl
2
O
4
: Eu (1%) and (dashed line) CaAl
2
O
4
: Eu (0.5%), Nd (0.5%). (b)
Decay profiles for (line a) commercial CaAl
2
O
4
: Eu, Nd and (line b) CaAl
2
O
4
: Eu
(0.5%), Nd (0.5%). Powders were excited at 365 nm for 6 minutes.

[1] J. Holsa et al., Spectrochimica Acta B 65 (2020) 301-305.
[2] T. Aitasalo et al., J. Phys. Chem. B 110 (2006) 4589-4598.
[3] L. Huihui et al., Nanoscale Res. Lett. 6 (2011) 5.
[5] http://www.glotechint.com/

69
Red persistent luminescence in biocompatible Ca
3
(PO
4
)
2
P 03
Aurlie Bessire
1,2
*, Aurlie Lecointre
1
, Gilles Wallez
1
, Bruno Viana
1
, Rajia At Benhamou
1,3
,
Emmanuelle Suard
4
*Corresponding author: aurelie-bessiere@chimie-paristech.fr
1
7574, Paris, France
2
Department of Physics, Goa University, Taleigao Plateau, Goa, India
3
Universit Cadi Ayyad, Laboratoire de la Matire Condense et de l'Environnement, Facult des Sciences-Semlalia,
Marrakech, Morocco
4
Institut Laue-Langevin, Grenoble, France

Keywords: red, persistent phosphor, calcium phosphate, manganese, bioimaging
-TriCalcium Phosphate (-TCP) belongs to the family of calcium monophosphates. The latter are
compounds that biologically form and constitute the major components of all mammalian calcified
tissues. With such a natural biological compatibility -TCP is widely used in biomedicine and food
industry as bone cement and bone substitution bioceramics, tooth polishing agent, food
additive...etc [1]. Because of this unquestionable biocompatibility property, TCP compounds
appear ideal for applications in biology. Our aim was to design them to be persistent red-emitting
luminescence phosphors suitable for a specific in vivo imaging application [2]. In this application
the persistent phosphor is used as a probe able to emit long-lasting phosphorescence (LLP) for
hours following a previous 5-10 minutes ex vivo excitation. The probe luminescence must be
situated in the optical window of biological tissues, i.e. between 600 nm and 1100 nm, to be
detected through the animals body.

Figure 1: The five calcium sites in -TCP.
In this work we have selected Mn
2+
as doping ion to obtain red luminescence in -TCP. LLP is due
to charge trapping at specific point defects and subsequent release of the charges towards a
luminescent center. Identifying the charge trapping defects and understanding the LLP mechanism
has always been a challenge and requires a thorough investigation of the materials structure in
addition to luminescence studies. -TCP presents an interesting crystal structure (shown in Figure

70
1). It has five distinct crystallographic sites for calcium ions, namely M1-5, with various
coordination numbers and sizes. Nine-fold coordinated site M3 is the most roomy, while M1O
8

and M2O
8
are roughly identical in volume. Smaller octahedral site M5 is located on a ternary axis,
similarly to M4 that shares a face with the P1O
4
tetrahedron, thus resulting in a very irregular
environment. M4 is only about half occupied in unsubstituted -TCP. A wide variety of doping ions
and local defects are therefore easily incorporated in -TCP structure, which can be used to taylor
specific luminescent properties, such as for instance long-lasting phosphorescence.
In this work we showed that annealing treatment in reductive conditions in TCP:Mn material
preparation was essential to induce proper charge trapping process under X-ray excitation [3].
However only low intensity LLP could be observed as the main peak of the Thermally Stimulated
Luminescence (TSL) glow curve was situated below room temperature (see Figure 2, red curve).
Instead a strong red persistent luminescence was induced by a specific Dy
3+
co-doping together
with a necessary annealing treatment in reductive atmosphere. TCP:MnDy then shows intense TSL
between 300 and 450 K (see Figure 2, green curve). Mechanisms for LLP will be discussed based on
both structural and optical (absorption, radioluminescence, TSL and LLP) investigations carried out
on Mn and Mn,Ln (Ln = Eu, Dy, Tb) doped -TCP.

Figure 2: TSL glow curves of TCP:Mn and TCP:Mn,Dy. R means the compound
was applied an annealing treatment in reductive conditions.

[1] S. V. Dorozhkin, Materials 2 (2009) 221-291 and 399-498
[3] A. Lecointre et al., Opt. Mater., in press.

100 200 300 400 500 600
0
10000
20000
TCPMn
TCPMnR
TCPMnDy
TCPMnDyR

I
n
t
e
n
s
i
t
y

(
a
r
b
.
u
.
)
Temperature (K)

71
Persistent luminescence and mechanoluminescence P 04
in MSi
2
O
2
N
2
:Eu
2+
(M = Ca, Sr, Ba)
Jonas Botterman*, Koen Van den Eeckhout, Dirk Poelman, Philippe F. Smet
*Corresponding author: jonas.botterman@ugent.be

Keywords: europium, oxynitride, persistent luminescence, mechanoluminescence
Europium doped oxynitrides of the form MSi
2
O
2
N
2
:Eu
2+
(with M = Ca, Sr, Ba) are recently proposed
to be excellent conversion phosphor materials for white-light-emitting LED applications based on
near ultraviolet (UV) or blue emitting InGaN LEDs. This is not only because of their strong
absorption in the near UV to blue-light region of the light spectrum, but also for their high
quantum efficiency and good thermal and chemical stability compared to oxide and sulfide
phosphors. [1, 2]
All three MSi
2
O
2
N
2
:Eu
2+
compounds show persistent luminescence. This is a disadvantage when it
comes to applying the materials in a phosphor converted white LED. Figure 1a and 1b show the
persistent luminescent intensity as a function of time for the different materials after 30 seconds
of excitation with 280 nm UV radiation and 425 nm violet light respectively. After excitation with
280 nm, all materials show persistent luminescence. Upon excitation with 425 nm, only
BaSi
2
O
2
N
2
:Eu
2+
show an appreciable afterglow. The SrSi
2
O
2
N
2
:Eu
2+
and CaSi
2
O
2
N
2
:Eu
2+
compounds
show an afterglow which is over one hundred times weaker than the afterglow after 280 nm
excitation and is well below 0.32 mcd/cm, a threshold value often used in industrial standards.
This makes only SrSi
2
O
2
N
2
:Eu
2+
and CaSi
2
O
2
N
2
:Eu
2+
suitable as conversion phosphors in
combination with a blue pumping LED if any afterglow should be avoided.

Figure 1: Decay of the afterglow of MSi
2
O
2
N
2
:Eu
2+
(with M = Ba, Sr, Ca)
after 30 sec. excitation with 280 nm UV radiation (a) and 425 nm violet light (b).
Beside its persistent luminescent property, BaSi
2
O
2
N
2
:Eu
2+
shows strong luminescence upon
mechanical stimulation such as friction or pressure. This phenomenon, known as non destructive
mechanoluminescence (ML), is not so common and might have application in pressure sensing
devices. The mechanoluminescence emission spectrum is similar to the photoluminescence (PL)

72
emission spectrum except for a shift towards longer wavelengths of about 4 nm (figure 2). This
makes the spectrum identical to that of the persistent luminescence, suggesting that the same
radiative recombination path is present for the mechanoluminescence and the persistent
luminescence.

