Journal of Alloys and Compounds 686 (2016) 533e539

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Structural and photoluminescence features of Pr3þ-activated different

alkaline sodium-phosphate-phosphors
A. Balakrishna a, *, Vinod Kumar a, b, Ashwini Kumar a, O.M. Ntwaeaborwa a, **
a
Department of Physics, University of the Free State, Bloemfontein ZA9300, South Africa
b
Photovoltaic Laboratory, Centre for Energy Studies, Indian Institute of Technology Delhi, New Delhi 110016, India

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

Article history: A series of Pr3þ activated alkaline-sodium-phosphate (NaMPO4, where M ¼ Mg, Ca, Sr and Ba) phosphors
Received 8 April 2016 were prepared by conventional solution combustion method with the fixed doping concentration of Pr3þ
Received in revised form (1.0 mol%). The crystal phase formation and morphology of the phosphates were analyzed by X-ray
12 May 2016
powder diffraction (XRD) and field emission scanning electron microscope (FE-SEM), respectively. The
Accepted 7 June 2016
Available online 8 June 2016
optical properties including reflectance, excitation and emission and the color coordinates were inves-
tigated. The band gap of the phosphors was calculated from diffuse reflectance spectra data using the
KubelkaeMunk function. The photoluminescence (PL) excitation spectra showed the excitation peaks
Keywords:
Pr3þ ion
ranging from 420 to 475 nm and emission peaks were observed in the visible region and were found to
Alkaline-sodium-phosphate vary for different hosts. Pr3þ-doped phosphors can display very distinct dominant red emission due to
Diffuse reflectance spectra the 3P0 / 3H5, 3P0 / 3H6, 1D2 / 3H4 and 1D2 / 3H5 transitions. The Pr3þ PL emission spectrum was
K-M function observed from NaMPO4 phosphors at 605 nm. This emission under 445 nm excitation makes these
materials possible candidates to serve as sources of red light in tricolor system used for solid state
lighting. Different results on the luminescence features of Pr3þ:NaMPO4 are discussed on the basis of
crystal structure. The Pr3þ ion has structure-dependent transitions due to the special microstructures
present in a given host. The results indicated that among the four different alkaline cations, Caþ2 not only
provides the most intense emission from Pr3þ but it also produces electric-dipole dominated transition
(3P0 / 3H5) resulting in the most intense reddish-orange emission.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
A great interest in phosphors has resulted in rapid development
of a variety of display and other related illumination technologies.
For general lighting applications such as in UV light-emitting di-
odes, various photoluminescent materials including different clas-
ses such as silicates, aluminates, aluminosilicates, nitrides, borates,
etc., play vital roles [1e4]. Among all these hosts studied, phos-
phate is considered an excellent host for preparing phosphor due to
advantages such as low synthesis temperature, ease of preparation,
good chemical and thermal stability and high luminescent bright-
ness for solid state lighting applications. A lot of work has been
done by different researchers on the successful synthesis and
luminescence of rare earths doped phosphate phosphors with the
* Corresponding author.
** Corresponding author.
E-mail addresses: balakrishna.veera@gmail.com (A. Balakrishna), ntwaeab@ufs.
ac.za (O.M. Ntwaeaborwa).
sole intention of producing novel phosphors suitable for solid state
lighting [5e7]. As an important family of luminescent materials,
orthophosphates are generating enormous interest because of their
excellent fundamental properties such as large band gap and the
high absorption of PO34 inVUV region, moderate phonon energy,
the high thermal and chemical stability, and the exceptional optical
damage threshold [8e10].
Phosphates usually show a rather short wavelength of optical
absorption edge, which makes them suitable as hosts to accom-
modate active rare earth ions [11]. Today, a variety of rare-earths
doped phosphates are being prepared and investigated. Among
various rare-earths ions, Pr3þ is a special optical activator, which
provides the possibility of simultaneous blue, green and red
emissions depending on the host lattice, which satisfies the com-
plementary color relationship. Alkaline earth ions (Mgþ2, Caþ2, Srþ2
and Baþ2) play an important role in the enhancement of the
luminescent efficiency of phosphors by modification of composi-
tion and charge compensation in many phosphors [12,13]. Phos-
phates with a general formula ABPO4 (A and B ¼ mono and divalent

