Current Applied Physics 11 (2011) S292eS295

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Current Applied Physics

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Synthesis, structural and luminescent properties of Pr3þ activated GdAlO3

phosphors by solvothermal reaction method
G. Seeta Rama Raju, Jin Young Park, Hong Chae Jung, R. Balakrishnaiah, Byung Kee Moon*,
Jung Hyun Jeong
Department of Physics, Pukyong National University, Daeyon3 Dong, Namgu, Busan 608-737, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: Different concentrations of trivalent praseodymium (Pr3þ) ions activated GdAlO3 nanophosphors were
Received 25 June 2010 synthesized by solvothermal reaction method. Thermogravimetric/differential thermal analysis (TG/DTA)
Accepted 28 January 2011 and X-ray diffraction (XRD) measurements were used to investigate the phase transformations that occur
Available online 5 February 2011
during the preparation of these phosphors. The morphology of the powder after heat treatment was
observed by scanning electron microscopy (SEM). The luminescent studies on these compounds have
Keywords:
been carried out from the measurements of their photoluminescence (PL) and photoluminescence
Pr3þ: GAP
excitation (PLE) spectra. The PL spectra show blue-green emission corresponding to the fef transitions of
TG/DTA
XRD
Pr3þ (3P0 / 3H4) and red emission corresponding to the fef transition of Pr3þ (3P0 / 3H6) by monitoring
PL the excitation with fef transition of Pr3þ (3H4 / 3P2) at 449 nm. Emission mechanism in these systems
PLE has also been elucidated by an energy level scheme.
Ó 2011 Elsevier B.V. All rights reserved.

1. Introduction co-precipitation method, sol-gel, combustion, hydrothermal syn-

Gd2O3eAl2O3 system consists of three pseudo-binary compo-
unds such as gadolinium aluminum garnet (GAG, Gd3Al5O12),
gadolinium aluminum perovskite (GAP, GdAlO3), and gadolinium
aluminum monoclinic (GAM, Gd4Al2O9) [1]. GAG exists in the cubic
form with a garnet structure [2]. GAP has an orthorhombic distorted
perovskite structure [3] and GAM is monoclinic [4]. There is another
GdAlO3 phase, which is a hexagonal modification (GAH) and found
only in chemically synthesized powders [5]. Among these
compounds, orthorhombic GAP has gained abundant interest in
their production for their potential applications in the development
of different luminescent display systems, when doped with the
trivalent rare-earth (RE3þ) ions. Among various RE3þ ions, Pr3þ is
a special optical activator, which provides the possibility of simul-
taneous blue, green and red emissions depending on the host lattice,
which satisfies the complementary color relationship [6].
In general, phosphors are prepared by traditional solid-state
reaction method. Due to insufficient mixing and low reactivity of raw
materials, several impurity phases easily co-exist in the product. In
addition, phosphor particles prepared through this solid-state reac-
tion method have large in size (generally in micrometer range) [7].
However, in recent years, several wet chemical techniques such as
* Corresponding author.
E-mail address: bkmoon@pknu.ac.kr (B.K. Moon).
thesis, solvothermal synthesis and spray-pyrolysis synthesis were
used to prepare the phosphor precursor [7e14]. Phosphor materials
synthesized by these wet chemical methods have many advantages,
i.e. high purity, homogenous composition and fine grains in nano-
meter range.
In this paper, we have synthesized the Pr3þ: GAP nanophosphors
by means of solvothermal process. This process is one of the most
prominent processes to control the particle size in nanometers,
morphology and distribution of phosphor particles with efficient
luminescent properties. Upon going through the literature, it has
become quite clear that the pure orthorhombic phase of Pr3þ acti-
vated GAP nanophosphors by means of solvothermal reaction have
not been reported so far. Here, the first time we report on the struc-
tural and luminescent properties of different concentrations of Pr3þ
activated GAP nanophosphors by means of solvothermal process.
2. Experimental
Different concentrations of Pr3þ doped GdAlO3 (GAP) nano-
phosphor samples were prepared by means of solvothermal process.
The stoichiometric amounts of high purity grade gadolinium nitrate
hexahydrate (Gd(NO3)3$6H2O), praseodymium nitrate hexahydrate
(Pr(NO3)3$6H2O), and aluminum isopropoxide {[(CH3)2CHO]3Al}
were dissolved in 40 ml of 2-proponol. All reagents were used
without any further purification and stirred vigorously by using