Figure 2: PL (excited at 370 nm) and ML emission spectra of BaSi
2
O
2
N
2
:Eu
2+
.

[1] P.F. Smet et al., J. Electrochem. Soc. 158 (2011) R37-R54.
[2] V. Bachmann et al., Chem. mater. 21 (2009) 316-325.
[3] M. Wang et al., J. Electrochem. Soc. 157 (2010) H178-H181.

73
Influence of titanium and lutetium P 05
on the persistent luminescence of ZrO
2

Jos M. Carvalho
1
1,2
, Jorma Hls
1,2,3
, Mika Lastusaari
2,3
, Luiz A.O. Nunes
4
,
Maria C.F.C. Felinto
5
, Oscar L. Malta
6
, Hermi F. Brito
1,
*

*Corresponding author: hefbrito@iq.usp.br
1
2
3
4
Universidade de So Paulo, Instituto de Fsica de So Carlos, So Carlos, Brazil
5
Instituto de Pesquisas Energticas e Nucleares, IPEN, So Paulo, Brazil
6
Universidade Federal de Pernambuco, Departamento de Qumica Fundamental - CCEN, Recife, Brazil

Keywords: persistent luminescence, zirconia, titanium doping, nanocrystalline, sol-gel method
Zirconia is one of the most important metal oxides with applications in photonic devices due to
the quite unique properties as thermal and chemical stability, high refractive index (2.152.18)
and low phonon energy [1-5]. The stretching frequency of the ZrO bond is about 470 cm
1
, which
is much lower than for AlO (870) or SiO (1100) though higher than YO (300380 cm
1
) [5]. The
wide band gap (5.05.5 eV) is important for the use as luminescent materials to suppress non-
radiative losses. The ZrO
2
system has a variety of applications, including fuel cell electrolytes,
thermal barrier coatings, electro-optical materials, and oxygen sensors [3-6]. ZrO
2
exhibits well
known polymorphism with three forms of different crystal structures: cubic, tetragonal and
monoclinic [2,7]. Though the monoclinic phase is stable at the room temperature, it is
transformed to the tetragonal one at 1170 C, and further to cubic at an even higher temperature
(2370 C) [8]. However, the tetragonal and cubic phases can be stabilized at the room temperature
by doping with trivalent rare earth (R
3+
), Mg
2+
or Ca
2+
ions, thus generating oxide vacancies [2,9].
In this work, the Ti
3+/IV
and Lu
3+
doped as well as non-doped luminescent nanocrystalline ZrO
2

materials were prepared with a sol-gel method using different [H
2
O]/[ZTB] (= W) ratios (ZTB:
zirconium tetrabutoxide) at temperatures between 600 and 1000 C. The nominal Lu or Ti dopant
concentrations were 0.5 mole-% of the zirconium amount. The materials were characterized with
X-ray powder diffraction (XRD), thermogravimetric analysis and infrared spectroscopy. The photo-
and thermally stimulated luminescence were also investigated.
The increasing calcination temperature increased the amount of the monoclinic phase whilst the
increasing W ratio increased the amount of tetragonal phase as observed in the X-ray diffraction
patterns (Fig. 1). The most intense persistent luminescence of the non-doped ZrO
2
was obtained
for W=3 at 1000 C, thus the Ti and Lu doped ZrO
2
were prepared at these conditions. The
excitation spectra (Fig. 2, top) of the materials show a broad band with a similar profile (though
not position) independently of the presence of dopants. The emission spectra (Fig. 2, bottom)
show a broad band with a maximum at 500 nm, characteristic to the monoclinic phase. The Ti
doping increased only the intensity of the (excitation and) emission spectra, indicating that
titanium is responsible for the luminescence of the non-doped ZrO
2
(present then as an impurity).

74

In conclusion, the persistent luminescence of the non-doped zirconia was shown to result from a
Ti
3+
impurity and the crystal structure was related to the persistent luminescence phenomenon.
However, more detailed studies are needed to develop a mechanism of persistent luminescence
for this system.

[1] A. Patra et al., J. Phys. Chem. B 106 (2002) 1909.
[2] L. Li et al., J. Nanosci. Nanotechn. 11 (2011) 350.
[3] K. Smits et al., Opt. Mater. 32 (2010) 827.
[4] A. Polman, J. Appl. Phys. 82 (1997) 1.
[5] I. Hyppnen et al., J. Fluoresc. 18 (2008) 1029.
[6] A. Orera et al., Chem. Mater. 22 (2010) 675.
[7] S. Shukla et al., Nano Lett. 3 (2003) 397.
[8] A.S. Foster et al., Phys. Rev. B 64 (2001) 224108.
[9] L.A. Diaz-Torres et al., J. Solid State Chem. 181 (2008) 75.

Figure 1: XRD patterns of the non-doped ZrO
2

for different W ratios.

Figure 2: Luminescence excitation (top)
and emission (bottom) spectra
of non-doped and doped ZrO
2
systems
a) excitation and b) emission spectra

75
The effects of Eu ions and Eu:Dy ratio on the structural, P 06
morphological and luminescence properties of
blue-green BaAl
x
O
y
:Eu
2+
,Dy
3+
nano phosphors
F.B. Dejene

*Corresponding author: dejenebf@qwa.uovs.ac.za

Keywords: BaAl
x
O
y
:Eu
2+
,Dy
3+
, long afterglow, traps, hexagonal, luminescence
Blue-green emitting BaAl
x
O
y
:Eu
2+
,Dy
3+
phosphor was synthesized by the solution=combustion
method. The influence of various parameters on the morphological, structural and
photoluminescence (PL) properties of the phosphor were investigated by various techniques.
Phosphor nanocrystallites with high brightness were obtained without significantly changing the
crystalline structure of the host. The EDS spectra of all samples show the expected chemical
components in the phosphors. The XRD spectra displayed in Fig. 1 give a clear indication of the
formation of particles in the nano range. The spectrum shows the expected hexagonal crystalline
phase for the nanopowders. The main diffraction peaks index well with the card file (JCPDS:17-
0306) in agreement with other reports [1].

Figure 1: XRD spectra of BaAl
x
O
y
:Eu
2+
,Dy
3+
nano phosphors
for different Eu
2+
:Dy
3+
molar ratios
In the PL studies, the excitation spectra show one broadband from 200 to 450 nm centred around
340 nm corresponding to the crystal field splitting of the Eu2 d-orbital. The prepared phosphor
compositions exhibit emission in the blue-green region. This is a strong indication that the Eu ion is
in a divalent rather than trivalent. It is to be noted that this result was obtained in the absence of
any deliberately designed reducing environment.
The emission band is symmetrical at about 504 nm, which is attributed to the typical 4f
6
5d
1
to 4f
7

transition of the Eu
2+
ion. The 504 nm emission wavelength indicates the dominance of the
hexagonal blue-green-emitting phase of the aluminate phosphor. Two other, minor peaks, at 614
and 711 nm indicate the presence of remnants of Eu
3+
ions as a result of incomplete reduction
during sample preparation [2]. The f-f transitions of the unreduced Eu
3+
ions are responsible for
red emissions. The phosphorescence decay characteristics of BaAl
2
O
4
:Eu
2+
,Dy
3+
phosphors show
15 20 25 30 35 40 45 50 55 60 65 70
1:0.5 +

R
e
l
a
t
i
v
e

I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
2O Angle (
o
)
B
+

D
1:4
1:1
+

F
1:2
+ Ba(NO
3
)
2
(
2
2
4
)
(
2
4
1
)
(
2
2
0
)
(
4
0
1
)
(
2
2
0
)
(
2
0
2
)
(
1
0
2
)
(
2
0
0
)

Eu
2+
:Dy
3+

76
that the initial luminescent intensity and the decay time of afterglow of phosphors are dependent
on Eu:Dy molar ratio. By increasing the Dy concentration, the initial luminescent intensity changed
such that the sample with the intermediate Dy3 concentration (1:2 of Eu
2+
:Dy
3+
ratio) has the
highest initial intensity and longest decay time. The Eu
2+
ion is the luminescent center while Dy
3+

ions act as trap centers in a photoionization process, which leads to the Eu
2+
emission after the
thermal bleaching of the electrons from the traps. The observed afterglow is ascribed to the
generation of suitable traps due to the presence of the co-doped Dy
3+
ions.

