J Mater Sci: Mater Electron

Synthesis and photoluminescence properties of a novel

red-emitting Eu3+-doped LiSrGd(WO4)3 phosphors
Kejun Zhong1 , Huihua Ye1, Xusheng Wang1,*, Yanxia Li1, and Xi Yao1

1
Key Laboratory of Advanced Civil Engineering Materials of the Ministry of Education, Functional Materials Research Laboratory,
School of Materials Science and Engineering, Tongji University, 4800 Cao’an Road, Shanghai 201804 China

Received: 31 January 2021 ABSTRACT

Accepted: 11 May 2021 Rare-earth (RE)-doped tungstate LiSrGd1-x(WO4)3:xEu red-emitting phosphors
were prepared by traditional high-temperature solid-state reaction method.
Ó The Author(s), under These samples were characterized by X-ray diffraction, scanning electron
exclusive licence to Springer microscopy, and photoluminescence (PL). PL spectrum exhibited characteristic
Science+Business Media, LLC, luminescent 5D0/7FJ (J = 0–4) intra-4f shell Eu3? ion transitions. Eu3?-activated
part of Springer Nature 2021 LiSrGd(WO4)3 phosphors could be excited by near-ultraviolet (NUV) light of
393 nm and blue light of 464 nm and showed excellent red emission lying
around 616 nm (5D0 ? 7F2). Eu3?-doped concentration in LiSrGd1-x(WO4)3:xEu
was x = 0.3. Arising temperature to 393 K, the red emission intensity of
LiSrGd1-x(WO4)3:xEu phosphor decayed by only 13.57 and 19.53 % relative to
room temperature, which indicates that the phosphor possesses good temper-
ature stability. The evaluated Commission International de l’Eclairage (CIE)
color coordinates of these phosphors were close to the standard red CIE color
coordinate published by the National Television Systems Committee. Hence
LiSrGd1-x(WO4)3:xEu phosphor is promising with potential for white LED.

1 Introduction emitting phosphors is the focus of future work.

Developing rare-earth (RE)-doped phosphors as
Nowadays, the White LEDs luminescent character- desirable and promising fluorescent materials has
istics, stability in high vacuum, broad application attracted much attention [5, 6].
prospects, and potentiality in decreasing excitation The Eu ions-doped phosphors can emit red, green,
energy and fossil fuel pollution has been compared to and blue light by different valence state of Eu ion,
traditional sulfide-based phosphors [1, 2]. However, such as BaZrSi3O9:Eu2?(blue) [7], Ca2MgSi2O7-xNx:-
the deficiency of red-emitting phosphors under blue Eu2?(green) [8], Na2Gd(PO4)(MoO4):xEu3?, and
or NUV light excitation restricted the color temper- LiGd(WO4)2:Eu3?(red) [9, 10]. Xia successfully pre-
ature and color developing performance of the pro- pared the red-emitting phosphor, which exhibits
duct [3, 4]. In view of this, how to improve the bright red-emitting luminescence arising from the
5
luminous efficiency and thermal stability of red- D0 ? 7F2 transition at 615 nm under the excitation

