Accepted Manuscript

3+
A hybrid treatment of Ba2LaV3O11:Eu nanophosphor system: First-principal and
experimental investigations into electronic, crystal and the optical structure

Mandeep Dalal, Jyoti Dalal, Sangeeta Chahar, Hina Dahiya, Sushma Devi, Priyanka
Dhankhar, Satish Kumar, V.B. Taxak, Dinesh Kumar, S.P. Khatkar
PII: S0925-8388(19)32545-9
DOI: https://doi.org/10.1016/j.jallcom.2019.07.053
Reference: JALCOM 51341

To appear in: Journal of Alloys and Compounds

Received Date: 16 February 2019

Revised Date: 25 May 2019
Accepted Date: 5 July 2019

Please cite this article as: M. Dalal, J. Dalal, S. Chahar, H. Dahiya, S. Devi, P. Dhankhar, S. Kumar,
3+
V.B. Taxak, D. Kumar, S.P. Khatkar, A hybrid treatment of Ba2LaV3O11:Eu nanophosphor system:
First-principal and experimental investigations into electronic, crystal and the optical structure, Journal of
Alloys and Compounds (2019), doi: https://doi.org/10.1016/j.jallcom.2019.07.053.

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

A Hybrid Treatment of Ba2LaV3O11:Eu3+ Nanophosphor System: First-Principal and

Experimental Investigations into Electronic, Crystal and the Optical Structure

Mandeep Dalala, Jyoti Dalala, Sangeeta Chahara, Hina Dahiyab, Sushma Devia, Priyanka
Dhankhara, Satish Kumara, V.B. Taxaka, Dinesh Kumarb, S.P. Khatkar a*
a
Department of Chemistry, Maharshi Dayanand University, Rohtak - 124001, India
b

PT
Department of Chemistry, Deenbandhu Chhotu Ram University of Science & Technology,
Murthal, Sonepat, 131039, India

Abstract

RI
A systematic computational analysis is integrated with the experimental records like Rietveld

SC
and Judd-Ofelt studies to have a deeper insight into the structural and optoelectronic
characteristics of Eu3+-doped Ba2LaV3O11 system. The vanadates used were developed via
solution combustion-synthesis (SCS) route, with all ab-initio calculations performed in the

U
density functional framework. The Rietveld refinement over Ba2La0.65Eu0.35V3O11 lattice
AN
confirmed the phase purity and crystal structure prototype (monoclinic with P21/a space
group). The first-principal routed structure-optimization of the pure host unveiled not only
the total energy but also the atomic positions which were unknown till date. The experimental
M

band-gap (3.724 eV) was found to be pretty much comparable to the value obtained
computationally (3.482 eV). The partial density of states (PDOS) were analyzed orbital- as
D

well as element-wise to understand the electronic structure in a more comprehensive manner.

TE

The calculation of dielectric function yielded the value of many important optical properties
like refractive index, extinction-coefficient, optical-conductivity, and loss-function. The
EP

photoluminescent (PL) excitation-emission and decay analysis revealed a very efficient

energy transfer from vanadate absorption of Ba2LaV3O11 to Eu3+; resulting in a significantly
intense emission with blue-white-red color tunability. Furthermore, the density-functional
C

assisted PL analysis also provided the Judd-Ofelt parameters (Ω2 = 3.3175 × 10-20 cm2 and Ω4
AC

= 0.1197 × 10-20 cm2), radiative-lifetime (2.03 ms), emission cross-sections (10.80 × 10−22
cm2), quantum efficiencies and radiative rates for 5D0 term. All optoelectronic results of
Ba2La0.65Eu0.35V3O11 phosphor suggest that it can be used in the nanocrystalline form for
white light emitting diodes (WLEDs) while potentially the bulk crystal in laser devices.
Moreover, the results of this report may find applications in designing novel material based
upon Ba2LaV3O11 lattice.

1
 ACCEPTED MANUSCRIPT
Keywords: DFT, Judd-Ofelt Parameters; X-Ray Diffraction; Optical Properties,
Nanophosphor

Corresponding Author: +91-9813805666, s_khatkar@rediffmail.com (S.P. Khatkar)

1. Introduction

For many years, energy production and the conservation of its sources has remained
one of the most challenging jobs for the current human civilization. Keeping the matters

PT
related to the global energy demands and environmental pollution in mind; material scientists
across the world are putting huge efforts to search new eco-friendly energy sources as well as

RI
tuning the technology to use the existing one in a more economic and nature-friendly way.
The fast-paced research in phosphors is also in the same league because these materials have

SC
been proved to be of significant potential for toxic-free global-illumination need [1, 2].
Furthermore, among different kind of phosphors, white-light emitters have now become a

U
new topic of research interest due to their application in the next generation solid-state
AN
lighting (SSL) technology [3]. In order to fabricate WLEDs, one of the most common routes
is to coat a blue InGaN LED chip with YAG:Ce3+ phosphor [4-6]. However, this method
suffers from poor color rendering index (CRI; Ra < 80) and high correlated color temperature
M

(TCCT > 7000K) as well [7]. Two more popular methods to eliminate these limitations involve
the covering of ultra-violet (UV) or near-ultraviolet (NUV) LED either with three different,
D

red-green-blue (RGB), phosphor component or by a single-phased while light emitter [6, 8].
TE

Therefore, it is highly encouraging to develop some new phosphor material with high
luminescence efficiency which can fulfill the demand of PC-WLEDs.
EP

Although, a wide range of reports on lanthanide doped nanocrystals are available, but
vanadates doped with Eu3+ are much more attractive as optical systems because of not only
the intra-configurational bands between 4f states but the self-activated nature of the vanadate
C

(charge transfer from 2p orbital of O2− to 3d orbital of V5+) [9, 10]. In addition to self-
AC

activated emission of VO43− group, it can also feed dopant ions (Eu3+) via energy transfer
phenomena [2], resulting in a combined emission profile corresponding to the dopant (Eu3+)
and VO43− group. The overall emission can be fine-tuned to produce color tunability from
deep blue (VO43− emission) to deep red (Eu3+ emission) just by increasing the activator ion
concentration. The present work is executed to develop a color-tunable, Eu3+-doped
Ba2LaV3O11, vanadate phosphor with good thermal stability for PC-WLEDs. In a previous
report of Eu3+ doped Ba2LaV3O11 phosphor, Niu and co-workers reported solid-state
synthesis with heat treatment at 1100°C for 6h [9]. To the best of the author’s knowledge;

2
 ACCEPTED MANUSCRIPT
there are no reports on the optical properties, or the atomic positions of the host; or the
crystallographic and Judd-Ofelt treatment of Ba2LaV3O11:Eu3+ system. We have obtained the
stable crystal structure of Ba2LaV3O11:Eu3+ nanophosphor only at 1000°C for 3h, facilitates
the commercial production.

