materials

Article
Synthesis of Rare-Earth-Doped Strontium Tungstate Phosphor
at Room Temperature and Applied Flexible Composite
Jung-Hyun Wi 1 , Jae-Yong Jung 2, * and Sang-Geon Park 3, *

1 Department of Smart Manufacturing Engineering, Changwon National University,

Changwon 51140, Republic of Korea
2 Research and Business Development Foundation, Engineering Building, Silla University,
Busan 45985, Republic of Korea
3 Department of Mechatronics Convergence Engineering, Changwon National University,
Changwon 51140, Republic of Korea
* Correspondence: [email protected] (J.-Y.J.); [email protected] (S.-G.P.);
Tel.: +82-51-999-6441 (J.-Y.J.); +82-55-213-3845 (S.-G.P.)

Abstract: In this study, we successfully synthesized rare-earth-doped crystalline SrWO4 at room

temperature by co-precipitation. The results from the X-ray diffraction analysis showed a main
diffraction peak related to the (112) plane. Phosphors doped with either Dy3+ or Sm3+ ions showed
strong light absorption in the UV region and blue-yellow and red light emission. To synthesize a white
light phosphor, Dy3+ and Sm3+ ions were co-doped to produce a SrWO4 :[Sm3+ ]/[Dy3+ ] phosphor.
When the Sm3+ ion concentration was increased and the Dy3+ concentration was maintained, the
red light intensity increased while the blue-yellow light intensity decreased. The composites were
combined with polydimethylsiloxane (PDMS), and a flexible composite material was fabricated. The
composite exhibited various luminescence properties under UV and visible light, which suggested
its potential for use as an LED color filter.
Citation: Wi, J.-H.; Jung, J.-Y.; Park,
S.-G. Synthesis of Rare-Earth-Doped Keywords: SrWO4 ; phosphor; luminescence; flexible
Strontium Tungstate Phosphor at
Room Temperature and Applied
Flexible Composite. Materials 2022,
15, 8922. https://doi.org/10.3390/ 1. Introduction
ma15248922 Phosphors doped with rare earth (RE) tungstates have attracted significant research in-
Academic Editors: Willem D van terest because they can be used as white-light-emitting diodes, solid-state lighting, displays,
Driel and Maryam Yazdan Mehr and in various lighting industries [1,2]. Tungstates such as barium tungstate (BaWO4 ), stron-
tium tungstate (SrWO4 ), and calcium tungstate (CaWO4 ) are chemically stable, have a broad
Received: 26 October 2022
absorption wavelength in the UV–vis region, and are capable of excellent energy transfer
Accepted: 12 December 2022
to rare earth ions [3–5]. Manufacturing a phosphor that emits a variety of colors with high
Published: 13 December 2022
luminescence intensity requires a thermally and chemically stable host structure doped
Publisher’s Note: MDPI stays neutral with rare earth ions such as terbium (Tb3+ ), europium (Eu3+ ), dysprosium (Dy3+ ), and
with regard to jurisdictional claims in samarium (Sm3+ ), which possess many energy levels in the visible light region [6,7]. Among
published maps and institutional affil- these rare earth ions, Dy3+ emits blue light via magnetic dipole transition (4 F9/2 →6 H15/2 )
iations. and yellow light via electric dipole transition (4 F9/2 →6 H13/2 ) [8]. Sm3+ emits orange light
via magnetic dipole (4 G5/2 →6 H7/2 ) transition and red light via electric dipole transition
(4 G5/2 →6 H9/2 ) [9]. Hence, Dy3+ and Sm3+ are both compelling doping candidates for
use in phosphor materials. Yu et al. synthesized a Ca3−x Lix (PO4 )2−x (SO4 )x :Dy3+ , Sm3+
Copyright: © 2022 by the authors.
phosphor by the sol–gel method and investigated the effect of Sm3+ ion concentration on
Licensee MDPI, Basel, Switzerland.
the crystal structure and luminescence intensity. The authors found that the co-doping of
This article is an open access article
Dy3+ and Sm3+ emitted warm white light and proposed that it was an effective method
distributed under the terms and
conditions of the Creative Commons
to implement [10]. Jung et al. synthesized BaWO4 and CaWO4 using the co-precipitation
Attribution (CC BY) license (https://
method and doped Tb3+ and Eu3+ rare earth ions to produce green and red phosphors that
creativecommons.org/licenses/by/ can impart luminescent properties to the host [11,12]. Tan et al. synthesized a NaLa(WO3 )2
4.0/). phosphor doped with Dy3+ and Sm3+ using the thermal decomposition method. They

