Chemical Engineering Journal 337 (2018) 91–100

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Facile synthesis of bifunctional Eu3+-activated NaBiF4 red-emitting T

nanoparticles for simultaneous white light-emitting diodes and field
emission displays
⁎ ⁎
Peng Dua, Xiaoyong Huangb, , Jae Su Yua,
a
Department of Electronic Engineering, Kyung Hee University, Yongin-si, Gyeonggi-do 17104, Republic of Korea
b
Key Lab of Advanced Transducers and Intelligent Control System, Ministry of Education and Shanxi Province, College of Physics and Optoelectronics, Taiyuan University
of Technology, Taiyuan 030024, PR China

H I G H L I G H T S G RA P H I C A L AB S T R A C T

• thesized
NaBiF :Eu
4
3+
nanoparticles were syn-
by an ultra-fast method.
EL spectrum of the fabricated WLEDs device. Inset illustrates the schematic diagram for the fabrication of LED
device. Luminescent images of the prepared WLEDs device without and with input current.
• UV excitation induced bright red
emissions with quantum efficiency of
73.1%.
• They possessed good thermal stability
with activation energy of 0.237 eV.
• The cathodoluminescence properties
of the nanoparticles were also studied.
• LED devices were fabricated by using
the nanoparticles and UV LED chips.

A R T I C L E I N F O A B S T R A C T

Keywords: A series of novel Eu3+-activated NaBiF4 nanoparticles were synthesized by an ultra-fast chemical precipitate
Luminescence method at room temperature. Under the excitation of 394 nm, all the compounds emitted glaring red emissions
Nanoparticles originating from the intra-4f transitions of Eu3+ ions. The optimal doping concentration was found to be 40 mol
WLEDs % and the concentration quenching mechanism was dominated by dipole–dipole interaction. The temperature-
Phosphors
dependent photoluminescence emission spectra revealed that the resultant nanoparticles possessed admirable
Eu3+
NaBiF4
thermal stability with an activation energy of 0.237 eV. The internal quantum efficiency of the synthesized
nanoparticles was estimated to be as high as 73.1%. Furthermore, the optical transition parameters of Eu3+ ions
were calculated using a facile method based on the Judd-Ofelt theory to explore the local structure environment
around the Eu3+ ions in the NaBiF4 host lattice. Additionally, the packaged light-emitting diode (LED) device,
which was composed of a near-ultraviolet LED chip, synthesized nanoparticles and commercial blue-emitting/
green-emitting phosphors, exhibited brightly white light with high color rendering index of 88.2 and proper
correlated color temperature of 6851 K. Ultimately, the studied nanoparticles also had splendid cath-
odoluminescence properties. These results suggest that the Eu3+-activated NaBiF4 nanoparticles were promising
bifunctional materials for simultaneous white LEDs and field emission displays.

⁎
Corresponding authors.
E-mail addresses: huangxy04@126.com (X. Huang), jsyu@khu.ac.kr (J.S. Yu).

https://doi.org/10.1016/j.cej.2017.12.063
Received 20 October 2017; Received in revised form 30 November 2017; Accepted 13 December 2017
Available online 14 December 2017
1385-8947/ © 2017 Elsevier B.V. All rights reserved.
P. Du et al.
1. Introduction
Recently, considerable interest in rare-earth ions activated in-
organic materials has been gained because of their practical applic-
ability in various fields, such as plant growth, medical diagnosis, clean
energy, solid-state lighting, optical thermometers, field emission dis-
plays (FEDs), and so on [1–11]. Especially, with the increasing issues of
environmental degradation and energy consumption, the white light-
emitting diodes (WLEDs), which are regarded as a promising candidate
to replace these traditional bulbs and treated as the next-generation
lighting source, have been extensively researched owing to their envi-
able characteristics of low-energy consumption, high luminescence ef-
ficiency, long working lifetime and environmentally friendly feature
[12–14]. Currently, the commercial WLEDs, which consist of an InGaN-
based blue LED chip and yellow-emitting phosphors (Y3Al5O12:Ce3+),
suffer from low color rending index (CRI < 80) and high correlated
color temperature (CCT > 7000 K) due to the absence of red-emitting
component in the luminescence spectrum [15,16]. For the purpose of
solving these aforementioned disadvantages, two available approaches
were proposed: one is utilizing the near-violet (NUV) LED chip to pump
the hybrid tricolor (blue, green and red) phosphors, and the other is the
combination of a blue LED chip with green-emitting and red-emitting
phosphors [17,18]. As demonstrated above, a highly efficient red-
emitting phosphor that can be excited by NUV or blue light is very
crucial to these two strategies. Up to date, some red-emitting phos-
phors, such as Sr[LiAl3N4]:Eu2+, Ca[LiAl3N4]:Eu2+, SrLiAl3N4:Eu2+
and LuxSr2-xSiNxO4-x:Eu2+, were developed and exhibited potential
applications in solid-state lighting [19–22]. Nevertheless, to prepare
these Eu2+ ions-based red-emitting phosphors, some harsh reaction
conditions including high sintering temperature, reduced atmosphere
and long reaction time are required, resulting in high cost and serious
environmental problems. Therefore, developing a novel red-emitting
phosphor that can be achieved at low temperature and short reaction
time is urgent.