Address correspondence to E-mail: xs-wang@tongji.edu.cn

https://doi.org/10.1007/s10854-021-06176-y
 J Mater Sci: Mater Electron

wavelength of 394 nm. When the Eu ion doping promising red-emitting phosphors for blue and near-
concentration is 60%, the emission intensity of the ultraviolet (NUV) and W-LEDs. In this work, single
sample is the highest, and the material also showed matrix white light-emitting materials were prepared
excellent thermal stability [11]. Hence, the red phos- by traditional high-temperature solid-state reaction
phors activated by Eu3? ions as efficient red-emitting method, and the effects of rare-earth ion doping
activators have been widely utilized in red-emitting concentration and sintering temperature on the
phosphors for W-LEDs, which can improve color luminescent properties of the phosphors were
rendering index, color temperature in the red spectral investigated.
region, and high luminescent efficiency [12]. Mean-
while, the spectra lines reveal the local site symmetry,
sizes of cations, and properties of the chemical 2 Experimental
bonding. When Eu3? is in the lattice position which
deviates from the inversion center, it usually has the 2.1 Synthesis of LiSrGd0.7(WO4)3:0.3Eu31
super sensitive transition 5D0 ? 7F2, and the emis- phosphors
sion is about 620 nm. Considering the color purity of
A series of red-emitting phosphors were synthesized
red, we should weaken the transition from 5D0 to 7F1,
by dynamic solid-state reaction. The starting materi-
and enhance the transition from 5D0 to 7F2 [13, 14].
als were strontium carbonate (SrCO3, A.R. grade),
Therefore, it is crucial to choose matrix materials.
europium oxide (Eu2O3, 99.99% purity), tungsten
Because of (WO4)2- group, tungstate has a strong
oxide (WO3, A.R. grade), gadolinium oxide (Gd2O3,
and wide charge transfer band in the near-ultraviolet
99.99% purity), and lithium carbonate (Li2CO3, A.R.
region of 200–300 nm, which can absorb the energy of
grade), respectively. All raw materials with stoichio-
near-ultraviolet and transfer it to the light-emitting
metric amounts in LiSrGd1-xEux(WO4)3 (x = 0.0, 0.1,
center, and improve the luminous intensity of the
0.2, 0.3, 0.4) were mixed homogeneously and ground
fluorescent activation center [15, 16]. When Eu3? ions
together in an agate mortar. The mixtures were fired
are doped into the tungstate matrix, they are ran-
in the air at 800–1000 °C for 4 h. After calcination,
domly distributed on the lattice sites of the non-in-
version symmetry center. Therefore, the characteristic wait for the temperature in the furnace to cool to
transition from 5D0 to 7F2 of red light emission is room temperature, take out the product, and grind it
dominant, and the emission light has good color again, and the obtained powder is the required pro-
duct for characterizations.
purity. Because the bond angle of O–W and Eu–O–W
in Eu3?-doped tungstate phosphors are greater than
2.2 Characterization
100° and the distance between luminescent centers is
large, it is difficult to transfer energy. Some Eu3?-
The X-ray powder diffraction (XRD) patterns of the
doped tungstate phosphors do not undergo concen-
samples were analyzed by a computer-automated
tration quenching [17–19]. At the same time, the
diffractometer (Rigaku D/max-3c) equipped with Cu
physical and chemical stability of the tungstate is
Ka radiation (k = 0.154056 nm) at room temperature.
ideal, resource-rich, green, and friendly [20–22].
The 2h range is 5°–80° with a step of 0.02°. Photolu-
Hence, tungstate can be used as a red-emitting
minescence (PL) excitation and emission spectra were
phosphor for white LED to improve color rendering
measured by using a fluorospectrometer (Varain
index and color temperature.
Cary Eclipse) with a Xe lamp as the excitation source.
Li, Na, and K ions exhibit chemical and thermal
stability and high luminescence intensity of Eu3?-
doped tungstate phosphors [23]. Moreover, the 3 Results and discussion
LiEu(WO4)2 phosphors exhibit better luminescence
property than that of K and Na-based double tung- 3.1 XRD analysis
state or molybdate phosphors [24], due to Li? ions, in
that phosphors can shorten the Li–O band distance Figure 1a shows the indexed powder X-ray diffrac-
and increase covalency of bonds [25]. tion patterns for LiSrGd0.7(WO4)3: 0.3Eu3? com-
This research will be helpful to the improvement of pounds calcined from 800 to 10008C. The major peak
photoluminescence property and the development of
J Mater Sci: Mater Electron