The results from density-functional theory (DFT) were combined with the X-ray
diffraction (XRD) and PL studies to obtain a comprehensive analysis of the optoelectronic

PT
and structural properties of Eu3+-doped Ba2LaV3O11 phosphor. The Rietveld refinement of
optimum-luminescent composition (Ba2La0.65Eu0.35V3O11) confirmed the phase purity and

RI
lattice prototype (monoclinic crystal system with P21/a space group symmetry). The
geometry-optimization of the pure host yielded the atomic positions, electronic band-

SC
structure, the density of states and dielectric function. The experimental band-gap given by
diffuse reflectance (DR) spectra was found to be 3.724 eV, which is quite comparable to what
has been obtained computationally i.e. 3.482 eV. The computed dielectric function was used

U
to obtain various important optical properties like the extinction-coefficient, refractive index,
AN
loss-function and optical-conductivity. The photoluminescent excitation (PLEX) and
photoluminescent emission (PLEM) spectra showed that the energy transfer from vanadate
M

absorption of Ba2LaV3O11 to Eu3+ is very efficient; accounting for the intense blue-white-red
emission. Additionally, the first-principal assisted PL study of Ba2La0.65Eu0.35V3O11 gave us
D

the Judd-Ofelt parameters, emission cross-sections, quantum efficiencies, radiative-lifetime

and total radiative transition rate for 5D0 state. All the structural and optoelectronic results for
TE

Ba2La0.65Eu0.35V3O11 system indicated that this phosphor can serve to WLEDs in

nanocrystalline form, while the bulk crystal may find application in laser devices. Moreover,
EP

the results of this report may also be used in designing novel material based upon
Ba2LaV3O11 host matrix.
C

2. Experimental
AC

2.1 Materials and Synthesis

The whole series of Ba2La1-xEuxV3O11 (x = 0–0.60) sample was prepared by solution

combustion method. Solution combustion synthesis has many advantages like high product
purity, facileness, time-saving, good homogeneity and controlled morphology [10, 11]. The
analytical-reagent (AR) grade Ba(NO3)2, La(NO3)3.6H2O, Eu(NO3)3.6H2O, NH4VO3.5H2O,
and urea were weighed and then dissolved in a ~30 mL purified water in a 500 mL capacity
pyrex beaker. The solution was heated on a hot plate (maintained at 100°C) for five minutes
with constant stirring to get a homogeneous redox mixture. The quantity of activator ion is

3
 ACCEPTED MANUSCRIPT
varied in each sample while the amount of the fuel was kept fixed. This is because the molar
ratio of metal nitrates to organic fuel (O/F) is independent due to the similar oxidation states
of La3+ and Eu3+ [12]. After that, this hot solution was put into a pre-heated microchip-
controlled furnace at 500 ± 10°C for ~20 minutes. The exothermic combustion of nitrate
yielding Ba2La0.65Eu0.35V3O11 nanophosphor can be described by the equation given below:

5.71Ba(NO3)2 + 1.85La(NO3)3.6H2O + Eu(NO3)3.6H2O + 8.57NH4VO3 + 12.38NH2CONH2

PT
→ 2.857Ba2La0.65Eu0.35V3O11 + 26.66N2(g) + 59.048H2O(g) + 12.38CO2

The white fluffy product was scraped out and ground to obtained very fine powder form.

RI
After that, all the products were put into an alumina-crucible and placed again in the muffle
furnace at 1000°C for 3 hours. The product obtained finally were ground again, pulverized

SC
and were stored in a desiccator until needed for the characterization purpose.

2.2 Materials Characterization

U
The XRD patterns for the whole of the Ba2La1-xEuxV3O11 (x = 0–0.60) series were
AN
recorded with Ultima-IV powder X-ray diffractometer (Rigaku, Japan) in Bragg-Brentano
geometry (goniometer radius = 285 mm). This instrument was equipped Cu X-ray source,
scintillation counter as the detector, and a nickel filter to eliminate Kβ radiation. The machine
M

was programmed to operate at 40 kV tube voltage and 40 mA tube current. The diffraction
data of all the samples, excepting Ba2La0.65Eu0.35V3O11 (5−105 at 1° min−1), were recorded in
D

the 2θ angular range from 10° to 80° with a scanning rate of 2° min−1 and scanning step was
TE

maintained at 0.02°. The Rietveld refinement technique by GSAS (General Structure

Analysis System) software is used to obtain the crystal structure and to refine the lattice
EP

parameters[13, 14]. The background refinement was carried out using the shifted Chebyschev
function with five terms. The whole pattern fitting (WPF) of diffraction peaks was done with
the Pseudo-Voigt function type.
C

The surface morphological properties and particle size distribution of the powder
AC

phosphor were inspected using Tecnai G2 FEI transmission electron microscope (TEM). The
DR spectrum was recorded in the range of 200−800 nm using an ultraviolet-visible-near-
infrared absorption spectrophotometer (Shimadzu UV-3600 Plus); equipped with an
integrated sphere accessory. The PL excitation-emission spectra and the decay curves were
recorded at room temperature using a Hitachi F7000 fluorescence spectrophotometer
equipped with Xe-lamp as the excitation energy source (PMT Voltage = 400V, slit width =
2.5 nm). The electronic structure and optical properties were obtained from DFT method
using the Cambridge Serial Total Energy Package (CASTEP) code [15]. For all the

4
 ACCEPTED MANUSCRIPT
computational work, the generalized gradient approximation (GGA) under the Perdew–
Burke–Ernzerhof (PBE) formulation was used with plane-wave basis cutoff energy of 571.4
eV. The k-point sampling scheme of 1×1×1 Monkhorst-Pack grid was used. The convergence
tolerance for geometry optimization was 1.0×10−6 eV per atom, the maximal ionic Hellmann-
Feynman force was 2.0×10−2, and the maximal displacement being within 1.0×10−3 Ǻ.

3. Results and discussion

PT
3.1 Structural analysis

Fig.1 presents the PXRD patterns of Ba2La1-xEuxV3O21 (x = 0–0.60) phosphors along

RI
with the JCPDS card number (41-0105), retrieved from International Centre for Diffraction
Data (ICDD) database. From the careful analysis of Fig.1, it can be concluded that the

SC
incorporation of activator ion (Eu3+) has not altered the phase-prototype because all the
observed peaks match well with standard Ba2LaV3O11 host. Fig.S1 reveals that some minor

U
apparent impurities peaking at about 31 (x = 0, 0.05, 0.15, 0.25, 0.30, 0.35 moles%) are found
AN
to be arising from Ba8V7O22. Fig.2 presents the Rietveld refinement of Ba2La0.65Eu0.35V3O11
phosphor, along with the difference between theoretically observed (black square) and
experimentally calculated (solid red line) X-ray diffraction profiles at the bottom by a blue
M

line. The inset of Fig.2 displays the unit cell view of Ba2La0.65Eu0.35V3O11 phosphor with
oxide-ion-coordinated cationic polyhedral units. The crystal system of Ba2La0.65Eu0.35V3O11
D

phosphor is identified as the monoclinic type with P21/a space group [2], with unit cell
TE

parameters refined to a = 12.5457(10) Å, b = 7.8289(6) Å, c = 11.3547(10) Å, α = 90⁰, β =

103.421⁰, γ = 90⁰, V = 1084.79(11) Å3 and Z = 4. The refinement successfully converged
to Rwp = 12.82%, Rp = 10.20%, and χ2 = 1.770. The comparison of crystallographic data of
EP

Ba2La0.65Eu0.35V3O11 phosphor with the pure Ba2LaV3O11 host [16] is listed in Table 1. We
claim that Eu3+ ions have replaced the La3+ ions randomly through in Ba2LaV3O11 host matrix
C

due to analogs oxidation state and comparable ionic radii. The observed decrease in the unit
AC

cell volume from 1100.46 Å3 to 1084.79(11) Å3 when Ba2LaV3O11 host is doped with 35
mol% of Eu3+ ions can be attributed to the smaller ionic radius of Eu3+ than La3+. The dopant
incorporation results in the increment of crystal density from 4.4807 to 4.5732 g cm−3 which
can be credited to both the cell-contraction and the increase in gram formula weight.

