Optical Materials 75 (2018) 122e126

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Optical Materials
journal homepage: www.elsevier.com/locate/optmat

Effects of X-ray irradiation on the Eu3þ / Eu2þ conversion in CaAl2O4

phosphors

s A. Gomes a, b, *, Je
Manasse
ssica C. Carvalho a, Adriano B. Andrade a, c,

lia S. Macedo a, Ma
Marcos V. Rezende d, Ze
rio E.G. Valerio a
a ~o Cristova
Laboratory of Preparation and Characterization of Materials, Physics Department, Federal University of Sergipe, 49100-000 Sa ~o, SE, Brazil
b ^ncavo of the Bahia, 44380-000, Cruz das Almas, BA, Brazil
Science Center and Technology, Federal University of the Reco
c
Materials Science and Engineering Department, Federal University of Sergipe, 49100-000, Sa~o Cristova
~o, Sergipe, Brazil
d
Group of Functional Nanomaterials (GNF), Physics Department, Federal University of Sergipe, 49500-000, Itabaiana, SE, Brazil

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

Article history: This paper reports structural and luminescence properties of Eu-doped CaAl2O4 produced by an alter-
Received 6 July 2017 native sol-gel method using coconut water. Results of differential thermal analysis (DTA), thermogra-
Received in revised form vimetric analysis (TGA), and X-ray diffraction (XRD) allowed us to identify the best synthesis conditions
15 September 2017
for sample preparation. Simultaneous measurements of X-ray absorption spectroscopy (XAS) and X-ray
Accepted 9 October 2017
excited optical luminescence (XEOL) were also performed in the X-ray energy range of the Eu LIII edge.
Results from photoluminescence (PL) showed only the characteristic Eu3þ emission. However, radio-
luminescence emission spectra from Eu-doped CaAl2O4 shows a process of conversion of Eu3þ to Eu2þ,
which is induced by X-ray irradiation and is dependent on the radiation dose energy. X-ray absorption
near edge structure (XANES) measurements corroborate Eu reduction due to irradiation, showing that
only the Eu3þ ion is present in stable form in the CaAl2O4.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction compounds such as SrAl2O4, Ca12Al14O33 [8], BaAl2O4 [9], and

The absorption of ionizing radiation and subsequent conversion
to visible light are important factors in the properties that define
applications of a phosphor material. Calcium aluminate (CaAl2O4) is
an inorganic material from the aluminates family that, when doped
with rare earth ions, presents luminescent properties [1,2]. There-
fore, it is very important to study the behavior of this material in
detail, in order to ensure efficient applications.
CaAl2O4 has been successfully produced by several methods,
such as the conventional sol-gel route [3], solid state reactions [4],
Pechini [5], and combustion [6]. The materials produced by solid
state and conventional sol-gel routes usually contain undesirable
additional phases of other calcium aluminate such as CaAl4O7,
Ca3Al2O6, Ca12Al14O33, and CaAl12O19 [3,4]. A new alternative sol-gel
route, called proteic sol-gel method, use coconut water as a starting
solvent [7]; it has been used to successfully produce aluminate
* Corresponding author. Laboratory of Preparation and Characterization of Ma-
~o Cristova
terials, Physics Department, Federal University of Sergipe, 49100-000 Sa
SE, Brazil.
E-mail address: manasses.fis@gmail.com (M.A. Gomes).
Sr3Al2O6 [10], as well as other oxides, for example, ZnO [11],
YVO4:Eu [12], and LiAlSi2O6 [13]. Generally, this route allows
phosphors production with high crystallinity using lower temper-
atures than those normally employed in the solid state route.
Eu-doped CaAl2O4 has luminescent properties with high in-
tensity emission that depends on the oxidation state of the Eu ion.
For Eu doping of CaAl2O4, the most favorable oxidation state is Eu3þ,
followed by additional defects as charge compensation. Previous
results, obtained via computational simulation, for BaAl2O4 [14]
and SrAl2O4 [15] show a high probability of the incorporation of
Eu3þ in Ba2þ/Sr2þ sites, compensating by oxygen interstitials (Oi).
The similarities between these aluminates with CaAl2O4 suggest
that the same charge compensation mechanisms may happen.
Wei et al., using a reduction atmosphere, showed that it is
possible to get Eu2þ in stable form in CaAl2O4 [16]. Souza and co-
workers reported the use of laser sintering to provide Eu2þ in sta-
ble form in CaAl2O4 using Dy3þ as co-dopant to get afterglow
characteristics [17]. Nevertheless, there has been no report of in-
vestigations of the ionizing radiation effect on the Eu3þ / Eu2þ
~o, conversion in CaAl2O4.
In this study, we report the synthesis conditions of Eu-doped