Figure 2: PL (a) excitation and (b) emission spectra of BaAl
2
O
4
:Eu
2+
,Dy
3+
phosphors
for different Eu
2+
:Dy
3+
molar ratio

[1] H. Ryu et al., Physica B, 403 (2008) 126.
[2] F. Clabau et al., Solid State Sci., 9 (2007) 608.

250 300 350 400 450
0
40
80
120
160
200
240
280
320
360
(a)
Eu
2+
:Dy
3+
molar ratio
1:4
1:8
1:1
1:2
1:0.8
1:0.5

I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Wavelength (nm)
400 450 500 550 600 650 700
0
50
100
150
200
250
300
350
(b)
Eu
2+
:Dy
3+
molar ratio
1:4
1:8
1:1
1:2
1:0.8
1:0.5

I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Wavelength (nm)

77
Solution combustion synthesis and photoluminescence property P 07
of Gd,YBO
3
:Tb
3+
phosphor powders

F.B. Dejene

*Corresponding author: dejenebf@qwa.uovs.ac.za

Keywords: Gd,YBO
3
:Tb
3+
, phosphors, nanocrystals, solcombustion, photoluminescence
Luminescent materials with quantum efficiency (QE) larger than unity might play an important role
in the development of certain lighting and display systems [1]. Large band gap materials doped
with rare earth ions are currently of great interest as new vacuum UV phosphors for lighting and
displays. In this study, GdYBO
3
:Tb
3+
nanocrystalline were successfully deposited by following a
modified solcombustion method, relative to those reported previously, using rare-earth nitrates,
urea and boric acid as starting materials. These samples were not subjected to any heat
treatments. The crystal structure, morphology, chemical composition and photoluminescence
property of the films were investigated by Scanning electron microscope (SEM), X-ray diffraction
(XRD) and Photoluminescence (PL). The results of SEM as shown if Fig. 1(a) revealed that the
powders were composed of spherical GdYBO
3
:Tb
3+
nanocrystals with average grain size of
between 50 and 100 nm. EDS (electron diffraction spectroscopy) confirm (see Fig. 1b) the
presence of the Gd, Y, B, O, and C.

Figure 1: (a) SEM and (b) EDS Micrographs of Gd,YBO
3
:Tb
3+
nano phosphors.
Formation of a single phase of the correct GdYBO
3
:Tb
3+
crystal structure grown at low temperature
from 500C to 1000C was confirmed on the basis of powder X-ray diffraction. The spectrum
shows the expected hexagonal crystalline phase for the nanopowders. The main diffraction peaks
index well with the card file (JCPDS:16-0277) in agreement with other reports [2]. The crystallite
size estimation based on the Scherrer equation analysis confirmed the size obtained using SEM
micrograph.

78
200 250 300 350 400 450 500 550 600 650 700
0
20
40
60
80
100
120
140
exc
= 225 nm
exc
= 250 nm
exc
= 340 nm
em
= 543 nm

W
a
v
e
l
e
n
g
t
h

(
a
.
u
.
)
Wavelength (nm)

Figure 2: Representative PL excitation and emission spectra
of Gd,YBO
3
:Tb
3+
phosphors.
In the PL studies, the excitation spectra show one broadband from 200 to 400 nm with peaks
around 224, 340 and 370 nm corresponding to the crystal field splitting of the Tb d-orbital. The
prepared phosphor compositions exhibit emission in the blue-green region. The GdYBO
3
:Tb
3+

powders exhibited emissions at 490, 545 and 585 nm, which were assigned to the
5
D
4
7
F
6
,
5
D
4
7
F
5

and
5
D
4
7
F
4
transitions of Tb
3+
, respectively. Among them, the green emission at 545 nm (
5
D
4
7
F
5
)
was dominant. The observed afterglow is ascribed to the generation of suitable traps due to the
presence of the defects ions.

[1] Q. Y. Zhang et al., Prog. Mater. Sci. (in press).
[2] X. H. Zhu et al., Appl. Surf. Sci. 254 (2008) 63626365.

79
Ca and Hf co-dopants as properties designing constituents P 08
of Lu
2
O
3
Dagmara Kulesza, Joanna Trojan-Piegza, Eugeniusz Zych*

Keywords: storage phosphors, persistent phosphors, lutetia, co-doping
The research on persistent and storage phosphors has been based on the trial and error
approach for years. This is only recently as investigators received a tool to make this quest more
predictable. The series of papers by Dorenbos [1-4] showing a possibility to project trapping sites
of defined energies opened greater possibilities to model persistent and storage phosphors more
deliberately. The Dorenbos method allows quite easily to position the depth of both hole traps
and electron traps formed by lanthanide ions immersed in a host lattice [5,6].
Yet, we do know that the process of energy storing and its subsequent releasing in persistent and
storage phosphors are complex processes and not yet everything is understood. In this report we
will present a summary of our knowledge on persistent and storage phosphors based on Lu
2
O
3
:Tb
composition. Most of all we will compare two compositions: Lu
2
O
3
:Tb,Ca and Lu
2
O
3
:Tb,Hf. The
former appears a surprisingly efficient persistent phosphor when prepared in reducing
atmosphere and high temperature (>1600 C, preferentially, at 1700 C). The latter is capable of
permanently store energy at room temperature, although some fading appears as proved by
results presented in Fig. 1.

Figure 1: TL glow curves of Lu
2
O
3
:Tb,Hf recorded with
different delay time. Noticeable fading was proved to occur.
Absorption spectra showed, Fig. 2, that irradiation with UV photons or X-rays generated an
extrinsic absorption band extending over blue and near-UV part of spectrum.

80

Figure 2: Variations in excitation spectra of Lu
2
O
3
:Tb,Hf green luminescence
upon stimulation with UV photons followed by irradiation with 440 nm light.
Upon stimulation with deep UV radiation or X-rays Lu
2
O
3
:Tb,Ca ceramics produces an efficient
green luminescence by Tb
3+
followed by a long-lasting emission of this ion once the irradiation was
stopped. The persistent luminescence of Lu
2
O
3
:Tb,Ca results from a trap producing TL glow band
peaking around 120 C.

Figure 3: Comparison of TL glow curves of Lu
2
O
3
:Tb
and its co-doped versions of Lu
2
O
3
:Tb,Ca, and Lu
2
O
3
:Tb,Hf.