Now because of the low-symmetry nature and a large number of atoms, we decided to
obtain the atomic positions in Ba2LaV3O11 unit cell by implementing the geometry-
optimization using first-principal rather than Rietveld refinement. The initial model built
using previously reported lattice parameters of the pure host (Ba2LaV3O11) by Huang and

5
 ACCEPTED MANUSCRIPT
coworkers [16], while the internal coordinates or the atomic positions were taken from
Ba2BiV3O11 lattice by simply adding La at the Bi site. The Broyden–Fletcher–Goldfarb–
Shanno (BFGS) iterations were finished in 51 optimization steps unveiling a 54991.8065 eV
crystal enthalpy. The optimized crystal structure of Ba2LaV3O11 (unit cell view along a-axis)
along with the coordinative environment of Ba2+, La3+ and V5+ ions is shown in Fig.3. It can
be clearly seen that the structure of Ba2LaV3O11 contains 1:1 orthovanadate [VO4]3− and

PT
pyro-vanadate [V2O7]3− groups. In both VO43− and V2O73− group, V5+ ion is tetra-coordinated
by four oxygen atoms. The Ba2+ ions occupy two different types of crystallographic sites
having coordination number eight and ten, respectively; while the La3+ ion forms an

RI
asymmetric LaO8 polyhedral unit. For the accurate calculation of the average crystallite size

SC
from broadening of diffraction peaks Scherrer’s equation [17] is used, which is described as:

0.941λ
= /
1
2θ − 2θ cosθ

U
AN
Where D is the crystallite size, λ represents the X-ray wavelength (Cu Kα), θ corresponds to
the diffraction angle. BO(2θ) and BSi(2θ) are full widths at half-maximum (FWHM, in radian)
for the observed and standard silicon pattern, respectively. The FWHM of the most intense
M

peak (2θ = 28.2) after the whole pattern fitting (WPF) was used to calculate the average
crystallite size. The average crystallite size (D) for Ba2La0.65Eu0.35V3O11 nanophosphor was
D

found to be 47 nm.
TE

The surface morphology and crystallite size of Ba2La0.65Eu0.35V3O11 nanoparticles were

confirmed by TEM micrograph (Fig.4). The morphology of the nanocrystals seems to be
EP

elliptical or semi-cylindrical with some agglomeration factor. The particle size distribution
reveals that smoothly surfaced particles have a small deviation in the range of 30−90 nm
C

Fig.4(d). The crystallite size obtained from two different methods, TEM analysis and
Scherrer’s equation, are in good agreement and suggesting the nano-dimensional character of
AC

Ba2La0.65Eu0.35V3O11 phosphor. The nano-scaled phosphor materials exhibit enhancement in

luminescence efficiency due to their exceptional behavior arising from quantum size effect,
high asymmetry, less internal scattering, or high value of surface to volume ratio [18].

In order to obtain the band-gap (Eg) values of Ba2LaV3O11 from DR spectrum, the
Kubelka-Munk theory was implemented [19, 20], giving plot between absorption coefficient
and photon energy for pure Ba2LaV3O11 host (Fig.5). The corresponding diffuse reflectance

6
 ACCEPTED MANUSCRIPT
spectra is shown in the inset. The general equation to calculate band-gap Eg, based on the
transformation of diffuse reflectance spectra, is given below:

ℎ !" = #$ℎ − %& ' 2

where C = constant of proportionality, hν = photon-energy, and Eg = the value of the band-

gap. The value of n = 0.5 and 2 for indirect-allowed and a direct-allowed transition; while n =
1.5 and 3 are taken for a direct and indirect forbidden transition, respectively. F(R∞) is the

PT
Kubelka-Munk function whose value is defined as:

1− (
= = 3

RI
2 )

Where K = absorption coefficient, S = scattering coefficient, and R∞ is simply the ratio of

SC
Rsample to Rstandard i.e Rsample/Rstandard. The extrapolation of the line for F(R∞)hν = 0 yielded a
band-gap of 3.724 eV for the pure host.

U
The electronic structural investigation of Ba2LaV3O11 is done by DFT calculations
AN
using CASTEP code; and the band structure, along with the PDOS of the same, is shown in
Fig.6. It is obvious from the results that the valence and conduction bands are separated by a
M

direct energy gap of 3.482 eV. This is slightly lower than the experimental value (3.724 eV)
obtained from the diffuse reflectance spectra and can be attributed to the GGA functional
D

type, which generally underestimates the band-gap magnitudes [21]. The high value of
optical band-gap makes Ba2LaV3O11 system a suitable host for the luminescent-center-
TE

doping, as it can accommodate large number free ion terms (including ground state) in
between [22]. The left-hand side of Fig.6 also reveals that the conduction band is composed
EP

mainly of d-orbitals and with significantly less but almost equal contributions from s- and p-
orbitals. On the other hand, the valence band is composed mainly of p-cloud and some d-
C

orbital, with almost negligible contribution from s-orbitals. A different element-wise

perspective for PDOS of nanocrystalline Ba2LaV3O11 powder is depicted in the Fig.7. The
AC

results show that the lower energy region of the conduction band is mainly dominated by
vanadium orbitals, with a significant amount of oxygen cloud; while the mid and high energy
regions are dominated by barium and vanadium, respectively (with a large number of
lanthanum orbitals too). The valence band of nanocrystalline Ba2LaV3O11 is almost covered
by the oxygen orbitals with an overall order of O2− > V5+ > Ba2+ ≈ La2+. The optical band-
gaps obtained for nanocrystalline Ba2LaV3O11 (3.724 eV) are higher than the values reported
for its bulk counterpart (3.35) [21]; showing that the nanoscaling has increased the band-gap
slightly, and hence does affect the band structure.

7
 ACCEPTED MANUSCRIPT
3.2 Optical Analysis

The photoluminescent excitation spectra of the complete Ba2La1-xEuxV3O11 (x = 0.01–

0.60) nanophosphor series is depicted in Fig.8. All the samples exhibit strong broad-band
absorption in the lower wavelength region, ranging from 225−370 nm; which can be ascribed
as the host’s absorption and charge transfer (CT) from O2– to Eu3+ ions [9]. The two sharp-
bands with lower intensity, extended over 370−400 nm, are attributed to intra-configurational

PT
f-f transitions between ground state (7F0) and excited state (5Lj) terms of Eu3+ ion. The host
absorption originates from the partially-allowed transition between 1A1 (ground state term) to

RI
1
T1,2 (excited state terms) of VO43– group [21]. The excitation energy difference between
1
A1→1T1,2 and O2–→Eu3+ transitions is much lower; results in a single broad band which can

SC
be deconvoluted into three distinct peaks using Gauss function. The deconvoluted excitation
profile of Ba2La0.65Eu0.35V3O11 phosphor is shown in Fig.9. Herein, the CT (O2–→Eu3+)

U
transition contributing as a shoulder peak, Ex2 (1A1→1T1) is a very low-intensity peak whilst
Ex1 (1A1→1T2) transition contributes as a major excitation band.
AN
Fig.10 presents the photoluminescent (PL) emission spectra of Ba2La1-xEuxV3O11 (x =
M

