Journal of Luminescence 175 (2016) 237–242

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Journal of Luminescence
journal homepage: www.elsevier.com/locate/jlumin

Full Length Article

Roles of fluorine and annealing on optical and structural properties

of Nd:YF3 phosphor
H.D.A. Santos, S.M.V. Novais, C. Jacinto n
Grupo de Fotônica e Fluidos Complexos, Instituto de Física, Universidade Federal de Alagoas, 57072-900 Maceió-AL, Brazil

art ic l e i nf o a b s t r a c t

Article history: The optical and structural properties of Nd:YF3 phosphors, synthesized by precipitation reaction using
Received 15 October 2015 ethylene glycol solvent, were investigated. The Y:F molar ratio of precursors, where NH4F was employed
Received in revised form as the fluorine source, was varied to prevent oxygen contamination during nucleation of the particles and
29 February 2016
to improve the photoluminescence efficiency. Structural investigations were carried out by means of X-
Accepted 5 March 2016
Available online 11 March 2016
ray diffraction, Fourier transform infrared spectroscopy and energy dispersive X-ray techniques. Samples
prepared using precursors in stoichiometric proportion presented orthorhombic YF3 structure. The use of
Keywords: fluorine source in excess promoted formation of NH4Y2F7 crystalline phase, which was decomposed into
Phosphors YF3 after annealing at 400 °C for 1 h. Emission spectra of samples thermally treated enhanced by over 50
Fluoride
times compared with the as prepared. The results obtained show the role of fluorine excess associated
Rare-earth
with thermal annealing to obtain YF3 with improved features.
Precipitation
Luminescence & 2016 Elsevier B.V. All rights reserved.

1. Introduction (o500 cm  1) [1–3]. The advantage of using YF3 as a host material is

Rare-earth (RE) doped fluorides such as NaYF4, LaF3, and YF3 are
well known hosts due to their low phonon energy [1–3], which
minimizes possible quenching mechanisms of excited state of RE3 þ
ions. This feature results in improved luminescence efficiency [4,5]
and makes these compounds suitable for upconversion emissions
[6,7], where low energy is converted into higher energy radiation.
Besides fluorides, heavy halides such as bromides, chlorides, and
iodides also exhibit low phonon energies (less than 300 cm  1), how-
ever they are hygroscopic and have limited use [8–10]. Regarding
oxides, which present high chemical stability, the stretching vibration
of the host accounts for relatively high phonon energies, generally
higher than 500 cm  1 [11]. Since fluorides overcome these problems,
attention has been paid to the synthesis of nano- or submicron-
particles doped with RE3 þ activators with potential applications in
scintillators [12–16], photo-catalysts [17,18], optical devices, lasers, and
light-emitting displays [19,20].
Among the variety of RE doped fluoride hosts, YF3-based phos-
phors have been one of the less studied. The crystal structure of this
host typically presents orthorhombic symmetry and Pnma space
group, with Y3 þ ions coordinated by nine F  [21–23]. Such arrange-
ment provides small oscillation frequency of the atoms, thus leading
to a wide band gap (410 eV) [24,25] and to low phonon energy
n
Corresponding author.
E-mail address: cjacinto@fis.ufal.br (C. Jacinto).
that Y3 þ can be easily substituted by trivalent RE ions with optical
activity, and no charge compensation is needed [26]. However, the
synthesis route must avoid possible contamination with oxygen and
use preferably short time and low temperature procedures. Further-
more, several works have shown that different morphologies of YF3
can be obtained simply varying conditions such as time, temperature
or precursors [27–30].
Methods based on the precipitation reaction between metal
nitrates/chlorides and HF/NaF/NH4F have been extensively used to
obtain RE doped fluoride materials [31]. In particular, polyol
assisted processes are considered efficient for preparation of
microsized and nanoscaled materials. The polyol (ethylene glycol,
diethylene glycol and glycerol, for example) acts as solvent and
stabilizer, binding to the surface of the growing particles and
limiting their growth, therefore, no other capping agent is needed
[27,28]. The interest on the synthesis of YF3 via polyol process has
increased [18,27,28,32–36] but, to our knowledge, there is no
report about Nd-doped YF3 prepared using fluorine excess to
prevent oxygen contamination and to improve optical and struc-
tural properties. The fluorine excess can be very interesting to
avoid oxygen contamination during the annealing procedure. In
this case, we have investigated conditions of production and the
optical and structural properties of Nd:YF3 using ethylene glycol
media while varying Y:F molar ratio of precursors. Nd3 þ was used
as emitter ion because its spectroscopic properties are well known
and it can act as both activator and sensitizer.