[1] P. Dorenbos, J. Lumin. 91 (2000) 91.
[3] P. Dorenbos, J. Phys.: Condens. Mater. 15 (2003) 8417.
[5] A.J.J. Bos et al., Radiat. Meas. 43 (2008) 222.
[6] N.R.J. Poolton et al., J. Phys. Cond. Mat. 22 (2010) 185403.

81
Effects of co-dopants in long lasting phosphorescence phosphors P 09
Chengyu Li*, Qiang Su
*Corresponding author: cyli@ciac.jl.cn
State Key Laboratory of Rare Earth Resources Utilization, Changchun Institute of Applied Chemistry, Chinese
Academy of Sciences, Changchun, China

For the synthesis of phosphors with long persistent emission, it is a very common method to add
other ions into the materials except the activator to improve the properties of the samples such as
phosphorescence intensity and emission life. It is generally considered that the co-dopants play a
role of trapping center to increase the storage ability of the phosphors, for which the most famous
examples are Dy in SrAl
2
O
4
: Eu, Dy and Nd CaAl
2
O
4
: Eu, Nd. However, we think that it is a very
complex situation for co-dopants in the long lasting phosphorescence (LLP) phosphors and not
only the increase of the storage ability induced by the co-addition is considered, the influence of
the change of the energy transfer on the performance of the phosphorescence should also be
given a special attention. In this article, we will discuss the action of co-dopants in several long
lasting phosphorescence phosphors.

82
Luminescent properties of CaAl
2
O
4
:Eu
2+,
Dy
3+
,Nd
3+
phosphors P 10
prepared by combustion method.
Bakang M. Mothudi
1,2,
*,

Martin O. Ntwaeaborwa
1
, Hendrik C. Swart
1

1
Department of physics, University of the Free State, South Africa
2
Department of Physics, University of South Africa, Pretoria, South Africa

Keywords: initiating combustion temperature, annealing temperature, photoluminescence
Abstract: Europium (Eu
2+
),dysprosium (Dy
3+
) and neodymium (Nd
3+
) doped CaAl
2
O
4
powder
phosphors

were prepared by combustion method using urea as a comburent. The phosphor
powders were annealed at 1200
o
C for 3- 9 hours. X-ray diffraction data show that the crystallinity
of the CaAl
2
O
4
structure greatly improved as the annealing time increased. The FT-IR absorption
bands of the annealed samples were investigated and they are consistent with the stretching
mode frequencies of CaAl
2
O
4
. Blue photoluminescence, with persistent/long afterglow, was
observed at 450 nm. This emission was attributed to the 4f
6
5d
1
- 4f
7
transitions of the Eu
2+
ions.
The phosphorescence decay curves were obtained by irradiating the samples with a
monochromatized xenon lamp at an excitation wavelength of 393 nm.
Introduction: Long lasting rare earth doped inorganic phosphors are a type of energy storage
material, which can absorb and trap ultraviolet energy form the sun and gradually release it in the
dark at a certain wavelength [0],[0]. The alkaline earth aluminates phosphors activated with
divalent europium (Eu
2+
) have attracted much attention since they show excellent properties such
as high quantum efficiency, long persistence phosphorescence as well as good chemical stability
compared to the sulphide phosphorescent phosphors [0]. These properties resulted in a wide
application of these materials in many fields [0]. The utility of phosphors depends on their
luminescence performance which also depends on the powder characteristics and therefore
different processes of phosphor synthesis are currently an active area of research [0]. In this study
CaAl
2
O
4
was synthesized via combustion method, using nitrates precursors as oxidizers and urea
as an organic fuel.
Results: Fig.1 shows the CaAl
2
O
4
:Eu
2+
,Dy
3+
,Nd
3+
phosphors prepared by combustion method. Fig
1.b shows the blue emission when the sample was excited with the UV light (360 nm) in the dark
room. Fig.2 shows the PL emission spectrum of CaAl
2
O
4
:Eu
2+
,Dy
3+
,Nd
3+
phosphor prepared by the
combustion method. Fig.2 depicts a narrow emission band spectrum of CaAl
2
O
4
:Eu
2+
,Dy
3+
,Nd
3+

which is symmetric around 450 nm. The narrowing of emission spectrum was also reported by
Chen et al. [1], and they proposed that this may be due to the existence of only one kind of
luminescent centre in CaAl
2
O
4
:Eu
2+
,Dy
3+
,Nd
3+
, the nine-coordinated Ca
2+
sites are substituted with
the Eu
2+
ions [1]. This emission can be attributed to the 4f
6
5d
1
- 4f
7
transitions of the Eu
2+
ions. The
phosphorescence decay curves were obtained by irradiating the samples with a monochromatized
xenon lamp at an excitation wavelength of 393 nm.

83

Figure 1: CaAl
2
O
4
:Eu
2+
,Dy
3+
,Nd
3+
phosphors prepared by combustion method.

Figure 2: The emission spectrum of CaAl
2
O
4
:Eu
2+
,Dy
3+
,Nd
3+
phosphor
excited with He-Cd Laser (325 nm).

[1] X. Y. Chen et al., J.Phys.Chem. C 113 (2009) 2685-2689.
[2] L. Qun et al., J. Rare Earths 28 (2010) 29.
[3] P. Huang et al., J. Sol-Gel Sci. Technol. 50 (2009) 308-313.
[4] N. Suriyamurthy et al., Ind. J. Eng. Mater. Sci. 16 (2009) 178-180.

0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
P
L

I
n
t
e
n
s
i
t
y

(
a
u
)
350 400 450 500 550 600 650 700
Wavelength (nm)
450 nm

84
Persistent luminescence behavior of materials P 11
doped with Eu
2+
and Tb
3+
ions
Lucas C.V. Rodrigues
1,2,
*, Hermi F. Brito
1
, Jorma Hls
1,2,3
, Mika Lastusaari
2,3
*Corresponding author: lucascvr@iq.usp.br
1
2
3

Keywords: persistent luminescence, mechanism, divalent europium, trivalent terbium
The study of the mechanisms for the persistent luminescence phenomenon is required to the
development of new efficient photonic materials. In the last two decades, the mechanisms for the
Eu
2+
persistent luminescence phenomenon have attracted much attention due to their potential
applications [1-3]. However, only few studies have been reported on the mechanisms of the
persistent luminescence of phosphors containing other dopants as Mn
2+
, Ce
3+
, Tb
3+
and Eu
3+
[4,5].
The study of the optical properties of the luminescent materials containing different dopants may
contribute significantly to the understanding of the persistent luminescence mechanisms.
In this work, the persistent luminescence mechanisms for Eu
2+
(in CaAl
2
O
4
) [6] and Tb
3+
(in CdSiO
3
)
[4] are discussed. Both mechanisms were developed based on the experimental results from
photoluminescence, synchrotron radiation UV-VUV spectroscopy and thermoluminescence
measurements. The positions of the ground state of the R
2+
and R
3+
ions (R: La-Nd, Sm-Lu) in the
hosts band structure were determined using the 4f5d and the ligand-to-metal charge-transfer
transitions [7].
In general, the mechanisms for both Eu
2+
and Tb
3+
consider that (Fig. 1): i) under irradiation of the
material, in addition to conventional luminescence, some electrons escape to the conduction band
(CB), ii) some of these electrons are trapped from CB to defects thus storing part of the excitation
energy and iii) the reverse process of freeing the electrons from the traps to the excited states via
CB precedes the radiative relaxation of the system back to the ground states of Eu
2+
or Tb
3+
thus
creating persistent luminescence. Despite these mechanisms present some similar steps, there are
differences in the photoluminescent processes. For example, the broad luminescence band of Eu
2+
involves the interconfigurational 4f
6
5d
1
4f
7
(
8
S
7/2
)

transition whilst the emission of Tb
3+
shows the
narrow bands characteristic of the intraconfigurational 4f4f transitions. Thus the lifetime of Eu
2+

