Vacuum 191 (2021) 110389

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Short communication

Tunable optical properties of Bi1/2Na1/2TiO3 materials via Sm1/2Na1/

2TiO3 addition

Nguyen Hoang Thoan a, Nguyen Huu Lam a, Ha Thi Thu Hieu b, c, Nguyen The Hoang a,
Pham Van Vinh d, Nguyen Van Hao b, Nguyen Ngoc Trung a, Duong Quoc Van d, **,
Dang Duc Dung a, *
a
Multifunctional Ferroics Materials Lab., School of Engineering Physics, Ha Noi University of Science and Technology, 1 Dai Co Viet road, Ha Noi, Viet Nam
b
Institute of Science and Technology, TNU - University of Sciences, Tan Thinh ward, Thai Nguyen City, Viet Nam
c
Bac Kan Center for Regular and Vocational Education, Bac Kan, Viet Nam
d
Faculty of Physics, Ha Noi National University of Education , 136 Xuan Thuy Street, Cau Giay District, Hanoi, Viet Nam

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

Keywords: In this work, the Sm1/2Na1/2TiO3-addition Bi1/2Na1/2TiO3 materials as solid solutions were synthesized via a
Bi1/2Na1/2TiO3 chemical route method. The X-ray diffraction and Raman scattering results indicated that Sm1/2Na1/2TiO3 ma­
Sm1/2Na1/2TiO3 terials were well solute into the host Bi1/2Na1/2TiO3 materials to form solid solutions. The optical bandgap of the
Sol-gel
pure Bi1/2Na1/2TiO3 materials was estimated from ultraviolet–visible spectroscopy of 3.07 eV. The bandgap
Photoluminescence
Solid solution
slightly reduced to 2.94 eV as increasing the Sm1/2Na1/2TiO3 amounts up to 9 mol.%. Strong photoluminescence
(PL) of Sm1/2Na1/2TiO3-addition Bi1/2Na1/2TiO3 materials was obtained in the visible wavelength range of
550–750 nm which related to photoluminescence of Sm cations randomly incorporated into the host lattice of
Bi1/2Na1/2TiO3 materials. Our work was promised to show a new method to integrate the PL properties in lead-
free ferroelectric materials.

1. Introduction field-induced strain Smax/Emax of 88 p.m./V [7,8]. The Bi1/2Na1/2TiO3

Lead-free ferroelectric Bi1/2Na1/2TiO3 materials had been attached
much attention because of their ability to replace Pb(Zr,Ti)O3-based
materials, which contain a large amount of Pb toxic elements to human
health and pollution protection [1]. In addition, ongoing research had
tried to extend the function of lead-free ferroelectric materials for
electro-optical applications that used ferroelectric and piezoelectric
properties of their materials [2,3]. Recently, the properties of lead-free
ferroelectric Bi1/2Na1/2TiO3 materials had been approved to extend
functional materials for smart material application [4]. The ferroelectric
Bi1/2Na1/2TiO3 materials, first discovered by Smolenski et al., exhibited
strong ferroelectric properties such as remanent polarization (Pr) ~ 38
μC/cm2, coercive field (EC) of 7.30 kV/mm, and a high Curie tempera­
ture (TC) of ~320 ◦ C [5,6]. However, the high EC values prevented the
transfer of the Bi1/2Na1/2TiO3 materials to actual industrial application
because a high electrical field required for polarizing process resulted in
poor piezoelectric properties of d33 ~ 58 pC/N and low electrical
materials exhibited weak-ferromagnetic properties at room temperature
due to the presence of various types of defects which were formed during
sample fabrication [4,9]. The Bi1/2Na1/2TiO3 materials exhibited direct
transition with an optical bandgap of approximately 3.02–3.11 eV,
depending on fabricating conditions and chemical defects [4,10].
Thanks to the well-solid solution, the properties of Bi1/2Na1/2TiO3
materials were greatly enhanced by using various perovskite materials
[7,12–17]. By co-addition of BaTiO3 and Bi2FeCrO6, the EC value of
Bi1/2Na1/2TiO3 materials was reduced to 28.7 kV/cm while Pr and d33
values were increased to 42.3 μC/cm2 and 214 pC/N, respectively [12].
The Pr and spontaneous polarization (PS) of the Bi1/2Na1/2TiO3 materials
increased to 48.5 μC/cm2 by Ba(Mg1/3Nb2/3)O3-modification [13]. The
dielectric constant and piezoelectric constant d33 of the Bi1/2Na1/2TiO3
materials increased to 144 pC/N and 893 pC/N, respectively, by adding
Bi1/2K1/2TiO3 [14]. Rahman et al. reported that the electrical
field-induced strain of the Bi1/2Na1/2TiO3 materials increased up to 500
p.m./V by 5.5 mol.%-BaZrO3 modification [8]. Shin et al. reported that

