PCCP

View Article Online

PAPER View Journal

Charge compensation assisted enhancement

of photoluminescence in combustion derived Li+
Published on 16 September 2016. Downloaded by Yeungnam University on 25/10/2016 14:44:31.

Cite this: DOI: 10.1039/c6cp04633a

co-doped cubic ZrO2:Eu3+ nanophosphors
D. Prakashbabu,ab H. B. Ramalingam,*c R. Hari Krishna,*d B. M. Nagabhushana,d
R. Chandramohan,e C. Shivakumara,f J. Thirumalaig and Tiju Thomash

Received 3rd July 2016,
Accepted 11th September 2016
DOI: 10.1039/c6cp04633a
www.rsc.org/pccp
Red light emitting cubic Zr0.99Eu0.01O2:Li+ (0–9 mol%) nanoparticles are synthesized by a low temperature,
self-propagating solution combustion method using oxalyl di-hydrazide (ODH) as fuel. In this study, we
report systematic investigation of the effect of lithium ion (Li+) concentration on the structural properties
and the photoluminescence of zirconia. With increasing lithium concentration, the crystallinity of the
samples increases and the lattice strain decreases. The higher crystallinity is likely due to charge
compensation achieved by replacing one Zr4+ ion by a Eu3+ and a Li+ ion. Scanning electron
micrographs (SEM) reveal a mesoporous structure characteristic of combustion derived nanomaterials.
Photoluminescence (PL) spectra show that the intensity of the red emission (606 nm) is highly
dependent on Li+ ion concentration. Furthermore there is a promising enhancement in the associated
lifetime. Upon Li+ doping, the PL intensity of the samples is found to increase by two fold compared to
the undoped sample. Variation of PL intensity with Li+ concentration is attributed to the differences in
probability of non-radiative recombination (relaxing). Intensity parameters (O2, O) and radiative properties
such as transition rates (A), branching ratios (b), stimulated emission cross-section (se), gain bandwidth
(se  Dleff) and optical gain (se  t) are calculated using the Judd–Ofelt theory. The calculated values
suggest that in optimally co-doped samples, in addition to improved crystallinity and charge
compensation, the lowering of Eu3+ site symmetry and the increase in the covalency of Eu–O bonding
due to interstitial Li are responsible for the observed enhancement in PL intensity.

1. Introduction
Substantial efforts towards fabrication of novel phosphors based
on rare-earth (RE) doped nano-structured materials are ongoing.
Investigations so far have aimed at combining the advantages of
sharp, atomic like 4f–4f intra-shell emission with the advantages
offered by nanomaterials.1–4 Some wide-band gap materials
doped with RE ions have been already commercialized as
luminescent phosphors.5 The motivation for pursuing new rare
a
Department of Physics, Bharathiar University, Coimbatore – 641 046, India
b
School of Physics, Reva University, Bangalore – 560 064, India
c
Department of Physics, Government Arts College, Udumalpet – 642 126, India.
E-mail: hbramalingamhb@gmail.com; Tel: +91 9886434109
d
Department of Chemistry, M.S. Ramaiah Institute of Technology,
Bangalore – 560 054, India. E-mail: rhk.chem@gmail.com
e
Department of Physics, Sevugan Annamalai College, Devakottai-630303, India
f
Solid State and Structural Chemistry Unit, Indian Institute of Science,
Bangalore – 560 012, India
g
Department of Physics, B.S. Abdur Rahman University, Chennai 600048, India
h
Department of Metallurgical and Materials Engineering,
Indian Institute of Technology, Madras, Chennai 600 036, India
earth doped phosphors comes from the fact that high quantum
yield is possible if intra-shell emission in the case of RE or
transition metal ions is optimized. More efficient light emitters
are needed for existing and future opto-electronic devices. One
of the main obstacles for the wider use of RE-doped materials
is the difficulty in achieving efficient 4f–4f excitation and
emission after host excitation. This is why 4f–5d or charge
transfer excitations are generally used, limiting the selection of
host materials.6 RE-doped ceramic nanoparticles are increasingly
viewed as preferred choices for achieving efficient excitation,
energy transfer, and emission.7
Zirconium oxide has a direct wide band gap of about 5.0 eV
and low phonon frequencies. These properties make this
compound a suitable host for RE ions, and have led to its
application in optoelectronics.8 For this and other reasons
(including mechanical properties associated with this material),
zirconia and yttria-stabilized zirconia (YSZ) have been widely
explored. This material possesses a stable crystallographic phase
of high symmetry (Fm3% m space group).9 According to Bokhimi
et al.,10 nanosized (10–40 nm) ZrO2 with 2.5–5.0 mol% yttria
contains only the tetragonal zirconia nanophase. On the other

This journal is © the Owner Societies 2016 Phys. Chem. Chem. Phys.