2h is 28.5°, with other peaks at 31°, 34°, 39°, 47°, 49°, to the high-temperature solid-state reaction, and the
54°, 58°, 59°, and 76°, which agreed well with the obtained crystals crystallized preferably.
Card JCPDS25-0829. The unit cell parameters are It is illustrated in Fig. 1b the indexed powder X-ray
a = b = 5.26 Å, c = 11.46 Å, a = b = c = 90°, and diffraction patterns for LiSrGd1-x (WO4)3: xEu3?
V = 317.32Å3, and the crystalline nature of the sam- (x = 0, 0.1, 0.2, 0.3, 0.4) compounds sintered at 900 °C.
ples LiSrGd(WO4)3: 0.3Eu3? possess the orthorhom- With the increase of Eu3? concentration, the position
bic scheelite structure with space group I41/a (88). and intensity of the peak is almost unchanged.
We did not see any impurity line of Eu2O3 in the Therefore, the doping of Eu3? ions has little effect on
powder XRD patterns, it implies that the Eu3? has the crystal structure of the LiSrGd(WO4)3.
doped into the matrix lattice. Europium and
Gadolinium are close to each other in the periodic 3.2 Surface morphology analysis
table, with similar radii and chemical properties,
Eu3? ions may substitute to Gd3? ions in Surface morphology plays an important role in the
LiSrGd(WO4)3 lattice. When increasing the concen- evaluation of prepared phosphors’ optical properties.
tration of the doping Eu3? ion, the diffraction peak The scanning electron microscope (SEM) offers a
shifts slightly to a large angle because the radius of convenient technique to obtain information about
Eu3? is smaller than that of Gd3?, which is consistent morphology, size distribution, and the shape of the
with the Bragg equation. On the contrary, if Eu3? ions synthesized phosphors. The microstructure of the
replaced Sr3? ions, the diffraction peak will shift to a samples was observed by field emission environ-
small angle because the radius of Eu3? ions is much mental scanning electron microscope of quanta200-
larger than Sr3? ions, which is inconsistent with the FEG made by Fei company of Germany. The label of
XRD data. In summary, Eu3? ions substituted to the SEM is accelerating voltage: 500–30 kV, continu-
8-coordinated Gd3? ions in LiSrGd(WO4)3 lattice. ously adjustable. The secondary electron, backscat-
With the increase of calcination temperature from tered electron morphology, and material composition
800 to 1000 °C, the impurity peaks of the XRD pattern can be observed in high vacuum mode, low vacuum
become less and the peak shape becomes narrower, mode, and environment scanning mode, respectively.
which indicates that the increase of calcination tem- Figure 2 a shows SEM images of LiSrGd(WO4)3, b
perature in this temperature range will intensify the shows LiSrGd0.7(WO4)3:0.3Eu3? compounds sintered
thermal movement of molecules, which is conducive at 900 °C, and c shows LiSrGd0.7(WO4)3:0.3Eu3? sin-
tered at 800 °C. By analyzing the data with Image-Pro

Fig. 1 a X-ray
diffraction patterns of
LiSrGd0.7(WO4)3: 0.3Eu3?
samples calcined from 800 to
1000 °C recorded at room
temperature; b X-ray
diffraction patterns of
LiSrGd1-x(WO4)3: xEu3?
(x = 0,0.1,0.2,0.3,0.4)samples
recorded at room temperature
 J Mater Sci: Mater Electron

Plus, in Fig. 2a, the minimum particle size is 1.78 lm, demonstrated by their particle size distribution chart,
the maximum is 23.74 lm, and the average particle shown in Fig. 2d–f. The histogram corresponding to
size is 4.52 lm. In Fig. 2b, the minimum particle size each SEM image shows the change of the crystallite
is 1.81 lm, the maximum is 33.00 lm, and the aver- size and crystallinity of phosphor powder. Compared
age particle size is 5.50 lm. In Fig. 2c, the minimum with the average particle size of the matrix material
particle size is 3.55 lm, the maximum is 26.05 lm, and doped with 30% Eu3? ions, due to the intro-
and the average particle size is 7.67 lm. The phos- duction of Eu3? ions, the crystal particle size is larger,
phor’s granularity characteristics can be further compared with the LiSrGd0.7(WO4)3:0.3Eu3?

Fig. 2 SEM micrographs of and the SEM micrographs of phosphors observed at 5000 magnification times and their
a LiSrGd(WO4)3, b LiSrGd0.7(WO4)3:0.3Eu3? sintered at corresponding particle size distribution (d-f)
900 °C, and c LiSrGd0.7(WO4)3:0.3Eu3? sintered at 800 °C;
J Mater Sci: Mater Electron

phosphors calcined at 800 °C and 900 °C, increasing phosphors may be candidate materials for applica-
the calcination temperature that can make the crystal tion in the field of near-UV-excited and blue-excited
grain finer in a certain range. white LEDs [26].
The emission spectra of LiSrGd1-x(WO4)3:xEu3?
3.3 Luminescence properties phosphors with different Eu3? concentrations under
of LiSrGd12x(WO4)3:xEu31 393 and 464 nm excitation wavelength are illustrated
in Fig. 3b, c. The emission spectrum of the sample is
3.3.1 Effect of Eu3? concentration mainly composed of a series of characteristic emis-
in LiSrGd1-x(WO4)3:xEu3? phosphor sion peaks of Eu3?, which at 600 nm and 616 nm
correspond to 5D0 ? 7F1 and 5D0 ? 7F2. The 5D0 !
The excitation spectra of powders calcined for 4 h at 7
F1 transition is a magnetic dipole transition, and the
900 °C are shown in Fig. 3 a. Monitoring the 616 nm 5
D0 ! 7F2 transition is an electric dipole transition.
emission of Eu3?, many narrow band absorption
According to Judd–Ofelt theory when the Eu ions are
peaks in the range of 350–550 nm are exhibited,
in the lattice position of the inversion symmetry
among which two intense excitation peaks are iden-
center, the magnetic dipole transition is dominant; on
tified as 393 and 464 nm, corresponding to near-ul-
the contrary, the electric dipole transition is domi-
traviolet and blue light region. It implies that these
nant. The emission intensity of 5D0 ! 7F1 transition