* Corresponding author.
** Corresponding author.
E-mail addresses: vandq@hnue.edu.vn (D.Q. Van), dung.dangduc@hust.edu.vn (D.D. Dung).

https://doi.org/10.1016/j.vacuum.2021.110389
Received 6 May 2021; Received in revised form 31 May 2021; Accepted 11 June 2021
Available online 15 June 2021
0042-207X/© 2021 Elsevier Ltd. All rights reserved.
 N.H. Thoan et al.
the (Sr0.7Bi0.2)TiO3-modified Bi1/2Na1/2TiO3-based materials exhibited
strong enhancement of electrostrictive strain up to 0.152% and elec­
trostrictive coefficient of 0.0297 m4/C2 [15]. In addition, Liu et al. re­
ported that properties of Bi1/2Na1/2TiO3-based materials slightly doped
with cerium and stannum could be improved by optimizing the sintering
processes [16,17]. In addition, the magnetic properties of Bi1/2Na1/2
TiO3 materials were strongly enhanced by doping various ABO3-type
materials such as CaFeO3-δ, BaFeO3-δ, SrMnO3-δ, BaCoO3-δ, NiTiO3, and
Bi(Ti1/2Fe1/2)O3 [4,18–22]. In other words, the properties of
Bi1/2Na1/2TiO3 materials were greatly enhanced via using various types
of impurity materials.
Recently, there was a new trend in advanced functional materials via
a combination of photoluminescence (PL) behavior of rare-earth-doped
lead-free ferroelectric materials [23–25]. Therefore, enhancement of the
PL properties of Bi1/2Na1/2TiO3 materials promised to create a new type
of electronic device. The Bi1/2Na1/2TiO3 materials are ferroelectric ones
[1,4–8]. However, inside ferroelectric materials, separated electron-hole
pairs were hard to recombine, resulting in low-efficiency photo­
luminescence [26]. Therefore, the photoluminescence of the
Bi1/2Na1/2TiO3 materials was most related to surface defects because
there were fewer bonding pairs at the surface than inside of materials [4,
18,19,26]. Doping of transition metals and/or solid solutions with
dopants containing transition metals resulted in suppression of the PL
properties of the Bi1/2Na1/2TiO3 materials [27–29]. Recently, the elec­
trical properties of lead-free Bi1/2Na1/2TiO3-based materials were re­
ported to be strongly enhanced via the addition of rare-earth materials
[17,30,31]. The PL performance of lead-free ferroelectric Bi1/2Na1/2
TiO3 materials could be improved via using rare-earth as impurities, e.g.
Sm, Ho, Er, Eu, Nd, Pr, etc. [32–37]. The rare-earth doping in
Bi1/2Na1/2TiO3 materials resulted in a strong enhancement of the
luminescence emission which was related to PL emission from 4f-to-4f
levels of rare-earth cations.
Sm1/2Na1/2TiO3 materials were first fabricated by a solid-state re­
action method by Barik et al. [38]. The Sm1/2Na1/2TiO3 materials had an
orthorhombic crystal structure with the parameters a = 3.8263(7) Å, b
= 3.8124(7) Å and c = 3.8425(7) Å where Sm and Na cations randomly
distributed at A-sites in the perovskite structure [38]. The dielectric
properties of the Sm1/2Na1/2TiO3 materials were reported to be
enhanced by filling polytetrafluoroethylene or doping with Cr2O3, Sm
(Mg0.5Ti0.5)O3, or (Al, Ta) co-doping [39–41]. Recently, the magnetic
properties of Bi1/2Na1/2TiO3 materials were reported to be strongly
enhanced via modification of impurity phases containing transition
metals as solid solutions [4,18–22,27–29]. Herein, materials containing
Sm cations as 4f materials were expected to luminesce. However, up to
date, there was no report on the optical properties of Sm1/2Na1/2TiO3
materials modified Bi1/2Na1/2TiO3 materials.
In this work, a new solid solution (1-x)Bi1/2Na1/2TiO3 +xSm1/2Na1/
2TiO3 system was well synthesized via a simple chemical method. The
structure of Sm1/2Na1/2TiO3 modified Bi1/2Na1/2TiO3 materials was a
distortion of rhombohedral symmetry. The optical bandgap of Sm1/
2Na1/2TiO3-modified Bi1/2Na1/2TiO3 materials was estimated in the
range of 3.07–2.94 eV depending on Sm1/2Na1/2TiO3 concentrations in
the solid solutions. Strong photoemission in the wavelength range of
550–750 nm was obtained from the Bi1/2Na1/2TiO3 materials as a
modification by Sm1/2Na1/2TiO3 addition.
2. Experimental
In this study, (1-x)Bi1/2Na1/2TiO3 +xSm1/2Na1/2TiO3 materials with
x = 0, 0.5, 1, 3, 5, 7, and 9 mol.%; named as pure BNT and BNT-xSm,
were synthesized by a simple chemical method. The starting materials
included bismuth nitrate pentahydrate (Bi(NO3)3⋅5H2O), sodium nitrate
(NaNO3), samarium nitrate hexahydrate (Sm(NO3)3.6H2O), and tetrai­
sopropoxytitanium (IV, C12H28O4Ti). First, Bi(NO3)3⋅5H2O was weighed
and added in the solutions of acetic acid and de-ions water with the
volume ratio of VH2O:VCH3COOH = 5:1. The solutions were kept under
2
­
­
­
Vacuum 191 (2021) 110389