Paper
hand, ZrO2 with 7.5–10.0 mol% yttria consists of only the nano-
crystalline cubic phase. It is well known that luminescence of
phosphors can be enhanced by modifying their compositions.11
It has been reported that sometimes even small amounts of
co-dopants lead to a great improvement of luminescence effi-
ciency of phosphors.12 Recently there has been significant work
on the development of high efficiency phosphors using a combi-
nation of rare earth (RE) dopants and non-RE co-dopants.13,14 The
role of RE co-dopants is generally related to the process of energy
Published on 16 September 2016. Downloaded by Yeungnam University on 25/10/2016 14:44:31.
up-conversion and transfer, and cross-relaxation.15 On the other
hand, the role of non-RE co-dopants is yet to be determined with
complete certainty.16 Consequently the effects of non-rare earth
co-dopants, which are believed to be responsible for the increase
of luminescence efficiency, have been the subject of recent
interest.17 Some co-dopant ions could enter into the host lattice
and (i) create oxygen vacancies and/or (ii) modify the crystal field
surrounding the activator. Both these situations could impact the
luminescence behaviour of the phosphor. In some cases, the
co-dopants may directly act as a flux or as a sensitizer.18,19
Yu et al.20 reported that alkali metal ion (such as Li+, Na+
and K+) co-doped SrZnO2:Eu3+ materials are used to modify the
local site symmetry of Eu3+ for improving the luminescence
efficiency. Doping of alkali ions is effective primarily owing to
their high electro positive nature, low oxidation states, and
distinct ionic radii. It may also be noted that the ionic radii of
RE3+ play an important role in the photoluminescence (PL) and
thermoluminescence (TL) properties. In this regard one may
consider the work by Li et al. as a case in point,21 wherein
studies on luminescence properties of CaAl2O4:Eu3+:R+ (R+ = Li,
Na, K) phosphor prepared by a solid state reaction method are
carried out. Kuang et al.22 studied the effect of RE3+ (RE3+ = Y,
La, Gd, Lu) as co-dopants in CdSiO3:Mn2+ obtained by a solid
state method. In light of these and other reports, it is important
to study the role of co-dopants in the lattice. Such studies would
further the understanding regarding the mechanisms involved
in enhanced luminescence in alkali ion and RE co-doped
materials. Systematic understanding regarding the same could
also help us to identify some more effective and cost efficient
co-dopants.23
In the present work, the alkali element Li+ is selected as
co-dopant, because of its wide application in luminescent
materials. Since the oxidation state of Li+ ions is different from
that of the host (Zr4+), the crystal lattice may get distorted and
hence high symmetry around the Eu3+ site is expected to be
destroyed, resulting in better colour purity.24 The main goal of
this work is to establish correlations between Li ion doping
concentrations, host material structure, and luminescence
efficiency for nanosized ZrO2 doped with Eu3+. We choose to
explore these correlations using ZrO2 nanocrystals doped with
1 mol% of Eu3+ and co-doped with 0 to 9 mol% of Li. 1 mol%
Eu doped samples are used for this study since it is the
concentration at which we found PL intensity to be maximum
for ZrO2. The precise reasons for this are currently being
investigated and will be published in a subsequent article.
Judd–Ofelt theory based calculations have been carried out to
understand the observed trend. The calculations suggest that in
Phys. Chem. Chem. Phys.
View Article Online
PCCP
co-doped samples, the lowering of Eu3+ site symmetry due to
Li incorporation in the interstitial site is largely responsible for
the observed enhancement in PL intensity.
2. Experimental section
2.1. Synthesis
The starting materials used for combustion synthesis are
analytical grade zirconyl nitrate (ZrO(NO3)2, 99.99%; Sigma
Aldrich Ltd), europium oxide (Eu2O3), and lithium nitrate
(LiNO3, 99.99%; Sigma Aldrich Ltd). Europium oxide is made
water soluble by converting it into europium nitrate (Eu(NO3)3)
using 1 : 1 HNO3. Oxalyldihydrazide (ODH) prepared in our
laboratory is used as fuel. Stoichiometric composition of the
redox mixtures is calculated based on propulsion chemistry
keeping the O/F ratio at unity. The aqueous solution of the
redox mixture containing zirconyl nitrate, europium nitrate,
lithium nitrate and ODH is taken in a crystalline dish and
introduced into a preheated muffle furnace maintained at
B500 1C. The reaction mixture undergoes dehydration and
smoldering, with the liberation of a large amount of gaseous
products. The energy required for the synthesis is provided by
the exothermic combustion process itself, without further
requirement of calcination.
2.2. Characterization
Powder X-ray diffraction (PXRD) measurements are made on a
Philips PW 1050/70 diffractometer using Cu Ka radiation with a
nickel filter. Scanning electron micrographs (SEM) are recorded
using a JEOL (JSM-840A) instrument after coating the samples
with gold. Transmission electron microscopy (TEM) based
analysis is performed on a Hitachi H-8100 (LaB6 filament,
accelerating voltage up to 200 kV) equipped with an energy
dispersive spectrometer (EDS; Keney Sigma TM Quasar, USA).
The photoluminescence (PL) measurements are performed on a
Jobin-Yvon spectrofluorimeter (Fluorolog-3) equipped with a
450 W xenon lamp as an excitation source at room temperature.
Room-temperature lifetime studies are made using a VARIAN
Cary Eclipse spectrophotometer equipped with a 150 W xenon
lamp as the excitation source.
3. Results and discussion
3.1. Powder X-ray diffraction
The crystallinity and crystal phases of synthesized nanoparticles
are examined by X-ray diffraction (XRD) and are shown in Fig. 1.
Several well defined diffraction peaks appeared in the pattern
confirming the formation of pure cubic ZrO2 (fcc). All the
observed peaks are well-matched with the standard JCPDS data
card no. 81-1551. Well resolved and broad diffraction patterns
obtained confirm that the particles are well-crystalline, and in
the nano-regime. No peaks corresponding to other crystalline
phases within the PXRD limit are observed. With the increase
in lithium ion concentration the intensity of the PXRD peaks
This journal is © the Owner Societies 2016

PCCP
Published on 16 September 2016. Downloaded by Yeungnam University on 25/10/2016 14:44:31.
Fig. 1 X-ray diffraction patterns of Zr0.99xO2:Eu3+0.01:xLi+ samples with
x = (a) 0.0, (b) 0.01, (c) 0.03, (d) 0.05, (e) 0.07 and (f) 0.09.
gradually increases, indicating better crystalline nature. Further,
the ionic radii of Li+ and Zr4+ for 8 CN are 0.92 and 0.84 Å
respectively. From these values it is evident that Li+ occupies the
interstitial sites rather than cationic sites.
The cubic ZrO2 phase can be achieved at a temperature in
the range of 2643–2983 K; however at room temperature,
it transforms to the monoclinic phase. The cubic phase of
zirconia can be stabilized at room temperature by doping with
elements like Ca2+, Mg2+ and Y3+.25 In the case of zirconia
ceramics, the ionic radius of oxygen ions is too large to
maintain the cubic fluorite structure. It seems that oxygen ions
are forced to remain in contact with each other in the cubic
fluorite structure. Therefore it may be possible to discuss the
phase stability of cubic-ZrO2 in terms of interaction between
the neighbouring oxygen ions in the lattice.26 The stability of
cubic zirconia is extensively studied by Shibata et al.26 They
suggest that the interaction between two neighbouring oxygen
ions in c-ZrO2 can be approximated to be their static electrical
repulsive force using the value of net charge obtained from the
calculation. They further estimated the Coulomb’s electrical
repulsive force (fc) using the following equation:
1 Qi Qj 2
fc ¼ e ½N (1)
4pe0 r2
where Qi is the net charge of the ith oxygen ion, r represents the
distance between the nearest O2 ions, e0 is the dielectric
constant of vacuum and e is the charge of an electron. Owing
to this repulsive force of the cluster of eight oxygen ions in
the centre, cubic zirconia transforms to monoclinic at room
This journal is © the Owner Societies 2016
View Article Online
Paper
temperature. In this context, it may also be recalled that nano-
structured materials often exhibit phases and crystal structures
different from those of coarser grained materials. For instance,
the high-temperature tetragonal phase can be retained at room
temperature in nanocrystalline ZrO2.27 In our previous work,28
we have reported synthesis of pure cubic zirconia by a solution
combustion method. In this method the formation temperature
can be considered constant for a fraction of a second. The cubic
phase formed in this small time interval finds no time for the
reversal of phase.
The reduction of the FWHM as well as the increase of
sharpness of the XRD peaks with Li+ incorporation indicates
that it acts as an agent for the enhanced crystallization of
Eu3+:ZrO2.29 Furthermore the crystallite size is estimated for
the powder from the full-width at half-maximum (b) of the
diffraction peaks, using Debye–Scherrer’s method:30
D = kl/b cos y (2)
In the above equation, ‘l’ is the wavelength of X-rays (1.542 Å),
‘y’ is the Bragg angle, and ‘k’ is a constant which depends on the
grain shape (0.94 for spherical). The estimated average crystallite
size is found to be in the range of 9 to 16 nm (for Li = 0 to 9 mol%).
The crystallite size is found to increase with the addition of Li+.
Table 1 shows variation of crystallite size with Li+ concentration.
The strain and crystallite size produce broadening of peaks
in the diffraction pattern. Scherrer’s method does not consider
the broadening due to lattice strain. But Williamson and Hall
(W–H) have suggested a method31 combining the domain size
and lattice microstrain effects on line broadening, when both
are operative. The W–H equation may be expressed in the form
kl
b cos y ¼ ð4e sin yÞ þ (3)
D
where b (FWHM in radians) is measured for different XRD
peaks which in turn correspond to different planes, k is the
shape factor, e is the strain developed, and D is the grain size.
This equation represents a straight line between 4 sin y (X-axis)
and b cos y (Y-axis). The slope of the line gives strain (e) and the
intercept (l/D) of this line on the Y-axis gives grain size (D). The
calculated values of the lattice parameter (a), crystallite size (D)
and strain (e) are presented in Table 1. It is observed that the
grain sizes determined from the W–H method for some samples
are slightly different from those calculated from Debye–Scherrer’s
method. This is particularly true for samples with higher Li+
concentration. The difference in the grain sizes obtained from
Table 1 Crystallite size and strain of as-formed ZrO2:Eu3+:Li+ obtained by
Scherrer’s method and W–H method
D (crystallite size) (nm)
+
Li concentration (mol%) Scherrer’s W–H Strain (104)
0 10.00 10.00 46.7
1 10.00 10.00 38.4
3 12.00 12.00 28.6
5 12.00 13.00 16.4
7 13.00 14.00 10.1
9 16.00 17.00 9.06
Phys. Chem. Chem. Phys.