(ca. one s) is three orders of magnitude shorter than that of Tb
3+
(a few ms). In the CaAl
2
O
4
material, the co-doping with R
3+
ions as Dy
3+
, frequently increases the efficiency of the persistent
luminescence. The R
3+
ions may act as traps. In the Tb
3+
doped CdSiO
3
, there is no need for the co-
doping since Tb
3+
is acting both as a luminescence center and creator of energy storing defects.
Despite the differences, the trap nature should be the same for the both systems, since the
proposed mechanisms suggest electron trapping, indicating that the defects are electron
acceptors as the oxide vacancies (
- -
O
V ). The influence of the trap depths and concentration on the
persistent luminescence phenomenon are similar for the two systems, suggesting that the
electrons migrate from the traps to the excited states of Eu
2+
/Tb
3+
via CB.

85
The forbidden energy gap (E
g
) between the valence and conduction bands should be smaller for
the Tb
3+
doped materials (as in CdSiO
3
) to enable efficient persistent luminescence to be excited
with low energy UV radiation or even with blue light.
In summary, the persistent luminescence mechanisms for Eu
2+
and Tb
3+
are rather similar, despite
the nature of the inter and intraconfigurational transitions, respectively. The traps are similar
(electron traps), though the R
3+
co-dopants may act in different ways in the two systems. Only
sparse data is available about the Tb
3+
doped persistent luminescence materials, thus more
detailed studies are needed on these systems.

Figure 1: Persistent luminescence mechanisms of Eu
2+

in CaAl
2
O
4
(left) and Tb
3+
in CdSiO
3
(right).

Acknowledgments: Financial support is acknowledged from the Coimbra Group, Turku University
Foundation, Academy of Finland (Finland), FAPESP, CAPES, CNPq, inct-INAMI and RERHNAMI (Brazil).

[2] T. Aitasalo et al., J. Phys. Chem. B 110 (2006) 4589.
[3] F. Clabau et al., Chem. Mater. 18 (2006) 3212.
[4] L.C.V. Rodrigues et al., 16
th
Int. Conf. Lumin. (ICL'11), June 27-July 1, 2011, Ann Arbor, Michigan USA.
[5] H. Bettentrup et al., IOP Conf. Ser.: Mater. Sci. Eng. 15 (2010) 012085.
[6] J. Hls et al., Spectrochim. Acta B 65 (2010) 301.

0
2
3
4
5
6
UV
kT
kT
Tb
3+
5
D
3
+
2S+1
L
J
0
6
5
D
4
7
F
J
E
n
e
r
g
y

/

e
V
Luminescence
CdSiO
3
:Tb
3+
E
g
: 5.28 eV
4f
7
5d
1
Trap Depths
0.6 - 0.75 eV
Irradiation
Conduction Band
Valence Band
5
D
4
7
F
J
1.84 eV
1.85
2.00
2.11
2.27 (max int.)
2.52
CaAl
2
O
4
:Eu
2+
,R
3+

E
g
: 6.7 eV
kT
8
S
7/2

4f
6
5d
1

Conduction Band
Valence Band
Eu
2+

UV
Irradiation
Luminescence
2.8 eV
Trap Depths
0.5 - 1.5 eV

86
Persistent luminescence in rare-earth doped nitrido-silicates P 12
Koen Van den Eeckhout*, Philippe F. Smet, Dirk Poelman

*Corresponding author: koen.vandeneeckhout@ugent.be

Keywords: nitrido-silicates, europium, thermoluminescence
The majority of persistent phosphors known today are based on aluminates or silicates and emit in
the blue or green region of the visible spectrum [1]. Orange or red phosphors, strongly desired for
emergency signage and medical imaging, are scarce. We prepared the yellowish-orange nitrido-
silicates M
2
Si
5
N
8
:Eu,R (M = Ca, Sr, Ba), and their rare-earth codoped variants (R = Nd, Dy, Sm, Tm)
through a solid state reaction, and investigated their luminescence and afterglow properties [2].
Additionaly, we investigated how the material behaves when exposed to water, air or heat for
extended periods of time, and compared this to several commercially available phosphors.

Figure 1: Decay of the afterglow intensity after 1 min excitation
with a Xe arc lamp at 1000 lux.
Persistent luminescence is present in all the prepared samples, but the brightness and duration of
the afterglow strongly depends on the host material, the codopant and the choice and ratio of the
starting products. This demonstrates the importance of charge carrier traps that are suitably
located (both physically and energetically), since these govern the maximum light storage and
release capabilities of a persistent phosphor. The number and depth of these traps are estimated
from the thermoluminescent glow curve, the integrated light output and the decay profile. Of all
the prepared materials, Ca
2
Si
5
N
8
:Eu,Tm is the most promising persistent phosphor with a bright
orange afterglow that remains visible for about an hour.


87
Preparation and persistent luminescence P 13
in rare earth doped Ca
2
Si
5
N
8
nanoparticles
G. Sraiki
1
, Bruno Viana
1
, Didier Gourier
1
, Thomas Maldiney
2
, Cyrille Richard
2
, Koen Van den
Eeckhout
3
, Philippe F. Smet
3
, Dirk Poelman
3
*Corresponding author: bruno-viana@chimie-paristech.fr
1
7574, Paris, France.
2
Unit de Pharmacologie Chimique et Gntique et d'Imagerie; CNRS, UMR 8151, Inserm, U1022, Universit Paris
Descartes, Facult des Sciences Pharmaceutiques et Biologiques, ENSCP, Chimie Paristech, France
3

Keywords: red persistent phosphor, nanoparticles in solution, bio-imaging
Focusing our research on the use of nanophosphors for in vivo imaging and diagnosis applications,
improved nanomaterials, excitable with UV light, and displaying the most intense afterglow in the
near-infrared region are investigated. For this purpose persistent nanophosphors used as a probe
should able to emit in the red and near infrared range long-lasting phosphorescence (LLP) for
hours following a previous ex vivo excitation [1]. It has been demonstrated that Ca
2
Si
5
N
8
:Eu,Tm is
well suitable for such application and can present outstanding long lasting luminescence at about
590 nm [2]. To go further in the application the particle size should be decrease in order to be well
accepted by the organism. Second, the long lasting phosphorescence should be maintained in
solution.

Figure 1: Principle of the PLAL method (from [3]) Figure 2: TEM picture of the Ca
2
Si
5
N
8
:Eu,Tm
NPs (bar scale 5 nm)

In order to obtain nanoparticles (NPs), laser ablation in liquid is used (see ref. [3] and the principle
is presented fig. 1). With such procedure and using surfactant very small NPs are obtained (see
figure 2).
The aim of this presentation is to describe (i) the first results obtained for the NPs preparation
with pulsed laser ablation in liquid (PLAL) as well as the characterization of the nanomaterials, and

88
then (ii) the investigation of the luminescence properties of the nanosize material. Potential for in-
vivo imaging will be discussed.