Fig. 3 a The excitation spectra of samples; d relation between the log(C) and the log(I/C) of
LiSrGd1-x(WO4)3:xEu3? (x = 0.1,0.2,0.3,0.4) samples; b, c the LiSrGd0.7(WO4)3:0.3Eu3? phosphor
emission spectra of LiSrGd1-x(WO4)3:xEu3? (x = 0.1,0.2,0.3,0.4)
 J Mater Sci: Mater Electron

(600 nm) is smaller than that of 5D0 ! 7F2 transition multipolar interactions in the energy transfer process
(616 nm), which indicates Eu ions in the asymmetric including dipole–dipole, dipole–quadrupole, and
central lattice environment [15]. The occurrence of quadrupole–quadrupole interactions. The type of
electric dipole transition in the 4F configuration of multipolar interaction can be determined as follows:
rare-earth ions requires rare-earth ions to occupy 1 k
non-centrosymmetric sites [27, 28]. Figure 3d pre- ¼ ðfor b  1Þ
C bCS=3
sents the probability of cross-relaxation (process 1)
between 7F1 and 5D0 that will increase, and the
where I is the emission intensity; C is the activator
energy of Gd3? ions relaxed to 6PJ level will be
concentration; S = 6, 8, or 10 for dipole–dipole,
transferred directly to Eu3? ions [29]. The other 4F !
dipole–quadrupole, or quadrupole–quadrupole
4F transitions of Eu3? are very weak, and this is
interaction, respectively; k and b are constants for the
beneficial to exhibit intense pure red-emitting. It
same excitation condition for a given host crystal. The
indicates that the samples can be used as red phos-
value of S can be calculated by the slope (- S/3) of
phors for white LEDs.
the plot log (I/C) versus log (C) as shown in Fig. 3d.
It is observed in Fig. 3b, c that the emission inten-
The slope value is - 2.0043 and thus the value of S
sity enhances as the Eu3? concentration enhances,
can be calculated as 6.0129 (relatively close to the
and the excitation and emission intensity reached the
theoretical value 6). This indicates that the dipole–
maximum when the Eu3?-doped concentration atta-
dipole interaction between Eu3? ions is the major
ches 30%. Then with the increase of the concentration,
mechanism for the concentration quenching.
the emission intensity decreases. Excessive doping
leads to concentration quenching for the Eu3? emis-
3.3.2 Effect of sintering temperature
sion. In the beginning, as the doping concentration of
Eu3? ions increases, the luminous center increases, Figure 4 a presents the excitation spectra, b-c pre-
and the luminous intensity of the fluorescent material sents the emission of LiSrGd0.7(WO4)3:0.3Eu3? pow-
increases, until the doping concentration reaches the ders calcined at 800 °C to 1000 °C for 4 h, and d, e the
critical quenching concentration, that is, the distance line chart of the emission intensity of phosphors sit-
between the activator Eu3? ions reaches the critical uated at the strongest peak. It is observed in Fig. 4d, e
distance, then increasing the concentration of Eu3? that the emission intensity increases as the sintering
ions will increase the probability of energy transfer in temperature increases and the emission intensity
the material. More energy is transferred to the reached the maximum when the sintering tempera-
quenching center and dissipated in the matrix lattice ture is about 900 °C, then with further increase of the
in the form of heat energy [30]. sintering temperature of phosphors, the emission
The non-radiative energy transfer between Eu3? intensity declines.
ions is mainly through resonance energy transfer,
which includes radiation reabsorption, electrical
3.3.3 Luminescence decay lifetimes
multistage interaction, and exchange interaction.
When the critical distance is less than 5 Å, exchange After the light transits, all the luminescent phenom-
interaction is dominant; on the contrary, the electrical ena will not disappear. When the end time of illu-
multistage interaction is dominant. The critical dis- mination is defined as t0, the luminous intensity is I0,
tance can be calculated by the following formula [31]: and the luminous intensity at t is It. When it falls to
 13 1/E of I0, it is the fluorescent lifetime of the fluores-
3V
Rc  2 cent material, expressed by s. The decay of fluores-
4pXc N
cence lifetime of rare-earth ions can be expressed as
V is the cell volume, N is the number of molecules in follows. The PL decay profiles of LiSrGd0.7(-
the cell, XC is the critical concentration, c&12.641Å. WO4)3:0.3Eu3? phosphors are represented in Fig. 5.
Because the critical distance is greater than 5 Å, the These data were recorded by 616 nm and 393 nm. As
energy transfer between Eu3? ions is mainly com- demonstrated in Fig. 5, the decay curves for the
pleted by the electrical multistage interaction. sample are best fitted with the single exponential
According to Dexter’s theory, there are three types of
J Mater Sci: Mater Electron