Materials 2022, 15, 8922. https://doi.org/10.3390/ma15248922 https://www.mdpi.com/journal/materials

Materials 2022, 15, x FOR PEER REVIEW 2 of 10

Materials 2022, 15, 8922 2 of 9

phosphor doped with Dy3+ and Sm3+ using the thermal decomposition method. They
found that when the doping concentration of Sm3+ increased, the intensity of the light
found
emitted that
by when the doping
Dy3+ decreased concentration
as energy of Sm3+ increased,
was transferred from Dy3+ to the
Smintensity
3+ [13]. Sunof et
theal.light
also
emitted 3+ 3+ 3+3+[13]. Sun3+et al.
reportedbya Dy color decreased
change due asto
energy
energy was transferred
transfer by thefrom Dy toofSm
co-doping Dy and Sm into
also reported
Ca3TeO 6 hostacrystals
color changeusing due to energy transfer
the solid-state reactionbymethod [14]. of Dy3+ and Sm3+ into
the co-doping
Ca3 TeO 6 hostwe
Herein, crystals
report using the solid-state
a successful reaction
synthesis method
of SrWO 4 by[14].
a co-precipitation method at
Herein, we report a successful synthesis
room temperature. We investigated the effect of doping of SrWO by
4 SrWOa co-precipitation
4 with either Dy method
3+ or Smat 3+,

room temperature. We investigated the effect of doping SrWO with either Dy 3+ or Sm3+3+,
and co-doping SrWO4 with both Dy and Sm as well as the4 effect of altering the Sm
3+ 3+

and co-doping This

concentration. SrWO 4 with
study both
also Dy3+ and Sm
characterized
3+ as well as the effect of altering the Sm3+
the luminescence intensity, crystal structure,
concentration.
and particle shape This study
of the also characterized
synthesized the luminescence
phosphors. intensity,
Finally, a flexible LED crystal
filterstructure,
was pro-
and
ducedparticle shape ofthe
by combing thesynthesized
synthesizedphosphor
phosphors. withFinally, a flexible LED filter was produced
a polymer.
by combing the synthesized phosphor with a polymer.
2. Materials and Methods
2. Materials and Methods
2.1. Synthesis of the Crystalline SrWO4 and SrWO4:RE3+ by Co-Precipitation
2.1. Synthesis of the Crystalline SrWO4 and SrWO4 :RE3+ by Co-Precipitation
Starting materials: Strontium acetate ((CH3CO2)Sr, Sigma-Aldrich), sodium tungstate
Starting materials: Strontium acetate ((CH CO2 )Sr, Sigma-Aldrich), sodium tungstate
(Na2WO4·2H2O, Sigma-Aldrich), dysprosium3 nitrate (Dy(NO3)3·xH2O, Dy3+, 3+ Sigma-Al-
(Na2 WO4 ·2H2 O, Sigma-Aldrich), dysprosium nitrate (Dy(NO3 )3 ·xH2O, Dy , Sigma-
drich), and samarium nitrate (Sm(NO3)3·6H2O, Sm3+, Sigma-Aldrich).
Aldrich), and samarium nitrate (Sm(NO3 )3 ·6H2 O, Sm3+ , Sigma-Aldrich).
A total of 1 mmol of (CH3CO2)Sr and 1 mmol of Na2WO4·2H2O were placed in beakers
A total of 1 mmol of (CH3 CO2 )Sr and 1 mmol of Na2 WO4 ·2H2 O were placed in beakers
‘A’ and ‘B’, respectively, and each beaker was combined with 100 mL of distilled water.
‘A’ and ‘B’, respectively, and each beaker was combined with 100 mL of distilled water.
The solutions in each beakers ‘A’ and ‘B’ were completely dissolved until the mixtures
The solutions in each beakers ‘A’ and ‘B’ were completely dissolved until the mixtures
were transparent in color. Next, the two solutions were combined and stirred for 30 min
were transparent in color. Next, the two solutions were combined and stirred for 30 min at
at ambient temperature. After mixing, the final mixture changed to an opaque white color
ambient temperature. After mixing, the final mixture changed to an opaque white color
and formed a powder precipitate. The mixture was centrifuged at 4000 rpm to recover the
and formed a powder precipitate. The mixture was centrifuged at 4000 rpm to recover
powder. The recovered powder was washed twice with distilled water to remove side
the powder. The recovered powder was washed twice with distilled water to remove side
productsand
products andunreacted
unreactedcompounds
compoundsand andthen
then centrifuged
centrifugedagain.
again. Finally,
Finally,thethepowder
powderwas was
dried at 80 ◦°C in an oven for 16 h (Figure 1). The phosphor was
dried at 80 C in an oven for 16 h (Figure 1). The phosphor was synthesized by adding synthesized by adding
0.25 mmol
0.25 mmoleach eachof ofDy Dy3+3+ and
and SmSm3+3+ to beaker ‘A’, and the remaining steps were performed
to beaker ‘A’, and the remaining steps were performed
as above.
as above. White
Whitelightlightphosphor
phosphorwas wassynthesized
synthesizedby byco-doping
co-dopingDy Dy andSm
3+3+and Sm3+3+ and
and fixing
fixing
the amount of Dy 3+
3+while altering the amount of Sm 3+. The
3+
the amount of Dy while altering the amount of Sm . The doping percentages for doping percentages for all sam-
all
ples are shown in Table
samples are shown in Table 1. 1.