http://dx.doi.org/10.1016/j.jallcom.2016.06.064
0925-8388/© 2016 Elsevier B.V. All rights reserved.
534 A. Balakrishna et al. / Journal of Alloys and Compounds 686 (2016) 533e539
cations, respectively) form a large family compounds with rich
structure types strictly depending on the relative sizes of A and B
[14]. In recent years, rare earth ions doped orthophosphates with
the general formula of ABPO4 have been prepared and investigated.
For example, Eu3þdoped NaCaPO4 [15], LiSrPO4 [16], LiBaPO4 [17],
NaBaPO4 [18], KBaPO4 [19], and KSrPO4 [20] have been recently
reported to be the new luminescent materials applied in white light
emitting diodes (LEDs). In this study we prepared Pr3þ doped
orthophosphate phosphors with the general formula NaMPO4
(where M ¼ Mg, Ca, Sr and Ba) and we investigated their crystal
structure, particle morphology and photoluminescent properties.
The NaMPO4 phase consists of a tetrahedral built MPO4 framework
hosting sodium metal cation. Therefore it is reasonable to evaluate
influence based on different alkaline metal cations on light emis-
sion from different rare earth ions (RE) in this kind of host. It is a
well known that the luminescence properties of RE ions are very
sensitive to the crystal structure, phase transitions and chemical
surroundings [21]. Especially Pr3þ ion has been used as a local
structure probe in determining the microscopic symmetries of
different sites available in various host lattices [22]. As the most
important activator that emits in the blue red wavelength region,
Pr3þ ion has emerged as a favorite for red emission.
In the present work, the effect of different cation on the properties
of Pr3þ doped NaMPO4 phosphors was investigated. The photo-
luminescence properties of Pr3þ ions were investigated by excitation
and emission spectra. Different alkaline cation based red emission
1
D2 / 3H4 transition of Pr3þ emission is reported in this work.
2. Experimental procedure
The Pr3þ activated NaMPO4:Pr3þ phosphates were prepared via
conventional solution combustion method. The starting materials,
namely magnesium nitrate Mg(NO3)2$6H2O calcium nitrate Ca(N-
O3)2$6H2O, strontium nitrate Sr(NO3)2 and barium nitrate
Ba(NO3)2, ammonium di-hydrogen phosphate (NH4H2(PO4)), so-
dium nitrate (NaNO3$9H2O) and urea (NH2CONH2) were of AR
grade (99.99%) and purchased from Merck and were used with
further purification. The mixture of reagents was ground together
to obtain a homogeneous powder. Pr3þ ions were introduced by
adding Pr(NO3) powder. The molar ratio of rare earth was varied in
phosphor samples in relation to Mg/Ca/Sr/Ba ions. For various
compositions of the metal nitrates (oxidizers) the amount of urea
(fuel) was calculated maintaining total oxidizing and reducing va-
lences of the components equal to unity, so that the heat liberated
during combustion was maximized. After stirring for about 45 min
the solution was transferred to a furnace preheated to 600  C and
the porous powder products were obtained. The balanced chemical
reaction equations are as follows:
1 NaNO3 þ Mg(NO3)2 þ NH4H2(PO4) þ 2NH2CONH2 /
NaMgPO4 þ 7H2O þ 2CO2 þ 4N2
2 NaNO3 þ Ca(NO3)2 þ NH4H2(PO4) þ 2NH2CONH2 /
NaCaPO4 þ 7H2O þ 2CO2 þ 4N2
3 NaNO3 þ Sr(NO3)2 þ NH4H2(PO4) þ 2NH2CONH2 /
NaSrPO4 þ 7H2O þ 2CO2 þ 4N2
4 NaNO3 þ Ba(NO3)2 þ NH4H2(PO4) þ 2NH2CONH2 /
NaBaPO4 þ 7H2O þ 2CO2 þ 4N2
Several complementary methods were used to characterize the
prepared phosphors. The crystalline characteristic of the product
was identified by X-ray diffraction analysis (Bruker AXS D8 Advance
X-ray diffractometer) using a nickel-filtered CuKa target
(l ¼ 0.154056 nm). The data was recorded in a wide range of Bragg
angles 2q (15  2q  70 ) with a counting time of 1 s for each step
size of 0.00756043 to identify the phases that were present in each
compound. The morphology study was carried out using JEOL JSM-
7800F field emission scanning electron microscope (FE-SEM). FTIR
spectra were recorded with a Nicolet 6700 Fourier transform
infrared (FT-IR) spectrometer with KBr pellet technique in the
spectral range from 4000 to 500 cm1. UVeVis diffusion reflection
spectra of present phosphors were recorded using a Perkin Elmer
Lambda 950 UVevis at room temperature in the range of
300e800 nm. The PL was measured using a Cary eclipse spectro-
photometer at room temperature using a 150 W monochromatized
Xenon flash lamp as an excitation source.
3. Results and discussion
3.1. Powder X-ray diffraction measurements
The crystal phase formations of the samples were checked by
powder XRD measurements. The XRD patterns of as-prepared
NaMPO4:Pr3þ are presented in Fig. 1 (a)e(d). The experimental
patterns are compared with the PDF2 cards selected in the Inter-
national Centre for Diffraction Data (ICDD) database. By a com-
parison between them, the position and intensity of the main peaks