1567-1739/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cap.2011.01.036
 G. Seeta Rama Raju et al. / Current Applied Physics 11 (2011) S292eS295 S293

a magnetic stirrer until the homogeneous solution was formed and

transferred into a stainless steel autoclave with a Teflon liner (80 ml
capacity and 50% filling). It was then heated to 230  C at a rate of
2  C/min and maintained for 5 h with magnetic stirring to make
stable networks of GdeOeAl and PreOeAl. After cooling gradually
down to room temperature, the precipitate was separated by
a centrifugal separator with 3000 rpm for 3 min and then dried at
60  C for a day in ambient atmosphere. The dried powder was sin-
tered at 800  C, 900  C, 1000  C, 1100  C, 1200  C and 1400  C for 5 h.
Thermogravimetric/differential thermal analysis (TG/DTA) of the
dried powder precursors was carried out with a Material Analysis
and Characterization TG-DTA 2000. This experiment was carried out
at a heating rate of 5  C/min and the samples were heated from room
temperature to 1300  C. X-ray diffraction patterns of Pr3þ: GAP
nanophosphors were recorded on X’ PERT PRO X-ray diffractometer
with CuKa ¼ 1.5406 Å. The morphology of the Pr3þ: GAP nano-
phosphors sintered at 1000  C was examined by means of field
emission scanning electron microscopy (FESEM) using JEOL JSM-
6700 FESEM. Osmium coating was sprayed on the sample surfaces by
using Hitachi fine coat ion sputter E-1010 unit to avoid possible
charging of specimens before FESEM observation was made. The
room temperature photoluminescence spectra of Pr3þ: GAP nano-
phosphors were recorded on a PTI (Photon Technology Interna-
tional) fluorimeter with a Xe-arc lamp of power 60 W.

3. Results and discussion

Fig.1 presents the TG/DTA curves of the powder precursor of Pr3þ

activated GAP obtained by the solvothermal method (range from
room temperature to 1300  C). The TG curve shows two distinct
weight loss steps up to 600  C; no further weight loss was registered
up to 1300  C. The weight loss is related to the decomposition of the
organic matrix. Simultaneously, four exothermic peaks were Fig. 2. Crystallographic unit cell of GdAlO3 perovskite system.
observed with maxima at 284, 356, 902  C and 1060  C on the DTA
curve during the process mass loss. The first two exothermic peaks
indicate that the thermal events can be associated with the burnout
GdO12 polyhedra site with Cs point symmetry [3]. The XRD patterns
of organic species involved in the precursor powders of the residual
of Pr3þ: GAP nanophosphors sintered at different temperatures
nitrogen and the third exothermic peak is due to crystallization of
from 750  C to 1400  C have also been shown in Fig. 3. The phos-
GAP powder from the amorphous component. The exothermic peak
phor was found to be amorphous until the precipitate powders
at 1060  C shows the phase transformation from hexagonal to
were sintering at 750  C and crystallized as pure hexagonal GAP at
orthorhombic phase of the GdAlO3 samples. These results were well
900  C without any intermediate phase. The GAP phosphor was
in agreement with the XRD analysis.
transferred to pure orthorhombic phase when sintered at 1000  C
The perovskite crystal structure of GdAlO3(GAP) has been
and above 1100  C GAG phase was presented. This process is well in
shown in Fig. 2. The Pbnm symmetry model of this perovskite
agreement with the sol-gel YAG-synthesis process modified by
GdAlO3 contains two cationic sites: (i) AlO6 octahedra site and (ii)
Yamaguchi et al. [8].

Amorphous precursor / H-YAP / O-YAP / YAG

In our present work, the formations of GAP phase mechanism

could follow:

ð900  C -1000  CÞ
Amorphous precursor / Hexagonal
ð1000  C -1400  CÞ above 1400  C
GAP / orthorhombic GAP / GAG Phase

It is well known that the pure phase is favorable for luminescent

Fig. 1. TG/DTA curves of Pr3þ: GAP powder precursor.
properties of phosphors. The diffraction peaks at 1000  C are in well
agreement with the standard JCPDS card [PDF (30-0015)] with
a space group Pbnm (62). The strongest diffraction peaks are used
to calculate the crystallite size of Pr3þ: GAP nanophosphor by
Scherrer equation, sintered at 1000  C, which yields an average
value of about 65 nm.
The morphological features of the Pr3þ: GAP nanophosphors sin-
tered at 1000  C were investigated by taking the FESEM image. The
S294 G. Seeta Rama Raju et al. / Current Applied Physics 11 (2011) S292eS295

Fig. 3. XRD patterns of Pr3þ: GAP phosphors at different sintering temperatures (c is Fig. 5. Excitation spectra of Pr3þ: GAP phosphors at various Pr3þ concentrations.
cubic phase).