0.01−0.60) phosphor series (excitation wavelength = 320 nm). The PL emission profiles of
series (1 to 60 mol%) show a broad band ranging from 400−570 nm; which is consisted of
D

characteristics emission of vanadate group at around 555 (3T1→1A1) and 494 nm (3T2→1A1).
In addition to this broad band, other two prominent peak profiles at 591 and 620 nm are also
TE

observed; which can successfully be ascribed to the characteristic emission of Eu3+ ion [5, 7,
21]. The most intense peak in emission spectra at 620 nm (5D0→7F2) is purely electric-dipole
EP

allowed transition [23], whereas the transition at 591 nm (5D0→7F1) is purely magnetic-
dipole allowed transition [24]. Moreover, three other characteristics emission peaks of
C

trivalent europium ion, with much lower intensity, also arises due to 5D0→7F0 (554 nm),
5
D0→7F3 (655 nm) and 5D0→7F3 (705 nm) transitions. It is very clear from the emission-
AC

profile that the PL emission intensity of 1A1→1T1,2 transitions decreases gradually with
increasing Eu3+ ion concentration, which confirms a systematic excitation-energy transfer
from the vanadate to dopant ion. However, after a continuous increase in the PL emission
intensity up to 35 mol% of Eu3+, the 5D0→7F2 transition begins to descend; which is
obviously due to the enhancement of non-radiative relaxation. From the previous literature; it
is well-known that the transition probability of magnetic-dipole transition between 5D0 and
7
F1 states is pretty much independent of the nature of host lattice [25]. Whereas, the transition

8
 ACCEPTED MANUSCRIPT
probability of electric-dipole allowed 5D0→7F2 transition is strongly influenced by local
structural environment and the asymmetry around the Eu3+ ion [23]. Therefore, the ratio of
5
D0→7F2 (red) to 5D0→7F1 (orange) transitions are determined to analyze the effect of dopant
on the local environmental symmetry. The values of hypersensitive ratio R(2/1) as a function
of dopant concentration are reported in Table 3, which shows a little increment from 1.2178
to 1.5856. The increasing R(2/1) values confirm a decrease in the coordinative symmetry of

PT
trivalent europium in Ba2La1-xEuxV3O11 (x = 0.01−0.60) nanophosphor.

The phenomena of photoluminescence excitation-emission, charge transfer, or various

RI
types of non-radiative relaxations can be explained using a systematic energy level diagram
as shown in Fig.11. The diagram primarily includes the ground (1A1) and four excited states

SC
(1T1, 1T2, 3T1 and 3T2) of VO43− group, along with ground and some excited states of trivalent
europium. Initially, the higher energy levels of VO43− group and Eu3+ ion can be populated
through excitation energy. The 1T1,2 states then partly relax down to 3T1,2 states, and partly

U
feeds the excited states of Eu3+ ions. This results in two weak emission bands of the host at
AN
494 and 555 nm, whilst the non-radiative relaxation of host-fed excited states of Eu3+
populates the 5D0 state. Finally, the radiative relaxation occurs for 5D0→7F0,1,2,3,4 transitions,
M

yielding the characteristics emission peaks of Eu3+ ion. The PL emission intensity of host
emission showed an almost regular decrease with the increasing activator concentration,
D

which is obviously due to the energy transfer phenomenon. Nevertheless, the observed
decrease in the PL intensity for 5D0→7F0,1,2,3,4 transitions after 35 mol% gives a much better
TE

understanding of the energy transfer mechanism between adjacent Eu3+ ions. The critical
distance of energy transfer for Ba2La0.65Eu0.35V3O11 phosphor can be calculated using the
EP

following equation [26] as:

/2
3 -
+ = 2, 1 4
4 Π /+ 0
C
AC

Where N is the number of replaceable cations per unit cell, V represents the volume of the
crystallographic unit cell, and xc corresponds to the optimal fluorescent composition. By
using xc = 0.35, V = 1084.79 Å3 and N = 4; the critical distance (Rc) is found to be 11.3941 Å.
The value of Rc ≤ 5 Å is required for exchange interactions; therefore, the possibility of
energy migration arising from exchange-interactions can be ruled out. Furthermore, as there
is no overlap between excitation and emission bands, the radiation reabsorption is also not
possible; indicating that the energy-transfer phenomena, in this case, must be governed by
multipolar-interactions, described by Dexter’s theoretical model [27].

9
 ACCEPTED MANUSCRIPT
The plot between dopant concentration v/s PL emission intensity at 620 nm (5D0 →
7
F2) is presented in Fig.12. The regular decrease photoluminescence intensity after 35 mol%
is a result of concentration quenching phenomena, and can be explained by the equation
given the Huang and co-workers in a previous report as follows [28]:

7 9
345 6 8 = − 345 / + 345 < 5
/ :

PT
Where, I/x belongs to intensity per activator ion concentration, x is the dopant molar
concentration equals to or larger than the optimum fluorescent concentration, f represents a

RI
constant (independent of dopant concentration) and d is the dimension of the sample. Here,
value of d = 3; and s is multipolar interactions constant (s = 10, 8, 6 for quadrupole-

SC
quadrupole (q-q), dipole-quadrupole (d-q) and dipole-dipole (d-d), interactions). The nature
of plot between log (I/x) v/s log (x) is a straight-line having slope of −1.9241, resulting the
value of s equals to 5.7723, which is quite close to the theoretical value of 6 (Fig.13). Thus,

U
all the results conclude that dipole-dipole interactions are primarily responsible for the energy
AN
migration and concentration-quenching phenomenon in Ba2LaV3O11:Eu3+ nano-phosphor
system.
M

For a better understand the optical nature of Ba2La1-xEuxV3O11 (x = 0.01−0.60)

phosphor system, normalized photo-luminescence decay curves corresponding to the
D

5
D0→7F2 transition at 324 nm excitation wavelength are depicted in Fig.14. Furthermore, the
TE

variation of the PL intensity for Ba2La0.65Eu0.35V3O11 as a function of time on the logarithmic

scale is shown in the inset of Fig.14. In all cases decay curves are well fitted by single
exponential behavior, presented by the following equation:
EP

B
7 = 7> exp 6− 8 6
C
C

Where I and I0 represent the photo-luminescence intensities at time t and 0, respectively;

AC

whilst the radiative decay time is symbolized by τ. The average photoluminescence lifetime
values for complete Ba2La1-xEuxV3O11 (x = 0.01−0.60) phosphor series are listed in Table 3.
The photo-luminescence lifetime values for 5D0 state (5D0→7F2 transition) of Eu3+ ion are
decreasing continuously from 1.32 to 0.82 ms when dopant concertation is increased from 1.0
to 60 mol%; suggesting the existence of energy-transfer process through a non-radiative
mechanism. The mono-exponential decay profile concludes the homogeneous distribution
and one crystallographic site availability for Eu3+ in Ba2LaV3O11 host matrix [29].