are the same. Samples contain mixture of crystalline phases: (a)
sample of NaMgPO4:Pr3þ contains crystalline phases of NaMgPO4
and Na3PO4 with PrO4 as minor phase; (b) sample of NaCaPO4:Pr3þ
contains crystalline phases of NaCaPO4 and Na3PO4 with PrO4 as
minor phase; (c) sample of NaCaPO4:Pr3þ contains crystalline
phases of NaMgPO4 and Na3PO4 with PrO4 as minor phase (d)
sample of NaBaPO4:Pr3þ contains crystalline phases of NaBaPO4
and Na3PO4 with PrO4 as minor phase [23,25].
3.2. Surface morphological analysis
The SEM images and corresponding Energy Dispersive Spec-
trometer (EDS) spectra are presented in Fig. 2 (a)e(d). The as-
obtained SEM micrographs shows that the particles of prepared
samples are agglomerated with irregular morphology with an
average diameter of about 1 mm.
Compositional analysis carried out using EDS confirms the
presence of all chemical elements by their weight percentages were
also estimated as shown in the inset of the EDS spectra. The EDS
spectrum of NaMPO4:Pr3þ (where M ¼ Mg, Ca, Sr and Ba) shows the
existence of Na, O, P, Mg, Ca, Sr, Ba and Pr elements with actual mole
ratios approaching the stoichiometric one. Furthermore, the
absence of other impurity elements in EDS profile evidenced the
phase purity of the obtained phosphor powders, consistent with
NaMgPO4, NaCaPO4, NaSrPO4, NaBaPO4, Na3PO4 and PrO4 structural
analyses.
3.3. Fourier transform-IR spectra-ortho phosphates groups (PO4)3
The structural elucidation of the prepared phosphors samples
were also investigated by Fourier transform infrared (FT-IR) spec-
troscopy by measuring the stretching frequency modes. Each of the
four samples was ground together with KBr in an agate mortar and
compressed to tablets using an electro hydraulic press. The FT-IR
spectra were measured within the broad range from 500 to
4000 cm1. All the spectra in Fig. 3 exhibit a series of strong,
asymmetric bands split between 950 and 1150 cm1 that are
associated with PO3
4 ions and correspond to asymmetric stretching
vibrations. The FT-IR spectra exhibit characteristic bands of the
orthophosphates for the as-prepared NaMPO4:Pr3þ. The IR ab-
sorption band of (PO4)3 has two regions at 1120e940 and
650e540 cm1. Three significant bands were observed at fre-
quencies 578, 1038 and 3430 cm1 [26,27]. The narrow band at
578 cm1 mainly due to the OePeO asymmetric bending
 A. Balakrishna et al. / Journal of Alloys and Compounds 686 (2016) 533e539
Fig. 1. Powder X-ray diffraction patterns of as-synthesized samples (a) (NaMgPO4):Pr3þ (b) (NaCaPO4):Pr3þ (c) (NaSrPO4):Pr3þ and (d) (NaBaPO4):Pr3þ.
vibrations, while the prominent band at 1038 cm1is due to the
asymmetric stretching vibrations of [PO4]3 tetrahedron [28]. A
medium IR band in 733e835 cm1 indicates the wagging modes of
vibration of the coordinated water and the metal-oxygen bond in
the complex. The higher peak at 3465 cm1 is ascribed to the OH
stretching vibration mode and 1983 cm1 is assigned to the
HeOeH bending vibration mode of the H2O molecule, respectively.
The characteristic vibrations of water molecule may arise from
absorbed moisture at sample surface during the measurement.
3.4. Optical properties-DRS spectra with band gap
The UVevis diffuse reflectance spectrum (DRS) of the
NaMPO4:Pr3þ phosphors are given in Fig. 4. It is obvious from the
energy level scheme of Pr ion that the characteristic absorption
bands can be attributed to the transitions from the ground level 3H4
to the higher energy levels of the Pr [29,30]. For the phosphors
applied in high emission optical activators, high absorption
535
efficiency around the 450e470 nm of blue LED emission and suit-
able transmittance efficiency in other visible spectral range are
necessary for commercial applications. For the diffuse reflectance
spectra of all the NaMPO4:Pr3þ in the region above 400 nm, several
optical bands were observed and each band originates from the
characteristic transition between two spin-orbit coupling levels of
the corresponding lanthanide ion and the absorption peaks are
assigned to the transitions of Pr3þ from the ground 3H4 to the
excited 3P2, 3P1, 1I6, 3P0 manifolds. Therefore, Pr3þ-doped NaMPO4
phosphors can be excited by nUVLEDs. The weak absorption peaks
around 600 nm are due to the 3H4 / 3D2 transitions of Pr3þ. It is
worthy to note that in the diffuse reflectance spectra of Pr3þ-doped
NaMPO4:Pr3þ the full width at half-maximums (FWHMs) of ab-
sorption bands of Pr3þ ions become wider, compared with other
Pr3þ-doped tungstates and alumino silicates [31,32]. Especially for
the absorption bands originating from the 3H4 / 3D2 transition, the
FWHMs of absorption bands are widen and the Stark components
become complicated. One possible reason for this observation is
536 A. Balakrishna et al. / Journal of Alloys and Compounds 686 (2016) 533e539