Figure 1. Schematic
Figure1. Schematic of
of co-precipitation
co-precipitationprocedure.
procedure.
Materials 2022, 15, 8922 3 of 9

Table 1. Reagents and moles used in the synthesis.

SrWO4 Up-Conversion Phosphor Synthesis

Reagents (CH3 CO2 )Sr Na2 WO4 ·2H2 O Dy(NO3 )3 ·xH2 O Sm(NO3 )3 ·6H2 O
Molecular weight (g/mol) 205.93 329.85 348.51 444.47
Used mole (mmol) 1 1 0.25 0.025~0.25
[Dy3+ ]/[Sm3+ ] Ratio
Reagents (CH3 CO2 )Sr Na2 WO4 ·2H2 O Dy(NO3 )3 ·xH2 O Sm(NO3 )3 ·6H2 O
1 1 0.25 0.025
1 1 0.25 0.05
1 1 0.25 0.075
Used mole (mmol) 1 1 0.25 0.1
1 1 0.25 0.15
1 1 0.25 0.2
1 1 0.25 0.25

2.2. Fabricated Flexible Color Composite

To prepare the composite, 0.1 g of the synthesized powder, 2 g of polydimethylsiloxane
(PDMS) polymer, and 0.2 g of curing agent were mixed until homogenous. Next, the
mixture was poured into a square mold and placed in an oven at 80 ◦ C for 1 h to form the
composite. The composite was then irradiated with an ultraviolet lamp to observe any
color change.

2.3. Characterization
X-ray diffraction analysis (XRD) (X’Pert PRO MPD, 40 kV, 30 mA, Cu–Kα radiation
(wavelength: 1.5406 Å)) was used to characterize the crystal structure of the synthesized
phosphor powder. The XRD analysis was carried out at a scan rate of 4◦ per minute at a
diffraction angle of 10◦ to 70◦ . The crystal grains’ size and microscopic surface shape were
characterized with a scanning electron microscope (CZ, MIRA I LMH, TESCAN), and a
fluorescence photometer (FS-2, Scinco) with a xenon lamp as a light source was used for
emission and absorption characteristics.

3. Results & Discussion

3.1. Characteristics of SrWO4 and Single Doped SrWO4
Figure 2a shows the XRD peaks of SrWO4 , SrWO4 :Dy3+ , and SrWO4 :Sm3+ . SrWO4
showed a tetragonal (a = 5.400 Å, b = 5.400 Å, c = 11.910 Å) structure that was in good
agreement with ICDD # 01-089-2568. The single-doped samples used 0.25 mmol of rare
earth ions. The XRD analysis showed a main diffraction peak on the (112) plane. Likewise,
the RE-doped SrWO4 samples exhibited a strong (112) main peak.
Figure 2b shows the lattice constant change with and without RE doping along the
(112) plane. The lattice constant of the (112) plane significantly changed due to the RE
doping (SrWO4 : 0.290 nm, SrWO4 :Dy3+ : 0.2891 nm, SrWO4 :Sm3+ : 0.2891 nm). This
change in the crystal lattice of SrWO4 by RE doping was attributed to the relatively large
ionic radius (Sr: 1.18 Å, W: 0.66 Å, Dy: 1.07 Å, Sm: 1.22 Å) of the RE dopants [15].
Figure 3 shows the absorption and emission spectra of each sample. The host SrWO4
showed absorption from 220 nm to 340 nm and peaked at 277 nm. When the sample was
excited at the highest peak (277 nm), a spectrum with a range of 350–650 nm peaking at
492 nm in a blue-white emission spectrum was observed (Figure 3a). Figure 3b shows the
absorption and emission spectra of the SrWO4 :Dy3+ phosphor powder. In the absorption
spectrum controlled with an emission wavelength of 572 nm, the charge transfer band
(CTB) absorption signal generated between the Dy3+ cations and O2- anions peaked at
253 nm. Moreover, several absorption narrow bands generated within the 4f-4f electron
arrangement of Dy3+ ions were observed [16]. Among them, the absorption wavelength at
351 nm had the strongest absorption intensity and signaled the 6 H15/2 →6 P7/2 transition of
Materials 2022, 15, 8922 4 of 9