https://doi.org/10.1016/j.optmat.2017.10.016
0925-3467/© 2017 Elsevier B.V. All rights reserved.
 M.A. Gomes et al. / Optical Materials 75 (2018) 122e126
CaAl2O4 produced using coconut water as solvent to the starting
reagents, and also the Eu3þ to Eu2þ conversion induced by ionizing
radiation. Additionally, we also report XANES and PL results to
confirm that the Eu conversion is due to X-ray irradiation. Based on
these results, we have proposed a mechanism to explain the radi-
oluminescence (RL) in Eu-doped CaAl2O4.
2. Experimental
2.1. Synthesis and structural characterization
Undoped CaAl2O4 and Eu3þ-doped CaAl2O4 (Ca0.97Eu0.03Al2O4)
phosphors were produced via a proteic sol-gel route [7]. The
samples were prepared by mixtures of stoichiometric amounts of
Ca(NO3)2$4H2O-99,0%, Al(NO3)3$9H2O-98,0%, and Eu(NO3)3-99,99%
dissolved in coconut water (Cocos nucifera), with final concentra-
tion of 0.3 mol/L. The final solution was maintained under magnetic
stirring at 60  C for 1 h to form the starting gel, which was then
dried at 100  C for 24 h, resulting in a xerogel.
In order to find the initial crystallization temperature, the
xerogel was thermally analyzed by differential thermal analysis
(DTA) and thermogravimetric analysis (TGA) using a TA In-
struments SDT 2960 under synthetic air flux and a heating rate of
10  C/min. In this analysis, the xerogel was then calcinated at four
different temperatures (1000, 1200, 1250, and 1300  C) for 2 h in an
open air atmosphere. X-ray diffraction (XRD) measurements were
carried out to check the crystalline phases of the samples using Cu
Ka radiation in a Rigaku Ultima þ RINT 2000/PC diffractometer in
the BraggeBrentano geometry, operating at 40 kV/40 mA. All XRD
measurements were performed within the 2q range from 10 to 80
in continuous scan mode, at a scan speed of 2 /min.
2.2. Luminescent characterization
Photoluminescence (PL) studies were done in an ISS-PC1 fluo-
rimeter equipped with a xenon lamp and a monochromator. An
Ocean Optics HR2000 spectrometer connected to an optical fiber
was used for detection. X-ray excited optical luminescence (XEOL)
was measured simultaneously with XANES, in the Brazilian Syn-
chrotron Light Laboratory (Proposal # 13512/12) at the X-ray ab-
sorption fine structure beamline using multi-bunch operation
fluorescence mode. XEOL curves were measured with photon en-
ergy around the Eu LIII-edge, and the light emission was collected
using a photomultiplier tube (PMT) coupled to an optical fiber. The
photomultiplier signal was synchronized with the synchrotron
beamline photon energy. To avoid temporal dependence on the
photon energy in the beamline, all spectra (XEOL and XANES) were
corrected by the incident photon flux (I0). Conventional RL mea-
surements were also obtained using Cu Ka radiation with dose rate
of 1.41 mGy/s at the sample position, using the same optical
detection system used for the PL emission spectra measurements.
For this work, all experiments were done at room temperature.
3. Results and discussion
Fig. 1(a) shows the results of thermal analysis of the xerogel of
the sample. The curves can be divided into three temperature re-
gions containing important events: I - A strong endothermic peak,
denoting weight loss, is observed approximately between 120 and
180  C. This variation may correspond to the loss of structural water
and H2O absorbed from the ambient; II - The events between 300
and 600  C correspond to organic solvent evaporation and nitrate
decomposition [18]; III - The small exothermic peak around 950  C
is possibly a crystallization event that may be connected to the
formation of the CaAl2O4 phase.
123
Fig. 1(b) shows in detail the first derivative of the thermog-
ravimetry of the third region of the thermal analysis curve. Around
900e960  C, it is possible to observe a mass loss peak in the dm/dT
curve, followed by a group of exothermic peaks in the same tem-
perature range. These events can be associated to the crystallization
of the material, suggesting that temperatures above this range can
be used during the calcination step.
Fig. 2 shows the XRD patterns of CaAl2O4 samples annealed at
different temperatures (1000, 1200, 1250, and 1300  C). The main
crystalline phase presents in the material is the CaAl2O4 monoclinic
phase. The XRD patterns of Eu-doped samples presented the same
characteristics as found in the undoped samples (not shown here),