Fig. 4 a–c Excitation and emission spectrum of LiSrGd0.7(WO4)3:0.3Eu3? samples sintered at 800, 850, 900, 950, and 1000 °C; d, e the
emission intensity (kex ¼ 393; 464 nm)of phosphors situated at the strongest peak

decay model which can be mathematically expressed 3.3.4 Asymmetry ratio

as [32]:
According to all the above emission spectra (Fig. 3b
I t ¼ I 0 þet=s
and c), we can see two main emission peaks at
In this paper, the FLS920 full-function steady-state 595 nm and 616 nm attributed to the magnetic dipole
transient fluorescence spectrometer manufactured by transition and electric dipole transition of Eu3?,
Edinburgh company is used to test the fluorescence respectively. The former is insensitive to positional
lifetime of samples. The detection range of sample symmetry, while the latter is hypersensitive to
wavelength is 190–870 nm, and the measurement structural symmetry. Obviously, in the present study,
range of sample fluorescence lifetime is 100 PS–10 s. the emission peak at 616 nm is much stronger indi-
The fluorescence lifetime of LiSrGd0.8(WO4)3:0.2Eu3? cating 5D0 ? 7F2 is the dominant transition. It reveals
phosphor is about 0.5550 ms, that of LiSrGd0.7(- that activator Eu3? ions have mainly occupied the
WO4)3:0.3Eu3? phosphor is about 0.5662 ms, and that asymmetric lattice sites in LiSrGd0.7(WO4)3. The ratio
of LiSrGd0.6(WO4)3:0.4Eu3? phosphor is about of emission intensity of electric dipole transition over
0.5623 ms. The sample’s decay lifetime belongs to a the magnetic dipole transition is a meaningful factor
millisecond order which reveals the suitability of which indicates the asymmetry ratio around Eu3?
these phosphors for many display and lighting ions. The asymmetry ratio (Rasy) is expressed as fol-
applications. lows [33]:
 J Mater Sci: Mater Electron

Fig. 5 PL decay time profile for

LiSrGd1-x(WO4)3:xEu3?(x = 0.2,0.3,0.4) phosphors
(kex ¼ 393nm)

I ð5D0 ! 7F2 Þ Fig. 6 CIE chromaticity color coordinates of

Rasy ¼
I ð5D0 ! 7F1 Þ LiSrGd0.7(WO4)3:0.3Eu3? phosphor (Color figure online)

The color purity of the sample can be obtained by LiSrGd0.7(WO4)3:0.3Eu3? phosphor are both illus-
numerical calculation of color coordinates, The color trated in Fig. 6. The CIE chromaticity color coordi-
purity is expressed as follows [34]: nate of the LiSrGd0.7(WO4)3:0.3Eu3? phosphor is
x  xw (0.666,0.334), which is very close to the standard red
Pe ¼
xk  xw CIE color coordinate published by the National
Television Systems Committee(NTSC), indicating
In the above formula, x represents the color coor- that the material has high color purity. This indicates
dinates of the sample, xw represents the color coor- that the LiSrGd0.7(WO4)3:0.3Eu3? phosphor has
dinates of the reference light source, and xk potential application in the field of white LED.
represents the coordinates of the dominant wave-
length. The calculated results are listed in Table 1. 3.3.6 Temperature-dependent properties of phosphor
According to these data, we can see LiSrGd0.7(-
WO4)3:0.3Eu3? phosphor’s asymmetry ratio and color It is known that the temperature of white light LED
purity. will increase due to the heat produced in their
working procedure. The lighting LED can work at
3.3.5 CIE chromaticity color coordinates analysis very low temperatures, but the maximum heat-re-
sistant temperature of the LED chip cannot exceed
The CIE chromaticity color coordinates and photo of 120 °C (393 K). Phosphors’ variable temperature
red fluorescence under ultraviolet light of