magnetic stirring until turning transparent. Then, NaNO3 and Sm
(NO3)3.6H2O were added. The solutions were continuously kept under
magnetic stirring for about 1 h. Thus, the acetylacetone was dropped to
the solutions with the volume ratio of acid acetic and acetylacetone of
1:1. Subsequently, the C12H28O4Ti were taken to drop into the solution.
The solutions were continuously kept under magnetic stirring for about
3–5 h to obtain homogeneous sols. The sols were dried in the oven at
100 ◦ C to form dry gels. The gels were simply filtered and annealed at
900 ◦ C for 5 h to form powder samples. To prevent the loss of Na during
gelling and sintering processes, NaNO3 was weighed to an extra amount
of about 30–50 mol.% [18–22,27–29]. The chemical composition of
pure Bi1/2Na1/2TiO3 and Sm1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 ma­
terials was qualified by energy-dispersive X-ray spectroscopy (EDS)
measurements. The crystal structural symmetry of pure Bi1/2Na1/2TiO3
and Sm1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 materials was determined
by X-ray diffraction (XRD) spectroscopy. The vibration modes of sam­
ples were measured by using Raman scattering. The optical properties of
pure Bi1/2Na1/2TiO3 material and Sm1/2Na1/2TiO3 -modified
Bi1/2Na1/2TiO3 materials were measured by Ultraviolet–visible spec­
troscopy (UV–Vis) and photoluminescence spectroscopy (PL)
measurement.
3. Results and discussions
The crystal structure of pure Bi1/2Na1/2TiO3 and Sm1/2Na1/2TiO3-
modified Bi1/2Na1/2TiO3 materials with various Sm1/2Na1/2TiO3 con­
centrations was characterized by the X-ray diffraction patterns, as
shown in Fig. 1 (a). The XRD results showed that pure Bi1/2Na1/2TiO3
material exhibited a rhombohedral structure because all peak positions
and their relative intensities were well matched with JCPDF card. With
the addition of Sm1/2Na1/2TiO3 materials, the materials exhibited follow
the structure of the host Bi1/2Na1/2TiO3 materials. No trade phase and/
or phase segregation could be observed under X-ray diffraction patterns,
revealing that the Sm1/2Na1/2TiO3 materials were well solute into host
Bi1/2Na1/2TiO3 materials. The role of Sm1/2Na1/2TiO3 solute phase in
Bi1/2Na1/2TiO3 materials was shown in Fig. 1 (b), where the X-ray
diffraction patterns were magnified in the 2θ-range of 31.0–34.0◦ . The
satellite (012)/(110) peaks were overlapped together which were orig­
inated from the symmetry of rhombohedral structure [18–22]. The peak
positions of Bi1/2Na1/2TiO3 materials trended to shift to higher 2θ angles
as increasing the Sm1/2Na1/2TiO3 amounts. The results provided solid
evidence for lattice parameter distortion of the host Bi1/2Na1/2TiO3
materials during the solid solution process of the Sm1/2Na1/2TiO3 phase.
The XRD peak positions of the pure Bi1/2Na1/2TiO3 and Sm1/2Na1/2
TiO3-modified Bi1/2Na1/2TiO3 materials were distinguished by the Lor­
entzian fitting with r-square higher than 0.99, as shown in red and blue
lines for (012) and (110) peaks, respectively. The fit results were
interesting and showed that the intensities and positions of the double
(012)/(110) peaks of the host Bi1/2Na1/2TiO3 materials were very
complex distorted, depending on the amounts of Sm1/2Na1/2TiO3 solute
in the host Bi1/2Na1/2TiO3 materials. Furthermore, the lattice parame­
ters a and c of the pure Bi1/2Na1/2TiO3 and Sm1/2Na1/2TiO3-modified
Bi1/2Na1/2TiO3 materials were estimated and shown in Fig. 1(c) as a
function of Sm1/2Na1/2TiO3 concentration. The results showed that
distorted lattice parameters of Bi1/2Na1/2TiO3 compounds were not
linear as a function of Sm1/2Na1/2TiO3 concentrations, which has com­
plexed distortion in lattice parameters. The complex distortion of the
lattice parameters of the host Bi1/2Na1/2TiO3 materials via
Sm1/2Na1/2TiO3 addition could be explained by the radius difference of
the impurity cations in the host matrix. Based on Shannon’s report, the
radius of Bi3+ cations (in the coordination of VIII) and Na+ cations (in
the coordination of XII) were 1.17 Å and 1.39 Å, respectively [42]. The
radius of Sm3+ cations (in the coordination of XII) was 1.24 Å [42].
Based on the Hume–Rothery rules, Sm cations enter at the substituted
A-site of Bi1/2Na1/2TiO3 materials because of the − 3.13% difference
between the radius of Sm cations and the average radius of
N.H. Thoan et al.
Fig. 1. (a) XRD patterns of pure Bi1/2Na1/2TiO3 and Sm1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 compounds with various of Sm1/2Na1/2TiO3 concentrations, (b) the
magnification with deconvolution peaks of XRD pattern in 2θ range from 31.0◦ to 34.0◦ , and (c) the (a,c) lattice parameters of Bi1/2Na1/2TiO3 as a function of the