Apart from the Eu2+ ion, Eu3+ ion is also regarded as a promising
red-emitting activator owing to its featured red emission at around
616 nm rising from the 5D0 → 7F2 transition [23–25]. It was revealed
that the Eu3+-activated inorganic materials can emit bright red emis-
sion under UV light excitation and exhibit promising applications in
indoor illumination [26,27]. As is well-known, the luminescence effi-
ciency of the rare-earth ions activated phosphors is strongly dependent
on the phonon energy and energy gap of the host material [28]. Gen-
erally, low phonon energy leads to high possibility of radiative transi-
tion as well as high luminescence efficiency [29,30]. Thus, choosing an
appropriate luminescent host material is a feasible route to realize the
efficient phosphors based on rare-earth ions. Nowadays, several types
of inorganic materials, such as molybdates, silicates, phosphates,
fluorides, borates and oxides, were successfully developed for designing
phosphors [31–37]. Particularly, much attention has been focused on
fluoride nanoparticles, which possess the general chemical formula of
NaMF4 (M = metal ion), due to their low phonon energy (∼350 cm−1).
It was reported that the NaCeF4:Eu3+ nanorods, which were prepared
by a hydrothermal method at 190 °C for 24 h, can emit dazzling orange-
red emissions [38]. Dong et al. pointed out that the NaGdF4:Eu3+ na-
nofibers, which were synthesized by means of an electrospinning
technique followed by a calcined process at 600 °C for 4 h, can exhibit
color-tunable emissions and were suitable for indoor illumination [39].
Clearly, both high synthetic temperature and long reaction time are
required to fabricate these rare-earth ions activated fluoride nano-
particles. Hence, it is very necessary to develop a fast and ecofriendly
technique for preparing the rare-earth ions activated fluoride crystals at
low temperature.
NaBiF4, as a crucial part of the fluorides, was found to be an ex-
cellent luminescent host material for upconversion emission and the
Er3+/Yb3+-codoped NaBiF4 nanoparticles had potential applications in
non-contact thermometry [40,41]. Although the upconversion emission
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Chemical Engineering Journal 337 (2018) 91–100
performance of the NaBiF4 nanoparticles has been systematically stu-
died, to best of our knowledge, the investigation on its photo-
luminescence (PL) and cathodoluminescence (CL) has not been carried
out yet. In this present work, the NaBiF4 was selected as the lumines-
cent host lattice and a series of Eu3+-activated NaBiF4 nanoparticles
were prepared by a facile and ultra-fast method at room temperature.
The phase composition, microstructure, thermal stability, quantum ef-
ficiency and PL/CL properties of the resultant nanoparticles were in-
vestigated in detail. Furthermore, the local crystal environment sur-
rounding the Eu3+ ions in the NaBiF4 host lattice was theoretically
analyzed utilizing the Judd-Ofelt theory. In addition, to explore the
practical application of the final compounds in solid-state lighting, a
WLED device was fabricated by integrating an NUV LED chip and a
mixture of the studied nanoparticles and commercial blue-emitting/
green-emitting phosphors.
2. Experimental process
2.1. Synthesis of Eu3+-activated NaBiF4 nanoparticles
The bifunctional NaBi1−xF4:xEu3+ (NaBiF4:xEu3+; x = 0.1, 0.2,
0.3, 0.4, 0.5, 0.6 and 0.7) nanoparticles were synthesized by a facile
route at room temperature. The high-purity powders of NaNO3, Bi
(NO3)3·5H2O, EuCl3 and NH4F, which were purchased from Sigma-
Aldrich Co., were applied as the starting materials to prepare the
NaBiF4:xEu3+ nanoparticles. Firstly, on the basis of the stoichiometric
ratio, solution I was prepared by dissolving 2 mmol of NaNO3, (1 − x)
mmol of Bi(NO3)3·5H2O and x mmol of EuCl3 into 10 ml of ethylene
glycol. Meanwhile, solution II was prepared by dissolving 5.5 mmol of
NH4F into 20 ml of ethylene glycol. Subsequently, the solution I was
gradually added to the solution II and this mixture was stirred for 1 min
at room temperature. Ultimately, the final compounds were collected
by means of centrifugation, washed with ethanol and de-ionized water
three times to remove the remained reagent, and then dried at 80 °C for
6 h in air.
2.2. Characterization of the resultant compounds
X-ray diffraction (XRD) measurement was carried out by means of
Bruker D8 Advance diffractometer with Cu Kα radiation
(λ = 0.15406 nm) and the recorded XRD data were dealt with JADE 5.0
software. The morphological behaviors of the final compounds were
examined by utilizing a field-emission scanning electron microscope
(FE-SEM; LEO SUPRA 5) equipped with an energy dispersive X-ray
(EDX) spectrometer and a transmission electron microscope (TEM)
(JEM-2100F, JEOL). The fluorescence spectrometer (Scinco FluroMate
FS5) equipped with Xe arc lamp was used to measure the PL excitation
and emission spectra. The temperature ranging from 303 to 483 K was
realized using a thermocouple (NOVA ST540). The decay curves of the
studied samples were measured by using an Edinburgh FS5 spectro-
fluorometer. With the help of Edinburgh FS5 spectrofluorometer
equipped with an integrating sphere coated with barium sulfate, the
internal quantum efficiency of the prepared samples was evaluated. The
multi-channel spectroradiometer (OL 770) was employed to detect the
electroluminescence (EL) properties of the fabricated LED devices. The
Gatan (UK) MonoCL3 system equipped with the SEM (Hitachi S-4300
SE) was employed to record the room-temperature CL spectra.