10
 ACCEPTED MANUSCRIPT
The optical properties of Ba2LaV3O11 host are calculated from dielectric-function
(obtained from DFT using CASTEP code), which can be described equation (7) as [30]:

E F = E F + GE F 7

Where the ε1 and ε2 represent the real part and imaginary part of the overall dielectric
function, respectively. The imaginary part depends upon the frequency and can be obtained
using equation (7) as:

PT
2IJ
E F = L |NOP+ |Q. R|OPS T| V %P+ − %PS − ℏF 8
KE>
P,S,+

RI
Where ⁰ω represents the energy of the incident phonon, Ω is the volume, and ε0 is the

SC
vacuum dielectric constant. The symbols v and c are for the valence and conduction bands,
respectively. The u.r is simply the momentum operator; whilst ψkv and ψkc are the
wavefunctions of the valence and conduction band point k, respectively. The variation of

U
dielectric function as a function of wavelength is shown in Fig. 15 (real as well as imaginary).
AN
Once the dielectric function is known, some very important properties like refractive index
(n), extinction coefficient (k), loss function (L) and optical conductivity (σ) can be calculated
M

using equation (9−12) as given below.

1 /
Y F = [ E F +E F ! +E F \ 9
√2
D

1 /
TE

] F = [ E F +E F ! −E F \ 10
√2
E F
^ F = 11
EP

E F + GE F

GF
_ F =− E F + GE F − 1! 12
4I
C
AC

The variation of all the optical properties of Ba2LaV3O11 host as a function of the wavelength
of the radiation is shown in Fig.16. The magnitude of the refractive index obtained from the
real part is found to be 2.23. Such a large value in the low energy region is indicative of a
large band gap [31], which has already been shown by the experimental and theoretical
results as shown in Fig. 5 and Fig.6.

The famous Judd-Ofelt theory, a scientific breakthrough achieved in 1962 by B.R. Judd
and George S. Ofelt, proposed three important parameters for the rationalization of emission

11
 ACCEPTED MANUSCRIPT
as well as absorption characteristics of Ln3+ complexes and doped glasses or crystals.
However, the refractive index of the host (in case of doped systems) or solvent (for
complexes) and the absorption spectra are the prerequisites for such calculations; and both of
these properties are hard to measure for non-transparent hosts. Some researchers found a
workaround this problem by using emission spectra of Eu3+ doped crystalline powders [32].
However, the recent development in density functional studies and increased computing-

PT
muscles encouraged us to opt a somewhat different route to find our J-O parameters. Herein,
we first used the refractive index of the host, calculated for polycrystalline geometry, to
obtain the spontaneous emission probability of 5D0→7F1 transition by equation (13) given

RI
below.

64 πg 2

SC
`abac =
de
Y2 )de 13
3ℎ 2h + 1

U
Where 2J + 1 is the degeneracy of the first state, h = 6.626 × 10-27erg s (Planck's constant), n
AN
is the refractive-index of polycrystalline geometry with value 2.03 (from Fig.16.), v is the
wavenumber for J→J’ transition, and Smd = 7.83 ×10-42 (the magnetic-dipole line strength).
After that, the radiative rate of 5D0→7F1 transition was put into the equation (14) to find the
M

radiative transition rates for other 5D0→7FJ transitions as follows [33]:

7>ba
D

>ba
`>ba = `>b × 14
7>b >b
TE

Where, the I0J and I01 are simply the integrated intensities; while ν0J and ν01 are energy
5
barycenter of D0→7FJ and 5
D0→7F1 transition, respectively. The value of A01 for
EP

Ba2La0.65Eu0.35V3O11 composition is 168.52 s−1 (from the previous step). The total radiative
rates for all 5D0→7FJ transitions are listed in Table 4.
C

To finish, the well-known expression for electric-dipole transitions from 5D0 state to
AC

7
F2,4,6 state can be used to obtain the values of Ω2,4,6 as [1, 32, 34]:

64 πg J 2 Y Y + 2
`aba
je
c = L Ωl oOa pq l pO′as t 15
3ℎ 2h + 1 9
lm ,g,n

Where e is the electronic charge (4.80 × 10-10 esu) and oOa pq l pO′as t is the square reduced-
matrix element for J→J’ transition. Solving the equation (15) for 5D0→7F2,4 transitions, we
get Ω2 = 3.3175 × 10-20 cm2 and Ω4 = 0.1197 × 10-20 cm2. Moreover, fluorescence branching
ratios are obtained using equation (16) [18, 34] and are reported in Table 5.

12
 ACCEPTED MANUSCRIPT
`abac
ua = 16
vam>, ,
` c
,2,g,w,n aba

The Judd-Ofelt parameter Ω2 includes of information related to the short-range characteristics

like the covalency and polarizability of chemical environment, while Ω4 is related to the
long-range parameters such as viscosity and rigidity of host-matrix [35]. For
Ba2La0.65Eu0.35V3O11 nanophosphor, a very high value of Ω2/Ω4 = 27.71 indicates the

PT
presence of non-centrosymmetric environment around the activator ion, which is also very
obvious from the crystallographic studies. This result is also in good agreement with R(2/1)

RI
ratio calculated from the emission spectrum (Table 3).

Moreover, once the radiative rates for all 5D0→7FJ transitions are known, the radiative

SC
lifetime can be obtained by the reciprocal of their sum as:
1
Cx = 17
∑ `abac

U
AN
The intrinsic or radiative lifetime for 5D0 state was found to be 2.03 ms, which in turn, was
used to obtain the values of quantum efficiency (ϕ) of the same state in all Ba2La1-
3+
xV3O21:xEu as [43]:
M

Cd `{
z = = 18
Cx `{ + `"{
D

Where, AR and AnR are the radiative and non-radiative rate, respectively; while τm represents
TE

the measured lifetime. The knowledge of both τr and τm also enables us to determine the
overall rate of non-radiative relaxation [44] (AnR):
1 1
EP

= + `"{ 19
C| C{
C

Where τR and τO are the radiative and observed lifetime of the excited state; while AR and AnR
are the rates of radiative and non-radiative relaxations respectively. The quantum efficiencies
AC

and rate of non-radiative relaxation from 5D0 state are listed in Table 3.
5
The intermanifold emission cross-sections of the D0→7F0,1,2,3,4 transitions for
Ba2La0.65Eu0.35V3O11 can be obtained using equation (20) as [36]:

}g~
Vj $}~ ' = • ƒ ` c 20
8I€Y •}j‚‚ aba

Where λp shows the emission-peak-wavelength, ∆λeff is the effective bandwidth

corresponding to the emission transition and c = 2.99792458 × 1010 cm/s (velocity of light).

13
 ACCEPTED MANUSCRIPT
The stimulated emission cross-section (δe) and effective bandwidth of the emission transition
(∆λeff) for each 5D0→7F0,1,2,3,4 transitions are listed in Table 5. The large magnitude of the
cross-section for 5D0→7F2 (10.80 × 10−22 cm2) is indicative of its potential use in laser
devices.

