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Chen, Y. Zhou, Z. Wan, M. Ding, W. Bai and Z. Ji, Dalton Trans., 2016, DOI: 10.1039/C5DT04909A.
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Page 1 of 18 Dalton Transactions
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DOI: 10.1039/C5DT04909A
Graphical Abstract
Dalton Transactions Accepted Manuscript

Published on 01 February 2016. Downloaded on 02/02/2016 02:09:36.
A novel perovskite La0.5Na0.5TiO3:Eu3+ red-emitting phosphor and the related
phosphor-in-glass (PiG) inorganic color converter for high-power warm w-LEDs
were fabricated. Through simply adjusting the contents of red phosphors in PiG, the
correlated color temperature of PiG-based w-LEDs evolved from cool white (6771 K)
to warm white (4417 K) and the color rendering index increased from 73.4 to 86.4.
Dalton Transactions Page 2 of 18
New Eu3+-Activated Perovskite La0.5Na0.5TiO3 Phosphors in Glass forView Article Online

DOI: 10.1039/C5DT04909A
Warm White Light Emitting Diodes
Jiasong Zhong1, Daqin Chen1, 2, *, Yang Zhou1, Zhongyi Wan1, Mingye Ding1, Wangfeng Bai1,
Zhenguo Ji1

1
College of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018, China
2
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese
Academy of Sciences, Fuzhou, Fujian 350002, PR China
Abstract: With increasing demand for high-power warm white light emitting diodes (w-LEDs),
discovery of efficient red-emitting inorganic color converters is greatly in demand. Herein, a
novel perovskite La0.5Na0.5TiO3:Eu3+ red-emitting phosphor with excellent thermal stability and
high quantum efficiency has been successfully synthesized by a traditional solid-state reaction.
Then, the developed La0.5Na0.5TiO3:Eu3+ red phosphor and commercial YAG:Ce3+ yellow
phosphor were incorporated into an innovatively designed low-melting glass. Impressively, the
destruction of La0.5Na0.5TiO3:Eu3+ and YAG:Ce3+ phosphor particles during glass melting was
quite low. Remarkably, the fabricated w-LEDs using an InGaN-based blue chip combined with
the Phosphor in Glass (PiG) plates exhibited improved chromaticity feature and superior optical
performance. Through simply adjusting the contents of red phosphors in PiGs, the correlated
color temperature of PiG-based w-LEDs evolved from cool white (6771 K) to warm white (4417
K) and the color rendering index increased from 73.4 to 86.4. Moreover, such PiG-based warm
w-LED presented superior thermal stability.
1. Introduction
Following an increasing awareness of energy crisis and environmental issue, energy efficiency
has become an very important criterion for pervasive products such as light sources.1,2 Compared
to the traditional incandescent and fluorescent, white-light-emitting diodes (w-LEDs) have
received increasing interest due to their superiorities of high efficiency, long lifetime,
environmental friendliness (mercury-free), high brightness and fast response time.3-5 At present,
white light can be obtained by different approaches, as shown in Fig. S1. One pattern to generate
white light with high color rendering is to couple tri-color (red, green and blue) phosphors pumped
1
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by a near-ultraviolet (NUV) LED. The major challenge with this approach is the low conversion
DOI: 10.1039/C5DT04909A
efficiency of the device, the strong re-absorption between different kinds of phosphors and
complex coating technology.2,6 The other pattern to generate white light is to combine a blue LED
chip with the YAG:Ce3+ yellow phosphors.7 Although this w-LED possesses high luminous
efficiency and simple structure, low color rendering index (CRI) and high correlated color