3. Results and discussion
3.1. Phase structure and morphology of NaBiF4:xEu3+ nanoparticles
The XRD patterns of the NaBiF4:xEu3+ nanoparticles were analyzed
to identify their phase composition. From the obtained XRD patterns
(Fig. 1(a)), it is evident that the detected diffraction peaks were con-
sistent well with the standard hexagonal NaBiF4 (JCPDS#41-0796)
P. Du et al.
Fig. 1. (a) XRD patterns of Eu3+-activated NaBiF4 nanoparticles sintered at room tem-
perature. (b) Magnified XRD patterns from 39 to 45°. (c) Rietveld XRD refinement for the
NaBiF4:0.4Eu3+ nanoparticles. (d) Crystal structure of NaBiF4.
without observing any impurity peaks from the secondary phase. This
implies that all the synthesized samples possessed pure single hex-
agonal phase and the Eu3+ ions were successfully incorporated into the
NaBiF4 host lattice. Furthermore, owing to the inconsistent ionic radii
between the Bi3+ and Eu3+ ions, the diffraction peaks gradually shifted
to the larger angle with increasing the Eu3+ ion concentration from 10
to 70 mol%, as shown in Fig. 1(b), resulting in the shrinkage of the
lattice. With the help of the General Structure Analysis System, the
Rietveld XRD refinement was performed to verify the crystal symmetry
and space group of the Eu3+-activated NaBiF4 nanoparticles and the
obtained result is depicted in Fig. 1(c). Herein, the NaEuF4 was em-
ployed as the structure model owing to its isostructural nature to
NaBiF4. As disclosed, the detected and calculated diffraction patterns
were in accordance well with each other, revealing that the studied
compounds exhibited pure hexagonal phase with the space group of P-
3(1 4 7). The values of Rp, Rwp and χ2 were demonstrated to be 4.62%,
5.79% and 1.71, respectively (see Table S1). Additionally, in compar-
ison with the pure NaBiF4 host material, the NaBiF4:0.4Eu3+ nano-
particles exhibited relatively smaller lattice parameters of
a = b = 6.05892 Å, c = 3.74217 Å and V = 118.97 Å3, as listed in
Table S1, further confirming that the Eu3+ ions were successfully doped
into the NaBiF4 host lattice without inducing the variation of the host
phase structure. Using the Diamond software, the unit cell crystal
structure of NaBiF4 was modeled and the corresponding result was
demonstrated, as can be seen in Fig. 1(d).
The microstructure and particle size of the final compounds were
evaluated by the FE-SEM and TEM images. The FE-SEM image shown in
Fig. 2(a) displayed that the resultant compounds were composed of
uniformly nanoparticles and the particle size was distributed in the
range of 50–100 nm, which was further confirmed by the TEM image
(see Fig. 2(b)). As disclosed in Fig. 2(c), the high-resolution TEM (HR-
TEM) image consisted of clear lattice fringes with the d-spacing of
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Chemical Engineering Journal 337 (2018) 91–100
around 3.07 Å corresponding to the distance between the adjacent
(1 0 1) planes of NaBiF4 (JCPDS#41-0796). Moreover, the selective
area electron diffraction (SAED) pattern presented in Fig. 2(d) exhibited
clear rings which are associated with the (0 0 2) and (1 1 1) planes of
NaBiF4. In addition, the elemental mapping results demonstrated that
the elements in the Eu3+-activated NaBiF4 nanoparticles were homo-
genously distributed over the whole particles, as illustrated in Fig. 2(e).
Ultimately, the observation of Na, Bi, F and Eu peaks in the EDX
spectrum further implied the formation of Eu3+-activated NaBiF4 na-
noparticles (see Fig. 2(f)).