[1] Q. Le Masne de Chermont et al., Proc. Natl. Acad. Sci. USA 104 (2007) 9266-9271.
[2] K. Van den Eeckhout et al., J. Lumin. 129 (2009) 1140-1143.
[3] G. Ledoux et al., Nanotechnol. 20 (2009) 445605.

89
Properties of blue emitting CaAl
2
O
4
:Eu
2+
, Dy
3+
phosphors P 14
Ali H. Wako
1,
*, Francis B. Dejene
1
, Hendrik C. Swart
2

*Corresponding author: dejenebf@qwa.ufs.ac.za
1
Department of Physics, University of the Free State (QwaQwa Campus), Phuthaditjhaba, South Africa
2

Keywords: CaAl
2
O
4
: Eu
2+
,Nd
3+
, luminescence, long afterglow, urea, boric acid
The long afterglow CaAl
2
O
4
:Eu
2+
, Nd
3+
phosphor was prepared by solution- combustion method.
The effects of the variation of flux (H
3
BO
3
) and the amount

of urea ((NH
2
)
2
CO) on the crystal
structure and photoluminescence (PL) properties of CaAl
2
O
4
:Eu
2+
, Nd
3+
systems were investigated.
X-ray diffraction analysis revealed the dominance of the monoclinic CaAl
2
O
4
phase (Contrast Joint
Committee on Powder Diffraction Standards (JCPDS) data file No.70-0134 (Fig. 1(a)). Addition of
H
3
BO
3
is seen to favor the formation of pure monoclinic
.
phase CaAl
2
O
4
because do parts of B in
the compound H
3
BO
3
entering crystal lattice replace Al. However, large parts of B not go into the
crystal lattice but melt at low temperature and act as flux for the synthesis of the phosphor and
help to urge activator ions enter crystal lattice and form luminescent and trap centers, which is
easier to obtain single pure phase of CaAl
2
O
4
. [1]

Figure 1: Effect of (a) amount of flux and (b) urea on the structure of the
CaAl
2
O
4
:Eu
2+
,Nd
3+
phosphor.
The variation of the amount of urea ((NH
2
)
2
CO), show mixed phases of CaAl
2
O
4
(JCPDS) data file
No. 70-0134, and CaAl
4
O
7
(JCPDS) data file No. 72-0767 (Fig. 1(b) although still predominantly
monoclinic due to the fact that the endothermic reaction during the solution-combustion process
are determined by decomposition and removal of nitric oxides and significantly vary depending on
the precursor composition and ratio of metal nitrate to urea [2]. Both urea and boric acid to some
extent also influence the emission intensity of the obtained phosphor [3]. H
3
BO
3
also affects the
afterglow properties of this phosphor. But its emission peak does not shift evidently because the
energy level difference of 4f-5d does not change obviously. The broad blue emissions consist
mainly of symmetrical bands having maxima at 440445 nm originate from the energy transitions
between the ground state (4f
7
) and the excited state (4f
6
5d
1
) of Eu
2+
ions while the narrow
emissions in red region arise from the f-f transitions of the remnant unreduced Eu
3+
ions. The
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90
0
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
22000
(a)
* CaAl
2
O
4
*
*
*
*
* *
*

R
e
l
a
t
i
v
e

I
n
t
e
n
s
i
t
y

(
a
.
u
)
2u
0
Degree
% Boric Acid
1%
2%
3%
4%
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90
0
5000
10000
15000
20000
25000
30000
(b)
^ CaAl
4
O
7
^ ^ ^
^
^
^
^
^
^
^^
^
^
^^
^
^
^
* CaAl
2
O
4
*
*
* *
*
*
*
*
*
*

R
e
l
a
t
i
v
e

I
n
t
e
n
s
i
t
y

(
a
.
u
)
2u
0
Degree
% Urea
0.4
0.6
0.7
0.9

90
decay spectra (Fig. 2) show that increased concentration of H
3
BO
3
generally reduces both intensity
and lifetime of the phosphor powders. The optimized content of H
3
BO
3
is 0.01 mol/mol for the
obtained phosphor with excellent properties.

Figure 2: Effect of amount of flux on the afterglow characteristics.

[1] X. Teng et al., J. Alloys Compd. 458 (2008) 446449.
[2] F.B. Dejene et al. ,J. Rare Earth 28 (2010) 272.
[3] D. Haranath et al., J. Phys. D: Appl. Phys. 38 (2005) 371-375.

0 5 10 15
0
1
2
3
4
5
6
7

R
e
l
a
t
i
v
e

I
n
t
e
n
s
i
t
y

(
a
.
u
)
Time (ms)
(% mol) Boric Acid
1%
2%
3%
4%

91
Effect of Eu
2+
and Nd
3+
2
O
4
:Eu
2+
, Nd
3+
P 15
Ali H. Wako
1,
*, Francis B. Dejene
1
, Hendrik C. Swart
2

*Corresponding author: dejenebf@qwa.ufs.ac.za
1
Department of Physics, University of the Free State (QwaQwa Campus), Phuthaditjhaba, South Africa
2

Keywords: CaAl
2
O
4
: Eu
2+
,Nd
3+
, Eu
2+
and Nd
3+
doping concentrations, solution-combustion method
The effects of the Eu
2+
and Nd
3+
doping concentrations on the phase transformations and
luminescent properties of CaAl
2
O
4
: Eu
2+
; Nd
3+
phosphor were investigated. The long afterglow
phosphor CaAl
2
O
4
:Eu
2+
, Nd
3+
was prepared by urea-nitrate solution-combustion method at 500
0
C.
These samples were not subjected to any heat treatments. The influence of various parameters on
the morphological, structural and photoluminescence (PL) properties of the phosphor were
investigated by various techniques. The EDS spectra of all samples show the expected chemical
components in the phosphors. Results of XRD analysis depict a dominant monoclinic phase that
indicates no change in the crystalline structure of the phosphor with an increase of Eu
2+

concentration or co-dopants Nd
2+
: Dy
2+
ratio Fig.1.(a) and (b).

Figure 1: Effect of (a) Eu
2+
and (b) on the structure of the phosphor.
The excitation spectra show one broadband from 200 to 300 nm centred around 240 nm
corresponding to the crystal field splitting of the Eu
2+
d-orbital. The prepared phosphor
compositions exhibit PL emission in the blue region with a maximum around 440 nm. This is a
strong indication that there was dominantly one luminescence centre Eu
2+
which represents
emission from transitions between 4f
7
(
8
S
7/2
) ground state and the 4f
6
-5d
1
excited state
configuration (Fig.2) Two other, minor peaks, at 580 and 614 nm indicate the presence of
remnants of Eu
3+
ions as a result of incomplete reduction during sample preparation [1].
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90
0
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
22000
24000
(a)
*
* *
*
*
*
*

R
e
l
a
t
i
v
e

I
n
t
e
n
s
i
t
y

(
a
.
u
)
2u
0
Degree
% Eu
2+
0.9
1.8
3.6
4.7
5.4
7.2
10 20 30 40 50 60 70

2u
0
Degree
0:1

R
e
l
a
t
i
v
e

I
n
t
e
n
s
i
t
y

(
a
.
u
)
0.25:0.75

0.5:0.5

0.75:0.5
*
*
*
*
(b)

b(Nd
3+
:Dy
3+
)
1:0

92

Figure 2: Effect of co-dopant concentration on emission characteristics.
The decay characteristics exhibit a significant rise in initial intensity with increasing Eu
2+
doping
concentration and decay time also increases with Nd
3+
co-doping. The observed afterglow is
ascribed to the generation of suitable traps due to the presence of the Nd
3+
and/or Dy
3+
trap
levels.