Sm1/2Na1/2TiO3 concentration.
(Bi1/2Na1/2)2+ [43–45]. The difference between the impurity Sm cations
and the host Bi and Na cations were +5.98% and − 10.79%, respectively.
Therefore, the random incorporation of Sm3+ cations into A-sites in the
Bi1/2Na1/2TiO3 perovskite structures resulted in a complex distortion of
lattice parameters. The substitution of Sm3+ cations in Bi3+-sites resul­
ted in compression of lattice parameters because the radius of Sm3+
cations is smaller than that of Bi3+ cations. However, the incorporation
of Sm3+ cation into Na + -sites resulted in an expansion of lattice pa­
rameters because of the larger radius of Sm3+ cations in comparison
with Na + ones at A-sites. In addition, the difference between the valence
states of Sm3+ impurity cations and Na + cations during incorporation
with the host Bi1/2Na1/2TiO3 lattices might create Na-vacancies. The
stable Na-vacancies in the host crystal Bi1/2Na1/2TiO3 structure resulted
in a distortion of lattice parameters, resulting in a reduction of the lattice
strain energy of host lattice Bi1/2Na1/2TiO3 materials [46–48]. In addi­
tion, Luo et al. reported that the Er cations were possibly doped at both
A-sites (Bi-, Na-sites) and B-sites (Ti-sites) in perovskite structure of
Bi1/2Na1/2TiO3 materials [49]. A similar effect was obtained in Eu doped
Bi1/2Na1/2TiO3 materials [50]. Taking account of our results, if we
considered the Sm3+ cations randomly filled to Ti-site in Bi1/2Na1/2TiO3
crystal during the solid solution, the distortion lattice parameter of host
Bi1/2Na1/2TiO3 materials became more complex. According to Shan­
non’s report, the size of Sm3+ cations at coordination of IV was 0.958 Å
which was larger than that of Ti4+ cations of 0.605 Å with the same
coordination, resulting in expansion of the lattice parameters of the host
Bi1/2Na1/2TiO3 crystals [42]. The differences between the radius of
Sm3+ cations and those of Ti4+ cations substituted at the Ti-site of
Bi0.5Na0.5TiO3 materials are 58.35%, which, according to the
Hume–Rothery rules, is too large to allow replacement because of the
increased lattice energy [43–45]. The large difference between the sizes
of the impurity Sm3+ cations and the host Ti4+ cations induced a large
local tensile strain in the crystal. However, the local strain in
3
Vacuum 191 (2021) 110389
Bi1/2Na1/2TiO3 crystal was possibly reduced because of oxygen va­
cancies nearby, where the size 1.31 Å of oxygen vacancies was smaller
than that of anion oxygen of 1.4 Å [51]. The flaccidity of the size of O
vacancies on the lattice parameters has a more significant influence than
that of dopants in perovskite Bi1/2Na1/2TiO3-based materials [4,18–22].
Note that the oxygen vacancies were created via the unbalance valence
state between Sm3+ and Ti4+ cations. Herein, we needed to note that the
oxygen bounding surrounds the Ti4+ cations were possibly reduced the
valence state of Ti cations from the Ti4+ state to the Ti3+ state [4,18,52].
We recently reported that Ti3+-defects were stable in Bi1/2Na1/2TiO3-­
based materials [18]. The reduction of the valence state of Ti4+ to Ti3+
resulted in local chemical tensile strain because the size 0.670 Å of Ti3+
cations was larger than 0.605 Å of Ti4+ cations [42]. At this moment, we
were unable to provide the main reason for the observation of lattice
parameter distortion of the host Bi1/2Na1/2TiO3 materials via
Sm1/2Na1/2TiO3 addition as numerous parameters contributed to the
suggestion. However, the observation of compression of lattice param­
eters of Bi1/2Na1/2TiO3 materials via a solid solution of Sm1/2Na1/2TiO3
as impurities provided strong evidence of random incorporation of im­
purity cations into the host Bi1/2Na1/2TiO3 lattices.
Fig. 2 (a) shows the Raman spectra of the pure Bi1/2Na1/2TiO3 and
Sm1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 materials with various Sm1/
2Na1/2TiO3 amounts at room temperature. The Raman spectrum of the
pure Bi1/2Na1/2TiO3 exhibited three overlapping humps. Unclear peaks
in the Raman scattering spectrum of pure Bi1/2Na1/2TiO3 materials came
from a random distribution of Na and Bi cations at A-sites in the
rhombohedral symmetry [53,54]. Our observation on Raman scattering
results of the pure Bi1/2Na1/2TiO3 was well consistent with recent arti­
cles for phonon scattering modes of Bi1/2Na1/2TiO3 materials synthe­
sized by sol-gel technique [18–22]. The Raman spectra of the
Sm1/2Na1/2TiO3-addition Bi1/2Na1/2TiO3 materials were similar in
shape with the pure BNT, further confirming the same crystal structure
N.H. Thoan et al. Vacuum 191 (2021) 110389