3.2. Room-temperature luminescent behaviors of NaBiF4:xEu3+
nanoparticles
Fig. 3(a) shows the typical PL excitation spectrum of the Na-
BiF4:0.4Eu3+ nanoparticles monitored at 616 nm. As presented, the PL
excitation spectrum was made up of a series of sharp peaks located at
around 316, 360, 373, 380, 394, 415 and 463 nm, which are assigned to
the 7F0 → 5H6, 7F0 → 5D4, 7F0 → 5G2, 7F0 → 5G3, 7F0 → 5L6, 7F0 → 5D3
and 7F0 → 5D2 transitions of Eu3+ ions, respectively [24,42]. In com-
parison with other excitation peaks, the excitation band at 394 nm,
which matches well with the emission wavelength of a commercial
NUV chip, exhibited the strongest intensity, implying that the prepared
nanoparticles can be efficiently pumped by the NUV light. Under the
excitation of 394 nm, the PL emission spectrum of the NaBiF4:0.4Eu3+
nanoparticles was recorded. From Fig. 3(a), it is obvious that the red
emission (∼616 nm) corresponding to the 5D0 → 7F2 transition of Eu3+
ions took the domination in the PL emission spectrum. Apart from the
intense red emission, three relatively weak emissions located at about
591, 649 and 696 nm were also detected in the PL emission spectrum,
which are associated with the 5D0 → 7F1, 5D0 → 7F3 and 5D0 → 7F4
transitions of Eu3+ ions, respectively [23,43]. As is known, the yellow
(5D0 → 7F1) and red (5D0 → 7F2) emissions are two characteristic
emissions of Eu3+ ions. Specially, the 5D0 → 7F2 transition (ΔJ = 2)
belongs to the hypersensitive electric dipole transition and its emission
intensity is greatly dependent on the crystal field surrounding the Eu3+
ions, while the 5D0 → 7F1 transition (ΔJ = 1) is regarded as the mag-
netic transition which is barely affected by the surrounding chemical
environment [16,27]. Normally, the red emission prevails in the lu-
minescent spectrum when the Eu3+ ions occupy the low symmetry sites
without an inversion center, whereas the yellow emission becomes the
strongest one when the Eu3+ ions are situated at the high symmetry
sites [14,24]. As demonstrated in Fig. 3(a), the 5D0 → 7F2 transition
exhibited much stronger intensity compared to the 5D0 → 7F1 transition,
revealing that the Eu3+ ions populated the low symmetry sites in the
NaBiF4 host lattice. For the purpose of comprehending the generation of
visible emissions in the NaBiF4:xEu3+ nanoparticles, the simplified
energy level diagram of the Eu3+ ions was modeled, as displayed in Fig.
S1. Briefly, under the irradiation of 394 nm light, the electrons popu-
lated at the ground state of 7F0 were excited to the 5L6 state. After that,
the non-radiative (NR) transition took place and the 5D0 excited state
was populated. Ultimately, the featured emissions of Eu3+ ions were
generated by means of the 5D0 → 7FJ (J = 1, 2, 3, 4) radiative transi-
tions (see Fig. S1).
Generally, the luminescent properties of the rare-earth ions-based
phosphors are largely dependent on the concentration of activators. To
figure out the optimal doping concentration of Eu3+ ions in the NaBiF4
host material, a series of NaBiF4:xEu3+ nanoparticles with various
Eu3+ ion concentrations were synthesized and their luminescent per-
formances were systematically studied. Fig. 3(b) illustrates the room-
temperature PL emission spectra of NaBiF4:xEu3+ nanoparticles excited
at 394 nm. As demonstrated, under the excitation of NUV light, all the
studied samples exhibited the featured emissions of Eu3+ ions and the
PL emission spectrum profiles were hardly varied with elevating the
concentration of activators except the emission intensity. It can be seen
from Fig. 3(c) that the emission intensity exhibited an upward tendency
P. Du et al.
Fig. 2. (a) FE-SEM image, (b) TEM image, (c) HR-TEM image, (d) SAED pattern, (e) elemental mapping and (f) EDX spectrum of the NaBiF4:0.4Eu3+ nanoparticles.
with the increase of Eu3+ ion concentration, achieving its optimum
value when x = 0.4. Nevertheless, the emission intensity deceased
markedly when the doping concentration was over 40 mol%, which is
ascribed to the concentration quenching effect. To better understand
the involved concentration quenching mechanism, the relation between
the emission intensity and doping concentration was analyzed using the
following expression [44,45]:
d/s
s d A (x −x i )2 + (y−yi )2
I ∝ α1 − s / dΓ ⎛1 + ⎞ and α = x Γ ⎛1− ⎞ ⎡X0 ⎜⎛1 + ⎟⎞ ⎤ , Color purity =
⎝ d⎠ ⎝ s ⎠⎢⎣ ⎝ γ ⎠⎥⎦
where I and x represent the emission intensity and dopant concentra-
tion, respectively, γ and d are intrinsic transition possibility of donor
and dimension of compounds, respectively, s = 6, 8 and 10 is associated
with dipole–dipole, dipole-quadrupole and quadrupole–quadrupole in-
teractions, respectively, and A and X0 are coefficients. In present work,
the d value was 3 since the energy transfer among Eu3+ ions occurred
in the inside of particles. As a consequence, the following equation was
achieved:
I s
log ⎛ ⎞ = − log(x ) + logf .
⎝x⎠ d (2)
Here, f is constant and is independent of doping concentration. In order
to estimate the s value, the plot of log(I/x) versus log(x) is depicted in
Fig. 3(d). Clearly, the experimental data can be linearly fitted with a
slope of around −2.02. As a consequence, s was determined to be 6.06
approaching to 6, demonstrating that the dipole–dipole interaction took
the domination in the concentration quenching mechanism of Eu3+
ions in the NaBiF4:xEu3+ nanoparticles.
3.3. Chromaticity and decay curves of studied nanoparticles
On the basis of the recorded PL emission spectrum, the Commission
International de I’Eclairage (CIE) chromaticity of the resultant com-
pounds with the optimal doping concentration was evaluated and the
corresponding result is illustrated in Fig. 3(e). As presented in Fig. 3(e),
the color coordinate of the NaBiF4:0.4Eu3+ nanoparticles was (0.644,
0.356), which is located in the red edge region. Clearly, the calculated
Chemical Engineering Journal 337 (2018) 91–100
color coordinate was not only very close to the ideal red light (0.670,
0.330) but also superior to the Y2O2S:Eu3+ (0.622, 0.351) commercial
red-emitting phosphors. Moreover, under the excitation of 394 nm, the
prepared nanoparticles emitted glaring visible red emission (see inset of
Fig. 3(e)). To get a deep insight into the chromatic behaviors of the
obtained red emission, its color purity was calculated with the help of
the following formula [24,46]:
× 100%.