The MATLAB software package has been used to analyze and confirm the emission
color of Ba2La1-xEuxV3O11 (x = 0.01−0.60) nano-phosphor series and are shown in

PT
Commission International De I’Eclairage (CIE 1931) chromaticity diagram for relative
studies. The chromaticity coordinates (x, y) of different mol% show a regular color tunability

RI
from blue (0.2410, 0.3024 for 1 mol%) to white (0.4465, 0.3435 for 10 mol%) to red (0.5500,
0.3369 for 60 mol%) region. All the color coordinates, as a function of Eu3+ concentration,

SC
are summarized in Table 3, have also been depicted graphically for a more general
observation (Fig.17). All results strongly suggest that these Eu3+-doped Ba2LaV3O11 “blue-
white-red” emitters are quite promising for the applications in RGB (red-blue-green) based
PC-WLEDs with near-ultra-violet excitation.
U
AN
4. Conclusions

In summary, a Rietveld and Judd-Ofelt assisted computational analysis is carried out

M

for a comprehensive of optoelectronic and structural character of Eu3+-doped Ba2LaV3O11

(synthesized via SCS) system. The structural prototype and lattice parameters of
D

Ba2La0.65Eu0.35V3O11 were confirmed by Rietveld technique, which unveiled a monoclinic

TE

lattice with P21/a space group. The structure of the pure host was optimized from first-
principal DFT framework, giving the atomic positions and total energy of the crystal. The
computational band-gap (3.482 eV) was found to be pretty much comparable to the value
EP

obtained experimentally (3.724 eV). The PDOS were studied element- as well as orbital-wise
to have a better understanding of the electronic structure. The calculation of dielectric
C

function yielded the value of many important optical properties like extinction-coefficient,
AC

refractive index (2.23), optical-conductivity and loss-function. The detailed analysis of PL

excitation-emission and decay curves revealed a very efficient energy transfer from VO43−
absorption of Ba2LaV3O11 to Eu3+ ion, resulting in a very intense emission with blue-white-
red color tunability. Additionally, the DFT assisted PL analysis also delivered the Judd-Ofelt
intensity parameters (Ω2 = 3.3175 × 10-20 cm2 and Ω4 = 0.1197 × 10-20 cm2), emission cross-
sections, radiative-lifetime, quantum efficiencies and total radiative transition rate for 5D0
state. All optoelectronic results suggested that the nanocrystalline form of
Ba2La0.65Eu0.35V3O11 phosphor find potential application in WLEDs. The large magnitude

14
 ACCEPTED MANUSCRIPT
emission cross section of 5D0→7F2 transition (10.80 × 10−22 cm2) claimed its probable
application in laser. Also, all the results of this paper may find significant importance in
designing new Ba2LaV3O11-based materials.

Acknowledgment

Ms. Jyoti Dalal, gratefully acknowledges the “Council of Scientific and Industrial
Research” (CSIR), New Delhi, India for their financial support to this work in the form of

PT
senior research fellowship (SRF, Award No: 09/382(0180)/2016-EMR-I).

RI
U SC
AN
M
D
TE
C EP
AC

15
 ACCEPTED MANUSCRIPT
References
[1] S. Chahar, R. Devi, M. Dalal, P. Boora, V.B. Taxak, S.P. Khatkar, Structural and
photoluminescent analysis in Judd-Ofelt framework of color tunable SrGd2(1-x)Eu2xAl2O7
nanophosphor for white light emitting materials, Journal of Luminescence, 194 (2018) 271-
278.
[2] M. Dalal, S. Chahar, J. Dalal, R. Devi, D. Kumar, S. Devi, V.B. Taxak, A. Khatkar, M.
Kumar, S.P. Khatkar, Energy transfer and photoluminescent analysis of a novel color-tunable
Ba2Y1-xV3O11:xSm3+ nanophosphor for single-phased phosphor-converted white LEDs,

PT
Ceramics International, 44 (2018) 10531-10538.
[3] V.R. Bandi, B.K. Grandhe, K. Jang, H.-S. Lee, D.-S. Shin, S.-S. Yi, J.-H. Jeong, Citric
based sol–gel synthesis and luminescence characteristics of CaLa2ZnO5:Eu3+ phosphors for

RI
blue LED excited white LEDs, Journal of Alloys and Compounds, 512 (2012) 264-269.
[4] F. Baur, F. Glocker, T. Jüstel, Photoluminescence and energy transfer rates and
efficiencies in Eu3+ activated Tb2Mo3O12, Journal of Materials Chemistry C, 3 (2015) 2054-

SC
2064.
[5] A. Chapel, R. Boonsin, G. Chadeyron, D. Boyer, A. Bousquet, R. Mahiou, W. Henrique
Cassinelli, C.V. Santilli, S. Therias, Preparation and characterization of a red luminescent

U
composite composed of an EVA copolymer and a Y3BO6:Eu3+ phosphor, New Journal of
Chemistry, 41 (2017) 12006-12013.
AN
[6] H.-Y. Chen, R.-Y. Yang, S.-J. Chang, Improving crystalline morphology and
photoluminescent properties of BaY2ZnO5:Eu3+ phosphors prepared using microwave
assisted sintering, Materials Letters, 64 (2010) 2548-2550.
M

[7] G.K. Behrh, R. Gautier, C. Latouche, S. Jobic, H. Serier-Brault, Synthesis and

Photoluminescence Properties of Ca2Ga2SiO7:Eu(3+) Red Phosphors with an Intense (5)D0 →
(7)
F4 Transition, Inorg Chem, 55 (2016) 9144-9146.
D

[8] S. Chahar, V.B. Taxak, M. Dalal, S. Singh, S.P. Khatkar, Structural and
photoluminescence investigations of Sm3+ doped BaY2ZnO5 nanophosphors, Materials
TE

Research Bulletin, 77 (2016) 91-100.

[9] P. Niu, X. Liu, Y. Wang, W. Zhao, Photoluminescence properties of a novel red-emitting
phosphor Ba2LaV3O11:Eu3+, Journal of Materials Science: Materials in Electronics, 29 (2017)
EP

124-129.
[10] M. Dalal, V.B. Taxak, Sheetal, D. Kumar, S.P. Khatkar, Crystal structure and
photoluminescent properties of BaZn1−xEuxV2O7 nanoparticles, Materials Chemistry and
C

Physics, 149-150 (2015) 713-720.

[11] S. Chahar, M. Dalal, S. Singh, R. Devi, V.B. Taxak, S.P. Khatkar, Structural and
AC

photoluminescent elucidation of the efficient green emitting erbium doped BaY2ZnO5

nanophosphor for light emitting materials, Journal of Materials Science: Materials in
Electronics, (2017).
[12] K. Patil, Combustion synthesis, Current Opinion in Solid State and Materials Science, 2
(1997) 158-165.
[13] B.H. Toby, EXPGUI, a graphical user interface forGSAS, Journal of Applied
Crystallography, 34 (2001) 210-213.
[14] A.C. Larson, R.B. Von Dreele, General Structure Analysis System (GSAS), Los Alamos
National Laboratory Report LAUR, (1994) 86-748.

16
 ACCEPTED MANUSCRIPT
[15] M.D. Segall, P.J.D. Lindan, M.J. Probert, C.J. Pickard, P.J. Hasnip, S.J. Clark, M.C.
Payne, First-principles simulation: ideas, illustrations and the CASTEP code, Journal of
Physics: Condensed Matter, 14 (2002) 2717-2744.
[16] J. Huang, Q. Gu, A.W. Sleight, Synthesis and Crystal Structure of a New Mixed
Orthovanadate-Pyrovanadate Series: MBa2V3O11 or MBa2V2PO11 with M = Bi, In, or a Rare
Earth, Journal of Solid State Chemistry, 110 (1994) 226-233.
[17] Q.Y. Zhang, X.Y. Huang, Recent progress in quantum cutting phosphors, Progress in
Materials Science, 55 (2010) 353-427.

PT
[18] X. Zhang, L. Zhou, Q. Pang, M. Gong, Synthesis, photoluminescence and Judd–Ofelt
analysis of red LiGd5P2O13 : Eu3+ phosphors for white LEDs, RSC Advances, 5 (2015)
54622-54628.