Fig. 2. (a) Raman scattering spectra and (b) the deconvolution of Raman scattering peaks of pure Bi1/2Na1/2TiO3 and Sm1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3
compounds with various Sm1/2Na1/2TiO3 amounts as solid solutions.

the addition of Sm1/2Na1/2TiO3. Furthermore, the Raman spectra of
Sm1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 materials did not show any
extra peaks, indicating that no extra phase or impurity-related phase
existed in our studied samples. The results were well consistent with the
single-phase crystal structure which had been confirmed by the XRD
study. The Raman peaks of pure Bi1/2Na1/2TiO3 and Sm1/2Na1/2TiO3-­
modified Bi1/2Na1/2TiO3 materials were distinguished by Lorentzian
fitting with r-square higher than 0.99, as shown in Fig. 2 (b). Nice peaks
were obtained in Raman spectra in the frequency range of 300–950
cm− 1. A smaller number of modes than theoretical predictions was
observed, which was possibly related to phonon-frequency degradation
or insufficient intensities arising from the small polarizability of several
modes [53,54]. The Raman peak positions were well consistent with
theoretical prediction and recent experimental results [18–22,53,54].
Lui et al. reported that the mode at 270 cm− 1 of Bi1/2Na1/2TiO3-based
materials was dominated by A1 mode assigned to Ti–O vibrations, while
the modes in the mid-wavenumber region of 450–700 cm− 1 related to
the vibration of TiO6 octahedra, and the modes in the high-wavenumber
region above 700 cm− 1 were linked to the overlapping bands A1(LO)
and E(LO) [55]. Liu et al. also reported that the modes near 100 cm− 1 of
Bi1/2Na1/2TiO3-based materials were related to vibration involving the
perovskite A-sites with A1 symmetry, and the broad bands near 240
cm− 1 and 300 cm− 1 were associated with the Ti–O vibrations, while the
high-frequency bands at about 490 cm− 1, 530 cm− 1, and 610 cm− 1 were
dominated by the TiO6-octahedra vibration and oxygen displacement
[56]. He et al. pointed out that the overlapping Raman spectra of
Bi1/2Na1/2TiO3-based materials could be divided into four main regions,
including: i) the modes in the wavenumber range below 200 cm− 1 are
assigned to the A-site vibration of perovskite oxides, ii) the modes in the
wavenumber range of 200–450 cm− 1 are associated with the Ti–O vi­
brations, iii) the modes in the range of 450–700 cm− 1 are related to the
vibrations of TiO6 octahedra, and iv) the modes with the wavenumber
higher than 700 cm− 1 are associated to longitudinal optical vibrations of
A1 and E overlapping bands [57]. Our fitting results pointed that the
Raman peaks at approximately 402 and 585 cm− 1 shifted to higher
frequencies as increasing the Sm1/2Na1/2TiO3 amounts in the host
Bi1/2Na1/2TiO3 materials. The shift of Raman scattering peaks was
possibly related to distortion of the Bi1/2Na1/2TiO3 structure due to
random distribution of impurity cations during Sm1/2Na1/2TiO3
solid-solution process into the host Bi1/2Na1/2TiO3 crystal.
Fig. 3 (a) showed the UV–Vis spectra of pure Bi1/2Na1/2TiO3 and
Sm1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 materials. The spectrum of
the pure Bi1/2Na1/2TiO3 material exhibited a single edge transition and
was tailored with a slight tail. The absorption edge of the pure Bi1/2Na1/

Fig. 3. (a) UV–Vis spectra, and (b) the plots of (αhν)2 as functions of photon energy (hν) of pure Bi1/2Na1/2TiO3 compounds and Sm1/2Na1/2TiO3-modified Bi1/2Na1/
2TiO3 compounds. The inset showed the dependence of Eg values of Bi1/2Na1/2TiO3 as a function of Sm1/2Na1/2TiO3 amounts.