Paper
the two methods is due to the fact that the Debye–Scherrer’s
approach assumes the strain component to be zero. In the
Debye–Scherrer method, the observed broadening of diffraction
peaks is considered to be only due to the decrease in grain
size.31 Fig. 2 shows W–H plots of the samples; the strain is
calculated for different concentrations of Li+ and is found to be
in the range 9.06 to 46.71  104. Variation of microstrain and
particle size with increasing Li+ concentration is shown in
Fig. 3. The observed decrease in strain (slope of the lines) with
Published on 16 September 2016. Downloaded by Yeungnam University on 25/10/2016 14:44:31.
the increase in Li+ concentration is attributed to the decrease in
lattice defects and the increase in crystallinity.
The lattice parameters of ZrO2:Eu3+ are calculated using
Rietveld refinement. The analysis is performed using the
FULLPROF program,32 by assuming Fm3% m space group for a
cubic type structure. A pseudo-Voigt function is used to fit the
parameters to the data. The experimental and calculated PXRD
Fig. 2 W–H plots of Eu3+ doped ZrO2 sample codoped with different
concentrations of Li+: (a) 0 mol%, (b) 1 mol%, (c) 3 mol%, (d) 5 mol%,
(e) 7 mol% and (f) 9 mol%.
Fig. 3 Variation of microstrain and crystallite size as a function of Li+ ion
concentration.
Phys. Chem. Chem. Phys.
View Article Online
PCCP
patterns obtained by Rietveld refinement of ZrO2 phase are in
good agreement with the literature.33,34 The refined parameters
such as occupancy, atomic functional positions, etc., for com-
bustion derived products are given in Table 2. Furthermore, the
crystal system, space group, lattice parameters, and cell volume
of ZrO2 are obtained by using Rietveld software and are also
summarized in Table 2. Fig. 4(a) shows the refined PXRD
pattern of ZrO2:Eu, Li (5 mol%) and Fig. 4(b) shows the unit
cell of Li+ co-doped ZrO2:Eu3+ cubic crystal structure considering
the lattice constant (a = 5.11 Å). The bond lengths are calculated
using the Diamond 3.2 program. It is estimated that the distance
between two body diagonal oxygen atoms is 4.43 Å and the
distance between the two oxygen atoms forming the face of the
cube is 2.56 Å, leaving a void of about 1.87 Å. Thus the void can
accommodate an atom roughly of the radius 0.9 Å.
When a Li+ ion is incorporated in this lattice, it cannot
replace either Zr4+ or Eu3+ because the electronegativity of Li+ is
less than that of Zr4+ or Eu3+. The electronegativity values of Zr,
Eu, and Li are 1.33, 1.2 and 0.98 respectively on the Pauling
scale.35 Hence we can expect Li+ ions to occupy the interstitial
site (i.e. at the centre of the void formed by the eight O2 ions).
In such a case the positive Li+ ion attracts the eight oxygen ions
inwards; this may cause shrinkage in the lattice constant.
Hence with the increase in Li+ concentration, the lattice shrinkage
is expected to increase. This is in fact reflected in the lattice
parameters calculated by Rietveld refinement. It can be seen from
Table 2 that the lattice constant does not change when the
concentration of Li+ is low. However, as the concentration of Li+
increases beyond x = 0.05, there is a clear decrease in the lattice
constant and cell volume. This result supports the fact that Li+
occupies the interstitial site rather than cationic site due to the
difference in ionic radii and electronegativity.
3.2. SEM and TEM analysis
An SEM micrograph of cubic ZrO2:Eu:Li (Li = 9 mol%) is shown
in Fig. 5a; it reveals mesoporous structure with a large number
of voids, which is characteristic of combustion derived products.
Formation of voids is due to the evolution of a large volume of
gases during synthesis. No significant morphological changes are
observed with varying concentrations of Li+ co-doping.
TEM observations are carried out to study the nature and
size of the particles. A TEM image of the sample with 1 mol%
Li+ concentration is shown in Fig. 5b. It clearly shows the
formation of spherical crystallites with size B10 nm. Fig. 5c
and d shows the magnified TEM images of the sample with
9 mol% Li+ concentration. Smooth and highly spherical particles
are clearly seen from the magnified TEM images. The average
diameter of the particles varies from 10 to 25 nm, with the
increase in Li+ concentration. This is in good agreement with
the crystallite size obtained from Scherrer’s method and W–H
method using PXRD data.
3.3. Photoluminescence studies
In order to study the luminescence properties of the ZrO2:Eu3+,
Li+ (Li+ = 0 to 9 mol%) phosphors, the excitation spectra are
recorded by monitoring emission at 612 nm (Fig. 6). The excitation
This journal is © the Owner Societies 2016
 View Article Online

PCCP Paper

Table 2 Structural parameters of as-formed ZrO2:Eu3+:Li+ nanopowders determined from XRD data by Rietveld refinement

Compounds ZrO2:E0.01 ZrO2:E0.01Li0.01 ZrO2:E0.01Li0.03 ZrO2:E0.01Li0.05 ZrO2:E0.01Li0.07 ZrO2:E0.01Li0.09