Table 1 The asymmetry ratio

(Rasy), color coordinate, and Eu3? Composition(/mol) Color coordinate Asymmetry ratio (Rasy) Color purity
color purity of
0 (0.6391, 0.3604) 7.7214 0.9969
LiSrGd0.7(WO4)3:0.3Eu3?
0.1 (0.6659, 0.3336) 13.9337 1.0004
phosphors (kex = 393 nm)
0.2 (0.6637, 0.3353) 14.4692 0.9939
0.3 (0.6660, 0.3340) 14.0621 1.0007
0.4 (0.6663, 0.3329) 14.0160 1.0016
J Mater Sci: Mater Electron

Fig. 7 a PL excitation spectra and b, c PL emission spectra of LiSrGd0.7(WO4)2: 0.3Eu3? at different temperatures; d the emission
intensity of phosphors situated at the strongest peak

fluorescence excitation and emission spectrum in the centers. This phenomenon is called the thermal
range of 20–120 °C (293–393 K) are shown in Fig. 7a– quenching effect [35–37]. By analyzing the line
c. The excitation spectra in Fig. 7a shows that with chart of peak intensity with temperature in the
the increase of working temperature, the emission Fig. 7d, these phosphors’ intensity of 393 K reduced
peak value decreases. These emission spectra have a to 86.43 and 80.47 % relative to that of room
similar shape and their major peak position and temperature.
corresponding FWHM did not exhibit significant To investigate the thermal quenching mechanism,
changes when temperature increases from 293 to the Arrhenius method was used. Figure 7 a, shows
393 K, due to the characteristic transition of Eu3? ions that data can be fitted well as a linear function
which is not easily affected by the external environ- according to the Arrhenius formula:
ment. However, phosphors emission intensity  
I0 DE
decreases when temperature increases due to the  1 ¼ Cexp 
I kT
temperature-dependent non-radiative transition pro-
cess of electron and thermally active phonon in both where I0 is initial emission intensity, I is emission
ground state and the excited state of luminescent intensity at a given temperature, C is a constant, k is
 J Mater Sci: Mater Electron

Fig. 8 a Relation between the 1/kT and the ln[I0/(I - 1)] of LiSrGd0.7(WO4)3:0.3Eu3? phosphor; b schematic diagram of crossover
process in Eu3? ions in place configuration coordinates

Boltzmann factor (8:61733  105 eVK1 Þ, DE is the 4 Conclusions

excitation energy, and T is temperature. The fitting
function can be written as follows: y ¼ 0:1891x þ A series of LiSrGd1-x(WO4)3:xEu3? phosphors were
4:0508 (DE ¼ 0:1892; c ¼ e4:0508 ¼ 57:4434). It shows successfully prepared by solid-state reactions. The
that the thermal quenching mechanism of Eu3? in structures of the samples were characterized by X-ray
LiSrGd(WO4)3 matrix can be described as the cross- diffraction. Fluorescence spectra showed that these
over process [38]. The crossover process can be phosphors could be excited by the near-UV light of
described by configuration coordinates as shown in 393 nm and the blue light of 464 nm, and showed
Fig. 8b, when Eu3? is excited, the electrons in the strong red emission lines at 616 nm. The optimum
ground state will jump to 5D1 level, and then reach doped concentration of Eu3? was 30 % in
5
D0 by cross-relaxation. Under the action of thermal LiSrGd(WO4)3, respectively. At this doping concen-
activation, a part of the electrons overcome the tration, the CIE chromaticity color coordinates of the
energy barrier and reach the Eu3?–O2- charge LiSrGd1-x(WO4)3:xEu3? phosphors are excellently
transfer band (process I). Then it relaxes along with situated in the red district. The thermal stability
process II and process III to the ground state 7FJ in a analysis of the phosphors shows that their emission
non-radiative form, and the rest of the electrons pass intensity is roughly stable as temperature increases. It
through 5D0-7FJ radiative transition and return to the was shown that these phosphors were promising red
ground state. In the above process, the excitation component candidates for white LEDs.
energy dissipates in the form of heat energy in the
lattice of the matrix. There are many reasons for the
thermal quenching of luminescent materials, but Acknowledgements
there are two main reasons: first, the lattice vibration
This work was supported by the National Natural
intensifies with the increase of temperature, which
Science Foundation of China (Grant No. 51572195).
makes the lattice relaxation of the luminescent center
increase, the probability of non-radiative transition
increases, and the luminous efficiency decreases, References
which is commonly known as the temperature char-
acteristic; The other is that the rise of temperature 1. F.K. Yam, Z. Hassan, Innovative advances in LED technol-
causes some essential changes in the state of the ogy. Microelectron. J. 36(2), 129–137 (2004)
luminous center or the surrounding microenviron- 2. S. Pimputkar, J.S. Speck, S.P. DenBaars et al., Prospects for
ment, thus reducing the luminous efficiency, which is LED lighting. Nat. Photonics 3(4), 180–182 (2009)
commonly known as ‘‘thermal stability’’ [39].
J Mater Sci: Mater Electron