(1) (x d−x i )2 + (yd −yi )2 (3)
In the expression, the (x, y), (xi, yi,) and (xd, yd) refer to the CIE co-
ordinates of the synthesized compounds, white illumination and dom-
inate wavelength, respectively. In this present work, (x, y) = (0.644,
0.356), (xi, yi,) = (0.310, 0.316) and (xd, yd) = (0.682, 0.317). As a
result, the color purity of the achieved red emission was demonstrated
to be about 90.4%, which is superior to the previous developed red-
emitting phosphors, such as SrMoO4:Eu3+ (color purity: 85.8%) and
Ca0.5Sr0.5MoO4:Eu3+ (color purity: 89.5%) [47,48]. In addition, from
the comparison emission spectra between the NaBiF4:0.4Eu3+ nano-
particles and commercial Y2O3:Eu3+ red-emitting phosphors (Fig. S2),
one can obtain that the emission intensity of the NaBiF4:0.4Eu3+ na-
noparticles was almost 2.5 times higher than that of the commercial
Y2O3:Eu3+ red-emitting phosphors, indicating that the NaBiF4:xEu3+
nanoparticles possessed superior PL properties. Thus, the Eu3+-acti-
vated NaBiF4 nanoparticles with good color coordinate, high color
purity and admirable PL performance are useful for indoor illumination
as a red-emitting phosphor.
In order to expound the involved luminescent dynamic, the room-
temperature luminescence decay curves of the studied samples were
examined. The typical decay curves of the NaBiF4:xEu3+ nanoparticles
with different Eu3+ ion concentrations (λex = 394, λem = 616 nm) are
depicted in Fig. 4(a). As disclosed in Fig. 4(a), the detected decay curves
can be well fitted to a single exponential decay model, as shown below:
I (t ) = I0 + Aexp(−t / τ ), (4)
where I(t) and I0 stand for the emission intensities at times t and t = 0,
respectively, A refers to the constant and τ is associated with the
94
P. Du et al.
Fig. 3. (a) PL excitation and emission spectra of the NaBiF4:0.4Eu3+ nanoparticles. (b) PL emission spectra of the Eu3+-activated NaBiF4 nanoparticles at different Eu3+ ion con-
centrations. (c) PL emission intensity as a function of Eu3+ ion concentration. (d) Plot of log(I/x) vs. log(x) for the NaBiF4:xEu3+ nanoparticles. (e) CIE chromaticity diagram of the
NaBiF4:0.4Eu3+ nanoparticles and ideal red light. The inset of (e) presents the luminescent image upon 396 nm excitation. (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)
lifetime. On the basis of the fitting results, the decay times of the Eu3+
ions in the NaBiF4:xEu3+ nanoparticles were demonstrated to be 4.96,
4.75, 3.24, 2.22 and 1.61 ms when x = 0.1, 0.2, 0.4, 0.6 and 0.7, re-
spectively (see Fig. 4(a)). Obviously, with increasing the Eu3+ ion
concentration, the lifetime deceased gradually, further verifying the
existence of concentration quenching in the NaBiF4:xEu3+ nano-
particles [4].
3.4. Judd-Ofelt analysis and optical transition parameters
From the recorded PL emission spectrum, it is observable that the
Eu3+ ions occupied the low symmetry sites with non-inversion center in
the NaBiF4 host lattice. For the sake of getting a deep insight into the
local structure environment around the Eu3+ ions in the NaBiF4 host
lattice, a theoretical calculation based on the Judd-Ofelt theory was
performed to estimate the intensity parameters (Ωλ, λ = 2, 4, 6). Since
the emission profiles were barely affected by the Eu3+ ion concentra-
tion (see Fig. 3(b)), the NaBiF4:0.4Eu3+ nanoparticles, which exhibited
the strongest emission intensity, were selected to study the optical
transition behaviors of Eu3+ ions. According to previous literatures, the
relation between the total relative integrated emission intensity (I) and
total radiative transition rate can be defined as [49,50]:
I= ∑ I 7FJ = α ∑ A 7FJ ,
J = 1,2,3,4 J = 1,2,3,4
Chemical Engineering Journal 337 (2018) 91–100
where I 7FJ and A 7FJ are relative integrated emission intensity and ra-
diative transition rate for the 5D0 → 7FJ transition, respectively, and α is
the constant. Meanwhile, the total radiative transition rate is reciprocal
to the lifetime (τ) which can be expressed as:
1
∑ A 7FJ = .
τ (6)
J = 1,2,3,4
3+
As demonstrated above, the lifetime of the NaBiF4:0.4Eu nano-
particles was 3.24 ms. Thus, with the help of Eqs. (5) and (6), the value
of α was determined to be about 0.00545. Accordingly, the radiative
transition rate for each 5D0 → 7FJ transition, which was based on the
relation of I 7FJ = αA 7AJ , was evaluated and the corresponding results are
listed in Table S2.
On the other hand, as declared above, the 5D0 → 7F1 transition of
Eu3+ ions pertains to the magnetic transition which is free from the
crystal field and its radiative transition rate can be expressed as follows
according to the Judd-Ofelt theory [51,52]:
64π 4v 3
AJMD
→J′ = n3SMD.