4
 N.H. Thoan et al.
2TiO3 material was estimated at approximately 418 nm, the tail was
prolonged to 580 nm. These results were well consistent with recently
obtained absorption spectra of pure Bi1/2Na1/2TiO3 materials fabricated
by the sol-gel method [4,10,18–22,58]. The appearance of a slight tail in
the absorption spectrum of the Bi1/2Na1/2TiO3 materials was originated
from self-defects such as vacancies of Bi, Na, Ti, or O, and/or
Ti3+-defects [4,22]. The addition of Sm1/2Na1/2TiO3 to the host
Bi1/2Na1/2TiO3 materials caused a slight shift in the edge transition,
indicating that the optical bandgap (Eg) of the host Bi1/2Na1/2TiO3
materials was tuned as a function of Sm1/2Na1/2TiO3 concentrations in
the solid solutions. In addition, it was suggested that the appearance of a
hump around 450–510 nm, as shown in the inset of Fig. 3 (a), was
related to the transition of electrons from 6H5/2 to 4I11/2 and 4M15/2
levels [59]. In recent reports, the UV–Vis absorption edge of
Bi1/2Na1/2TiO3 materials tended to shift to a higher absorption wave­
length as increasing the dopant amounts, e.g. Fe, Co, Ni, Mn, and Cr [11,
60–63]. However, unlike single transition-metal dopants, the influence
of Sm cations on the absorption edge was complex, which was strongly
dependent on the Sm amounts randomly incorporated with the host
Bi1/2Na1/2TiO3 lattices. Recently, we predicted that the electronic band
structural of Bi1/2Na1/2TiO3 materials consisted of Bi-6p and Ti-3d or­
bitals for building the valence band while the conduction band was
composed of O-2p orbitals where the direction transition was suggested
to charge transfer from the critical point Γ(0, 0, 0) in the reciprocal space
[64]. Zeng et al. reported that the optical properties of Bi1/2Na1/2TiO3
materials were possibly determined by charge-transfer transitions from
O-2p to Ti-3d or Bi-6p states [65]. Thus, the Wood-Tauc method was
used to estimate Eg values, where the Eg values of the Bi1/2Na1/2TiO3
materials were obtained from extrapolation to zero of the linear fittings
of (αhγ)2 vs. photon energy (hγ) plots, as shown in Fig. 3 (b) [4,10,22].
The pure Bi1/2Na1/2TiO3 materials exhibited the Eg value of about 3.07
eV, which was well consistent with recently observed Eg values of
Bi1/2Na1/2TiO3 materials synthesized by sol-gel technique [4,10,11,
60–63]. The addition of Sm1/2Na1/2TiO3 to the host Bi1/2Na1/2TiO3
materials resulted in a reduction in the Eg values. However, Eg values of
Bi1/2Na1/2TiO3 materials did not simply follow in one direction as
increasing the Sm1/2Na1/2TiO3 concentrations. In fact, the Eg values of
Bi1/2Na1/2TiO3 materials were very complex distorted and slightly
reduced to 2.94 eV for 9 mol.% Sm1/2Na1/2TiO3 solid solution. Our re­
sults were well consistent with recent observations of the influence of
rare-earth-doped lead-free ferroelectric Bi1/2Na1/2TiO3 materials such
as Ce, Nd, Pr, etc. [66–68]. The optical bandgap values of the
Bi1/2Na1/2TiO3 materials as a function of the Sm1/2Na1/2TiO3 amounts
materials were affected by many parameters. First, the random incor­
poration of Sm3+ cations at A-sites and B-sites in the host Bi1/2Na1/2TiO3
materials resulted in creating various new localized states of Sm cations
which were dependent on the substituted site [69]. Secondary, Na- and
O-vacancies, which were created due to random multi-site substitution
of Sm3+ cations for Na + -sites or Ti4+-sites, also resulted in a formation
of new local states of self-defects in the electronic band structure of the
host Bi1/2Na1/2TiO3 materials [4,22]. Moreover, the possible valence
state of Ti4+ cations might reduce to the Ti3+ state via oxygen vacancies
bounding around, resulting in new local states in the electronic band
structure of the Bi1/2Na1/2TiO3 materials [4,22]. In addition, Behara
et al. predicted that compression strain led to an expansion of the optical
bandgap of Bi1/2Na1/2TiO3 materials while tensile strain resulted in
lower bandgap values [70]. In other words, many parameters affected
the electronic band structure of Bi1/2Na1/2TiO3 via Sm1/2Na1/2TiO3
addition as solid solutions. In fact, at this moment, the complex
dependence of optical band gap energy of Bi1/2Na1/2TiO3 materials on
Sm1/2Na1/2TiO3 concentrations was not well understood and need
further theoretical investigation. However, the observation of tunable
the optical band gap energy of the host Bi1/2Na1/2TiO3 materials via
Sm1/2Na1/2TiO3 addition provided important indirect evidence for
random incorporation of impurity cations during the formation of the
solid solutions.
5
­