RI
[19] T. Manohar, S.C. Prashantha, R. Naik, H. Nagabhushana, H.P. Nagaswarupa, K.S.
Anantharaju, K.M. Girish, H.B. Premkumar, A benign approach for tailoring the photometric
properties and Judd-Ofelt analysis of LaAlO3:Sm3+ nanophosphors for thermal sensor and

SC
WLED applications, Sensors and Actuators B: Chemical, 243 (2017) 1057-1066.
[20] D. Deng, H. Yu, Y. Li, Y. Hua, G. Jia, S. Zhao, H. Wang, L. Huang, Y. Li, C. Li, S. Xu,
Ca4(PO4)2O:Eu2+ red-emitting phosphor for solid-state lighting: structure, luminescent

U
properties and white light emitting diode application, Journal of Materials Chemistry C, 1
(2013).
AN
[21] J. Zhao, C. Guo, T. Li, D. Song, X. Su, Near-infrared down-conversion and energy
transfer mechanism in Yb(3+)-doped Ba2LaV3O11 phosphors, Phys Chem Chem Phys, 17
(2015) 26330-26337.
M

[22] Y.Q. Li, N. Hirosaki, R.J. Xie, T. Takeka, M. Mitomo, Crystal, electronic structures and
photoluminescence properties of rare-earth doped LiSi2N3, Journal of Solid State Chemistry,
182 (2009) 301-311.
D

[23] S. Das, A. Amarnath Reddy, S. Ahmad, R. Nagarajan, G. Vijaya Prakash, Synthesis and
optical characterization of strong red light emitting KLaF4:Eu3+ nanophosphors, Chemical
TE

Physics Letters, 508 (2011) 117-120.

[24] J.T. Ingle, R.P. Sonekar, S.K. Omanwar, Y. Wang, L. Zhao, Combustion synthesis and
photoluminescence study of novel red phosphor (Y1−x−y,Gdx)BaB9O16:Eu3+y for display and
EP

lighting, Journal of Alloys and Compounds, 608 (2014) 235-240.

[25] E. Pavitra, G. Seeta Rama Raju, J.Y. Park, Y.H. Ko, J.S. Yu, Synthesis and luminescent
properties of novel red-emitting CaGd4O7: Eu3+ nanocrystalline phosphors, Journal of Alloys
and Compounds, 553 (2013) 291-298.
C

[26] G. Blasse, Energy transfer in oxidic phosphors, Physics Letters A, 28 (1968) 444-445.
AC

[27] D.L. Dexter, J.H. Schulman, Theory of Concentration Quenching in Inorganic

Phosphors, The Journal of Chemical Physics, 22 (1954) 1063-1070.
[28] Y. Tian, B. Chen, B. Tian, R. Hua, J. Sun, L. Cheng, H. Zhong, X. Li, J. Zhang, Y.
Zheng, T. Yu, L. Huang, Q. Meng, Concentration-dependent luminescence and energy
transfer of flower-like Y2(MoO4)3:Dy3+ phosphor, Journal of Alloys and Compounds, 509
(2011) 6096-6101.
[29] A.A. Reddy, S. Das, S. Ahmad, S.S. Babu, J.M.F. Ferreira, G.V. Prakash, Influence of
the annealing temperatures on the photoluminescence of KCaBO3:Eu3+ phosphor, RSC
Advances, 2 (2012).

17
 ACCEPTED MANUSCRIPT
[30] B. Luo, X. Wang, E. Tian, G. Li, L. Li, Electronic structure, optical and dielectric
properties of BaTiO3/CaTiO3/SrTiO3 ferroelectric superlattices from first-principles
calculations, Journal of Materials Chemistry C, 3 (2015) 8625-8633.
[31] X.D. Zhang, M.L. Guo, W.X. Li, C.L. Liu, First-principles study of electronic and
optical properties in wurtzite Zn1−xCdxO, Journal of Applied Physics, 103 (2008).
[32] B. Tian, B. Chen, Y. Tian, X. Li, J. Zhang, J. Sun, H. Zhong, L. Cheng, S. Fu, H. Zhong,
Y. Wang, X. Zhang, H. Xia, R. Hua, Excitation pathway and temperature dependent
luminescence in color tunable Ba5Gd8Zn4O21:Eu3+ phosphors, Journal of Materials Chemistry
C, 1 (2013) 2338–2344.

PT
[33] Q.P. Li, B. Yan, Novel luminescent hybrids by incorporating rare earth beta-diketonates
into polymers through ion pairing with an imidazolium counter ion, Photochem Photobiol

RI
Sci, 12 (2013) 1628-1635.
[34] M. Dalal, V.B. Taxak, S. Chahar, J. Dalal, A. Khatkar, S.P. Khatkar, Judd-Ofelt and
structural analysis of colour tunable BaY2ZnO5:Eu3+ nanocrystals for single-phased white

SC
LEDs, Journal of Alloys and Compounds, 686 (2016) 366-374.
[35] V. Mahalingam, J. Thirumalai, Facile hydrothermal synthesis and pulsed laser
deposition of Ca0.5Y1−x(WO4)2:xEu3+ phosphors: investigations on the luminescence, Judd–

U
Ofelt analysis and charge compensation mechanism, New Journal of Chemistry, 41 (2017)
493-502.
AN
[36] P.S. Wong, M.H. Wan, R. Hussin, H.O. Lintang, S. Endud, Structural and luminescence
studies of europium ions in lithium aluminium borophosphate glasses, Journal of Rare Earths,
32 (2014) 585-592.
M
D
TE
C EP
AC

18
 ACCEPTED MANUSCRIPT
Table 1. Comparison of crystal structure data and the goodness of fit for
Ba2La0.65Eu0.35V3O11 phosphor system with pure Ba2LaV3O11 host matrix.

Formula Ba2La0.65Eu0.35V3O11 Ba2LaV3O11

Formula weight (g mol−1) 746.9525 742.3834

Crystal system Monoclinic Monoclinic

PT
Space group symmetry P21/c (14) P21/c (14)

RI
a (Å) 12.5457(10) 12.645

b (Å) 7.8289(6) 7.82

SC
c (Å) 11.3547(10) 11.5160

U
α = γ (degree) AN 90 90

β (degree) 103.421 104.9

Volume (Å3) 1084.79(11) 1100.46

M

Z 4 4

Density (g cm−3) 4.57 4.48

D

Pearson code mP68 mP68

TE

Wyckoff Sequence e17 e17

C EP
AC

1
 ACCEPTED MANUSCRIPT
Table 2. Refined positions of all atoms in Ba2LaV3O11 host from geometry optimization
using first principal.

Atom Label Ion Type site Fill x/a y/b z/c

La1 La3+ 4e 1 0.00254 0.49537 0.29119

O1 O2− 4e 1 0.02294 0.2053 0.38541

PT
O2 O2− 4e 1 0.0233 0.28626 0.13365

RI
V1 V3+ 4e 1 0.10158 0.24996 0.0306

O3 O2− 4e 1 0.11789 0.03139 0.02925

SC
O4 O2− 4e 1 0.18662 0.56503 0.27755

O2−

U
O5 4e 1
AN 0.22095 0.35502 0.06295

Ba1 Ba2+ 4e 1 0.23954 0.72471 0.05672

V2 V5+ 4e 1 0.31491 0.016 0.33312

M

V3 V5+ 4e 1 0.31538 0.48348 0.32368

O6 O2− 4e 1 0.32639 0.24959 0.33465

D

Ba2 Ba2+ 4e 1 0.44551 0.25012 0.11104

TE

O7 O2− 4e 1 0.60796 0.05633 0.26632

EP

O8 O2− 4e 1 0.60916 0.43943 0.0352

O9 O2− 4e 1 0.62562 0.05528 0.037

C

O10 O2− 4e 1 0.63029 0.44161 0.27557

AC

O11 O2− 4e 1 0.81457 0.44008 0.18525

2
 ACCEPTED MANUSCRIPT
Table 3. CIE 1931 chromaticity index, photoluminescence lifetime, Hypersensitive ratio,
non-radiative rates and Quantum efficiencies for Ba2La1-xEuxV3O11 (x = 0.01–0.60)
nanophosphors.