3h (2J + 1) (7)
In this formula, v stands for the center wavenumber of the J → J’
transition, h refers to the Planck coefficient and its value is
6.626 × 10−27 erg s, n presents the refractive index of the studied
(5) samples and SMD denotes the magnetic dipole strength with a fixed
95
P. Du et al.
Fig. 4. (a) Representative luminescence decay curves of the NaBiF4:xEu3+ (x = 0.1, 0.2, 0.4, 0.6, and 0.8) nanoparticles. (b) Normalized emission intensity as a function of temperature.
(c) Plot of ln(I0/I − 1) vs. 1/kT for the NaBiF4:0.4Eu3+ nanoparticles.
value of 7.83 × 10−42. As a consequence, the refractive index of the
NaBiF4:0.4Eu3+ nanoparticles was estimated to be around 1.87. Ad-
ditionally, from the Judd-Ofelt theory, the radiative transition rates of
the electric dipole transitions of 5D0 → 7FJ (J = 2, 4 and 6) can be de-
fined as:
64π 4v 3e 2 n (n2 + 2)2
AJED
→J′ = Ωλ 〈ψJ ‖U λ‖ ψ′J ′〉2 .
3h (2J + 1) 9 (8)
Here, e is the elementary charge (4.8 × 10−10 esu) and 〈ψJ ‖U λ‖ ψ′J ′〉2
denotes the reduced matrix element for the J → J′ electric dipole tran-
sitions, whose values are 0.0032 and 0.0023, respectively, when J′ = 2
and 4. Since the 5D0 → 7F6 transition was not detected in the PL emis-
sion spectrum, it is difficult to calculate the Ω6 value. On the basis of Eq.
(7), the values of Ω2 and Ω4 were found to be 2.96 × 10−20 and
1.36 × 10−20 cm−2, respectively. Generally, Ω2 is associated with the
crystal field and large Ω2 corresponds to the low symmetry site of the
rare-earth ions, whereas Ω4 is insensitive to the surrounding environ-
ment and is related to the bulk property as well as the rigidity of the
luminescent host lattice [47]. Since the calculated Ω2 is much larger
than the Ω4, it reasonable for us to consider that the site symmetry
occupied by the Eu3+ ions in NaBiF4 host lattice was low, which is in
accordance well with the result deduced from the PL emission spec-
trum. Ultimately, the fluorescence branch ratios for the 5D0 → 7FJ
transitions were evaluated by the following expression:
AJ → J ′
β= .
∑J = 1,2,3,4 AJ → J ′
With the help of Eq. (9), the β values for the 5D0 → 7FJ transitions were
calculated and the corresponding results are listed in Table S2. It is
evident that the electric dipole transition took the domination and the
5
D0 → 7F2 transition exhibited the highest value, further implying that
the Eu3+-activated NaBiF4 nanoparticles were suitable for indoor
lighting as a red-emitting phosphor.
Chemical Engineering Journal 337 (2018) 91–100
3.5. Thermal stability and quantum efficiency of Eu3+-activated NaBiF4
nanoparticles
Since the thermal stability has a distinct influence on the optical
properties, such as working lifetime, CRI value and light output, of the
fabricated LED devices, the thermal quenching behavior of the studied
samples should be investigated to explore their feasibility for WLED
applications. Under the excitation of 394 nm, the temperature-depen-
dent PL emission spectra of the NaBiF4:0.4Eu3+ nanoparticles in the
temperature range of 303–483 K were measured (Fig. S3). As disclosed,
with elevating the temperature from 303 to 483 K, the positions of the
emission bands were scarcely varied, which helps to achieve the stable
emission color at high temperature. On the contrary, the emission in-
tensity became weakened gradually due to the thermal quenching ef-
fect. Nevertheless, the emission intensity at 423 K still remained about
68.9% of its initial value at room temperature, as presented in Fig. 4(b),
revealing that the resultant nanoparticles possessed good thermal sta-
bility and were suitable for high-power WLED applications. To under-
stand the temperature-dependent thermal quenching behavior, the ac-
tivation energy was studied by means of following formula [53,54]:
I ΔE
ln ⎛ 0 −1⎞ = lnA− ,
⎝I ⎠ kT (10)
where I0 stands for initial emission intensity, I corresponds to the
emission intensity at various temperatures, A is the coefficient, ΔE de-
notes the activation energy, k is the Boltzmann coefficient with a fixed
(9) value of 8.629 × 10−5 eV/K and T is the temperature. Fig. 4(c) shows
the plot of ln(I0/I − 1) versus 1/kT for the NaBiF4:0.4Eu3+ nano-
particles. As demonstrated, the experimental data were linearly fitted
with a slope of approximately −0.237, suggesting that the activation
energy for thermal quenching of the Eu3+ ions in the NaBiF4 nano-
particles is 0.237 eV. Note that the estimated activation energy is higher
than the previous reports, such as Li3Gd3Te2O12:Eu3+ (0.22 eV),
BaZrGe3O9:Eu3+ (0.175 eV) and K2Gd(PO4)(WO4):Eu3+ (0.19 eV)
96
P. Du et al.
Fig. 5. PL excitation and emission spectra of the NaBiF4:0.4Eu3+ nanoparticles and re-
ference sample, measured by using a spectrofluorometer attached with an integrating
sphere for quantum efficiency measurement. Inset illustrates the zoomed emission spectra
in the wavelength range of 500–750 nm.