Dy3+ . The absorption wavelengths at 325, 364, and 386 nm, which had relatively weaker
absorptions, were identified as 6 H15/2 →6 P3/2 transitions. These absorption signals were
generated by the 6 H15/2 →6 P5/2 and 6 H15/2 →4 I13/2 transitions [17]. After excitation at
253 nm, the SrWO4 :Dy3+ phosphor powder exhibited a yellow emission spectrum with a
peak at 572 nm due to the 4 F9/2 →6 H13/2 electric dipole transition of Dy3+ ions. Furthermore,
the blue emission band belonging to the host was also observed. Since the emission peak
was strong due to the electric dipole transition, the Dy3+ ion doped in the SrWO4 host
lattice was in a non-inversion symmetric site [18]. For the phosphor doped with Sm3+
ions, when the emission wavelength was controlled at 643 nm, a CT band with a peak at
248nm and an absorption band with a peak at 297nm were observed. This absorption signal
originated from the Sm3+ ions located within the host lattice. When the synthesized sample
was excited at 248 nm, blue light emission by the SrWO4 matrix, green light emission at
560 nm (4 G5/2 →6 H15/2 ), orange light emission at 599 nm (4 G5/2 →6 H9/2 ), and red light
emission signals at 643 nm (4 G5/2 →6 H11/2 ) were generated [19]. Since the intensity of the
red emission caused by electric dipole transition was about 1.1 times stronger than that
caused by magnetic dipole transition, the Sm3+ ions in the SrWO4 host crystal were located
in non-inversion symmetric sites [20]. In addition, as in the undoped SrWO4 sample, blue
Materials 2022, 15, x FOR PEER REVIEW 4 of 10
light emission was observed in the doped specimen due to absorption and emission by the
matrix in a wide range of light absorptions.

(a) (b) 0.2910

SrWO4:Sm3+ d
(112)
0.2905
XRD intensity (a.u.)

d(112)spacing(nm)

SrWO4:Dy3+ 0.2900

0.2895
SrWO4
0.2890
(112)

ICDD No. 01-089-2568 SrWO4

0.2885
(204)
(101)

(312)
(200)
(004)

(116)
(220)
(211)

(224)

(008)

(400)

0.2880
10 15 20 25 30 35 40 45 50 55 60 65 70 Host Dy3+ Sm3+
2 theta (o) Dopant
Materials 2022, 15, x FOR PEER REVIEW 5 of 10
(a)XRD
XRDpatterns
patternsofofcrystalline
crystallineSrWO
SrWO4 4and
andSrWO
SrWO 3+ and (b) d
Figure2.2.(a)
Figure 4 :RE
4:RE 3+ and (b) d(112)(112) spacing
spacing of samples.
of samples.