http://dx.doi.org/10.1016/j.jlumin.2016.03.008
0022-2313/& 2016 Elsevier B.V. All rights reserved.
238 H.D.A. Santos et al. / Journal of Luminescence 175 (2016) 237–242

2. Experimental section
2.1. Reagents
Yttrium (III) nitrate tetrahydrate (Y(NO3)3  4H2O, Aldrich, 99.99%),
neodymium (III) nitrate hexahydrate (Nd(NO3)3  6H2O, Aldrich,
99.99%) were selected as RE precursors. Ammonium fluoride (NH4F,
Aldrich, 99.99%) was used as fluoride source and ethylene glycol (EG)
(Aldrich, 99.5%) as solvent.
2.2. Synthesis procedure
In a typical procedure, 0.98 mmol of Y(NO3)3  4H2O and 0.02 mmol
of Nd(NO3)3  6H2O were dissolved in 20 ml of EG, heating the solution
at  80 °C to facilitate the dissolution process. Then, 3 mmol of NH4F
was added and the mixture was kept at 120 °C for 1 h under vigorous
stirring. After cooling to room temperature naturally, the white pre-
cipitate was collected by centrifugation, washed several times with
ethyl alcohol and also with distilled water to remove residual EG. The
resulting product was dried at 60 °C at ambient atmosphere for 48 h.
Similar routes were carried out using other Y:F molar ratios such that
the amount of F  ions should be enough to prevent oxygen con-
tamination during nucleation of the particles. Summary of the synth-
esis conditions is presented in Table 1. All samples were thermally
treated at 400 °C for 1 h in an open atmosphere furnace.
temperature (120 °C) used during the synthesis procedure [27]. Using
excess of NH4F content, one can observe for sample 15F that YF3 host
is still obtained. In this case, peaks become sharper and some differ-
ences in the relative peak intensities are noticed in comparison with
the sample 0F. According to Ref. [36], the microstructure of these
samples might be different, although both correspond to orthor-
hombic YF3. On the other hand, samples 30F, 45F, and 60F presented
the formation of cubic NH4Y2F7 (PDF#00-043-0847) as the single
crystalline phase. Such result indicates that the amount of precursors
lead to hydrogen bonding effect N–H–F between NH4 þ cations and F 
anions (which is a critical factor responsible for the stability of the
NH4Ln2F7 structure [37]) in addition to the desired formation of YF3.
Fortunately, this compound can be easily decomposed into YF3 at
temperatures around 350 °C [38].
Table 2 shows the inverse of full width at half maximum (FWHM)
of the diffraction peak associated to the plane (410) measured from
XRD patterns for samples 30F, 45F, and 60F. It is predicted from
Scherrer's equation [39] that the increasing of 1/FWHM corresponds
to larger crystallite size and improved crystallized samples. As can be
seen in Table 2, from samples 30F to 60F, the growth process is
improved and slightly higher crystallite sizes were obtained. There-
fore, for samples with fluorine excess, starting with the 30F sample,
the most crystalline cubic NH4Y2F7 phase is associated to the excess of
fluoride precursor used.

2.3. Characterization techniques

X-ray diffraction (XRD) measurements were performed in an XRD-

6000 Shimadzu diffractometer using CuKα radiation (λ ¼1.5418 Å)
operating at 40 kV/30 mA. The data were collected in continuous
mode, in the 2θ range from 10° to 70° with scan speed of 2°/min. (e)
Quantitative composition of the powders was determined using a
Hitachi TM3000 scanning electron microscope equipped with a Swift
ED3000 energy dispersive X-ray (EDX) spectrometer. FTIR spectra
were recorded using a Shimadzu IR Pretige-21 spectrophotometer, in (d)
the range of 400–4000 cm  1, using the KBr pellet technique. Optical
Intensity (a.u)

measurements were performed using a Chameleon Vision laser source

at 797 nm ( 150 mW of pump power) to excite Nd3 þ ions. The
detection system was composed by an iHR320 HORIBA spectrometer, (c)
an InGaAs detector (Electro-Optical System, model IGA-030-TE2-H),
and a SR530 lock-in amplifier (Stanford Research Systems). All mea-
surements were performed at room temperature. (b)
(111)
(020)
(101)