Vacuum 191 (2021) 110389
Fig. 4 (a) showed the PL emission spectra of Sm1/2Na1/2TiO3-modi­
fied Bi1/2Na1/2TiO3 materials with different Sm1/2Na1/2TiO3 concen­
trations under an excitation wavelength of 475 nm. The results were
important to point out that the strong emission was obtained in wide
wavelength regions. The PL of Sm1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3
materials overcame the PL of the pure Bi1/2Na1/2TiO3 materials [4,18,
22,26]. The Sm1/2Na1/2TiO3 addition into host the Bi1/2Na1/2TiO3 ma­
terials exhibited strong photoluminescence which overcame the sup­
pression of photoluminescence intensity of the host Bi1/2Na1/2TiO3
materials via the addition of transition metals [4,18,22]. The results
were also important to indicate that the random incorporation of
rare-earth Sm3+ cations into host Bi1/2Na1/2TiO3 materials exhibited
stronger photoluminescence than that of self-defect and/or
surface-defect-mediated photoluminescence of lead-free ferroelectric
materials [4,18,22,26]. PL emission of rare-earth Sm3+ cations doped in
the lead-free ferroelectric Bi1/2Na1/2TiO3 materials in this study was
stronger than that of the same materials doped with transition metals [4,
18,22]. As shown in Fig. 4 (a), four main peaks in the visible region
corresponded to intra-4f transitions of Sm3+ cations from 4G5/2 level to
6
H5/2, 6H7/2, 6H9/2, and 6H11/2 levels. These results agreed with the ones
recently reported for Sm3+ emission transitions in the visible region [32,
71–74]. Furthermore, the PL intensity as a function of Sm1/2Na1/2TiO3
concentrations was compared with strong photoemission peaks. Fig. 4
(b) showed the relative PL intensity of the strongest peak (at approxi­
mately 601 nm, 4G5/2 → 6H7/2) as a function of Sm3+ concentrations in
our studied samples. The 4G5/2 → 6H7/2 emission intensity increased
with increasing Sm3+ concentrations in the lower content region until
getting saturation for the sample with 5 mol.% Sm3+, then decreased
slightly. The decrease could be explained by concentration-quenching
processes: a Sm3+ doping level higher than 5 mol.% caused a decrease
of the distance between Sm3+ cations and non-radiative energy transfer
from one PL activator to another activator, leading to the lowering of the
PL intensity [32]. Interestingly, most reports on the PL influence of Sm3+
doped lead-free ferroelectric Bi1/2Na1/2TiO3-based materials, such as
pure Bi1/2Na1/2TiO3, SrTiO3–Bi1/2Na1/2TiO3, BaTiO3–Bi1/2Na1/2TiO3
materials, focused on the up-conversion; but the relation between Sm3+
emission and excitation through the host was not well reported [32,75,
76]. Recently, we provided that the Bi1/2Na1/2TiO3 materials were
exhibited photoluminescence in the range from 476 to 510 nm where
maximal emission was obtained around 489 nm [4,18,22]. The
multi-emission peaks observed in the wavelength from 476 to 510 nm
were most related to self-defect and/or surface defects rather than
electron transitions from the conduction band to the valence band, as
considering optical bandgap values [4,18,22]. Note that the
Bi1/2Na1/2TiO3 materials are ferroelectric materials, which existed nat­
ural domain polarization, preventing the photo-hole and
photon-electron recombination to generate photoemission [26]. There­
fore, the emission peaks of lead-free ferroelectric materials were mostly
related to defects rather than photoemission peaks from band-to-band
transitions [4,18,22,26]. Recently, the photoemission of Bi1/2Na1/2
TiO3 materials was suppressed by doping the transition metals [4,18,
22]. The observed results pointed out that the local defects of impurity
transition metals in the electronic band structure absorbed photons
emitted from natural defects of the host Bi1/2Na1/2TiO3 materials,
resulting in suppression of photoemission intensity. In other words, the
local defects of transition metal impurities made the trapping of
photoemission of natural defects of the host Bi1/2Na1/2TiO3 materials.
Recently, Rosales et al. proposed that the possible secondary transitions
of photons from the conduction band to an inter-band level of Yb3+
cations resulted in photoluminescence activation [77]. Therefore, we
suggested that the possible transitions from natural defects to a Sm3+
inter-band level were active for photoluminescence of 4f-4f level tran­
sitions. However, the detail of nature defects in Sm3+ cations in host
Bi1/2Na1/2TiO3 materials needed further study via theoretical
calculation.
Fig. 5 showed the magnifications of the PL spectra of the pure Bi1/
 N.H. Thoan et al. Vacuum 191 (2021) 110389