temperature (CCT) limit its application due to the shortage of red emission in the luminescence
spectrum.8 Furthermore, silicone or organic resin is usually used to encapsulate the blue LED chip
and yellow phosphors in the commercial w-LEDs, which lead to the degradation in luminous
efficiency and shifting of chromaticity under the high temperature and high photon radiation
environment.9, 10 Hence, it is urgently required to develop a novel red phosphor with satisfactory
stability and efficient luminance properties to apply in warm w-LEDs; besides, a novel inorganic
material as an alternative to organic sealing polymer is highly desired.
Up to now, most commercial red phosphors are based on Eu2+ or Ce3+ activated (oxy)nitride
compounds.11,12 However, these materials still have several drawbacks such as extremely harsh
preparation conditions and high production-cost.13 In comparison with (oxy)nitride, Eu3+ doped
oxide-based red emitters have been extensively investigated because of their easy preparation,
eco-friendliness and impressive chemical stability.14 In addition, Eu3+ ions have the direct
excitation peaks at about 393 nm (7F0-5L6) and 465 nm (7F0-5D2) in oxide hosts, which could
match well with the ultraviolet or blue LED chip. Recently, perovskite type compounds with
chemical formula ABO3 constitute an attractive class of materials in which unusual dielectric and
optical behaviors can be integrated.15 Among them, rare-earth doped Bi0.5Na0.5TiO3 (BNT)
phosphors are attractive to researchers because of its excellent photoluminescence and
ferroelectric properties.16 In particular, strong red emissions with high quantum efficiency and
excellent thermal stability can be realized by doping Eu3+ or Pr3+.17,18 Unfortunately, Bi3+ ions
exhibit intrinsic luminescence and variable valence, which strongly affect the luminance efficacy.
To solve this problem, using non-luminous La3+ ions to replace Bi3+, a novel perovskite oxide
La0.5Na0.5TiO3 (LNT) is expected as an alternative to BNT. Moreover, LNT is more suitable
environment for the Eu3+ ions owing to both La3+ and Eu3+ ions belong to the lanthanides.
On the other hand, to avoid the deterioration of the organic resin matrix which is utilized to fix
2
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phosphor layer onto the blue LED chip and protect LED chip, glass-based encapsulantDOI:
has10.1039/C5DT04909A
been
considered as a feasible substitute.19 In fact, phosphor-based glasses including phosphor-in-glass
(PiG), glass-ceramic and ceramic plate can be adopted.15,20 Among them, PiG has been considered
as the promising encapsulant and has been studied extensively due to its outstanding
advantage.21-26 It is a simple mixture of phosphors and glass frits, and then sintered at an optimal

temperature to form a stable matrix. In the sintering process, the glass melting temperature is
considerably low that the phosphors remain solid without degradation. In addition, the phosphor
with excellent luminescent performance can be distributed uniformly in the glass matrix. More
importantly, different phosphors can be easily mixed with different ratios to adjust the CRI and
CCT as required.23 Herein, the newly synthesized Eu3+-activated LNT red phosphor and
commercial YAG:Ce3+ yellow phosphor with different ratios have been successfully introduced
into the TeO2-based glass matrix by the PiG method, and the CCT and CRI can be effectively
tuned.
2. Experimental and characterization
2.1 Preparation
A series of LNT:xEu3+ (0≤x≤0.3) were synthesized by a conventional high temperature
solid-state reaction. Stoichiometric amounts of Na2CO3 (99.8%), La2O3 (99.99%), Eu2O3 (99.99%)
and TiO2 (99.8%) were accurately weighed and ground in an agate mortar. The mixtures were first
pre-sintered at 600 oC for 6 h, then reground thoroughly, and finally heated at 1000 oC for 6 h in
air atmosphere. Afterwards, the products were obtained by cooling down to room temperature
gradually.
PiGs were fabricated by a low-temperature co-sintering route.26 Two key steps were involved
in fabricating glass phosphor including: (1) preparation of tellurate mother glass; (2) introducing
the synthesized LNT:Eu3+ red phosphors and YAG:Ce3+ yellow phosphors into glass matrix. The
glass matrix composed of TeO2, ZnO, Sb2O3, Al2O3, B2O3 and Na2O was mixed and melted at
1000 oC for 0.5-1.5 h in air atmosphere. Then, the melt was poured into a cold copper mold and
gradually cooled to room temperature, followed by milling to powders using a ball grinder.
Afterwards, LNT:Eu3+ red phosphors and YAG:Ce3+ yellow phosphors (purchased from XinLi
Illuminant Co. LTD) were thoroughly mixed with the glass matrix powder followed by sintering at
3
600 oC for 30 min. Then, the molten glass was poured into a 300 oC pre-heated copper DOI:
mold andView Article Online
10.1039/C5DT04909A
annealed at 230 oC for 5 h to relinquish inner stress. Finally, these PiG were cut into various
shapes for optical measurement and LED application.
2.2 Characterization
The composition and phase purity of the as-obtained phosphors were studied by X-ray powder