[1] F. Clabau et al., Solid State Sci. 9 (2007) 608.

400 450 500 550 600 650 700
0
100
200
300
400

R
e
l
a
t
i
v
e

I
n
t
e
n
s
i
t
y

(
a
.
u
)
Wavelength (nm)
% Nd:Dy
0:1
0.25:0.75
0.5:0.5
0.75:0.25
1:0

93
Controlling storage properties of Lu
2
O
3
:Tb, and Lu
2
O
3
:Pr phosphors
Eugeniusz Zych
1,2,
*, A. Wiatrowska
1
, D. Kulesza
1
, J. Trojan-Piegza
1

1
2
Wroclaw Research Centre EIT+, Wrocaw, Poland
Keywords: storage phosphors, thermoluminescence, optically stimulated luminescence, trap depth
It was rather disappointing to find that Lu
2
O
3
:Tb performed quite insignificantly upon stimulation
with X-rays [1]. What is more, the scintillation signal was accompanied by intense and long
afterglow [2]. While the efficacy of X-ray excited luminescence (XEL) could not be improved to any
significant degree the afterglow appeared to be sensitive to variations in preparation conditions,
the dopant content as well as the presence of co-dopants. Especially influential were aliovalent
impurities, like Ca
2+
or Hf
(IV)
, with the former being able to drastically enhance both intensity and
duration of the afterglow up to about 10 hours and the latter capable of reducing the afterglow
totally. Yet, Hf
(IV)
was found to produce abundant deep traps in the Lu
2
O
3
:Tb compositions
transforming the material into a new storage phosphor with significant performance. Recently, it
has been proved that also Lu
2
O
3
:Pr,Hf compositions were able to permanently store energy
delivered through stimulation with short UV or X-ray photons. Fig. 1 presents 3D graphs showing
the thermally stimulated luminescence of both Tb,Hf and Pr,Hf co-doped materials.

Figure 1: 3D graphs showing thermoluminescence of Lu
2
O
3
:Pr,Hf (top)
and Lu
2
O
3
:Tb,Hf (bottom). Relative population of the deeper traps in the
Pr,Hf co-doped compositions can be controlled to some degree, as seen.
Thermal stimulation is not the only way to recover the energy deposited in the materials, whether
Pr,Hf or Tb,Hf co-doped, by high energy radiation. Low energy stimulation with infrared (IR) or red
photons is also able to free the trapped carriers from their traps and lead to the red (Pr,Hf) or

94
green(Tb,Hf) emissions. Fig. 2 shows how 980 nm and 780 nm photons influence the TSL glow
curves in both compositions, and thus how the energy stored in both materials can be recovered
through such stimulations.
In the case of Tb,Hf co-doped composition the 980 nm radiation is hardly able to remove the
carriers from their traps, see Fig. 2 (left). Intensity of the TSL before and after such an optical
stimulation gets reduced only slightly. Nevertheless, the green luminescence upon 980 nm
photons is produced, which is seen even by eye. When the energy of the stimulation radiation gets
higher (780 nm light) the tapped carriers get freed much more efficiently and shortly only a
remnant TSL signal can be recorded.
Even more intriguing behavior is observed in the case of Pr,Hf co-doped material, see Fig. 2 (right).
The 980 nm radiation allows to recover energy from the shallowest (~110 C) and the intermediate
trap (~200 C). After such an optical stimulation energy stored in the deepest trap remains
unchanged. This can be recovered with 780 nm radiation, and certainly with yet more energetic
photons. Hence, energy stored in the Pr,Hf composition could be read in two independent steps
by means of different energy photons. One may find it useful.

Figure 2: Glow curves of Lu
2
O
3
:Tb,Hf and Lu
2
O
3
:Pr,Hf irradiated with
254 nm photons and additionally bleached with IR radiation of 980 nm
and 780 nm wavelengths. Note that the Pr,Hf co-doped material allows
for sequential recovering of the energy stored in the deeper traps.

[1] A. Lempicki et al., Nucl. Instr. Meth. A 488 (2002) 579-590.
[2] E. Zych et al., J. Appl. Phys., 94 (2003) 1318-1324.

95

I 01 Persistent luminescence mechanisms: Human imagination at work 12
I 02 Storage and read-out mechanisms in the best photostimulable 14
I 03 Thermoluminescence as a tool to study the mechanism 15
I 04 Persistent phosphorescence through persistent energy transfer 17
O 01 Synthesis and characterization of BaAl
2
O
4
:Eu
2+
19
O 02 DFT and synchrotron radiation study of the Eu
2+
doped BaAl
2
O
4
21

O 03 Surface characterization and luminescent properties 23
of SrAl
2
O
4
:Eu
2+
,Dy
3+
nano thin films
O 04 Fabrication of long-lasting glass-ceramic phosphors 25
O 05 Luminescence studies of a combustion-synthesized 26
blue-green BaAl
x
O
y
:Eu
2+
,Dy
3+
nanophosphors
O 06 Synthesis, persistent luminescence, and thermoluminescence 28
3
SiO
5
:Eu
2+
,RE
3+
and orange Sr
3-x
Ba
x
SiO
5
:Eu
2+
,Dy
3+
phosphor
O 07 Yellow persistent luminescence in Sr
2
SiO
4
:Eu
2+
,Dy
3+
30
O 08 What electron paramagnetic resonance spectroscopy teaches us 32
2+
centers in CsBr:Eu
2+

96
O 09 Influences and improvements on the brightness 34

O 10 Elaboration of nanoparticles with persistent luminescence 35
for in vivo imaging
O 11 Thermoluminescence characteristics of 37
Lu
2
O
3
Aneta Wiatrowska, University of Wroclaw, Poland
O 12 Evaluating the brightness of persistent phosphors: 39
beyond the candela
O 13 Water soluble afterglow nanoparticles for biomedical imaging 41
O 14 Thermoluminescence study of persistent luminescence fading 43
in Sr
2
MgSi
2
O
7
:Eu
2+
,R
3+
materials
O 15 Thermally stimulated luminescence: 45
an algorithm for analyzing phosphorescence curves

O 16 Charging behaviour in persistent phosphors 46
O 17 Photoionization of lanthanide defects and how that affects 47
O 18 Controlling trap depth to enhance persistent luminescence 49
O 19 An x-ray absorption study of SrAl
2
O
4
:Eu,Dy powders 51
O 20 ZnGa
2
O
4
:Cr
3+
: a new red long-lasting phosphor with high brightness 53
O 21 IR laser stimulated afterglow fluorescence of 56
Eu(III) doped LaAlO
3
nanocrystals