(210)

(131)

3. Results and discussion

(221)
(022)
(212)
(002)

(321)
(121)

3.1. Structural investigations (a)

XRD patterns of the as prepared precipitates (without annealing)

are shown in Fig. 1. For the sample 0F, produced with the reagents in
stoichiometric proportion, the majority phase is indexed to orthor-
hombic YF3 (PDF#00-070-1935). The peaks are relatively broad, likely
related to the presence of small size particles due to the low 10 20 30 40 50 60 70
2θ (degree)
Table 1
Samples produced varying the molar ratio Y:F, with fluoride excess in relation to Fig. 1. XRD patterns of as prepared (a) 0F, (b) 15F, (c) 30F, (d) 45F, (e) 60F samples.
the sample in stoichiometric proportion (0F). Bars represent orthorhombic YF3 and symbols NH4Y2F7 patterns.

Sample Y(NO3)3 Nd(NO3)3 NH4F (mmol) Fluorine excess

(mmol) (mmol) Table 2
1/FWHM associated to the plane (410) measured from the X-ray patterns of Fig. 1,
0F 0.98 0.02 3.00 0 for samples as prepared with excess of NH4F.
15F 0.98 0.02 3.45 15%
30F 0.98 0.02 3.90 30% 30F 45F 60F
45F 0.98 0.02 4.35 45%
60F 0.98 0.02 4.80 60% 1/FWHM 3.414 70.006 3.6177 0.003 3.756 7 0.009
 H.D.A. Santos et al. / Journal of Luminescence 175 (2016) 237–242 239

Fig. 2 shows XRD patterns of the samples after annealing at Table 4

400 °C for 1 h. In all the cases, one can observe well defined peaks EDX measurements quantifying the amounts of atoms for samples as prepared.
Values in wt%.
corresponding to single phase of YF3. The 1/FWHM values asso-
ciated to the plane (1 1 1) are reported in Table 3. From sample 0F 0F 15F 30F 45F 60F
to 30F, the increasing 1/FWHM value can be associated to the
rising of the crystallite size, which should be explained by the high Nitrogen 1.2 7 0.3 1.0 7 0.4 2.5 7 0.3 2.5 7 0.3 2.6 7 0.3
Oxygen 3.7 7 0.2 3.2 7 0.3 1.7 7 0.2 1.0 7 0.2 1.5 7 0.4
release of F  1 anions [16,30], that improve the crystallinity of YF3
Fluorine 41.8 7 0.9 43.6 7 0.7 46.9 7 0.9 45.9 7 0.6 44.4 7 1.2
structure. In contrast to that, decrease of crystallite size seems to Yttrium 51.5 7 0.8 50.17 0.6 47.17 0.9 48.67 0.7 49.47 1.2
occur as varying from sample 30F to 60F. Such result might be Neodymium 1.8 7 0.2 2.17 0.3 1.8 7 0.2 2.0 7 0.2 2.17 0.4
explained due to the fact that from sample 30F to 60F more
crystalline NH4Y2F7 phase is obtained (see Table 2), thus more
Table 5
hydrogen bonding N–H–F takes place. Consequently, during the
EDX measurements quantifying the amounts of atoms for annealed samples. Values
decomposition of the NH4Y2F7 into YF3, more time is needed to in wt%.
break the N–H–F bonds and less time is spent in the growth
process of the crystallite. 0F 15F 30F 45F 60F
EDX measurements were used to quantify the weight percentage
Nitrogen 0.4 7 0.2 0.7 7 0.4 0.6 7 0.1 0.5 7 0.1 0.7 7 0.2
of atoms in the different samples. The results obtained for the as Oxygen 1.4 7 0.2 0.6 7 0.1 1.17 0.2 0.6 7 0.1 1.0 7 0.2
prepared powders are presented in Table 4. One can observe that in Fluorine 45.3 7 0.8 43.8 7 0.8 44.5 7 0.5 43.0 7 0.7 43.7 7 0.4
addition to the elementary components Y, Nd and F, small amounts of Yttrium 51.2 7 0.9 52.9 7 0.8 51.7 7 0.6 54.0 7 0.7 52.9 7 0.5
Neodymium 1.8 7 0.1 2.2 7 0.2 2.0 7 0.2 2.17 0.2 1.8 7 0.2
nitrogen and oxygen were detected. Indeed, with increasing NH4F
content during the synthesis, the amount of nitrogen also increased,
which is in accordance with XRD results. On the other hand, the important to demonstrate that the use of fluoride excess was efficient
presence of oxygen was not clear in these measurements and is to avoid oxygen absorption (see Table 4). For thermally treated sam-
ples, results are presented in Table 5. These samples presented single
crystalline phase of YF3 confirmed by XRD, with negligible levels of
nitrogen and oxygen encountered by EDX. Nevertheless, the sample
0F, prepared with reagents in stoichiometric proportion, presented the
(e)
highest amount of oxygen in the composition and this corroborates to
the fact that this condition is not the most suitable to synthesize pure
fluorides.
FTIR measurements for as prepared powders are shown in Fig. 3.
(d) Three bands at approximately 1427, 1640 and 3375 cm  1 were iden-
tified and can be related to NH4 þ cations, and to the bending H–O–H
and stretching OH  vibrations of hydroxyl groups, respectively. The
Intensity (a.u.)