diffraction (XRD) measurements using Bruker D8 advance automatic diffractometer at 40 kV and
40 mA. The X-ray Rietveld refinement data was collected over 2θ range of 10o to 120o at intervals
of 0.01o and analyzed using a general structure analysis system (GSAS). The photoluminescence
(PL), PL excitation (PLE), temperature-dependent PL spectra and decay curves were measured
using a fluorescence spectrometer (Edinburgh Instrument FS5) equipped with a 150 W continuous
and pulsed Xenon lamp as light sources. The quantum efficiency (QE) was recorded using a
BaSO4 coated integrating sphere that attached to the spectrophotometer. The surface morphologies
and structures of the obtained PiG were characterized using a scanning electron microscope (SEM,
FEI, operated at an acceleration voltage of 15 kV) with an attached energy-dispersive X-ray
spectrometer (EDX). The photoelectric properties including LE, CCT, CRI and Commission
International de I’Eclairage (CIE) chromaticity coordinates of the fabricated w-LEDs were
evaluated by an integrating sphere (HAAS-2000; Everfine Photo-E-Info Co. Ltd, Hangzhou,
China) at an operating current of 60 mA.
3. Results and discussion
3.1 Phase purity and crystal structure
The phase purity and crystal structure are analyzed by GSAS Rietveld refinements for the
representative LNT:0.05Eu3+, and ICSD-43771 (La0.5Na0.5TiO3) is served as the starting model to
refine LNT, as shown in Fig. 1. By comparing the experimental spectrum with the calculated data,
no impurity or secondary phases are observed. The refinement data converge to Rw = 5.89 %, Rwnb
= 6.83 %, Rb = 4.49 %, and Rexp = 3.94 %. The lattice parameters are fitted to be a = b = c = 3.865
Ǻ and cell volume V = 57.74 Ǻ3, which are smaller than those of LNT due to the different ionic
radium between Eu3+(r = 1.07 Ǻ, CN = 8) and La3+(r = 1.16 Ǻ, CN = 8). A schematic diagram of
the LNT structure is displayed in the inset of Fig. 1. Compounds La0.5Na0.5TiO3 belongs to cubic
system with the space group Pm3m and their crystal structure diagram is plotted with Diamond
4
3.1. The crystal structure is derived from the typical perovskite ABO3, i.e., La3+ and NaDOI:
+
cations View Article Online
10.1039/C5DT04909A
occupy the A site, while Ti4+ on the B site. In LNT, La3+ ions can be easily replaced by other rare
earth activators, indicating that it can serve as an excellent phosphor host.27
The XRD patterns of the as-prepared LNT:xEu3+(0≤x≤0.3) phosphors are presented in Fig. S2.
All of the diffraction peaks share the same characteristic peaks to the standard data of

La0.5Na0.5TiO3 (JCPDS no.39-0065), indicating that the introduction of Eu3+ ions into LNT host
lattice does not result in any change for the host structure. The magnified XRD patterns of
LNT:xEu3+(0≤x≤0.3) between 32o and 34o demonstrate the gradually shifting of diffraction peaks
towards the higher-angle direction with increase of Eu3+ doping content, confirming the
substitution of the larger La3+ ions in the host by the smaller Eu3+ ones.
Observed
Calculated
Difference
Intensity (a.u.)
20 40 60 80 100 120
2/degree
Fig. 1 XRD profiles for Rietveld refinement results of LNT:0.05Eu3+. Inset is the crystal structure
of LNT.
3.2 Photoluminescence of LNT:Eu3+ phosphors
The PLE spectrum of LNT:0.05Eu3+ phosphor by monitoring 615 nm emission corresponding to
the Eu3+ 5D0→7F1 transition is shown in Fig. 2a. There are several peaks from 350 to 500 nm
corresponding to the typical Eu3+ intra-configurational 4f-4f transitions.28,29 Obviously, the f-f
transitions are much higher than the Eu-O charge transfer band, indicating that the phosphor can
be a promising candidate for solid-state lighting.30 Furthermore, the two strong peaks at 397 nm
and 465 nm are attributed to 7F0→5L6 and 7F0→5D2 transitions, which match well with the output
5
wavelength of near-ultraviolet and blue chips. The PL spectrum consist of several sharp linesView Article Online
DOI: 10.1039/C5DT04909A
ranging from 575 to 750 nm, which are attribute to the 5D0→7FJ (J=0, 1, 2, 3, 4) transitions of
Eu3+.31 According to the magnetic dipole (MD) transition selection rule (ΔJ=0, ±1) and electric
dipole (ED) transition (ΔJ≤6, when J or J’ =0, ΔJ=2, 4, 6) selection rule, the 5D0→7F1 transition is
the MD transition and the crystal field has little effect on its intensity while the 5D0→7F2 transition