[55–57], clarifying its good thermal stability and its potential applica-
tion in high-power WLEDs.
Apart from the above characteristics, quantum efficiency is another
vital parameter to identify the applicability of the resultant compounds
for solid-state lighting. Under 394 nm excitation, the internal quantum
efficiency of the NaBiF4:0.4Eu3+ nanoparticles was measured. The PL
excitation and emission spectra of the reference sample and
NaBiF4:0.4Eu3+ nanoparticles are shown in Fig. 5. The internal
quantum efficiency of the synthesized nanoparticles was calculated by
using the following expression:
∫ LS
η= , characteristic emissions of Eu3+ ions. Additionally, a weak emission
∫ ER− ∫ ES
where η is the internal quantum efficiency, LS shows the PL emission
spectrum of the studied samples, ER and ES present the excitation
spectra of the excitation light with and without synthesized compounds,
respectively. Hence, according to the detected excitation and emission
spectra (see Fig. 5), the internal quantum efficiency of the Na-
BiF4:0.4Eu3+ nanoparticles was determined to be as high as 73.1%,
which is much higher than the commercial Y2O3:Eu3+ (η = 12%) red-
Chemical Engineering Journal 337 (2018) 91–100
emitting phosphors and recently developed Eu3+-activated red-emit-
ting phosphors, such as Sr2La0.8SbO6:Eu3+ (48.3%), Y2WO6:Eu3+
(63.1%) and LiGd(WO4)2:Eu3+ (69%) [43,58,59], indicating that the
Eu3+-activated NaBiF4 nanoparticles are a promising red-emitting
phosphor for indoor illumination.
3.6. EL performance of fabricated LED device
For the purpose of evaluating the practical feasibility of the syn-
thesized samples for solid-state lighting, a red-emitting LED device was
prepared by integrating an InGaN NUV chip (∼385 nm) and the
NaBiF4:0.4Eu3+ nanoparticles. Under the forward bias current of
100 mA, the EL spectrum of the fabricated red-emitting LED device was
recorded as shown in Fig. 6(a). Clearly, the EL spectrum was composed
of five emission peaks. The emission band located at approximately
385 nm was assigned to the center wavelength of the NUV chip, while
the other four peaks centered at 591, 616, 649 and 696 nm are related
to the 5D0 → 7F1, 5D0 → 7F2, 5D0 → 7F3 and 5D0 → 7F4 transitions of
Eu3+ ions, respectively. Moreover, the prepared LED device can emit
brightly red emission that can be seen by the naked eye (see
Fig. 6(b)–(c)), revealing that the Eu3+-activated NaBiF4 nanoparticles
are promising red-emitting phosphors for WLEDs. To further verify the
applicability of the resultant compounds for indoor illumination ap-
plication, a WLED device was fabricated by coating the blended Na-
BiF4:0.4Eu3+ nanoparticles and commercial BaMgAl10O17:Eu2+
(BAM:Eu2+) blue-emitting phosphors/(Ba,Sr)2SiO4:Eu2+ (BaSrSi:Eu2+)
green-emitting phosphors onto the NUV chip. The EL spectrum of the
packaged WLED device driven by a forward bias current of 100 mA is
shown in Fig. 7(a). As disclosed, the recorded EL spectrum was mainly
made up of two broad bands and several narrow peaks. Specially, these
two broad bands located in the blue and green region were associated
with the emissions of commercial BAM:Eu2+ blue-emitting phosphors
and BaSrSi:Eu2+ green-emitting phosphors, respectively, whereas these
sharp peaks ranging from 575 to 750 nm were associated with the
(11)
band centered at around 385 nm was related to the center wavelength
of the NUV chip. Fully packaged WLED device is presented in Fig. 7(b).
Under a forward bias current of 100 mA, the developed LED device
exhibited dazzling white light (see Fig. 7(c)). The CRI and CCT values of
the fabricated WLED device were found to be 88.2 and 6851 K, re-
spectively, when the forward bias current was 100 mA. These results
indicate that the Eu3+-activated NaBiF4 nanoparticles are suitable for
WLEDs as a red-emitting phosphor.
Fig. 6. (a) EL spectrum of the fabricated red-emitting LED
device under a forward bias current of 100 mA. (b) Fully
packaged LED device. (c) Luminescent image of the fabri-
cated LED device under a bias current of 100 mA. (For in-
terpretation of the references to color in this figure legend,
the reader is referred to the web version of this article.)