Crystal system Cubic Cubic Cubic Cubic Cubic Cubic
Space group Fm3% m (No. 225) Fm3% m (No. 225) Fm3% m (No. 225) Fm3% m (No. 225) Fm3% m (No. 225) Fm3% m (No. 225)
Lattice parameter a (Å) 5.111(3) 5.111(5) 5.110(6) 5.111(5) 5.110(2) 5.102(8)
Cell volume (Å3) 133.54(11) 133.55(13) 133.47(9) 133.55(8) 133.44(11) 132.79(11)
Atomic positions
Zr/Eu/Li (4a) (4a) (4a) (4a) (4a) (4a)
x 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
y 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Published on 16 September 2016. Downloaded by Yeungnam University on 25/10/2016 14:44:31.

z 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

01 (8c) (8c) (8c) (8c) (8c) (8c)

x 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500
y 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500
z 0.2500 0.2500 0.2500 0.2500 0.2500 0.2500

RFactors (%)
Rp 8.27 7.92 8.04 8.91 8.00 8.94
Rwp 10.80 10.20 10.30 11.50 10.40 11.40
Rexp 10.98 10.40 10.70 10.90 10.31 10.59
w2 0.96 0.96 0.93 1.12 1.02 1.15
RBragg 3.70 2.95 3.63 4.18 3.17 3.45
RF 2.50 2.30 2.44 2.56 2.08 2.65

Fig. 4 (a) Refined PXRD pattern of Zr0.94O2:Eu3+:Li+ (5 mol%), (b) packing diagram of Eu3+ doped ZrO2 samples, and (c) diagram showing the
environment and co-ordination around Zr4+ in the unit cell.

maximum is detected at B395 nm due to 7F0 - 5L6 transition;

Fig. 5 (a) SEM and (b) TEM images of ZrO2:Eu:Li (1 mol%), (c and d) TEM
images of ZrO2:Eu:Li (9 mol%) at different magnification.
other secondary excitation peaks are detected at B361 nm
(7F0 - 5D4), 380 nm (7F0 - 5G2–6, 5L7–10), 414 nm (7F0 - 5D3),
465 nm (7F0 - 5D2) and 525 nm (7F0 - 5D1).36 It can be clearly
seen that the maximum excitation peaks exist mainly at 465 nm
and 399 nm; these are attributed to 7F0 - 5D2 and 7F0 - 5L6
transitions of Eu3+ ions. The observed intensities of these transi-
tions clearly indicate that the ZrO2:xEu3+ phosphor is a promising
candidate for blue and near-UV LED excited red phosphor.
The room temperature emission spectra with different doping
concentrations of Li+ are shown in Fig. 7 and 8 for excitation
wavelength at 395 and 465 nm respectively. The luminescence
spectra consist of sharp lines associated to 5D0 - 7FJ ( J = 0 to 4)
transitions (570–690 nm; orange-red region of the spectrum) of
Eu3+ ions.37 The hypersensitive transition 5D0 - 7F2 (612 nm) is
prominent; other emission peaks are observed at 579, 594, 650 and
680 nm. Among these, the peaks at 612 nm and 594 nm are
dominant. These correspond to the Eu3+ electric dipole transi-
tions (5D0 - 7F2). The 5D0 - 7F2 electric dipole transition is

This journal is © the Owner Societies 2016 Phys. Chem. Chem. Phys.

Paper
Published on 16 September 2016. Downloaded by Yeungnam University on 25/10/2016 14:44:31.
Fig. 6 Photoluminescence excitation spectra of Zr0.99xO2:Eu3+:xLi+
(x = 0–0.09) nanophosphor monitored at 575 nm.
Fig. 7 Photoluminescence emission spectra of Zr0.99xO2:Eu3+:xLi+
(x = 0–0.09 mol%) nanophosphor excited at 395 nm. In the figure, (a) x = 0,
(b) x = 0.01, (c) x = 0.03, (d) x = 0.05, (e) x = 0.07 and (f) x = 0.09.
Fig. 8 Photoluminescence emission spectra of Zr0.99xO2:Eu3+:xLi+
(x = 0–0.09) nanophosphor excited at 465 nm.
hypersensitive to the crystal environment, while the magnetic dipole
5
D0 - 7F1 transition is insensitive to the crystal environment.38
Phys. Chem. Chem. Phys.
View Article Online
PCCP
Fig. 9 Variation of 613 nm emission intensity with Li+ ion concentration.
The variation of PL emission intensity with increasing Li+
concentration for both excitation wavelengths is shown in
Fig. 9. It can be observed that the optimized concentration of
Li+ is 5 mol% in Zr0.99xO2:Eu3+:xLi+ phosphor.
The results are to be interpreted based on the chemical
physics of ZrO2:Eu3+. It is well known that the RE dopant, Eu3+,
has emission peaks that are narrow due to the shielding effect
of 4f electrons by 5s and 5p electrons.39–41 Doping of a trivalent
ion, which is Eu3+ in this case, by substituting for a tetravalent
ion (Zr4+ here) creates charge imbalance in the system. To
maintain the charge balance, four Eu3+ ions have to substitute
three Zr4+ ions. This would clearly result in vacancies in the
ZrO2 lattice; it is well known that these point defects can act
as luminescence quenchers (Fig. 10a). However monovalent
positive ions can be used as charge compensators in such
doped systems. Generally the outer electronic configuration
of alkali metals is nS1, and they acquire mono-positive charge
after losing their electron. Therefore alkali metals can be used
for charge compensation in Eu3+ doped ZrO2 phosphors. In the
samples used in the study here, charge compensation is
achieved by replacement of one Zr4+ ion by a Eu3+ and a Li+
ion (Fig. 10b). It can be observed that the emission wavelengths
(PL peak positions) are independent of Li+ concentration,
whereas luminescence intensity is greatly influenced by Li+
concentration. The emission intensity of Li+ co-doped samples
Fig. 10 Schematic representation of charge compensation (a) without Li+
co-doping and (b) with Li+ co-doping in ZrO2:Eu3+.
This journal is © the Owner Societies 2016
 View Article Online

PCCP Paper

has significantly increased compared to the Li+ free sample.

This enhanced PL emission is due to the charge compensation
assisted by the Li+ ion in the lattice. The charge compensation
by the Li+ ions provides better chemical stability and improves
crystal quality which has a significant influence on the enhance-
ment of PL peak intensities in the Li+ co-doped sample.42
The enhancement in PL performance with Li+ co-doping
may also be due to improved crystallinity leading to higher
oscillating strengths for the optical transitions.43 The relative
Published on 16 September 2016. Downloaded by Yeungnam University on 25/10/2016 14:44:31.