is attributed to ED transition and its intensity is very sensitive to the local structure surrounding of
the Eu3+ ions. 28, 32 Based on the Judd-Ofelt theory, the MD transition is permitted when the Eu3+ is
located at site with inversion symmetry, whereas the ED transition is allowed only when the Eu3+
ions occupies a site without an inversion centre.33-35 Therefore, the intensity ratio value (R) of
5
D0→7F2 to 5D0→7F1 is a good parameter to detect the symmetry of the coordinated environment
around Eu3+ ions.35 In LNT perovskite (ABO3) structure, Eu3+ activators enter into the LNT host
by substituting La3+, and Na+ and La3+ cations randomly occupy the A-site. In this case, the
calculated R values for LNT:xEu3+(0.025≤x≤0.3) phosphors are around 2.85 (Fig. S3), indicating
that Eu3+ ions do locate in the sites without the inversion symmetry.
(a) PLE em=615 nm PL ex=465 nm (b) ex= 465 nm

F0 D2
F0 L6
Relatively Intensity (a.u.)

5
D0 F2
Relatively Intensity (a.u.)
7
7
7
6.7
6.6
log (I/)
6.5
F0 L7
D0 F1
5
D0 F4
6.4
F0 D3
Slope=-3.42
5
7
6.3
5
D0 F3
D0 F0
6.2
7
7
-0.66 -0.63 -0.60 -0.57 -0.54 -0.51

log ()
5
5
250 300 350 400 450 500 550 600 650 700 750 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35
3+
Wavelength (nm) Eu Concentration (mol)
2
Emission spectrum of sample
Excitation line of BaSO4
1
Intensity (a.u.)
Intensity (a.u.)
0
Ln (I0/IT-1)
-1 data
linear fit
slope=-0.27
-2 550 600 650 700 750
Wavelength (nm)
-Ea/kT=Ln(I0/IT-1)
Enlarged profile
-3
24 26 28 30 32 34 36 38 40 42 450 500 550 600 650 700 750
-1 Wavelength (nm)
1/kT (eV )
6
Fig. 2 (a) PLE (λem=615 nm) and PL (λex=465 nm) spectra of LNT:0.05Eu3+ phosphor.DOI: View Article Online
(b)10.1039/C5DT04909A
The
emission intensity as a function of Eu3+ concentration in LNT:xEu3+ (0.025≤x≤0.3). Inset is the
dependence of log (I/x) versus log (x) in LNT:Eu3+ phosphors. (c) The calculated activation energy
for thermal quenching of LNT:0.225Eu3+. (d) Excitation line of BaSO4 and emission spectrum of
the selected LNT:0.225Eu3+ phosphor collected by an integrating sphere. Inset is the magnification

of the emission spectrum.
The PL spectra of the LNT:xEu3+ (0.025≤x≤0.3) phosphors are presented in Fig. S3. The
luminescence intensity enhances with increase of Eu3+-doping content, reaches a maximum