indicating that the small quantity of doping of the CaAl2O4 matrix is
not enough to cause noticeable changes in the XRD pattern.
Fig. 3 shows the PL emission spectrum of the samples that
presented the best synthesis conditions (Eu3þ-doped CaAl2O4
calcined at 1200  C/2 h) excited at 255 nm. The Eu3þ emission
spectrum is composed of the characteristic 4f/4f
(5D0/7Fj¼0,1,2,3,4) transitions [19], with narrow lines between 550
and 750 nm.
The allowed magnetic dipole transition, 5D0/7F1, is not affected
by changes in the crystal field environment [20] and the electric
dipole transition, 5D0/7F2, has high sensitivity to ambient condi-
tions. Therefore, the emission intensity varies greatly with envi-
ronmental changes [20]. The strongest emission peak, at 620 nm, is
assigned to the electric dipole transition, 5D0/7F2, of Eu3þ. The
main PL peak position corresponds to Eu3þ emission, according to
the literature; Guanghuan et al. [19] reported a strong peak located
at 615 nm, and Jana
kova et al. [21] and Wiglusz et al. [20] reported a
peak at 613 nm corresponding to the 5D0/7F2 transition. This
strong peak is an indication of the low symmetry of the site occu-
pied by Eu3þ. An important contribution to the low local symmetry
is due to the deformation caused in the matrix when the Eu3þ ion
replaces a lattice ion of the lattice [22].
Eu3þ ions could, in principle, be incorporated into the lattice at
either Ca2þ or Al3þ sites. Due to the similar ionic radii of Ca2þ, 1.0
and 1.18 Å, and Eu3þ, 0.947 and 1.12 Å, for VI and IX coordination,
respectively, incorporation of the Eu3þ into the Ca2þ site is more
probable than incorporation into the Al3þ site which has ionic
radius of 0.535 Å [23]. In this case, charge compensation is required
and can happen in one of the following ways: a) by a Ca2þ vacancy;
b) by CaAl
antisite (Ca2þ ion displaced to an Al3þ site); c) by oxygen
interstitials; and d) by Al3þ vacancy. The charge compensation
contributes to the increase in the local deformation of the sites,
influencing the increase in intensity of the 5D0/7F2 electric dipole
transition [22]. Previous results of computer simulation for BaAl2O4
and SrAl2O4 hosts reported a higher probability of Eu3þ ion incor-
poration at Ba2þ/Sr2þ sites and charge compensation by oxygen
interstitials [14,15].
Fig. 4(a) shows the RL spectrum of CaAl2O4:Eu3þ excited using a
Cu Ka (Ea1 ¼ 8046 eV, Ea2 ¼ 8026 eV) X-ray source. RL measure-
ments were performed using several radiation doses. In the pre-
sented RL spectra, the presence of an emission band around
550 nm, together with the low intensity characteristic of Eu3þ
emission, is observed. This emission band is attributed to the
typical 4f65d1/4f7 transitions from Eu2þ, suggesting the presence
of Eu2þ in the material; however, PL measurements suggest that no
Eu2þ exists in the material before irradiation.
The position of the emission band related to the Eu2þ transition
is dependent on the host matrix. The literature has reported a peak
at around 440 nm, corresponding to Eu2þ in a CaAl2O4 host [24,25].
However, in this work it appears at approximately at 550 nm. This
difference may be due to the way in which Eu2þ was produced in
the CaAl2O4. In previous work [24,25], Eu reduction occurred dur-
ing sample calcination and the Eu dopant was dissolved in the
124 M.A. Gomes et al. / Optical Materials 75 (2018) 122e126
Fig. 1. (a) Thermal analysis curves (TGA and TDA) of the CaO-Al2O3 xerogel. (b) Expanded view of the DTA and the DTG curves in region above 700  C.
Fig. 2. XRD of some samples annealed at different temperatures.
Fig. 3. Emission spectrum of CaAl2O4:Eu3þ excited at 255 nm.
structure already in the divalent oxidation state. On the other hand,
in this work, the Eu reduction process occurs due to the X-ray
excitation. A different process (gas flux during synthesis and X-ray
irradiation) can generate changes in the local symmetry, influ-
encing Eu2þ transitions that are more sensitive to environmental
changes, since the 5d orbital is external to the 4f shielded region.
The process of Eu reduction under X-ray irradiation also take into
account the neutralization of the defect in the host, e.i., formation
of the O3
2 molecule by O
2 lattice anion and the O trapping the
i standard trivalent Eu in Eu2O3, indicating that there are only Eu
hole. The most probable mechanism to explain the Eu3þ/Eu2þ is
that the electrons generated in the conduction band after the X-ray