emission intensity is maximum when the Li+ concentration is

5 mol%. The luminescence intensity of ZrO2:Eu3+,Li+x (x = 0.05)
increased by a factor of 2.5 times compared with that of lithium
free ZrO2:Eu3+. Beyond x = 0.05 of Li+, the emission intensity
decreases. This is likely due to the non-radiative transitions
which reduce the emission intensity. Furthermore, beyond a
certain Li+ concentration, an excess of oxygen vacancies might
be created which also lead to luminescence quenching.
The integrated intensity ratio of 5D0 - 7F2 (612 nm) to the
5
D0 - 7F1 (590 nm) emission, known as the electric dipole to
magnetic dipole (ED/MD) ratio, can be used to determine the
site symmetry where Eu3+ ions are located. Usually a higher
symmetry of the crystal field around Eu3+ will result in a lower
ED/MD value.44 The ED/MD intensity ratio of the excitations at
395 and 465 nm with varying Li+ concentration is presented in
Fig. 11. It shows a decreasing trend with increasing Li+. It is
well known that the electric dipole (ED) 5D0 - 7F2 transition
is forbidden in a centro-symmetric environment, while the
magnetic dipole (MD) 5D0 - 7F1 transition is insensitive to
local symmetry.45 The decrease in the ED/MD ratio implies that
the site symmetry of the Eu3+ environment increases with Li+
ion concentration, implying an increase in the crystallinity of
the samples with lithium ion concentration.
Fig. 12 represents the schematic energy level diagram of the
Eu3+ ion showing the states involved in the luminescence
process and transition probabilities. The sharp excitation tran-
sitions around 396 and 465 nm correspond to the transitions
7
F0 - 5L6 and 7F0 - 5D2 respectively. The relaxation event
Fig. 12 Energy level diagram of Eu3+ showing the f–f transitions observed
in ZrO2:Eu3+.
thereafter results in a transition to the 5D0 energy level of Eu3+,
where the radiative transitions to 7FJ (J = 0, 1, 2,. . .) occur,
resulting in 5D0 - 7F1 (592 nm) and 5D0 - 7F2 (613 nm)
emission peaks. The Li+ co-doped ZrO2:Eu3+ phosphor particles
can be excited by more photons than Li+ free ZrO2:Eu3+ phosphor
using the same excitation conditions and more photons will
be emitted in the Li+ co-doped samples.46 Thus, it is reasonable
that the Li+ co-doped ZrO2:Eu3+ phosphors have higher photo-
luminescence efficiency than the ZrO2:Eu3+ phosphors.
3.4. Lifetime studies
To study the influence of Li+ co-doping on lifetimes in ZrO2:Eu3+,
luminescence decay studies are carried out. Fig. 13 shows the
decay curves of ZrO2:yEu3+,xLi+ (x = 0.01 to 0.09) for 5D0 - 7A2
emission upon excitation at 395 nm. Attempts to fit the decay
 t
curves by the mono-exponential equation I ¼ I0 exp  , where
t
I and I0 are the intensities at time t and at time 0, and t is the
lifetime, resulted in curves with a large difference between experi-
mental and calculated data. This suggests that the environment of
the Eu3+ ions in the lattice with the co-doping of Li+ is not the same
in different positions.47 Subsequently the decay data are fitted
using a bi-exponential decay equation given by
   
t t
t t
I ¼ I1 e 1 þ I2 e 2 (4)

where I1 and I2 are the intensities at different time intervals, and t1

and t2 are their corresponding lifetimes. The outcomes of this fitting
on data from Li+ co-doped ZrO2:Eu are shown in Fig. 13(A and B).
The average lifetime can be calculated using the equation48
I1 t1 þ I1 t2
tav ¼ (5)
Fig. 11 Variation of the ED/MD ratio as a function of Li+ ion concentration. I1 þ I2

This journal is © the Owner Societies 2016 Phys. Chem. Chem. Phys.
 View Article Online

Paper PCCP
Published on 16 September 2016. Downloaded by Yeungnam University on 25/10/2016 14:44:31.

Fig. 13 Lifetime multi-exponential fitted decay curves of ZrO2:Eu3+ samples (a) without Li+ and with (b) 3 mol% Li+, (c) 5 mol% Li+ and (d) 7 mol% Li+.

The fitting parameters obtained from the bi-exponential curve
fitting are summarized in Table 3. The average PL decay lifetime
(tav) for the sample Li0 is found to be 1.15 ms and the values of t1
and t2 are 0.59 and 1.58 ms respectively. The average PL lifetimes
of the 5D0 - 7F2 transition in samples with Li dopants are more
than that of undoped samples. The average lifetime of the
samples increases with Li+ concentration up to 5 mol% and
decreases there onwards. The lifetime values obtained are in good
agreement with the reported values for Eu3+ emission (1–2 ms).49
It has to be noted that in the literature, the lifetime achieved by
Beatriz Julián et al.50 is 1.3 ms. They suggest that the Eu3+:ZrO2
system is specially promising for photonic applications since its t
value is greater than the corresponding values for other inorganic
or hybrid matrices in which Eu3+ ions are complexed. The
increase in lifetime with Li+ co-doping may be attributed to the
(i) increase in crystallinity and/or (ii) increase in particle size
which result in decreased non-radiative transitions due to f
surface defects. Beyond 5 mol% the decrease in lifetime may be
due to (i) the increase in site symmetry and/or (ii) Li+ acting as
luminescence quenchers. Similar trends have been reported by
Parchur et al.51
3.5. Judd–Ofelt intensity parameters and radiative properties
The spectra of trivalent lanthanides in a crystal lattice or in solution
arise from forbidden transitions within the 4fn-configuration to
which the Judd–Ofelt (JO)52 theory has been successfully applied
for quantitative determination of optical properties. Werts et al.53
have studied the application of JO theory for the quantitative
analysis of Eu3+ emissive properties. The work done so far may
be summarized as follows.
Radiative relaxation from an excited state CJ of a lanthanide
ion usually occurs to various lower lying states C 0 J 0 , giving rise
to several lines in the emission spectrum. The red lumines-
cence of Eu3+ is a result of 5D0 - 7FJ (J = 2, 4, 6) transitions.
According to JO theory, the spontaneous emission probability
A(CJC 0 J 0 ) of the transition CJ - C 0 J 0 is related to the intensity
parameter Ol (l = 2, 4, 6) according to the following equation:
 
  64p4 n 3 e2 n n2 þ 2 2 X    
A CJ C0J 0 ¼ Ol C0J 0 Ul CJ 2 (6)
3hc3 9ð4peo Þ l¼2;4;6
where ‘‘n’’ is the frequency, ‘‘h’’ is the Planck constant, ‘‘e’’ is
the charge of the electron, ‘‘e0’’ is permittivity of free space,
 2
n n2 þ 2
is Lorentz field correction and ‘n’ is the refractive
9
index of the material. For zirconia the refractive index is 2.2.54
The term hC 0 J 0 JUlJCJi2 is the square of the reduced matrix
elements. The values of reduced elements are independent of
the chemical environment of Eu3+ and are listed in Table 4. One
can observe from Table 4 and eqn (5) that each electric dipolar
5
D0 - 7FJ (J = 2, 4, 6) transition depends only on one squared
reduced matrix element. This unique feature for Eu3+ ions
facilitates the determination of JO parameters from the emission
spectra.55
JO parameters have been calculated aiming to study the site
symmetry and luminescence behaviour of Eu3+ ions in the host.
This is also done to predict some important radiative properties
such as radiation transition probability (AT), branching ratios
(br), stimulated emission cross-section (s) and radiative life-
time (tr). The polarization and symmetry behaviour of the Eu3+