Figure 2b shows the lattice constant change with and without RE doping along the
(112) plane. The lattice constant of the (112) plane significantly changed due to the RE
doping (SrWO4: 0.290 nm, SrWO4:Dy3+: 0.2891 nm, SrWO4:Sm3+: 0.2891 nm). This change
in the crystal lattice of SrWO4 by RE doping was attributed to the relatively large ionic
radius (Sr: 1.18 Å, W: 0.66 Å, Dy: 1.07 Å, Sm: 1.22 Å) of the RE dopants [15]. Figure 3 shows
the absorption and emission spectra of each sample. The host SrWO4 showed absorption
from 220 nm to 340 nm and peaked at 277 nm. When the sample was excited at the highest
peak (277 nm), a spectrum with a range of 350–650 nm peaking at 492 nm in a blue-white
emission spectrum was observed (Figure 3a). Figure 3b shows the absorption and emis-
sion spectra of the SrWO4:Dy3+ phosphor powder. In the absorption spectrum controlled
with an emission wavelength of 572 nm, the charge transfer band (CTB) absorption signal
generated between the Dy3+ cations and O2- anions peaked at 253 nm. Moreover, several
(a) Luminescence
Luminescence spectra :Dy3+3+ 3+. 3+ .
Figure 3.
Figure 3. (a)
absorption narrow bandsspectra of SrWO
of
generated SrWO44,,(b)
within(b)SrWO
SrWO44:Dy
the 4f-4f , and(c)(c)SrWO
, and
electron SrWO 4 :Sm
4:Sm
arrangement of Dy3+ ions
were observed
The FE-SEM
FE-SEM [16].images
Amongofthem, the absorption
all samples
samples showedthat wavelength
thatthey
theyall at
allhad
had 351long
nm cylindrical
had the strongest shapes.
The
absorption intensityimages
and of all
signaled the showed
6H15/2 → 6P7/2 transition of Dy 3+long
. The cylindrical
absorption shapes.
wave-
For SrWO
For SrWO , the particle size was ~6.2 µm and ~1.92 µm in the longitudinal
4, the particle size was ~6.2 µm and ~1.92 µm in the longitudinal and transverse
4 and transverse
lengths at 325, 364,
direction, respectively and 386
respectively (Figurenm, which
(Figure 4a).
4a). For had
For the relatively
the RE-doped weaker
SrWO44:Dy absorptions,
3+
:Dy3+ ,the were
theparticle identified
particle sizeaver- aver-
direction,
as 6H15/2→6P3/2 transitions. These absorption RE-doped
signals wereSrWO generated ,by the 6H15/2→size 6P5/2 and

6aged
H15/2→~5.09
4I13/2 µm (longitudinal)
transitions andexcitation
[17]. After ~1.49 µm at (transverse)
253 nm, the(FigureSrWO44b), :Dy3+and for SrWO
phosphor 4:Sm3+,
powder
the particles
exhibited measured
a yellow ~5.61spectrum
emission µm (longitudinal)
with a peak and 1.49nm
at 572 µmdue (transverse)
to the 4F9/2(Figure
→6H13/24c). electric
dipole transition of Dy3+ ions. Furthermore, the blue emission band belonging to the host
was also observed. Since the emission peak was strong due to the electric dipole transition,
the Dy3+ ion doped in the SrWO4 host lattice was in a non-inversion symmetric site [18].
 Figure 3. (a) Luminescence spectra of SrWO4, (b) SrWO4:Dy3+, and (c) SrWO4:Sm3+.

Materials 2022, 15, 8922 The FE-SEM images of all samples showed that they all had long cylindrical shapes. 5 of 9

For SrWO4, the particle size was ~6.2 µm and ~1.92 µm in the longitudinal and transverse
direction, respectively (Figure 4a). For the RE-doped SrWO4:Dy3+, the particle size aver-
aged ~5.09
~5.09µm (longitudinal) and
and ~1.49
~1.49 µm (transverse) (Figure 4b), and for SrWO44:Sm3+ 3+ ,
aged µm (longitudinal) µm (transverse) ,
the particles
the particles measured
measured ~5.61
~5.61µm (longitudinal) and
µm (longitudinal) and 1.49
1.49 µm (transverse) (Figure 4c).
µm (transverse)

Figure
Figure 4.
4. FE-SEM
FE-SEMimages
imagesof
of(a)
(a)SrWO
SrWO44, ,(b)
(b)SrWO
SrWO4:Dy , and (c) SrWO4:Sm3+ powders.
3+3+ 3+
4 :Dy , and (c) SrWO4 :Sm powders.