Fig. 2. SEM micrographs and EDS of the phosphors as-synthesized samples (a) (NaMgPO4):Pr3þ (b) (NaCaPO4):Pr3þ (c) (NaSrPO4):Pr3þ and (d) (NaBaPO4):Pr3þ prepared by using
combustion method.

that in the NaMPO4 systems there are three nonequivalent crystal
lattice sites among which the alkaline ions (Mþ2 ¼ Mgþ2, Caþ2, Srþ2
and Baþ2) are eight-fold coordinated, while Naþ is six-fold coor-
dinated and two other are eight fold coordinated, and the Pr3þ ions
occupying the Mþ2 sites can reside in more than one crystallo-
graphic sites, therefore the absorption lines of Pr3þ ions become
more intense and wider, which has been observed in different rare
earth ion doped hosts [24,33]. The wider FWHMs of absorption
bands of Pr3þ in NaMPO4:Pr3þ are helpful to tolerate the excitation
wavelength shift of blue LED chips.
The band gap of the as-prepared NaMPO4:Pr3þ (where M ¼ Mg,
Ca, Sr and Ba) phosphors were determined by the Kubelka-Munk
[34] theory. The DR spectra of the phosphors were transformed
to the absorption spectra by using the KubelkaeMunk function,
given by
ð1  R∞ Þ2 K
FðR∞ Þ ¼ ¼ (1)
2R∞ S
where, R ¼ the diffuse reflectance of the sample, K ¼ absorption
 A. Balakrishna et al. / Journal of Alloys and Compounds 686 (2016) 533e539 537

Fig. 3. FT-IR transmission spectra of combustion-driven phosphors (NaMPO4, where M ¼ Mg, Ca, Sr and Ba) doped with Pr3þ ion.

coefficient and S ¼ scattering coefficient. The band gap Eg and linear

absorption coefficient a of a material is related through the well-
known Tauc relation [35]:

n=2
ahv ¼ C1 hv  Eg (2)

where n is the photon energy and C1 is a proportionality constant.