absorption are trapped in the Eu3þ, while the hole generates a Vk-
type centre. In this case, the Eu2þ produced only under X-ray
irradiation will have a different local symmetry than Eu2þ incor-
porated during the production of the material [26]. Similar
behavior also was observed in Eu3þ-doped BaAl2O4 [27] and in the
Eu3þ doped SrAl2O4 [26].
Fig. 4(b) shows the time-resolved RL decay curve acquired at
room temperature. The curve was acquired using the total light
yield upon direct excitation using pulsed X-ray source. No band
pass filter was used to separate the emissions from Eu2þ and Eu3þ.
The decay times of Eu doped CaAl2O4 were calculated by the curve
fitting using a double exponential components. Two different decay
times were found, a fast decay time of 0.59 ms corresponding to
93% of the total luminescent decay and a slow decay time of 8.81 ms
corresponding to 7% of the initial intensity of decay. Both compo-
nents can be attributed to Eu3þ, since Eu2þ have a fast decay of 0.9
ms for similar BaAl2O4 and SrAl2O4 hosts [28]. For Eu3þ in similar
hosts, is expected that the time decay is in order of few millisec-
onds, as found for MgAl2O4:Eu3þ (1.95 ms) [29], BaAl2O4:Eu3þ
(0.96e1.11 ms) [30]. Furthermore, is well know that the synthesis
conditions and doping concentration also contribute to different
time decay in aluminates hosts [30,31]. Two components decay
(2.16 ms and 63.85 ms) were found for Eu3þ doped SrAl2O4 by
Sashu et al., the authors attributed these components due the
presence of very shallow traps, leading to a quick escape of charge
carriers from the traps resulting in a recombination process in
milliseconds, exciting Eu3þ [32]. This mechanism can explain a slow
component decay (8.81 ms) observed in this work for the
CaAl2O4:Eu.
The RL response to radiation dose shows a change of relative
intensity in the Eu3þ and Eu2þ emissions. Eu2þ emission intensity
increases, while Eu3þ emission intensity decreases, as dose in-
creases. Considering that the peak intensities are proportional to
the number of luminescent centers, we can conclude that there is
an increase in the number of centers of Eu2þ and a decrease in Eu3þ
centers in this case. This behavior indicates that the X-ray irradia-
tion induces the Eu reduction and generates a competition between
the Eu species, as can be better seen in Fig. 5.
The presence of Eu2þ in the structure of the CaAl2O4 matrix was
investigated by XANES measurements around the Eu LIII-edge.
Fig. 6 shows the X-ray absorption spectroscopy (XAS) curves of the
CaAl2O4:Eu3þ samples, and also the XANES of the Eu2O3 standard
for Eu3þ. The position of the maximum absorption peak in the XAS
curve observed for Eu in CaAl2O4 is the same as observed for the
 M.A. Gomes et al. / Optical Materials 75 (2018) 122e126
Fig. 4. RL spectra of the Eu doped CaAl2O4 in function of the X-ray accumulated radiation dose (a), Time-resolved radioluminescence decay curve (b).
Fig. 5. RL results around the most intense peaks of the Eu3þ and Eu2þ emission spectra
performed at several X-ray irradiation doses. The symbols represent the experimental
measurements and the solid line is just a guide for the eye.
Fig. 6. XANES spectrum and area XEOL excited at the Eu LIII-edge of CaAl2O4:Eu3þ.
ions in the trivalent state in the stable form in our samples. These
measurements corroborate PL results, indicating that Eu2þ is pre-
sent only during X-ray irradiation (Eu3þ/Eu2þ) as has been re-
ported by Montes et al. [15] in Eu3þ-doped SrAl2O4 phosphors, by
Gomes et al. [33] in Eu3þ-doped BaAl2O4 and also by Bezerra et al.
[26]. However, the presence of Eu3þ and Eu2þemission indicates
that the X-ray irradiation only promotes reduction of some of the
Eu3þ ions. Fig. 6 also shows that the integrated XEOL curve displays
a linear increase in intensity as the excitation energy increases.
PL measurements performed after X-ray irradiation present no
emission related to divalent Eu, suggesting that Eu2þ created in this
process is not stable in the CaAl2O4 structure.
125
To better understand the luminescence process, the XEOL curves
were analyzed from the point of view of X-ray absorption processes.
The areas under the XEOL curve, as a function of the incident
photon energy (Fig. 6), are caused by Eu2þ and Eu3þ emissions that
are produced during irradiation, after the main core absorption has