Eu3+ Color coordinates Lifetime Hypersensitive Non- Quantum

concentration (x,y) at λex = 320 (ms) ratio R (2/1) radiative efficiency
(mol%) nm rates (s−1) (%)

PT
1.0 0.2410, 0.3024 1.32 1.2178 263.84 65.12

RI
5.0 0.3311, 0.3095 1.31 1.3910 270.04 64.59

10.0 0.4465, 0.3435 1.30 1.4589 275.94 64.09

SC
15.0 0.3585, 0.3191 1.29 1.5139 282.26 63.57

U
20.0 0.4067, 0.3324 1.28
AN 1.5370 288.30 63.08

25.0 0.4097, 0.3295 1.27 1.5509 288.41 63.07

30.0 0.4311, 0.3353 1.25 1.5523 305.94 61.68

M

35.0 0.4378, 0.3322 1.21 1.5548 328.72 59.97

40.0 0.4749, 0.3422 1.15 1.5609 370.39 57.08

D

45.0 0.4567, 0.3249 1.08 1.5614 430.66 53.35

TE

50.0 0.4994, 0.3317 0.98 1.5675 518.82 48.70

EP

55.0 0.5064, 0.3327 0.91 1.5842 601.49 45.02

60.0 0.5500, 0.3369 0.82 1.5856 726.72 40.40

C
AC

3
 ACCEPTED MANUSCRIPT

Table 4. The nature, wavenumbers and total radiative transition rates for 5D0→7FJ (J= 0, 1, 2,
3 and 4) emissions of Eu3+ in Ba2La0.65Eu0.35V3O11 nanophosphors.

Transition Type Wavenumber (cm-1) Total Radiative

Transition Rate (s−1)

PT
5
D0 → 7F0 Forbidden 18050.5415 29.45667
5
D0 → 7F1 Magnetic dipole 16920.4737 168.52004

RI
5
D0 → 7F2 Electric dipole 16129.0322 271.36819

SC
5
D0 → 7F3 Forbidden 15267.1755 17.78275
5
D0 → 7F4 Electric dipole 14184.3971 4.82187

U
5
D0 → 7F5 Forbidden – --
AN
5
D0 → 7F6 Electric dipole – --
M

Table 5. The Effective bandwidth (∆λeff), stimulated emission cross section (δe) and
fluorescence branching ratios (β) for 5D0→7FJ (J = 0, 1, 2, 3 and 4) emissions in
D

Ba2La0.65Eu0.35V3O11 nanophosphors.
TE

Transition Effective bandwidth Emission cross section β (%)

−22 2
(nm) (× 10 cm )
EP

5
D0 → 7F0 22.12 0.18 5.98774
C

5
D0 → 7F1 11.52 5.74 34.25556
AC

5
D0 → 7F2 11.95 10.80 55.1618
5
D0 → 7F3 17.26 0.61 3.61475
5
D0 → 7F4 1.22 3.41 0.98016
5
D0 → 7F5 – – –
5
D0 → 7F6 – – –

4
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
Fig. 1. XRD pattern of Ba2La1-xEuxV3O11 (x = 0−0.60) nanophosphor system along with the
M

standard JCPDS data of Ba2LaV3O11 host lattice.

D
TE
C EP
AC

Fig. 2. Rietveld refinement of Ba2La0.65Eu0.35V3O11 nanophosphors with χ2 = 1.770, Rwp (%)

= 12.82, Rp (%) = 10.20.

1
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D

Fig. 3. The unit cell view along a-axis and coordinative environment of various cations in
TE

Ba2LaV3O11 lattice after geometry optimization using first-principal.

C EP
AC

Fig. 4. Transmission electron micrograph of Ba2La0.65Eu0.35V3O11 nanophosphor powder.

2
 ACCEPTED MANUSCRIPT

PT
RI
U SC
Fig. 5. The relationship between absorption coefficient and photon-energy for Ba2LaV3O11
AN
host-matrix (corresponding diffuse reflection spectra in inset).
M
D
TE
C EP
AC

Fig. 6. Electronic band structure and the partial density of states for Ba2LaV3O11 lattice.

3
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
C EP
AC

Fig. 7. The element-wise contribution to the partial density of states (DOS) in Ba2LaV3O11
host lattice.

4
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
Fig. 8. Excitation spectrum of Ba2La1-xEuxV3O11 (x = 0.01−0.60) phosphor series monitored
M

at λem = 620 nm.

D
TE
C EP
AC

Fig. 9. Excitation spectrum of Ba2La0.65Eu0.35V3O11 nanophosphor studied at λem = 620 nm.

5
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
Fig. 10. Emission spectrum of Ba2La1-xEuxV3O11 (x = 0.01−0.60) phosphor at λex = 320 nm.
M
D
TE
C EP
AC

Fig. 11. Energy level diagram for Eu3+ doped Ba2LaV3O11 nanophosphor.

6
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
Fig. 12. Variation of photoluminescence emission intensity as function of dopant
M

concentration (in mole%) in Ba2LaV3O11:Eu3+ nanophosphor.

D
TE
C EP
AC

Fig. 13. Plot of log(I/x) as a function of log(x) in Ba2LaV3O11:Eu3+ nanophosphor.

7
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
Fig. 14. The luminescence decay curve for the emission of Ba2La1-xEuxV3O11 (x = 0.01−0.60)
nanophosphors at 620 nm (5D0→7F2).
M
D
TE
C EP
AC

Fig. 15. The variation of dielectric function with wavelength for Ba2LaV3O11 system.

8
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D

Fig. 16. The variation of (a) refractive index (b) extinction coefficient (c) optical conductivity
TE

and (d) loss function as a function of radiation-wavelength.

C EP
AC

Fig. 17. CIE chromaticity diagram for Ba2La0.65Eu0.35V3O11 crystals when excited at 320 nm.

9
 ACCEPTED MANUSCRIPT

Research Highlights
The research paper entitled “A Hybrid Treatment of Ba2LaV3O11:Eu3+ Nanophosphor
System: First-Principal and Experimental Investigations into Electronic, Crystal and the

PT
Optical Structure” is original research work and it highlights significant scopes in the field of
luminescent nanomaterials. Main highlight points are:

RI
• Judd-Ofelt parameters for Ba2La0.65Eu0.35V3O11 nanocrystals have been determined.
• Atomic positions and optical properties for Ba2LaV3O11 are calculated from DFT.

SC
• Lattice parameters for Ba2La0.65Eu0.35V3O11 have been found from Rietveld method.
• Optical band-gap for Ba2LaV3O11 host is obtained theoretically and experimentally.

U
• Quantum-efficiency and emission cross-sections are obtained for 5D0 state.
AN
M
D
TE
C EP
AC