concentration upto 1 mol% and above 1 mol% the intensity of exci-

typical morphological image is shown in Fig. 4. The particles showed
tation bands decreases due to concentration quenching.
sphere-like morphology formed from agglomeration between the
The emission spectra at different concentrations of Pr3þ activated
GAP particles during the period of sample sintering. It is well known
GAP nanophosphors by exciting at 449 nm have been shown in Fig. 6.
that the spherical-shaped particles are of greater importance because
From the figure, clearly, the shapes of emission spectra with different
of their higher packing density, lower scattering of light and brighter
Pr3þ concentrations upon sintering at 1000  C are similar. For all
luminescence performance. The particle sizes are in good agreement
samples under investigation, the spectra mainly consists of mani-
with the calculated crystallite sizes from XRD patterns.
folds arising from the emission of the 3P0 state to the 3H4,5,6 and 3F2
Fig. 5 shows the excitation spectra for the different concentrations
states, in the visible region near 492, 550, 610 and 645 nm, respec-
of Pr3þ: GAP phosphors at room temperature, which were obtained
tively and a weak peak at 530 nm due to 3P1 / 3H4 transition.
by monitoring emission at 492 nm (3P0 / 3H4). The excitation spectra
Additionally, very weak peaks were observed around 600 nm and
showed the broad excitation band centered at 294 nm due to 4fe5d
660 nm corresponding to the transition 1D2 / 3H4 and 1D2 / 3H5,
transition and the intense sharp excitation peaks between 440 and
respectively. Emission from the 1D2 level was more difficult to
480 nm due to of 4f2e4f2 intraconfiguration of Pr3þ ions. The peaks at
obtain, because the multi-phonon relaxation is not very efficient.
449 and 473 correspond to 3H4 / 3P2 and 3H4 / 3P1 transitions,
The energy gap of about 4000 cm1 between the 3P0 and the next
respectively. The structure observed inside each band is due to the
lower lying level, the 1D2, is larger than the low-phonon energy of
Stark splitting of the multiplet induced by the crystal-field of the
the host lattice. The approximate frequency of the highest-energy
matrix. It is expected that the Pr3þ ion substitute for the Gd3þ ions in
phonons in aluminate is 950 cm1 [16]. With this phonon frequency,
the GdAlO3 phosphor and the amount of Stark splittings of a multiplet
more than four phonons needed to bridge the energy gap between
depends on its J value. The main transitions are assigned from
the previous data [15] and are labeled in the figure. The intensity of
the excitation bands increases linearly with increasing the Pr3þ

Fig. 4. SEM image of Pr3þ: GAP phosphors sintered at 1000  C. Fig. 6. Emission spectra of Pr3þ: GAP phosphors at various Pr3þ concentrations.
 G. Seeta Rama Raju et al. / Current Applied Physics 11 (2011) S292eS295
Fig. 7. Energy level scheme of the Pr3þ: GAP nanophosphor.
the 3P0 and 1D2 levels are much less likely to be significant [17,18].
This supposition is supported by the weakness of 1D2 luminescence.
The intensity of the 1D2 emission was more sensitive to the doping
concentration than that caused by 3P0 transitions. It is known that
the emission intensity of 1D2 / 3H4 transition decreases as the Pr3þ
concentration increases due to cross-relaxation between neigh-
boring Pr3þ ions [19]. The following cross-relaxation may occur in
the system[20]:
1 [15] W.T. Carnall, P.R. Fields, K. Rajnak, J. Chem. Phys. 49 (1968) 4424e4442.
D2 (Pr3þI) þ 3H4 (Pr3þII) / 1G4 (Pr3þI) þ 3F4 (Pr3þII)
1
D2 (Pr3þI) þ 3H4 (Pr3þII) / 3F4 (Pr3þI) þ 1G4 (Pr3þII)
It is also well known that the luminescence intensity of phos-
phor materials is always dependent on the doping concentration. A
S295
series of Gd(1x)PrxAlO3 samples were synthesized as the dopant
concentration ranged from x ¼ 0.5 mol% to 3 mol%. When the Pr3þ
concentration increases from 0.5 mol% to 1 mol% the emission
intensity also increases. When the Pr3þ concentration further
increased above 1 mol% the emission intensity decreased due to
concentration quenching. The concentration quenching might be
elucidated by the following two factors, (i) the excitation migration
due to resonance between the activators is enhanced when the
doping concentration is increased, and thus the excitation energy
reaches quenching centers, and (ii) the activators are paired or
coagulated and are changed to quenching center.
An energy level scheme has been shown in Fig. 7 to explain the
mechanism involved in the emission process in Pr3þ: GAP
nanophosphors.
4. Conclusion
In conclusion, we have successfully synthesized the different
concentrations of Pr3þ: GAP nanophosphors by means of the
solvothermal reaction method and were sintered at 1000  C. The
structural properties of these phosphors have been investigated by
DSC, XRD and SEM measurements. The luminescence properties of
Pr3þ: GAP nanophosphors have been studied by measurement of
their excitation and emission spectra. The emission spectra showed
the strong band in the bluish green region and also some week
peaks in green and red regions. Based on the 3P0 / 3H4 emission
performance, the Pr3þ concentration has been optimized to be at
1 mol%. The emission mechanism of Pr3þ: GAP nanophosphors has
also been explained in terms of an energy level scheme. Such
a brightly luminescent phosphor could be considered as potential
optical material for the development of new optical display
systems.
Acknowledgments
This research was supported by NCRC (National Core Research
Center) program through the National Research Foundation of
Korea funded by the Ministry of Education, Science and Technology
(2010-0001-226).
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