97
P. Du et al.
3.7. CL behaviors of Eu3+-activated NaBiF4 nanoparticles
In continuation to the PL analysis, the CL performances of the Eu3+-
activated NaBiF4 nanoparticles as a function of accelerating voltage and
filament current were studied to evaluate their availability for FED
applications as a red-emitting phosphor. The representative CL spec-
trum of the NaBiF4:0.4Eu3+ nanoparticles, which was recorded at an
accelerating voltage of 8 kV and a filament current of 71 μA, is depicted
in Fig. 8(a). As presented, the CL spectrum consisted of three narrow
emission peaks at about 591 nm (5D0 → 7F1), 616 nm (5D0 → 7F2) and
696 nm (5D0 → 7F4) corresponding to the characteristic emissions of
Eu3+ ions and the red emission took the domination in the CL spec-
trum, which is well consistent with the PL emission spectrum (see
Fig. 3(b)). It is noticeable that the CL intensity is strongly dependent on
the accelerating voltage and filament current. When the filament cur-
rent was fixed at 71 μA, a gradual enhancement in the CL intensity was
observed with elevating the accelerating voltage from 5 to 8 kV, as
described in Fig. 8(b). Similarly, with increasing the filament current
98
Chemical Engineering Journal 337 (2018) 91–100
Fig. 7. (a) EL spectrum of the fabricated WLED device
consisting of NUV chip, NaBiF4:0.4Eu3+ nanoparticles and
commercial blue emitting/green emitting phosphors. (b)
Packaged WLED device. (c) Luminescent image of the pre-
pared WLED device under a forward basis current of
100 mA. (For interpretation of the references to color in this
figure legend, the reader is referred to the web version of
this article.)
Fig. 8. (a) CL spectrum of the NaBiF4:0.4Eu3+
nanoparticles. CL emission intensity as a function
of (b) accelerating voltage and (c) filament cur-
rent.
from 51 to 71 μA, the CL intensity was also greatly enhanced when the
accelerating voltage was 8 kV (see Fig. 8(c)). As for CL, the Eu3+ ions
were excited by the plasma induced by the incident electrons. As is
known, more plasma are generated with the increment of accelerate
voltage and filament current, leading to more excited Eu3+ ions as well
as increased CL intensity [60]. Furthermore, the deeper penetration of
the electrons into the host body and the larger electron beam current
density can also contribute to the enhanced CL intensity. According to
previous literatures, one obtains that the electron penetration depth can
be evaluated utilizing the following empirical formula [61,62]:
A E n 1.2
L = 250 ⎜⎛ ⎟⎞ ⎛ 1/2 ⎞ and n = .
⎝ ρ ⎠⎝ Z ⎠ 1−0.29lnZ (12)
In these expressions, L refers to the electron penetration depth, A stands
for the molecular weight of the studied samples, ρ denotes the density, E
is the accelerating voltage and Z is the number of electrons per mole-
cule. For the NaBiF4:0.4Eu3+ nanoparticles, the values of A, ρ and Z
P. Du et al.
were demonstrated to be 307.94, 4.2 and 130, respectively. Thus, on
the basis of Eq. (12), it is evident that the electron penetration depth for
the NaBiF4:0.4Eu3+ nanoparticles is proportional to the accelerating
voltage and it can be increased with increasing the accelerating voltage,
resulting in the improved CL intensity (Fig. 8(b)). Additionally, as
presented in Fig. 8, the CL intensity did not show any distinct saturate
tendency with elevating the accelerating voltage and filament current.
From these results, the Eu3+-activated NaBiF4 nanoparticles possessed
splendid CL properties which make it suitable for FED applications as a
red-emitting phosphor.
4. Conclusions
In summary, a series of highly efficient bifunctional Eu3+-activated
NaBiF4 nanoparticles were successfully prepared by means of a facile
and ultra-fast route at room temperature. The resultant nanoparticles
could be efficiently excited by the commercial NUV chip and emitted
brightly visible red emission with a high color purity of approximately
90.4%. The optimal doping concentration of Eu3+ ions in the NaBiF4
host material was determined to be as high as 40 mol% and the dipo-
le–dipole interaction contributed to the concentration quenching. With
the help of the Judd-Ofelt theory, the intensity parameters were eval-
uated and the larger Ω2 value confirmed that the Eu3+ ions occupied
the low symmetry sites in the NaBiF4 host lattice. The temperature-
dependent PL emission spectra revealed that the studied nanoparticles
possessed excellent thermal stability with an activation energy of
0.237 eV. Furthermore, the internal quantum efficiency of the
NaBiF4:0.4Eu3+ nanoparticles was found to be 73.1%. In addition, the
WLED device, which was composed of a NUV chip, NaBiF4:0.4Eu3+
nanoparticles and commercial blue-emitting/green-emitting phosphors,
can emit glaring white light with proper CCT (6851 K) and high CRI
(88.2) values. Ultimately, the Eu3+-activated NaBiF4 nanoparticles
exhibited splendid CL performance and the CL intensity was greatly
dependent on the accelerating voltage and filament current. These re-
sults suggest that the Eu3+-activated NaBiF4 nanoparticles are expected
to be a promising red-emitting phosphor for simultaneous WLED and
FED applications.
Acknowledgements
This work was supported by the National Research Foundation of
Korea (NRF) grant funded by the Korea government (MSIP) (No.
2017R1A2B4011998), the National Natural Science Foundation of
China (No. 51502190), the Program for the Outstanding Innovative
Teams of Higher Learning Institutions of Shanxi, the Start-up Research
Grant of Taiyuan University of Technology (No. Tyutrc201489a), the
Excellent Young Scholars Research Grant of Taiyuan University of
Technology (No.2014YQ009, No. 2015YQ006 and No. 2016YQ03) and
the Open Fund of the State Key Laboratory of Luminescent Materials
and Devices (South China University of Technology, No. 2017-skllmd-
01).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.cej.2017.12.063.
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