intensity at x=0.225 (22.5 mol%), and then decreases gradually owing to concentration quenching.
Generally speaking, the concentration quenching phenomenon usually occurs as a result of
exchange interaction, radiation re-absorption or multipole–multipole interaction.35,36 To
investigate the mechanism of energy transfer in phosphor, the critical distance (Rc) among Eu3+
ions for energy transfer can be estimated using the relation given by Blasse:37
13
 3V 
Rc  2  
 4 XC
N  (1)
Where V is the volume of the unit cell, N is the number of the substituted host cation (La3+) in the
unit cell, and Xc is the critical concentration of Eu3+ ions. In the case of LNT:Eu3+ phosphors, N =1,
V = 57.74 Å3, and Xc=0.225. Therefore, Rc is calculated to be 7.89 Å. The exchange interaction
become ineffective when the critical transfer distance is larger than 5 Å, and the radiation
re-absorption is unlikely to occur as there is no overlap between PL and PLE spectra in present
case.38 Thus, the concentration quenching mechanism of Eu3+ ions in LNT system is dominated by
the multipole-multipole interaction. In generally, there are three types of electric multipole
interactions, including dipole-dipole (d-d), dipole-quadrupole (d-q) and
quadrupole-quadrupole(q-q) ones. According to the Dexter theory, the interaction type can be
calculated by the following formula:39, 40
I K

 1  (  ) 3 (2)
7
where x is Eu3+ concentration beyond the quenching concentration; I is the integrated PLDOI:
emission View Article Online
10.1039/C5DT04909A
intensity; K and β are constants for the given host crystal; θ is a function of multipolar interaction,
and θ = 6, 8, 10 are related to d-d, q-d, q-q interactions, respectively. As shown in the inset of
Fig.2b, it is evident that the linear relationship between log(x) and log (I/x) can be obtained, and
the slope fits to be -3.42. Therefore, the value of θ is 10.26, which is close to 10, indicating that

the concentration quenching mechanism of Eu3+ in LNT host is the q-q interaction. To further
validate the concentration quenching effect of Eu3+ in LNT:Eu3+, the PL decay curves monitored
at the 5D0→7F2 emission (615 nm) are investigated, as displayed in Fig. S4. Evidently, the decay
lifetimes decline from 0.83 to 0.50 ms as the doping contents increases from 2.5 to 30 mol%.
As a phosphor applied in lighting, especially used in high-power devices, its luminescence
stability on thermal quenching is one of the most important technological parameters because it
has great influence on the CIE coordinates and light output.41 The temperature-dependent PL
spectra of LNT:0.225Eu3+ is measured under the excitation of 465 nm, as presented in Fig. S5.
The relative peak intensity of LNT:0.225Eu3+ decreases with rising temperature. It reaches about
60% of initial value at 423 K, which is better than the reported Sr1.7Zn0.3CeO4:Eu3+ (20% at 423 K)
and Ba2ZnB2O6:Eu3+ (30% at 423 K).28,42 Furthermore, based on the Arrhenius equation, the
experimental data can be well fitted by a linear fit, and the experimental activation energy is
evaluated to be 0.27 eV. The QE is defined as the ratio of the number of photons emitted to that of
photons absorbed and the value can be calculated as the following:
QE 
L S
 E - E
R S
(3)
where LS is the luminescence emission spectrum of the sample, ER and ES are the spectra of the
excitation light without and with the sample in the sphere, respectively. The PL QE of
LNT:0.225Eu3+ phosphor under the excitation of 465 nm reached 47.1%, which is comparable to
those of previously reported LiGd5P2O13:Eu3+ (46.5%) and Sr1.7Zn0.3CeO4:Eu3+ (46.1%)
phosphors.42,43
3.3 Microstructure and luminescence of PiG containing LNT:Eu3+ and YAG:Ce3+ Phosphors
XRD curves of the LNT:Eu3+ PiG, and LNT:Eu3+ and YAG:Ce3+ PiG are displayed in Fig. 3.
As shown in Fig. 3a, all of the diffraction peaks are well consistent with the standard data of
8
La0.5Na0.5TiO3 (JCPDS no.39-0065), suggesting that the LNT:Eu3+ phosphor particles have been View Article Online
DOI: 10.1039/C5DT04909A
successfully introduced into the host lattice. From the Fig. 3b, the YAG and LNT crystal phases
are clearly indentified without other phases in LNT:Eu3+ and YAG:Ce3+ co-doped PiG, indicating
that the LTO:Eu3+ and YAG:Ce3+ particles have been incorporated into the glass host. The
amorphous hump is originated from the TeO2-based glass matrix.