Table 4 Squared reduced matrix elements used for the calculation of JO

Table 3 Experimental lifetime values for ZrO2:Eu3+:Li+ samples parameters of the allowed induced ED transitions in the emission spectra
of Eu3+
ZrO2:Eu0.01,Lix t1 l1% t2 l2 % tav
Transition hC 0 J 0 JU2JCJi2 hC 0 J 0 JU4JCJi2 hC 0 J 0 JU6JCJi2
X = 0.00 0.59 67.23 1.58 32.77 1.15
X = 0.03 0.54 60.3 1.71 39.7 1.33 5
D0 - 7F2 0.0032 0 0
X = 0.05 0.36 43.3 1.97 56.7 1.78 5
D0 - 7F4 0 0.0023 0
X = 0.07 0.52 50.8 1.62 49.2 1.35 5
D0 - 7F6 0 0 0.0002

Phys. Chem. Chem. Phys. This journal is © the Owner Societies 2016
 View Article Online

PCCP Paper

ions are determined by intensity parameters whereas the other Table 5 JO intensity parameter values and radiative parameters for
intensity parameter O6 depends on long range effects. The ZrO2:Eu3+:Li+ samples
potential radiative properties of RE ions in different host Li+ concentration (x)
matrices are generally known by the knowledge of these inten- J–O and radiative
parameters 0.00 0.01 0.03 0.05 0.07 0.09
sity parameters.56
1
The experimental coefficients of spontaneous emission (A0J) AR (s ) 504 547 819 946 582 502
ANR (s1) 587 542 772 734 612 552
are obtained using the relation AT (s1) 1091 1089 1591 1680 1194 1055
Z (%) 46.19 50.23 51.27 56.3 48.74 47.63
I0J n 01 b01 (%) 29.5 30.9 32.2 34.7 36.8 34.8
A0J ¼ A01 (7)
I01 n 0J b02 (%) 49.9 50.2 48.3 50.4 48.7 47.6
Published on 16 September 2016. Downloaded by Yeungnam University on 25/10/2016 14:44:31.

b04 (%) 11.9 7.7 8.4 6.4 5.6 7.5

where n01 and n0J (J = 2, 4) represent the frequency of the s01 ( 1022 cm2) 0.714 0.626 0.894 1.211 0.816 0.683
s02 ( 1022 cm2) 1.047 1.027 1.29 1.559 1.091 0.943
transitions 5D0 - 7F1 and 5D0 - 7FJ=2,4 for Eu3+, and A01 is s04 ( 1022 cm2) 0.629 0.431 0.681 0.719 0.425 0.503
Einstein’s coefficient of spontaneous emission corresponding s02  Dlp ( 1022 cm2) 21.92 26.01 41.02 59.91 27.03 29.36
to magnetic dipole transition. For Eu3+, A01 can be determined s04  Dlp ( 1022 cm2) 3.25 2.39 5.96 6.65 5.09 2.33
O02 ( 1020 cm2) 6.45 7.03 9.24 12.15 7.48 7.03
as 50 s1, and I0J is the integrated intensity of the transition O04 ( 1020 cm2) 2.09 3.51 5.22 5.03 2.83 5.82
hC 0 J 0 JUlJcJi2.57 Thus using eqn (6) and (8), the values of O2
and O4 are calculated. Moreover, the emission spectra of Eu3+
consist of only two transitions 5D0 - 7F2 and 5D0 - 7F4, hence The stimulated emission cross-section (slp) has been used to
O6 could not be estimated. identify the potential laser transitions of RE ions in a host
The value of O2 depends on both calcination temperature material. A good laser transition should have a large stimulated
and concentration of the dopant. Moreover, the value of the O2 emission cross-section. The gain bandwidth (slp  Dlp) is one
parameter changes with the asymmetry and also with the of the parameters which is critical to predict the amplification
covalency of the Eu3+–O2 bond. The trend of the Judd–Ofelt of the medium in which the RE ions are situated. A good optical
parameter values obtained (O2 4 O4) confirms low site sym- amplifier should have larger slp and slp  Dlp values. The gain
metry of Eu3+ ions and higher covalency of the Eu3+–O2 bond. bandwidth is an important parameter in the choice of materials
If the Li+ ion replaces the Zr4+ ion then the Eu3+ ion will be in a for optical fibre amplifiers.59 In this context, it is interesting to
more ionic site, which could have resulted in the smaller O2 note that the sample doped with 5 mol% Li+ has better optical
values. On the other hand, if Li+ ions are in the interstitial site gain, higher efficiency and high lifetime (Table 5). These results
then the Eu3+ ion will be in a more covalent site leading to a are consistent with the experimental data obtained from PL and
larger O2 value. So in the present work it is understood that the lifetime studies.
Li+ ions occupy the interstitial site rather than the Zr4+ site,
which matches well with the XRD results.
3.6. CIE chromaticity diagram
The radiative transition probability (A) for a transition from
an excited manifold J to a lower manifold J0 can be calculated Most often the lighting specifications are given in terms of the
by CJ - C 0 J 0 is obtained by the sum of electric (Aed) and 1931 CIE chromatic color coordinates.60 The variation of color
magnetic (Amd).58 The electric (Aed) dipole radiative transition due to the influence of Li+ co-doping concentration in
probability can be evaluated using the following expression: ZrO2:Eu3+ is presented in the CIE 1931 (Commission Interna-
 2 tionale de I’Eclairage, 1931) chromaticity diagram (Fig. 14). The
64p4 y3 e2 n n2 þ 2 X    2
Aed ¼  e2 Oi CJ Ul C0J 0 (8) CIE coordinates are calculated using a color calculator program.
3hð2J þ 1Þ 9 i¼2;4;6 Since Li+ works as a sensitizer in the co-doped ZrO2:Eu3+ phos-
phor, it enhances the observed PL intensity. The color coordinates
The total radiative transition probability (AT) for an excited state for Li+ free ZrO2:Eu3+ are found to be (0.50, 0.47); it varies from red
is given by to orange red (0.55, 0.4) when Li+ ion concentration goes up to
X 7 mol%. For 9 mol% it turns back to red (0.52, 0.46). The details of
AT ðCJ Þ ¼ Ajj0 (9)
j the coordinates are tabulated as the inset of Fig. 14.
An alternative way to uniquely characterize the location of a
The fluorescence branching ratio (bR) of each transition can be phosphor on the chromaticity diagram is using a combination
determined from the spontaneous transition probability of color purity and dominant wavelength. These are in fact
according to the equation often preferred over color coordinates. We have followed a
 0 method described by Fred Schubert61 to calculate the color
A CJ CJ
bR ðCJ Þ ¼ (10) purity of the sample using the following formula:
AT ðCJ Þ

The peak stimulated emission cross-section at lp is given by qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

ðx  xee Þ2 þðy  yee Þ2
lp4 Color purity ¼ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi  100 (12)
sðlp Þ ðCJ Þ ¼ AT ðCJ Þ (11) ðxd  xee Þ2 þðyd  yee Þ2
8pcn2 Dleff

This journal is © the Owner Societies 2016 Phys. Chem. Chem. Phys.