3.2. Characteristics
3.2. [Sm3+3+]/[Dy
Characteristicsofof[Sm ]/[Dy3+3+ ] Co-Doped
] Co-Doped SrWO
SrWO 4 4

Figure 5a
Figure 5a shows
shows the
the XRD peaks of SrWO4 co-doped co-doped with the rare earth ions Dy3+ and
3+ and
3+
Sm3+ forforsynthesis
synthesisasasa awhite-light-emitting
white-light-emittingphosphor.phosphor.The The XRD pattern did not indicate
Sm XRD pattern did not indicate a
a secondary
secondary phase
phase caused
caused by theby the RE doping
RE doping but exhibited
but exhibited the diffraction
the diffraction signalsignal
of the of
mainthe
main(112).
peak peak Figure
(112). Figure
5b shows 5b the
shows theconstant
lattice lattice constant
change in change in the
the (112) (112)which
plane, plane, which
was the
was the main peak of the RE-co-doped SrWO :[Sm 3+ ]/[Dy3+ ] samples. As reported above,
main peak of the RE-co-doped SrWO4:[Sm ]/[Dy 3+ 4 3+ ] samples. As reported above, the lattice
the latticeof
constants constants
the SrWO of 4the
:Dy3+ SrWO :Dy3+ 4and
and 4SrWO :Sm3+SrWO
samples
3+ samples decreased compared
4 :Smdecreased compared to the un-
to the un-doped
doped sample. However,
sample. However, as seen asinseen in Figure
Figure 5b, the5b, the lattice
lattice constantsofof the
constants the
SrWO44:[Sm
SrWO :[Sm3+3+ ]/[Dy
]/[Dy
3+ ] sample increased. The higher lattice constants could have been
3+] sample increased. The higher lattice constants could have been
Materials 2022, 15, x FOR PEER REVIEW 6 of 10
caused by
caused by crystal
crystal lattice
lattice distortion
distortion or orstructural
structural change
change induced
induced by bythe
theadditional
additionalamount
amount
of RE
of RE ions
ions having
having aa rather
rather large
large ionic
ionic radius.
radius.

(a) SrWO4:[Sm3+]/[Dy3+] ~ 1 (b) 0.2920 d(112)

SrWO4 :[Sm3+]/[Dy3+] ~ 0.8 0.2915
XRD intensity (a.u.)

d(112)spacing(nm)

SrWO4:[Sm3+]/[Dy3+] ~ 0.6
0.2910
SrWO4:[Sm3+]/[Dy3+] ~ 0.4
0.2905
SrWO4:[Sm3+]/[Dy3+] ~ 0.3
0.2900
SrWO4:[Sm3+]/[Dy3+] ~ 0.2
0.2895
SrWO4:[Sm3+]/[Dy3+] ~ 0.1
0.2890
(112)

ICDD No. 01-089-2568 SrWO4

0.2885
(101)

(200)

(204)

(224)
(004)

(116)

(008)
(211)

(220)

(400)
(312)

0.2880
10 15 20 25 30 35 40 45 50 55 60 65 70 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
2 theta (o) [Sm3+]/[Dy3+]

Figure 5.
Figure (a) XRD
5. (a) XRD patterns
patterns of
of crystalline
crystalline SrWO :[Sm3+3+
SrWO44:[Sm ]/[Dy
]/[Dy
3+ ] and (b) d
3+] and (b) d(112)(112) spacing
spacing of samples.
of samples.

Figure 66shows
Figure showsthe theFE-SEM
FE-SEM image
image and
and EDSEDS mapping
mapping component
component analysis
analysis of theofsyn-
the
synthesized SrWO :[Sm 3+ ]/[Dy3+ ] phosphor. The particle shape grew in the longitudinal
4
thesized SrWO4:[Sm3+]/[Dy3+] phosphor. The particle shape grew in the longitudinal direc-
direction of a cylindrical shape and resembled a dumbbell, with an estimated size of
tion of a cylindrical shape and resembled a dumbbell, with an estimated size of 5.26 µm
5.26 µm and 2.33 µm in the longitudinal and transverse directions, respectively. The EDS
and 2.33 µm in the longitudinal and transverse directions, respectively. The EDS compo-
component analysis showed the presence of Sr, W, O, Dy, and Sm, which confirmed that
nent analysis showed the presence of Sr, W, O, Dy, and Sm, which confirmed that the RE
the RE ions were doped (Figure 6b,c).
ions were doped (Figure 6b,c).
 Figure 6 shows the FE-SEM image and EDS mapping component analysis of the syn-
thesized SrWO4:[Sm3+]/[Dy3+] phosphor. The particle shape grew in the longitudinal direc-
tion of a cylindrical shape and resembled a dumbbell, with an estimated size of 5.26 µm
and 2.33 µm in the longitudinal and transverse directions, respectively. The EDS compo-
Materials 2022, 15, 8922 nent analysis showed the presence of Sr, W, O, Dy, and Sm, which confirmed that the 6REof 9

ions were doped (Figure 6b,c).

Figure
Figure6.6.(a)(a)
FE-SEM image
FE-SEM of of
image SrWO 4:[Sm3+]/[Dy
SrWO 3+ 3+], (b)
3+ EDS layered image, and (c) elemental map-
4 :[Sm ]/[Dy ], (b) EDS layered image, and (c) elemental
ping analysis.
mapping analysis.