Y3Al5O12 JCPDS no.33-0040
 (a) 4 wt% NLT:Eu

3+
 3+
(b) 4 wt% NLT:Eu +3 wt% YAG:Ce
3+

Intensity (a.u.)
(b)  NLT:Eu
3+
 YAG:Ce
3+
 
   
    
 
 
(a)
Na0.5La0.5TiO3 JCPDS no. 39-0065
20 30 40 50 60 70 80
2/degree
Fig. 3 XRD patterns of the as-fabricated PiG containing: (a) 4 wt% LNT:0.225Eu3+ phosphor, and
(b) 4 wt% LNT:0.225Eu3+ and 3 wt% YAG:Ce3+ phosphors. The standard cubic La0.5Na0.5TiO3
(JCPDS no. 39-0065) and Y3Al5O12 (JCPDS no. 33-0040) are also shown.
The distribution and microstructure of LNT:Eu3+ and YAG:Ce3+ phosphor particles in the glass
matrix are analyzed by SEM. The homogeneous distribution of YAG:Ce3+ phosphor particles
(yellow circles) and NTL:Eu3+ particles (red circles) can be found in the glass matrix, as depicted
in Fig. 4, indicating that the glass-melting procedure has not significantly influence on the doped
phosphors. The EDX line scans across the particles marked by a green frame in SEM image
clearly proved the phosphors and glass matrix. The profiles of Al and Y are recorded along a line
through one particle as labeled in yellow circle, and Na, La, Ti and Eu are detected in another
particle as signed in red circle, demonstrating characteristic composition of phosphor phases. Te
and Zn signals are detected in glass matrix. These results further confirm that the coexistence of
YAG:Ce3+ particles and LNT:Eu3+ particles in the glass matrix. Optical transmission spectra of the
blank glass and LNT:Eu3+ and YAG:Ce3+ co-doped PiG, as presented in Fig. S6, shows that the
9
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transmittance reaches about 58% for glass and 51% for PiG sample at 800 nm. DOI: 10.1039/C5DT04909A
(a)

70 16 100
60
(b) 14
(c) (d) 120
(e)
80 100
50 12
10 60 80
40
8 60
30 40
6
20 40
4
20
10 2 20
0 0 0 0
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
Tellurium Zinc Yttrium Aluminum
35 40 18
30
(f) 35 (g) 25
(h) 15
(i)
30 20
25
12
25
20 15
20 9
15
15 10
6
10
10
5 3
5 5
0 0 0 0
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
Sodium Titanium Lanthanum Europium
Fig. 4 (a) SEM image of PiG, yellow and red circles corresponding to YAG:Ce3+ and LNT:Eu3+
particles, respectively. EDX line scan curves of (b) Te, (c) Zn, (d) Y, (e) Al, (f) Na, (g) Ti, (h) La,
and (i) Eu profiles across two representative phosphor particles in the PiG sample are shown.
The PLE and PL spectra of the LNT:Eu3+ PiG, LNT:Eu3+ and YAG:Ce3+ co-doped PiG are
displayed in Fig. 5a. The LNT:Eu3+ PiG exhibits red luminescence with several Eu3+: 5DJ→7F0
sharp peaks in PL spectrum and two main excitation peaks locate at 393 nm and 465 nm in PLE
spectrum. For the LNT:Eu3+ and YAG:Ce3+ co-doped PiG, except the characteristic
intra-configuration f-f transition of Eu3+, a typical Ce3+:4f↔5d broadband excitation (peak at 465
nm) and emission (peak at 550 nm) can be observed. Especially, the Ce3+:5d→4f yellow-emitting
10
and Eu3+: 5D0→7F2 red-emitting can be simultaneously achieved under 465 nm blue lightView Article Online
DOI: 10.1039/C5DT04909A
excitation, indicating that the investigated PiG is a promising candidate for warm w-LEDs.44
(a) PLE
3+
4 wt%NLT:Eu +3 wt%YAG:Ce
3+
(b)
7 5
em=615 nm F0 D2
Normalized Intensity (a.u.)
5 7
D0 F2
5d4f
7 5 4f5d
F 0 L 6