When the material scatters in a perfectly diffuse manner (or when
it is illuminated at 60 incidence), the absorption coefficient K
becomes equal to 2a. Considering the scattering coefficient S as
constant with respect to the wavelength and using Eqs. (1) and (2),
the following expression can be written:

n
½FðR∝ hvÞ2 ¼ C2 hv  Eg (3)

the value of n is 1 for direct allowed transitions, 2 for non-metallic

materials, 3 for direct forbidden transitions, 4 for indirect allowed
transition and 6 for an indirect forbidden transition. Now, among
the plot of [F(R∞)hn]2, [F(R∞)hn], [F(R∞)hn]2/3, [F(R∞)hn]1/2, [F(R∞)
hn]1/3 as a function of photon energy hn, the best fitting was ob-
tained with n ¼ 1 in Eq. (2) i.e., [F(R∞)hn]2 as a function of hn
indicating that the band transitions occurred are direct in nature, as
suggested by Tauc et al. [35]. From the plot of [F(R∞)hn]2 versus hn,
the value of Eg was obtained by extrapolating the linear fitted re-
gions to [F(R∞)hn]2 ¼ 0 as shown in Fig. 5. The band gap energies
calculated from the DR spectra using the KeM function F (R∞) for all
different alkaline NaMPO4:Pr3þ (where M ¼ Mg, Ca, Sr and Ba)
phosphors were found to be 5.04, 5.45, 5.01 and 5.02 eV, respec-
tively. Among all the prepared phosphors, the high band gap energy
is noticed in the NaCaPO4:Pr3þ phosphors. Furthermore, it can be
seen from Fig. 5 that the band gap energies have increased from
5.04 / 5.45 eV in case from NaMgPO4:Pr3þto NaCaPO4:Pr3þ where
as in the case of NaSrPO4:Pr3þ and NaBaPO4:Pr3þ approximately
similar energy band gap was found. So, the different energy band
gap observed in all phosphors may be due to different crystalline
size of the material [36,37].
Fig. 4. The UVevisible DRS spectra of different alkaline sodium-phosphate-phosphors
(NaMPO4, where M ¼ Mg, Ca, Sr and Ba) doped with Pr3þ ion.
3.5. Photoluminescence studies reddish-orange emission of Pr3þion
Fig. 6 shows comparative photoluminescence (PL) and photo-
luminescence excitation (PLE) spectrum of the NaMPO4:Pr3þ
phosphors. The excitation spectra monitored at 602 nm exhibits
excitation band ranging from 420 to 500 nm with peaks around
443, 470, and 480 nm, which covered the emission wavelength of
all commercial blue LEDs (450e470 nm) [13,19]. This means that
NaMPO4:Pr3þ phosphors may be potentially useful in blue-based
white LEDs. From the PLE spectra it is observed that the broad
band with a maximum intensity at 445 nm (stronger excitation
band). Under the excitation of 445 nm, the photoluminescence
spectra of NaMPO4:Pr3þ (where M ¼ Mg, Ca, Sr and Ba) phosphor
compositions were recorded at room temperature. The strong
sharp emission band with peaks around 593, 602, 621 and 628 nm
538 A. Balakrishna et al. / Journal of Alloys and Compounds 686 (2016) 533e539
Fig. 5. Energy band gap in as synthesized a of different alkaline sodium-phosphate-
phosphors (NaMPO4, where M ¼ Mg, Ca, Sr and Ba) doped with Pr3þ ion. The line
represents the best linear fit to determine the energy band gap.
attributed to the typical fef transitions of Pr 3þ
and these
are3P0 / 3H5, 3P0 / 3H6, 1D2 / 3H4 and 1D2 / 3H5 [20e22].
However, some differences are observed in emission modes of their
emission peaks: (a) the strongest splitting peak is observed at
593 nm (3P0 / 3H5) for NaMgPO4 while, the weak splitting peaks
are present at 621 nm (1D2 / 3H4) and 628 nm (1D2 / 3H5) for
NaMgPO4:Pr3þ and NaBaPO4:Pr3þ. It indicates that excitation en-
ergy is reassigned between 3P0 / 3H5 and 1D2 / 3H4 and
1
D2 / 3H4 in different phosphors. This single red color emission
characteristic indicates the excellent color purity of the phosphors,
which showed the activator Pr3þ is successfully incorporated in the
host lattice of synthesized phosphors. At the same time, the red
emission may also be useful in various display devices [23] such as
Fig. 6. Room-temperature PL and PLE spectra of different alkaline sodium-phosphate-
phosphors (NaMPO4, where M ¼ Mg, Ca, Sr and Ba) doped with Pr3þ ion. The PL and
PLE spectra were measured at lexc ¼ 445 nm and lemi ¼ 601 nm, respectively.
field emission display, vacuum fluorescent displays and plasma
display panels. Moreover, red emission varies with incorporation of