Figure 7a shows the emission spectrum of the SrWO4 :[Sm3+ ]/[Dy3+ ] phosphor powder
co-doped while changing the Sm3+ ion concentration (the Dy3+ ion concentration was fixed).
When excited at 253 nm and as the doping concentration of Sm3+ increased, the following
were simultaneously observed: blue light at 492 nm, yellow light at 572 nm, orange light at
599 nm, and red light at 643 nm. As the concentration of Sm3+ ions increased, the intensity
of yellow light emission by the Dy3+ ions decreased. The lower yellow light emission
intensity meant that the emission energy was converted from the Dy3+ ions in the host
lattice to the Sm3+ ions (Figure 7b). The energy transfer efficiency from the Dy3+ to Sm3+
ions can be expressed by Equation (1) [21].

η = 1 − I/I0 (1)

where I is the emission intensity of Dy3+ ions in SrWO4 :[Sm3+ ]/[Dy3+ ] phosphors and
I0 is the emission intensity of Dy3+ ions in the SrWO4 :Dy3+ phosphors. As shown in
Figure 7c, the energy transfer efficiency tended to increase as the amount of Sm3+ ions
added increased. However, as the emission intensity decreased, a concentration-quenching
phenomenon due to excessive rare earth doping was observed [22].
 𝜂 = 1 − 𝐼/𝐼 (1)
where I is the emission intensity of Dy3+ ions in SrWO4:[Sm3+]/[Dy3+] phosphors and I0 is
the emission intensity of Dy3+ ions in the SrWO4:Dy3+ phosphors. As shown in Figure 7c,
the energy transfer efficiency tended to increase as the amount of Sm3+ ions added in-
Materials 2022, 15, 8922 7 of 9
creased. However, as the emission intensity decreased, a concentration-quenching phe-
nomenon due to excessive rare earth doping was observed [22].

(a) λex = 253 nm (b) 572 nm, 643 nm

(c) 1.00
Sm

Energy transfer efficiency (η)

[Sm]/[Dy] ~ 0.8 0.95
[Sm]/[Dy] ~ 0.6
PL intensity (a.u.)

Intensity (a.u.)
0.90
[Sm]/[Dy] ~ 0.5

[Sm]/[Dy] ~ 0.4 0.85

[Sm]/[Dy] ~ 0.3
0.80
[Sm]/[Dy] ~ 0.2
0.75
[Sm]/[Dy] ~ 0.1

0.70
Dy

0.65
300 350 400 450 500 550 600 650 700 750 800 Dy3+ 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 Sm3+
0.0 0.2 0.4 0.6 0.8 1.0
3+ 3+
Wavelength (nm) [Sm ]/[Dy ]
[Sm3+]/[Dy3+]

7. (a) PL
Figure 7. PL spectra
spectra of
ofSrWO :[Sm3+
SrWO44:[Sm ]/[Dy3+
3+]/[Dy3+ ] ]under
under253
253nm,
nm,(b)
(b)change
changein
in PL
PL intensity
intensity at 572 nm
and 643 nm, and (c) energy transfer efficiency.
and 643 nm, and (c) energy transfer efficiency.

The electrons located

located atat the
the ground
groundstate, 6H
state,6H 15/2, of the DyDy
of the 3+ ions
3+ ions absorbed energy
absorbed un-
energy
15/2,
der a 253
under nmnm
a 253 excitation energy
excitation and and
energy laterlater
jumped to thetoexcited
jumped state. Since
the excited state. the high
Since energy
the high
level was
energy unstable,
level these electrons
was unstable, dropped
these electrons successively
dropped to the lower-energy
successively excited
to the lower-energy state,
excited
state, 4 4
4 F9/2, byF9/2, by non-radiative
non-radiative transition
transition (NR).the
(NR). With With the populated
populated 4 F9/2the
F9/2 level, level, the radiative
radiative transi-
transitions
tions of Dy3+ Dy3+ occurred
ofoccurred with yellow
with yellow emissionsemissions
due to due4F9/2→to6H4F →6 H13/2 transitions,
9/2transitions,
13/2 re-
respectively.
spectively.
In the interim,In thepartial
interim, partial electrons
electrons located atlocated
the 4F9/2 the 4 Fof
at level 9/2Dylevel of Dy
3+ were 3+ were relaxed
relaxed to the 6Gto5/2
Materials 2022, 15, x FOR PEER REVIEW 6 3+ by the resonance between the two levels, which ultimately 8 of 10
the
levelGof5/2Sm level
3+ byof Smresonance
the between the two levels, which ultimately gave rise to gave
the
rise to the characteristic 3+ (Figure 8).
characteristic emissions emissions of Sm8).
of Sm3+ (Figure