PL ex=465 nm
 =465 nm 4 wt%NLT:Eu3+
F0 L6 F0 D2 PL ex
7 5 7 5
PLE 5 7
em=615 nm D0 F2
5 7
D0 F1 5 7
D0 F4
300 350 400 450 500 550 600 650 700 750
Wavelength (nm)
Fig. 5 (a) PLE and PL spectra of LNT:Eu3+ single-doped PiG and LNT:Eu3+ and YAG:Ce3+
co-doped PiG. (b) Photograph of LNT:Eu3+ PiG in the daylight and under 365 nm UV light
excitation (left), and LNT:Eu3+ and YAG:Ce3+ PiG–based LED in the daylight and under 465 nm
blue light excitation (right).
Considering the practical application in high power w-LEDs, the junction temperature of the
chips will reach as high as 150–200 oC. Therefore, the thermal stability of the inorganic color
converter is of key important. The influence of temperature on the relative emission intensity of
YAG:Ce3+ and LNT:Eu3+ co-doped PiG is presented in Fig. 6. When temperature increases from
30 to 270 oC, the PL intensity of PiG gradually declines due to the enhanced nonradiative
relaxation. Impressively, compared to room temperature, the PiG remains an emission intensity of
79 % at 150 oC. This result mainly originates from higher thermal conductivity of PiG than that of
the organic resin, which benefits to release the heat emitted and then reduce the probability of Eu3+
nonradiative transitions in the phosphor.45 The fluorescence decay lifetimes of PiG composite also
illustrate a strong dependence on the temperature, as shown in Fig. 6. As the temperature increases,
the lifetime decreases from 0.66 to 0.36 ms. The PL QE of the YAG:Ce3+ and LNT:Eu3+ co-doped
PiG is measured to be 89.6%.
11
0.70 View Article Online

100
DOI: 10.1039/C5DT04909A
Relative Integrated Intensity (%)

0.65
80
0.60
Lifetime (ms)
60 0.55
0.50
40

0.45
20
0.40
0 0.35
0 50 100 150 200 250 300
o
Temperature ( C)
Fig. 6 Temperature-dependent emission intensity and average lifetime of PiG.
As we all know, the current leading commercial w-LEDs technology has an innate deficiency
in red component; therefore, an additive red phosphor is highly demanded. To validate the
availability of this approach, LNT:Eu3+ red phosphors with various concentrations (1-11 wt%) and
3 wt% YAG:Ce3+ yellow phosphors have been introduced into glass matrix. To evaluate the device
performance, the w-LEDs are fabricated by encapsulating the PiG plates on the InGaN blue chip.
The electroluminescent (EL) spectra of the PiG with different concentrations of LNT:Eu3+, driven
under 60 mA current, are displayed in Fig. 7a. Evidently, with increase of LNT:Eu3+ contents from
1 to 11 wt%, the Eu3+ red emissive component increases gradually. As a result, the photoelectric
parameters of these w-LEDs are modified correspondingly, as tabulated in Table 1. The related
chromaticity color coordinates are plotted on the CIE 1931 chromaticity diagram in Fig. 7b. As
expected, the emitted white-light develops gradually from cool to warm (inset of Fig. 7b), the CIE
coordinate experiences an approximately linear shifts from point (0.2998, 0.3450) to (0.3768,
0.4328), the CCT decreases from 6771 to 4417 K and the CRI increases from 73.4 to 86.4. These
results indicate that the incorporation of LNT:Eu3+ red phosphor can effectively improve the CCT
and CRI values to more suitable for indoor illuminations applications.
12
View Article Online

(a) 11wt%NLT:Eu
3+
(b) DOI: 10.1039/C5DT04909A
3+
9wt%NLT:Eu
EL Intensity (a.u.)
3+
7wt%NLT:Eu
3+
5wt%NLT:Eu