taken place. The emission is attributed to a cascade of processes
that involve X-ray fluorescence and Auger electrons. Both processes
contribute to the creation of holes close to the top of the valence
band (VB) and electrons in the conduction band (CB).
When a sample is excited at the Eu LIII-edge, the Eu ions absorb
the X-rays, ejecting an LIII shell electron. An electron from the M
shell fills the hole left in the LIII shell, releasing the typical La and Lb
X-ray fluorescence lines of Eu. The Auger process, which involves a
recombination of one electron from the M shell with the hole in the
LIII shell, releases energy which is absorbed by another electron in
the M shell that is, in turn, ejected into the CB. Thus, the Auger
process leaves behind a secondary electron with the second hole in
the M levels of the Eu ions. Following this process, a number of
electrons are generated in the CB and then decay to the bottom of
this band via electron-electron inelastic scattering.
Most of the electrons now at the bottom of the CB recombine
with the holes at the top of the VB, and others are captured by
empty Eu3þ excited states to become Eu2þ. The energy from direct
recombination is enough to excite an electron from the Eu3þ
ground state. The 5D0 excited states from Eu3þ decay to the ground
states 7F0-4, emitting photons with a wavelength in the range
600e700 nm. On the other hand, Eu2þ in the excited state decays
from the 4f65d1 excited state configuration to the 4f7 (8S7/2) ground
state, generating a broad emission band around 550 nm.
An increase in the incident X-ray energy promotes an increase in
the kinetic energy of the primary photoelectron, increasing the
probability of electron-electron inelastic scattering that will lead to
higher numbers of electrons in the CB. In turn, the concentration of
electrons in the CB increases the probability of Eu3þ ions trapping
electrons, reducing to Eu2þ, and increasing the emission from Eu2þ
ions, as observed in Fig. 5. This explanation, however, is not enough
to explain the relative intensity variation as the radiation dose is
increased. One possible hypothesis for this behavior is the presence
of hole trapping centers, which act to capture holes from the VB,
decreasing the quantity of holes available for recombination, and
increasing the probability of Eu2þ creation.
Up to now the trapping centers have not been identified.
However, based on defects presented by other aluminates of the
same family, we are led to believe that Oi released via charge
compensation, due to Eu3þ in the Ca2þ site, can act as a hole trap-
ping center [14]. Further research must be performed to confirm
this hypothesis.
126 M.A. Gomes et al. / Optical Materials 75 (2018) 122e126
4. Conclusions
In summary, Eu3þ-doped CaAl2O4 was successfully produced
using an alternative sol-gel method. XRD confirmed the formation
of monoclinic CaAl2O4. The RL measurements resulted in charac-
teristic emissions from Eu3þ, and a broad band around 550 nm
corresponding to the 5d4f6 e 4f7 transition from the Eu2þ ion,
although only Eu3þ was used as a starting reagent. This, combined
with PL results showing only Eu3þ emission and Eu3þ characteristic
spectra in the XANES curves, lead us to conclude that Eu reduction
occurred during the X-ray irradiation. Besides this, the emission
intensity corresponding to Eu3þ and Eu2þ changes for different
irradiation doses; when the X-ray dose increases, the emission
intensity of Eu2þ increases while that of Eu3þ decreases. The XEOL
area measurements showed that luminescence emissions increase
proportionally with the incident photon energy. The luminescence
increase from Eu2þ indicates that the filled CB favors electron
capture by empty states into the band gap, minimizing the rate of
recombination of the charge carriers.
The model proposed to explain this behavior suggests the ex-
istence of hole trapping centers as the main cause of the intensity
variation of Eu3þ and Eu2þ emissions during the RL process.
Acknowledgments
The authors gratefully acknowledge the Brazilian funding
agencies FINEP, CAPES, CNEN, INAMI-CNPq, and LNLS for financial
support. Synchrotron radiation measurements were obtained at the
Brazilian Synchrotron Light Laboratory, National Center for
Research in Energy and Materials, Ministry of Science, Technology
and Innovation (LNLS/CNPEM/MCT) under proposal number XAFS1
#13512/12.
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