Figure 8. Schematic of energy level structure of the Dy3+ and Sm3+ ions.
Figure 8. Schematic of energy level structure of the Dy3+ and Sm3+ ions.
3.3. Application in a Flexible Composite LED Filter
3.3. Application
To exploreinthe
a Flexible Composite
applicability LED
of the Filter
synthesized phosphor, herein referred to as an LED
colorTofilter,
explore the applicability
a flexible compositeofwas
the synthesized phosphor,
fabricated by herein
mixing the referredwith
phosphor to as aanPDMS
LED
polymer,
color filter,as explained
a flexible in detail
composite wasinfabricated
Section 2.2. The manufactured
by mixing composite
the phosphor with a PDMS showed
poly-
characteristics
mer, as explained ofinblue-white, blue-yellow,
detail in Section and main redcomposite
2.2. The manufactured light in response to UV light.
showed characteris-
Theofcomposite
tics blue-white, was flexible byand
blue-yellow, hand andred
main appeared
light insuitable
responsefor
to use
UV as an LED
light. color filter
The composite
(Figure 9).
was flexible by hand and appeared suitable for use as an LED color filter (Figure 9).
 3.3. Application in a Flexible Composite LED Filter
To explore the applicability of the synthesized phosphor, herein referred to as an LED
color filter, a flexible composite was fabricated by mixing the phosphor with a PDMS poly-
mer, as explained in detail in Section 2.2. The manufactured composite showed characteris-
Materials 2022, 15, 8922 8 of 9
tics of blue-white, blue-yellow, and main red light in response to UV light. The composite
was flexible by hand and appeared suitable for use as an LED color filter (Figure 9).

Figure 9.
Figure 9. Images
Images of
of flexible
flexible composite
composite under
underdaylight
daylightand
andUV
UVlight.
light.

4.
4. Conclusions
Conclusions
We
We successfully
successfully synthesized
synthesized crystalline
crystalline SrWO
SrWO44 at
at room
room temperature
temperature using
using the
the co-
co-
precipitation method. When doped with Dy 3+ and Sm3+ , yellow and red phosphors were
precipitation method. When doped with Dy and Sm , yellow and red phosphors were
3+ 3+
obtained.
obtained. The
The crystal
crystal structure
structure of
of the
the synthesized
synthesized phosphor
phosphor was
was tetragonal,
tetragonal, and
and aa change
change
in the lattice constant was observed due to the Dy3+ and Sm3+ dopants. The synthesized
in the lattice constant was observed due to the Dy3+ and Sm3+ dopants. The synthesized
phosphor
phosphor possessed
possessed aa cylindrical
cylindrical shape,
shape, as
as confirmed
confirmed byby the
theFE-SEM
FE-SEMimages.
images. ForFor the
the
SrWO4 :[Sm ]/[Dy ] phosphor, the intensity of blue-yellow light emitted by the Dy3+
3+ 3+

ions decreased as the concentration of Sm3+ ions increased. We also fabricated a flexible
composite by mixing the synthesized phosphor with a PDMS polymer to demonstrate the
potential applicability of the RE-doped phosphor produced in this study. The composite
showed blue-white, blue-yellow, and red light emissions under UV and visible light,
suggesting its potential application as an LED color filter.

Author Contributions: Conceptualization, J.-Y.J. and S.-G.P. methodology, J.-Y.J.; software, J.-Y.J. and
J.-H.W.; validation, J.-Y.J., J.-H.W. and S.-G.P.; formal analysis, J.-Y.J.; investigation, J.-Y.J. and S.-G.P.;
resources, J.-Y.J. and S.-G.P.; data curation, J.-Y.J. and J.-H.W.; writing—original draft preparation,
J.-Y.J., J.-H.W. and S.-G.P. writing—review and editing, J.-Y.J. and S.-G.P.; visualization, J.-Y.J. and
J.-H.W.; supervision, J.-Y.J. and S.-G.P.; project administration, J.-Y.J.; funding acquisition, S.-G.P. All
authors have read and agreed to the published version of the manuscript.
Funding: This research is funded by the Financial Program for Self-Directed Research Capacity in 2022.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Conflicts of Interest: The authors declare no conflict of interest.

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