97
O 22 Synthesis and characterization of Y
2
O
2
S:Eu nanophosphors 58

O 23 Persistent phosphorescence in Ce
3+
-doped Lu
2
SiO
5
59
O 24 Long-lasting phosphorescence in Ce
3+
-doped garnet crystals 60
O 25 Synthesis and characterization of calcium titanium oxide based 62
P 01 Energy transfer by ZnO to SiO
2
:Ce
3+
matrix 66
P 02 Improvement on CaAl
2
O
4
:Eu
2+
,Nd
3+
: 67
Nursen Avci, Ghent University, Belgium
P 03 Red persistent luminescence in biocompatible Ca
3
(PO
4
)
2
69
P 04 Persistent luminescence and mechanoluminescence 71
in MSi
2
O
2
N
2
:Eu
2+
(M = Ca,Sr,Ba)
Jonas Botterman, Ghent University, Belgium
P 05 Influence of titanium and lutetium on 73
the persistent luminescence of ZrO
2

Hermi Brito, Universidade de So Paulo, Brazil
P 06 The effects of Eu ions and Eu:Dy ratio on the structural, 75
morphological and luminescence properties
of blue-green BaAl
x
O
y
:Eu
2+
,Dy
3+
nano phosphors
P 07 Solution-combustion synthesis and photoluminescence property 77
of Gd,YBO
3
:Tb
3+
phosphor powders
P 08 Ca and Hf co-dopants as properties designing constituents 79
of Lu
2
O
3
Dagmara Kulesza, University of Wrocaw, Poland
P 09 Effects of co-dopants in long lasting phosphorescence phosphors 81
Chengyu Li, Changchun Institute of Applied Chemistry, China

98
P 10 Luminescent properties of CaAl
2
O
4
:Eu
2+
,Dy
3+
,Nd
3+
phosphors 82
prepared by combustion method
Bakang M. Mothudi, University of South Africa, South Africa
P 11 Persistent luminescence behavior of materials 84
doped with Eu
2+
and Tb
3+
ions
Lucas Rodrigues, Universidade de So Paulo, Brazil
P 12 Persistent luminescence in rare-earth doped nitrido-silicates 86
P 13 Preparation and persistent luminescence in 87
rare-earth doped Ca
2
Si
5
N
8
nanoparticles
Bruno Viana, LCMCP Paris, France
P 14 Properties of blue emitting CaAl
2
O
4
:Eu
2+
,Dy
3+
phosphors 89
P 15 Effect of Eu
2+
and Nd
3+
2
O
4
:Eu
2+
,Nd
3+
91
P 16 Controlling storage properties of Lu
2
O
3
:Tb, and Lu
2
O
3
:Pr phosphors 93
Eugeniusz Zych, University of Wrocaw, Poland

99
Aishima, Kotaro O - 24
Ali, Abdub G. O - 22 P - 01
Avci, Nursen P - 02
Batentschuk, Miroslaw I - 02
Benhamou, Rajia At P - 03
Bessire, Aurlie O - 10 O - 18 O - 20 P - 03
Bessodes, Michel O - 18
Bos, Adrie J.J. I - 03 O - 17
Botterman, Jonas P - 04
Brito, Hermi F. I - 01 O - 02 O - 14 P - 05 P - 11
Callens, Freddy O - 08
Carvalho, Jos M. P - 05
Caselli, Eduardo O - 15
Chanac, Corinne O - 10
Chen, Wei O - 13
Dejene, Francis B. O - 03 O - 05 O - 22 P - 01 P - 06 P - 07 P - 14 P - 15
Dorenbos, Pieter I - 03 O - 17
Dutczak, Danuta O - 07
Felinto, Maria C.F.C. O - 02 P - 05
Guchowski, Pawe O - 21
Gourier, Didier O - 18 O - 20 P - 13
Hackenschmied, Peter I - 02
Hagemann, Hans O - 25
Han, Thomas P.J. O - 23
Hls, Jorma I - 01 O - 02 O - 14 P - 05 P - 11
Jacquart, Sylvaine O - 20
Jungner, Hgne O - 14
Jstel, Thomas O - 07
Katayama, Yumiko O - 04
Korthout, Katleen O - 19
Kroon, R.E. (Ted) O - 03
Kulesza, Dagmara P - 08 P - 16
Laamanen, Taneli I - 01 O - 02 O - 14
Lastusaari, Mika I - 01 O - 02 O - 14 P - 05 P - 11
Leblans, Paul O - 08
Lecointre, Aurlie O - 18 O - 20 P - 03
Lephoto, Mantwa A. O - 01
Lester, Marcelo O - 15
Li, Chengyu P - 09
Li, Baohong O - 06
Li, Ye O - 06
Maegli, Alexandra O - 25
Maldiney, Thomas O - 18 P - 13
Malkamki, Marja I - 01 O - 02 O - 14
Malta, Oscar L. P - 05
Marcazz, Julin O - 15
Matthys, Paul O - 08
Meert, Katrien O - 12

100
Milbrat, Alexander O - 07
Molina, Pablo O - 15
Mothudi, Bakang M. O - 01 P - 10
Nakanishi, Takayuki O - 04
Nakayama, Tomomi O - 23
Novk, Pavel O - 02
Nsimama, P.D. O - 03
Ntwaeaborwa, Martin O. O - 01 O - 03 P - 10
Nunes, Luiz A.O. P - 05
Ohsumi, Yusuke O - 23
Osvet, Andres I - 02
Otal, Eugenio H. O - 25
Pitale, Shreyas O - 01
Poelman, Dirk O - 12 O - 16 O - 19 P - 02 P - 04 P - 12 P - 13
Priolkar, Kaustubh O - 20
Richard, Cyrille O - 18 P - 13
Rodrigues, Lucas C.V. I - 01 O - 02 O - 14 P - 05 P - 11
Rosticher, Cline O - 10
Santiago, Martin O - 15
Scherman, Daniel O - 18
Smet, Philippe F. O - 12 O - 16 O - 19 P - 02 P - 04 P - 12 P - 13
Sraiki, G. P - 13
Stefani, Roberval O - 02
Strk, Wiesaw O - 21
Su, Qiang (Changchun) P - 09
Su, Qiang (Guangzhou) O - 06
Suard, Emmanuelle P - 03
Swart, Hendrik C. O - 01 O - 03 O - 22 P - 01 P - 10 P - 14 P - 15
Tahon, Jean-Pierre O - 08
Tanabe, Setsuhisa O - 04 O - 24
Terblans, J.J. (Koos) O - 03
Trojan-Piegza, Joanna P - 08 P - 16
Ueda, Jumpei O - 04 O - 24
Van den Eeckhout, Koen O - 16 O - 19 P - 04 P - 12 P - 13
Veziridis, Angelika O - 25
Viana, Bruno O - 10 O - 18 O - 20 P - 03 P - 13
Vrielinck, Henk O - 08
Wako, Ali H. P - 14 P - 15
Walfort, Bernhard O - 09 O - 25
Wallez, Gilles P - 03
Wang, Xiaojun I - 04
Wang, Jing O - 06
Weidenkaff, Anke O - 25
Wiatrowska, Aneta O - 11 P - 16
Winnacker, Albrecht I - 02
Yamaga, Mitsuo O - 23
Yoon, Songhak O - 25
Zhang, Jiahuan I - 04
Zverev, Dmitry O - 08
Zych, Eugeniusz O - 11 P - 08 P - 16

101

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