different alkaline metal ions into the sodium-phosphate phosphors.
The variation in intensity of emission peaks with different alkaline
metal ions follows the order: Caþ2 > Srþ2 > Baþ2 > Mgþ2. As shown
in Fig. 7, the PL brightness of Pr3þ ion in different divalent alkaline
ions based sodium phosphors are more intense compared with that
observed from other hosts such as Sr2Al2SiO7 [38] and ZnWO4 [39].
However, among all the prepared samples the NaCaPO4:Pr3þ
phosphors emit high PL brightness, therefore the Pr3þ doped cal-
cium phosphate phosphors can be regarded as a promising candi-
date for the fabrication of phosphor converted white LEDs
applications. The enhanced PL performance for the NaCaPO4:Pr3þ
phosphors comes from the improved crystallinity due to the charge
balance [40,41]. However, with the dopant contents further in-
crease, because the radii are different between replaced host ions
Naþ, alkaline ions (Mgþ2, Caþ2, Srþ2 and Baþ2) and dopant Pr3þ,
more and more defects (such as oxygen vacancies) will produce and
result in the different luminescent properties in intensity as well as
in the splitting to different peaks.
3.6. CIE parameters
Commission Internationale de l’Eclairage (CIE) coordinates is
frequently used to characterize and express color of a phosphor.
The CIE coordinates (x, y) can be obtained from tristimulas values X,
Y and Z (which were obtained by color matching functions and
spectral power distribution) by formulae as follows [42]:
X Y
x¼ y¼
XþYþZ XþYþZ
Based on the corresponding PL spectra, the CIE (Commission
International de l’Eclairage, France) system was used to calculate
the chromaticity coordinates of the NaMPO4:Pr3þ (where M ¼ Mg,
Ca, Sr and Ba) phosphor compositions and are shown in Fig. 7. The
Fig. 7. CIE chromaticity coordinates for the different alkaline sodium-phosphate-
phosphors (NaMPO4, where M ¼ Mg, Ca, Sr and Ba) doped with Pr3þ ion.
 A. Balakrishna et al. / Journal of Alloys and Compounds 686 (2016) 533e539
calculated CIE chromaticity coordinates are (0.5580, 0.4419),
(0.5580, 0.4419), (0.5580, 0.4419) and (0.5580, 0.4419) respectively.
The calculation results showed that the chromaticity coordinates of
all samples are lying in the red color region, which indicate that the
difference among all the samples is too small to affect the chro-
maticity coordinates of the samples. It is also clearly observed that
samples of different alkaline metal based sodium phosphate
phosphors are all emit reddish-orange region light, respectively,
indicating color of all NaMPO4:Pr3þ (where M ¼ Mg, Ca, Sr and Ba)
phosphors is most reddish-orange.
4. Conclusions
In summary, a series of Pr3þ doped NaMPO4 phosphors were
prepared by the solution combustion method and their photo-
luminescent properties were investigated. The XRD results
confirmed that the samples contain mixture phases of crystals. The
optical band gaps were evaluated by DRS spectra and Kubelka-
Munk function and noticed higher in NaCaPO4. SEM images show
that the grains have an irregular shaped particle with a size less
than 3e4 mm. The absorption peaks obtained in the FT-IR spectrum
confirmed the water of crystallization, symmetric as well as
asymmetric stretching and bending vibration of PO4 units and
metal-oxygen bonds in prepared crystals. Prepared phosphors were
exhibited broad excitation band ranging from 445 to 480 nm,
which can perfectly match a blue LED chip. The PL emission is
strongly observed in the reddish-orange region of the spectrum
due to transition of Pr3þ ions in the NaMPO4, where M ¼ Mg, Ca, Sr
and Ba phosphors.
Acknowledgements
The authors acknowledge with gratitude financial assistance
from the South African National Research Foundation (Competitive
Programme for Rated Researchers Grant No.
CPR20110724000021870; Mobility travel Grant No. 82521) as well
as assistance from the Rental Pool Programme of the National Laser
Centre (Grant No. NLC-LREGM00-CON-001). The financial assis-
tance from the University of the Free State is highly appreciated.
One of the authors (VK) is thankful to DST, New Delhi, India for
support through DST-Inspire faculty award.
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