relative low intensity of the band associated with NH4 þ ions for
(c) samples 0F and 15F can be assigned to the less amount of NH4F
precursor used in these cases. Such experimental conditions were
suitable for formation of YF3, but it is possible that NH4 þ ions are
adsorbed on the particles surface. On the other hand, saturated solu-
(b) tions favored NH4Y2F7 complexes as in the samples 30F, 45F and 60F,
leading to intense vibrations detected on the FTIR spectra of these
samples. The influence of the environment was also noticed mon-
itoring the bands associated to hydroxyl groups. In both cases
(bending H–O–H and stretching OH  ), bands become narrower and
(a) significantly decreased the intensity with the fluorine excess from
sample 0F to 60F. Complementary to the EDX measurements, these
results show that oxygen atoms were partly incorporated in the
structure of water molecules, being efficiently removed using fluorine
precursor in excess.
The effects caused by the heating treatment were also inves-
tigated by FTIR spectra and are presented in Fig. 4. The most noti-
10 20 30 40 50 60 70
ceable change occurred for the band at 1427 cm  1, attributed
2θ (degree)
to the presence of NH4 þ , which has almost disappeared for all
Fig. 2. XRD patterns of samples with thermal annealing at 400 °C for 1 h. (a) 0F, samples. Therefore, thermal annealing was able to decompose
(b) 15F, (c) 30F, (d) 45F, (e) 60F samples. Bars represent orthorhombic YF3.
NH4Y2F7 into YF3 with negligible trace of NH4 þ ions adsorbed
possibly on the particles surface. This result corroborates the
Table 3 breaking of the N–H–F bond by removing NH4 þ cations and lib-
1/FWHM associated to the plane (1 1 1) measured for the X-ray patterns in Fig. 2, erating NH3 gas, supposed for samples 30F, 45F and 60F according
for samples with excess of NH4F after heating treatment at 400 ºC for 1 h.
to 1/FWHM values (see Table 3). Furthermore, the bands at 1640
0F 15F 30F 45F 60F and 3375 cm  1 also suffered a strong reduction, since most of
water molecules and the corresponding hydroxyl groups were
1/FWHM 2.767 0.02 3.92 70.02 5.647 0.04 5.54 7 0.04 5.46 70.04
eliminated with the thermal treatment.
240 H.D.A. Santos et al. / Journal of Luminescence 175 (2016) 237–242

(e)

(e)

(d)

(d)

Transmittance
(c)
Transmittance

(c)

(b)

(b)

(a)
(a)
+
NH 4
H-O-H bending vibrations
-
OH stretching vibrations

4.0 3.5 3.0 2.5 1.5 2.0 1.0 0.5

4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 3 -1
3 Wavenumber (10 cm )
Wavenumber (10 cm-1)
Fig. 4. FTIR spectra of YF3:Nd3 þ samples with thermal annealing at 400 °C. (a) 0F,
Fig. 3. (color online): FTIR spectra of as prepared (a) 0F, (b) 15F, (c) 30F, (d) 45F, (b) 15F, (c) 30F, (d) 45F, (e) 60F samples.
(e) 60F samples.