Paper
Published on 16 September 2016. Downloaded by Yeungnam University on 25/10/2016 14:44:31.
Fig. 14 Color coordinates of ZrO2:Eu:xLi (x = 0–0.09 mol%). The CIE 1931 coordinates are obtained using the PL spectrum obtained using 395 nm. For
clarity, zoomed-out (left) and zoomed-in (right) versions of the diagram are shown. The table in the inset shows variation of coordinates with varying Li+
concentration.
where (x, y), (xee, yee) and (xd, yd) are the chromaticity coordi-
nates of the sample point, equal energy point, i.e. (0.33, 0.33),
and the dominant wavelength point. The dominant wavelength
point can be calculated from the intersection of the connecting
line between the equal energy point and the sample point. The
color purity of ZrO2:xEu3+,yLi+ (x = 0.01, y = 0.05) phosphors is
found to be in the range of 86%. Hence, these results show that
due to enhanced PL emission and high color purity, ZrO2:
xEu3+,yLi+ phosphors are promising candidates for various
luminescence (and other optical) applications.
4. Conclusion
Phase-pure Eu3+ doped and Li+ co-doped cubic ZrO2 nanophos-
phors are obtained using a one pot solution combustion
synthesis. From the XRD results we confirm that the crystal
size varies significantly with variation in the Li+ co-dopant
concentration. TEM results confirm the formation of highly
nanocrystalline spherical particles of size B10 nm. Furthermore,
varying Li+ concentration not only influences crystallographic
characteristics (e.g. lattice constants), but also affects the
luminescence behaviour. The addition of Li+ enhances the
luminescence intensity of Eu3+ by B200%. This is due to a
combination of (i) improved crystallinity, (ii) charge compensa-
tion effect, and (iii) interstitial Li and a concomitant increase in
the covalency of the Eu–O bond (as suggested by J–O analysis).
The sample doped with 5 mol% Li+ shows higher lifetime
compared to other samples. The results also show that the
ratio of electric dipole and magnetic dipole transitions varies
with Li+ concentration, which can be attributed to structural
changes that influence the Eu3+ environment. From the Judd–
Ofelt analysis, we observe that the intensity parameter, O2, is
greater than O4 for ZrO2:Eu3+,Li+ phosphors. The color quality
and hue of the red emitting phosphor are calculated from CIE
coordinates. These results show that due to enhanced PL emission
Phys. Chem. Chem. Phys.
View Article Online
PCCP
intensity and high color purity (B86%), the phase-pure Eu3+
doped and Li+ co-doped cubic ZrO2 is a promising phosphor.
Acknowledgements
Author D. Prakashbabu thanks the Chancellor, Management and
Principal of REVA University, Bangalore for their constant support
and encouragement. R. Hari Krishna is grateful to the Management,
Principal and HOD Chemistry of M.S. Ramaiah Institute of Techno-
logy, Bangalore, for their constant support and encouragement.
References
1 S. Möller, J. D. Fidelus and W. Lojkowski, Solid State
Phenom., 2007, 128, 97.
2 X. Fu, S. Niu and Q. Xin, Mater. Sci. Eng., B, 2006, 129, 14.
3 A. Opalinska, C. Leonelli, W. Lojkowski, R. Pielaszek,
E. Grzanka, T. Chudoba, H. Matysiak, T. Wejrzanowski
and K. J. Kurzydlowski, J. Nanomater., 2006, 2006, 98769.
4 J. D. Fidelus, S. Yatsunenko, M. Godlewski, W. Paszkowicz,
E. Werner-Malento and W. Łojkowski, Scr. Mater., 2009, 61, 415.
5 S. J. Pearton, C. R. Abernathy, M. E. Overberg, G. T. Thaler,
A. H. Onstine, B. P. Gila, F. Ren, B. Lou and J. Kim, Mater.
Today, 2002, 5, 24.
6 F. Ramos-Brito, M. Garcı́a-Hipólito, R. Martı́nez-Martı́nez,
E. Martı́nez-Sánchez and C. Falcony, J. Phys. D: Appl. Phys.,
2004, 37(5), L13–L16.
7 M. Godlewski, S. Yatsunenko, A. Nadolska, A. Opalińska,
W. Łojkowski, K. Drozdowicz-Tomsia and E. M. Goldys, Opt.
Mater., 2009, 31(3), 490–495.
8 J. D. Fidelus, W. Lojkowski, D. Millers, K. Smits, L. Grigorjeva
and R. R. Piticescu, Solid State Phenom., 2007, 128, 141.
9 E. Pereyra-Perea, M. R. Estrada and M. Garcı́a, J. Phys. D:
Appl. Phys., 1998, 31, L7.
10 X. Bokhimi, A. Morales, A. Garcia-Ruiz, T. D. Xiao, H. Chen
and P. R. Strutt, J. Solid State Chem., 1999, 142, 409.
This journal is © the Owner Societies 2016