3. K. Zhang, H.Z. Liu, W.B. Hu, Advances in the study of 19. Q. Zhang, Q.Y. Zhu, Y. Tian, X.H. Feng, J.T. Sun, S.C. Lv,
phosphor for white LEDs. J. Mater. Rep. 9, 50–53 (2005) Luminescent properties of Eu3? doped Gd2WO6 and Gd2(-
4. J.C. Zang, Y. Qi, Y.X. Liu, Solid white lighting and rare earth WO4)3 nanophosphors prepared via co-precipitation method.
luminescence materials. J. Mater. Rep. 7, 6–9 (2006) J. Rare Earths 29(09), 815–821 (2011)
5. Y.H. Wang, G. Zhu, S.Y. Xin, Q. Wang, Recent development 20. Z. Liu, Q. Meng, H. Liu et al., Energy transfer and electron–
in rare earth doped phosphors for white light emitting diodes. phonon coupling properties in Gd2(WO4)3: Eu phosphor. Opt.
J. Rare Earths 33(01), 1–12 (2015) Mater. 36(2), 384–389 (2013)
6. M.M. Haque, M. Kudrat-E-Zahan, N.A. Jahan et al., Eu3?- 21. Q. Zeng, P. He, M. Pang et al., Sr9R2-xEuxW4O24(R=Gd and
activated potential red-emitting phosphor for solid-state Y) red phosphor for near-UV and blue InGaN-based white
lighting. Optik Int. J. Light Electron Optics 133, 1–8 (2017) LEDs. Solid State Commun. 149(21), 880–883 (2009)
7. T. Komukai, Y. Sato, H. Kato, M. Kakihana, A high-lumi- 22. G. Yan, Y. Chao, J. Pengfei et al., Synthesis, crystal structure
nescence BaZrSi3O9:Eu2? blue-green-emitting phosphor: of LiCaRE5(BO3)6(RE = Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,
synthesis and mechanism. J. Lumin. 181, 211–216 (2017) Yb, Lu, Y) and Eu3? luminescence in LiCaRE5(BO3)6 (RE =
8. Z. He, X. Huang, R. Zhou et al., Synthesis and luminescence Gd, Y, Lu). Solid State Chem. 293, 121821 (2021)
properties of a new green emitting Ca2MgSi2O7-xNx:Eu2? 23. X. Zhao, Y. Ding, Z. Li et al., An efficient charge compen-
phosphor. J. Alloys Compd. 658, 36–40 (2016) sated red phosphor Sr3WO6: K?, Eu3? For white LEDs.
9. X. Huang, H. Guo et al., Eu3?-activated Na2Gd(PO4)(MoO4): J. Alloys Compd. 553, 221–224 (2013)
a novel high-brightness red-emitting phosphor with high color 24. S. Zitzer, F. Schleifenbaum, T. Schleid, Na2Y3Cl3(TeO3)4:
purity and quantum efficiency for white light-emitting diodes. synthesis, crystal structure and spectroscopic properties of the
J. Alloys Compd. 720, 29–38 (2017) bulk material and its luminescent Eu3?-doped samples.
10. G. Sivaramaiah, J.L. Rao et al., Investigation of new UV- ChemInform 69(2), 150–158 (2014)
emitting, Gd-activated Y4Zr3O12 phosphors prepared via 25. H. Wang, Y. Li, Z. Ning et al., A novel red phosphor LixNa1-
combustion method. J. Lumin. Interdis. J. Res. Excit. State xEu(WO4)2 solid solution: influences of Li/Na ratio on the
Process. Condens. Matter 57, 133–138 (2015) microstructures and luminescence properties. J. Lumines. S2,
11. P. Shi, Z. Xia, M.S. Molokeev et al., Crystal chemistry and 56–61 (2018)
luminescence properties of red-emitting CsGd1-xEux(MoO4)2 26. Y. Wang, X. Liu, P. Niu et al., Novel Gd2Mo4O15: Eu3? red-
solid-solution phosphors. Dalton Trans 43(25), 69–76 (2014) emitting phosphor for UV, NUV and blue LED applications.
12. S. Ekambaram, M. Maaza, Combustion synthesis and lumi- J. Lumines. 184, 1–6 (2017)
nescent properties of Eu3?-activated cheap red phosphors. 27. A. Kn, B. Xm, A. Pl et al., Synthesis and luminescence
J. Alloys Compd. 395(1–2), 132–134 (2005) properties of apatite-type red-emitting Ba2La8(GeO4)6-
13. K. Binnemans, Interpretation of europium(III) spectra. Coord. O2:Eu3? phosphor-ScienceDirect. J. Rare Earths 257,
Chem. Rev. 295, 45–51 (2015) 1431–1437 (2020)
14. D. Feng, C. Ke et al., Pyrethroids as promising marine anti- 28. S.P. Horvath, J. Wells, M.F. Reid et al., Electron paramagnetic
foulants: laboratory and field studies. J. Chem. Phys. 77, resonance enhanced crystal field analysis for low point-group
163–167 (2009) symmetry systems. J. Phys. Condens. Matter Inst. Phys. J. 31,
15. Q. Liu, X. Li, B. Zhang et al., Structure evolution and delayed 92–103 (2019)
quenching of the double perovskite NaLaMgWO6:Eu3? 29. Y.H. Chen, B. Liu, C.S. Shi et al., GdPO_4: ‘‘Gd-Eu’’ energy
phosphor for white LEDs. Ceram. Int. 134, 15294–15300 transfer in Eu3? and GdBO3:Eu3?. J Chin Rare Earth Soc 04,
(2016) 50–54 (2005)
16. B. Han, Y. Dai, J. Zhang et al., Photoluminescence properties 30. H. Wu, J. Stuckelberger, D. Kang et al., Micro-photolumi-
of a double perovskite tungstate based red-emitting phosphor nescence studies of shallow boron diffusions below polysili-
NaLaMgWO6:Sm3?. Ceram. Int. 213, 3734–3740 (2017) con passivating contacts. Sol. Energy Mater. Sol. Cells 22(7),
17. X. Zhaojie, Study on the Synthesis and Luminescence 329–346 (2018)
Properties of Tungstate and Titanium Phosphor (Guangdong 31. M. Tsuta, S. Nakamura, A. Kato, Micronization of
University of Technology, Guangzhou, 2020). KSrPO4:Eu and KBaPO4:Eu phosphor particles for white
18. D.L. Shruthi, A.J. Reddy, G. Kumar et al., Judd Ofelt theo- light-emitting diodes by pulsed laser ablation in liquid. Opt.
retical analysis, luminescence and cathodoluminescence Laser Technol. 135, 106–125 (2021)
properties of Eu3?-activated LiGd(WO4)2 phosphors. J. Lu- 32. I. Ayumi, A. Yuya, H. Ayaka et al., Multicolor upconversion
mines. 222, 117–167 (2020) luminescence of dye-coordinated Er3? at the interface of
 J Mater Sci: Mater Electron