3+
3wt%NLT:Eu
3+
1wt%NLT:Eu
400 450 500 550 600 650 700 750

Wavelength (nm)
Fig. 7 (a) EL spectra of the 3 wt% YAG: Ce3+ and y wt% LNT: Eu3+ (y=1, 3, 5, 7, 9, 11)
PiG-based LED devices under a 60 mA driving current. (b) CIE coordinates of the PiG-based
LEDs; insets are photographs of the PiGs and PiG-based LEDs in operation.
Table 1. Measured optical parameters of the PiG-based LEDs under a 60 mA driving current
No. LNT:Eu3+ Chromaticity coordinate

LE (lm/W) CCT (K) Ra
content (wt%) X Y
a 1 0.2998 0.3450 109.3 6771 73.4
b 3 0.3132 0.3611 103.6 6180 78.9
c 5 0.3269 0.3817 99.8 5607 80.5
d 7 0.3474 0.4106 97.5 5122 82.6
e 9 0.3606 0.4205 93.4 4813 84.1
f 11 0.3768 0.4328 89.1 4417 86.4
The color stability for high-quality lighting applications is usually detected by the color
deviation of a LED device under various driving currents.46 The EL spectra of the fabricated
w-LEDs using an InGaN-based blue chip combined with the PiG under the current regulation
from 60 to 600 mA are presented in Fig. 8. The shape of transmitted blue LED peaks (λmax=465
nm) and emitted yellow YAG:Ce3+ (λmax=560 nm) and red LNT:Eu3+ (λmax=615 nm) are consistent
under different operating currents. Upon increasing the forward-bias current from 60 to 600 mA,
the CIE chromaticity coordinates of the fabricated LED are found to be slightly blue-shifted from
13
(0.3768, 0.4328) to (0.3743, 0.4253), the CCT increases from 4411 K to 4439 K andDOI: CRIView Article Online
the10.1039/C5DT04909A
decreases from 89.2 to 87.2, as shown in Fig. 9. These results demonstrate that the developed
PiG-based w-LEDs possess excellent color stability.
60 mA
1.0
120 mA
180 mA
240 mA

0.8
EL Intensity (a.u.)
300 mA
360 mA
0.6 420 mA
480 mA
540 mA
0.4 600 mA
0.2
0.0
400 450 500 550 600 650 700 750
Wavelength (nm)
Fig. 8 EL spectra of the fabricated PiG-based w-LEDs at various driving currents (60–600mA)
4800 110
(a)0.434 (b)4600
105
60 mA
4400
0.432
100
180 mA 120 mA 4200
Tc (K)
0.430
CIE Y
Ra
240 mA 4000 95
300 mA
0.428 3800
420 mA 360 mA 90
540 mA 3600
0.426 480 mA 85
3400
600 mA
0.424 3200 80
0.3740 0.3745 0.3750 0.3755 0.3760 0.3765 0.3770 0 100 200 300 400 500 600
CIE X Current (mA)
Fig. 9 (a) The variation of the CIE chromaticity coordinates of the white LEDs under different
forward bias currents. (b) The variation of CCT and CRI in the PiG-based warm w-LED operated
at different currents.
4. Conclusions
In summary, the LNT:Eu3+ phosphors have been synthesized and systematically investigated.
XRD patterns indicate that only one phase crystallized in the cubic perovskite-type structure with
the Pm3m space group are observed. These phosphors can be efficiently excited by UV and blue
light and exhibit a dominant peak at 615 nm due to the electric dipole 5D0 →7F2 transition of Eu3+.
The optimal concentration of Eu3+ in the LNT reached as high as 22.5 mol% with QE of 47.1%,
and the corresponding concentration quenching mechanism is certified to be
14
quadrupole-quadrupole interaction. Furthermore, the developed LNT:Eu3+ red phosphor andView Article Online
DOI: 10.1039/C5DT04909A
commercial YAG:Ce3+ yellow phosphor can be introduced into a special low-melting glass and
applied to fabricate w-LEDs. Impressively, such PiG-based w-LEDs exhibited excellent thermal
stability, and the CCT and CRI can be finely tuned through adjusting the concentration of red
phosphors in the PiG.

Acknowledgments
This work was supported by the Natural Science Foundation of Zhejiang Province (LR15E020001,
LQ14E020006, LQ15E020004), National Natural Science Foundation of China (21271170,
51502066, 61372025 and 51572065) and the 151 talent’s projects in the second level of Zhejiang
Province.
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