PCCP
11 D. Kim, H.-E. Kim and C.-H. Kim, PLoS One, 2016, 11, e0145434.
12 X. Liu, K. Han, M. Gu, L. Xiao, C. Ni, S. Huang and B. Liu,
Solid State Commun., 2007, 142, 680.
13 R. Hari Krishna, B. M. Nagabhushana, H. Nagabhushana,
R. P. S. Chakradhar, N. Suriya Murthy, R. Sivaramakrishna,
C. Shivakumara, J. L. Rao and T. Thomas, J. Alloys Compd.,
2014, 589, 596.
14 J. H. Jeong, J. S. Bae, S. S. Yi, J. C. Park and Y. S. Kim, J. Phys.:
Condens. Matter, 2003, 15, 567.
Published on 16 September 2016. Downloaded by Yeungnam University on 25/10/2016 14:44:31.
15 G. Blasse and B. C. Grabmaier, Luminescent Materials,
Springer, New York, 1994.
16 H. Jiu, Superlattices Microstruct., 2015, 83, 627.
17 K. C. Patil, M. S. Hegde, T. Rattan and S. T. Aruna, Chemistry
of Nanocrystalline Oxide Materials, Combustion Synthesis,
Properties and Applications, World Scientific Press, 2008.
18 S. S. Yi, J. S. Bae, K. S. Shim, J. H. Jeong, J. C. Park and
P. H. Holloway, Appl. Phys. Lett., 2004, 84, 353.
19 L. S. Chi, R. S. Liu and B. J. Lee, J. Electrochem. Soc., 2005,
152, J93.
20 X. Yu, X. Xu, C. Zhou, J. Tang, X. Peng and S. Yang, Mater.
Res. Bull., 2006, 41, 1578–1583.
21 G. Li, Y. Lai, T. Cui, H. Yu, D. Liu and S. Gan, Mater. Chem.
Phys., 2010, 124, 1094.
22 J. Kuang, Y. Liu and B. Lei, J. Lumin., 2006, 118, 33.
23 J. Li, Y. Wang and B. Liu, J. Lumin., 2010, 130, 981.
24 S. Shi, J. Gao and J. Zhou, Opt. Mater., 2008, 30, 616.
25 Y. Cong, B. Li, S. Yue, D. Fan and X. Wang, J. Phys. Chem. C,
2009, 113(31), 13974.
26 N. Shibata, J. Katamura, A. Kuwabara, Y. Ikuhara and
T. Sakuma, Mater. Sci. Eng., A, 2001, 312, 90.
27 P. M. Abdala, M. C. a Fantini, A. F. Craievich and
D. G. Lamas, Phys. Chem. Chem. Phys., 2010, 12, 2822.
28 D. Prakashbabu, R. Hari Krishna, B. M. Nagabhushana,
H. Nagabhushana, C. Shivakumara, R. P. S. Chakradar,
H. B. Ramalingam, S. C. Sharma and R. Chandramohan,
Spectrochim. Acta, Part A, 2014, 122, 216–222.
29 D. L. Monika, H. Nagabhushana, R. Hari Krishna, B. M.
Nagabhushana, S. C. Sharma and T. Thomas, RSC Adv., 2014,
4, 38655.
30 P. Klug and L. E. Alexander, X-Ray Diffraction Procedure,
Wiley, New York, 1954.
31 G. K. Willamson and W. H. Hall, Acta Metall., 1953, 1, 22.
32 J. Rodrigueg-carvajal, FULLPROF 2000: a program for Rietveld,
profile matching and integrated intensity refinements for X-ray
and neutron data, version 1.6, Laboratorie Leon, Brillounin,
Gifsuryvette, France, 2009.
33 M. S. Niasari, M. Dadkhah and F. Davar, Polyhedron, 2009,
28(14), 3005–3009.
34 M. H. Tahir, L. Gorgishvili, J. Li, T. Gorelik, U. Kolb,
L. Nasdala and W. Tremel, Solid State Sci., 2007, 9, 1105.
35 L. Pauling, The Nature of the Chemical Bond, Cornell Univ.,
USA, 3rd edn, 1960.
36 R. Bagga, V. G. Achanta, A. Goel, J. M. F. Ferreira, N. P.
Singh, D. Paul Singh, V. Contini, M. Falconieri and
G. Sharma, Opt. Mater., 2013, 36, 198.
37 K. Y. Jung and H.-K. Jung, J. Lumin., 2010, 130, 1970.
This journal is © the Owner Societies 2016
View Article Online
Paper
38 A. K. Parchura and R. S. Ningthoujam, RSC Adv., 2012, 2, 10859.
39 J. S. Bae, J. H. Jeong, K. S. Shim, B. K. Moon, S.-S. Yi,
J. H. Kim, Y. S. Kim and J. S. Lee, Appl. Surf. Sci., 2006,
252, 4564.
40 T. Thomas, M. Chandrashekhar, C. B. Poitras, J. Shi, J. C.
Reiherzer, F. J. DiSalvo, M. Lipson and M. G. Spencer,
2008 MRS Fall Meeting, 2009.
41 T. Thomas, X. Guo, M. V. S. Chandrashekhar, C. B. Poitras,
W. Shaff, M. Dreibelbis, J. Reiherzer, K. Li, F. J. DiSalvo,
M. Lipson and M. G. Spencer, J. Cryst. Growth, 2009,
311(19), 4402.
42 A. K. Ambast, J. Goutam, S. Som and S. K. Sharma, Spectro-
chim. Acta, Part A, 2014, 122, 93.
43 K. C. Misbra, J. K. Berkowitz, K. H. Johnson and P. C.
Schmidt, Phys. Rev. B: Condens. Matter Mater. Phys., 1992,
45, 10902.
44 A. Jagannatha Reddy, M. K. Kokila, H. Nagabhushana,
C. Shivakumara, R. P. S. Chakradhar, B. M.
Nagabhushana and R. Hari Krishna, Spectrochim. Acta, Part
A, 2014, 132, 305.
45 M. Ayvacıkl, A. Canimoglu, Y. Karabulut, Z. Kotan,
L. K. S. Herval, M. P. F. de Godoy, Y. GalvãoGobato,
M. Henini and N. Can, J. Alloys Compd., 2014, 590, 417.
46 K. N. Shinde and S. J. Dhoble, Adv. Mater. Lett., 2010, 1(3),
254.
47 N. Yaiphaba, R. S. Ningthoujam, N. S. Singh, R. K. Vatsa,
N. R. Singh, S. Dhara, N. L. Misra and R. Tewari, J. Appl.
Phys., 2010, 107, 034301.
48 V. Sudarsan, F. C. J. M. van Veggel, R. A. Herring and
M. Raudseppc, J. Mater. Chem., 2005, 15, 1332.
49 M. N. Luwang, R. S. Ningthoujam, S. K. Srivastava and
R. K. Vatsa, J. Am. Chem. Soc., 2011, 133, 2998.
50 B. Julián, R. Corberán, E. Cordoncillo, P. Escribano,
B. Viana and C. Sanchez, Nanotechnology, 2005, 16, 2707.
51 A. K. Parchur and R. S. Ningthoujam, RSC Adv., 2012, 2, 10859.
52 G. S. Ofelt, J. Chem. Phys., 1962, 37, 511.
53 M. H. V. Werts, R. T. F. Jukes and J. W. Verhoeven, Phys.
Chem. Chem. Phys., 2002, 4, 1542.
54 N. M. Ravindra, P. Ganapathy and J. Choi, Infrared Phys.
Technol., 2007, 50, 21.
55 L. Dacanin, S. R. Lukic, D. M. Petrovic, M. Nikolic and
M. D. Dramicanin, Physica B, 2011, 406, 2319.
56 S. Som, A. K. Kunti, V. Kumar, V. Kumar, S. Dutta,
M. Chowdhury, S. K. Sharma, J. J. Terblans and H. C.
Swart, J. Appl. Phys., 2014, 115, 193101.
57 W. T. Carnall, P. R. Fields and K. Rajnak, J. Chem. Phys.,
1968, 49, 4424.
58 M. Ferhi, C. Bouzidi, K. Horchani-Naifer, H. Elhouichet and
M. Ferid, J. Lumin., 2015, 157, 21.
59 S. Som, S. Das, S. Dutta, H. G. Visser, M. K. Pandey,
P. Kumar, R. K. Dubey and S. K. Sharma, RSC Adv., 2015,
5, 70887–70898.
60 S. Shionoya and W. M. Yen, Phosphor Handbook, Phosphor
Research Society, CRC Press, 1998, p. 459.
61 E. Fred Schubert, Light Emitting Diodes, Cambridge University
Press, Cambridge, 2nd edn, 2006.
Phys. Chem. Chem. Phys.