3.2. Optical properties 60F 4 4

F3/2 → I11/2 Integrated area (a.u.)
0.6

1.5 45F
Emission intensity (a.u.)

Emission spectra of the as prepared samples under 797 nm exci- 30F 0.4

tation are presented in Fig. 5. In all cases, bands around 890 nm, 15F
1060 nm and 1340 nm were detected, corresponding respectively to 0F 0.2
the 4F3/2-4I9/2, 4F3/2-4I11/2 and 4F3/2-4I13/2 transitions of Nd3 þ ions. 1.0
The most intense emission is observed for the sample 0F, most likely
0.0
due to the sole YF3 crystalline phase, whereas the NH4Y2F7 showed to 0F 15 F 30F 45F 60 F
Sample
be an inefficient matrix to host RE activators. As can be seen in Fig. 5,
those samples that have majority orthorhombic YF3 phase (0F and 0.5 4 4
15F) exhibit higher emission intensity than those with cubic NH4Y2F7 F3/2 → I9/2
phase (see inset of Fig. 5). This can be explained since the optical 4 4
F3/2 → I13/2
properties of RE3 þ ions depend on the crystalline structure of the host
[40]. Although lack of knowledge about the phonon energy of cubic 0.0
NH4Y2F7 sample, it belongs to the fluorides family and might possess 0.9 1.0 1.1 1.2 1.3 1.4
low phonon energy similarly. Therefore, the large differences in the Wavelength (μm)
emission intensities between NH4Y2F7 and YF3 phases cannot be
Fig. 5. Emission spectra of samples as prepared under 797 nm excitation.
explained simply by differences in their phonon energies. In this case,
differences between crystal symmetries should be relevant. In fact,
After heating treatment, all samples present orthorhombic YF3
low symmetry hosts, such as orthorhombic YF3, typically exert crystal-
fields that contain more uneven components around the dopant ions phase and their emission spectra are shown in Fig. 6. Again, transition
than high symmetry ones, such as cubic NH4Y2F7 [7,30,41]. Since lines are attributed to the dopant Nd3 þ ions. It is interesting to notice
uneven components enhance the electronic coupling between 4f that the sample 0F presented lower luminescence than samples 15F
energy levels and the higher electronic configuration, the f–f transi- and 30F, i.e., prepared with 15% and 30% excess of fluorine precursor.
tion probabilities of the RE3 þ ions increase, enhancing emission This result can be related to the higher amount of oxygen in the
intensities [7]. Consequently, the orthorhombic structure of YF3 favors composition, showing the importance of preventing such con-
higher emission efficiency than cubic NH4Y2F7 from the point of view tamination. Indeed, one must notice that the sample 15F presented
of crystal symmetry. Furthermore, NH4Y2F7 phase is highly hygro- the most intense emission detected (inset of the Fig. 6). In this case,
scopic and may lose efficiency due to non-radiative energy transfers the intensity of the peak at 1060 nm is approximately twice higher
to hydroxyls groups. than that of sample 30F and three times higher than those of 0F, 45F,
 H.D.A. Santos et al. / Journal of Luminescence 175 (2016) 237–242 241

60F 4 4 3 and usually particles with larger sizes are desired due to smaller
12 F3/2 → I11/2

Integrated area (a.u.)

45F surface-to-volume ratios that reduce possible surface quenching in
30F the nanoscale regime. However, when the growing process results in
Emission intensity (a.u.)