Fig. 4. (a) PL spectra Sm1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 compounds as a function of Sm1/2Na1/2TiO3 concentrations, and (b) the comparison of intensity
photoluminescence of 4G5/2 to 6H7/2 transition as a function of Sm1/2Na1/2TiO3 amounts.

Fig. 5. Magnifications of the PL spectra of Sm1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 compounds as a function of Sm1/2Na1/2TiO3 concentrations in the wavelength
ranges of (a) 550–750 nm, (b) 750–1000 nm, (c) 1000–1600 nm, and (d) 1600–2000 nm.

2Na1/2TiO3 and Sm1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 materials in
different wavelength ranges. Fig. 5 (a) showed the PL spectra in the
wavelength range from 550 to 750 nm. There are four main PL peaks
located at approximately 565, 601, 647, and 711 nm, which are related
to transitions from Sm3+ 4G5/2 level to 6H5/2, 6H7/2, 6H9/2, and 6H11/2
ones. Our results were well consistent with the recent observation in PL
spectra of Sm doped lead-free ferroelectric Bi1/2Na1/2TiO3 materials
[32]. Interestingly, we obtained the emission of 4f-4f electron transi­
tions of Sm3+ cations randomly incorporated into the host Bi1/2Na1/2
TiO3 lattices at near-infrared and infrared regions. In Fig. 5 (b), we
observed three weak PL peaks at around 780, 885, and 959 nm, that
were assigned to electron transitions from Sm3+ 4G5/2 level to 6H13/2,
6
F3/2, and 6F5/2 ones, respectively. Fig. 5 (c) presented PL spectra in the
1000–1600 nm range, showing four medium peaks. The peak at 1132
nm might be assigned to the 6H11/2 → 6H7/2 transition. The emission
around 1205 nm arises by 4G5/2 → 6F9/2 or 6F9/2 → 6H7/2 transition. The
last one at about 1435 nm was assigned to 6F7/2 → 6H7/2 or/and 6F9/2 →
6
H9/2 transitions. In Fig. 5 (d), three weak PL peaks at around 1690,
1810, and 1950 nm were observed, which might be related to transitions
from the (6H15/2, 6F3/2, 6F1/2) manifold or other 6F levels to 6H levels.
Recently, Starecki et al. found two PL emission transitions by Sm3+ at
around 1650 nm and 1950 nm by 1450 mn excitation, that ascribed to
6
F1/2 → 6H5/2 and 6H13/2 → 6H5/2 transitions [74]. Other transitions
related to (6H15/2, 6F3/2, 6F1/2) manifold did not occur in Sm3+-doped

6
­
N.H. Thoan et al.
Ga5Ge20Sb10Se65 fiber because the Sm3+ concentration was low (500
ppm) [60]. In this study, we suggested that at higher Sm3+ concentration
levels up to 9 mol.% in our studied samples, up-conversion processes
might occur because of interactions between neighboring Sm3+ ions. We
also observed a new peak at 1800 nm. We suggested that the peak was
ascribed to 6F3/2 → 6H7/2 transition. However, the evidence is unclear,
and one needs further measurements to confirm the assumption.
4. Conclusion
The Sm1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 materials were well
synthesized by the simple chemical route. The Sm1/2Na1/2TiO3-modified
Bi1/2Na1/2TiO3 materials were well synthesized by a simple chemical
route method. The Sm1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 com­
pounds exhibited the rhombohedral structure that followed the struc­
ture of the host Bi1/2Na1/2TiO3 lattice. The optical bandgap of Bi1/2Na1/
2TiO3 materials was slightly varied in the range of 3.07–2.94 eV as a
function of Sm1/2Na1/2TiO3 amounts solid solute into the host Bi1/2Na1/
2TiO3 materials. The strong photoluminescence of Sm1/2Na1/2TiO3-
modified Bi1/2Na1/2TiO3 materials was obtained with the highest in­
tensity for the BNT-5Sm sample containing 5 mol.% Sm1/2Na1/2TiO3
dopants. The Sm1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 materials
exhibited the NIR region emissions of Sm ions. We expected our work to
be an extension of the functional lead-free ferroelectric Bi1/2Na1/2TiO3
materials for optical applications.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This research is funded by Vietnam National Foundation for Science
and Technology Development (NAFOSTED) under grant number
103.02–2019.366 and this research was partially supported by the
Nippon Sheet Glass Foundation.
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