Er2O3 and CaF2 nanoparticles. Sci. Technol. Adv. Mater. a single-phased Sc2O3:Bi3?, Eu3? phosphor. Ceram. Int.
20(1), 1876–1899 (2019) S02(72), 88–112 (2018)
33. X. Li, W. Cai, H. Guan et al., Highly stable CsPbBr3 quantum 37. H. Yamamoto, S. Seki, J. Jean-Pierre et al., Thermal
dots by silica-coating and ligand modification for white light- quenching of luminescence in a disordered compound:
emitting diodes and visible light communication. Chem. Eng. EuNa2Mg2 (VO4)3. J. Electrochem. Soc. 127(3), 694–701
J. 41(9), 277–294 (2021) (1980)
34. T. Kunihiko, O. Shin, T. Harukazu et al., In vivo imaging of 38. W. Jun, Luminescence properties of LB films based on
particle-induced inflammation and osteolysis in the calvariae heteropolytungstate of rare earth. Mater. Sci. Eng. 97(1),
of transgenic mice. J. Biomed. Biotechnol. 62(43), 197–215 83–86 (2003)
(2010) 39. Y. Luo, Y. Liu, C. Wang et al., Near-infrared anti-Stokes
35. Y. Huang, L. Zhou, L. Yang et al., Self-assembled 3D flower- luminescence from neodymium doped perovskite calcium
like NaY(MoO4)2:Eu3? microarchitectures: hydrothermal titanate particles for optical temperature sensors. Sens.
synthesis, formation mechanism and luminescence properties. Actuators A 3(26), 904–922 (2021)
Opt. Mater. 33(6), 777–782 (2011)
36. W. Xie, H. Huang, J. Li et al., Controlling the energy transfer Publisher’s Note Springer Nature remains neutral with
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