15F 2 formation of aggregates, it is possible that nonradiative energy tra-

0F nsfer interactions occur, thus reducing the luminescence [42]. The
8 appropriate size of the nanoparticles therefore is not necessarily the
1 largest one. The results of this work estimate that the use of 15%
0F 15F 30F 45 F 60 F
excess of fluorine precursor is useful not only to prevent oxygen
Sample contamination but also to obtain the most suitable composition to
form efficient luminescent YF3.
4 On comparing the samples with and without annealing, the
4 4 samples after heating treatment have shown enhanced emission
F3/2 → I9/2
4 4 intensity of more than one order of magnitude for all the samples
F3/2 → I13/2
(Fig. 7). In fact, the sample 0F presented an increment by 10 times and
0 the others by over 50 times. This can be ascribed to three main rea-
0.9 1.0 1.1 1.2 1.3 1.4 sons: first, the removal of gases NH3(g)þHF(g) and hydroxyls groups
at heating temperature due to the hygroscopic NH4Y2F7 phase. Sec-
Wavelength ( μm)
ond, the particles of the samples had their crystallinity improved
Fig. 6. Emission spectra of samples after heating treatment under 797 nm during the thermal annealing. Third, it is likely that phase transition
excitation. from cubic to pure orthorhombic enhances the luminescence due to
local symmetry of the crystal.
Thermal annealing
As prepared 4. Conclusions

0F samples Neodymium doped YF3 phosphors were successfully synthesized

using a procedure that demands short time and low temperature,
being efficient to avoid oxygen contamination. FTIR bands associated
to molecules of water and hydroxyl groups become narrower and
significantly decreased the intensities when increasing NH4F content
x10 15F samples over Y:F stoichiometric proportion. However, in addition to the
Emission intensity (a.u.)

desired formation of YF3, the excess of fluorine precursor leads to

hydrogen bonding effect N–H–F between NH4 þ cations and F 
anions of YF3, conducting to the formation of cubic NH4Y2F7 phase.
This compound was decomposed into desired orthorhombic YF3
phase after simple annealing. Optical characterization showed higher
x10 30F samples emission intensity for those samples thermally treated, being the
most efficient that one prepared with 15% excess of NH4F. Results
presented in this work demonstrate the consequences of preventing
oxygen contamination on the crystallinity and luminescent behavior
of rare earth fluorides.
x10 45F samples

Acknowledgments

The authors gratefully acknowledge the financial support from

60F samples
x10
0.9 1.0 1.1
Wavelength (μm)
Fig. 7. Emission spectra for samples with and without thermal annealing.
and 60F. Such behavior can be consequence of the structure formed
during precipitation of the particles. Although XRD measurement
indicates YF3 phase, the relative intensity of the peaks reveals a slight
different arrangement of the lattice in comparison to the pattern (see
Fig. 1(b)). Submitted to annealing, the composition of the sample 15F
becomes very similar to the others, which is further confirmed by EDX
and FTIR analysis. Nevertheless, results of 1/FWHM for the sample 15F
points out that the particle size is larger than that of sample 0F but not
as big as in the case of samples 30F, 45F and 60F (see Table 3). The
growth process is certainly dependent on the primary constitution
Brazilian agencies: FAPEAL (Fundação de Amparo a Pesquisa do
Estado de Alagoas) through the Project PRONEX no. 2009-09-006),
FINEP (Financiadora de Estudos e Projetos), CNPq (Conselho Nacional
de Desenvolvimento Científico e Tecnológico) through the grants INCT
NANO(BIO)SIMES and Project Universal no. 483238/2013-9), CAPES
1.2 1.3 1.4 (Coordenadoria de Aperfeiçoamento de Pessoal de Ensino Superior) –
Project PVE A077/2013. The researches of Dr. S.M.V. Novais is sup-
ported by a Post Doctoral Fellowship grant of the Programa Nacional
de Pós-Doutoramento (PNPD/CAPES) at the Universidade Federal de
Alagoas (UFAL) through the Project no. 02727/09-9. The researches of
H.D.A. Santos is supported by a graduate studentship from CNPq. The
authors also thank the Central Analítica of the Instituto de Química e
Biotecnologia and the Grupo de Ótica e Nanoscopia (GON – headed by
prof. Eduardo J.S. Fonseca), both at UFAL, for the use of structural
analyses equipments (XRD and FTIR).
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