Optical properties of a new (1-x)Bi1/2Na1/2TiO3+xPr1/2Na1/2TiO3 solid

solution system
D.D.Dung1,*, N.H.Lam1, L.T. K.Phuong2, N.H.Thoan1, L.H.Bac1, D.T.Trang2, P.V.Vinh3,
N.D.Quan1, and D.Q.Van3
1
Ha Noi University of Science and Technology, Ha Noi, Viet Nam
2
Hong Duc University, Thanh Hoa, Viet Nam
3
Ha Noi National Education University, Ha Noi, Viet Nam
Abstract
The solid solutions of Bi1/2Na1/2TiO3 and Pr1/2Na1/2TiO3 materials were successfully synthesized
by a simple chemical method. X-ray diffraction measurements of the Pr1/2Na1/2TiO3-modified
Bi1/2Na1/2TiO3 materials indicated that Pr1/2Na1/2TiO3 was well dissolved into the host
Bi1/2Na1/2TiO3 materials, resulting in the random incorporation of Pr cations in the host
materials. The optical bandgap of the Pr1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 materials slightly
reduced as increasing Pr1/2Na1/2TiO3 concentrations, from 3.04 eV for the pure Bi1/2Na1/2TiO3
material to 2.95 eV for the sample with 9 mol.% of Pr1/2Na1/2TiO3. We observed strong
photoluminescence emission at 610 nm in the Pr1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 system,
which originated from electron transitions from 3P0 to 3H6 levels of Pr3+ cations. We expected
that our work would provide a simple method to combine photoluminescence properties in lead-
free ferroelectric materials for smart electronic device applications.
Keywords: Bi1/2Na1/2TiO3; Pr1/2Na1/2TiO3; lead-free ferroelectric; sol-gel method;
photoluminescence
Corresponding e-mail: dung.dangduc@hust.edu.vn

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I. Introduction
Recently, lead-free ferroelectric materials have been used not only in current electronic devices
as a function of ferroelectric, piezoelectric, or dielectric properties, but also in the extension of
ferromagnetic and photoluminescence properties in smart electronic device applications [1-3].
Among lead-free ferroelectric materials, Bi1/2Na1/2TiO3-based materials exhibited significant
ferroelectric and piezoelectric properties which were compared to the properties of Pb (Zr,
Ti)O3-based materials [1]. The photoemission of Bi1/2Na1/2TiO3 materials almost related to
surface defects because the polarization domain of ferroelectric materials prevented the
recombination of electrons and holes to generate photons [2, 4, 5]. Recently, lots of research on
the photoluminescence properties of Bi1/2Na1/2TiO3 was carried out by injecting rare-earth
impurities, Pr, Ho, Sm, Nd, Eu, Er, etc. [6-11]. Tian et al. reported that the photoemission
intensity of Pr3+-doped Bi1/2Na1/2TiO3 materials was tuned by using an external electrical field
[12].
However, the limitation of the number of 4f-elements in the periodic table hindered extending
research on improving photoluminescence of Bi1/2Na1/2TiO3 materials. Recently, the
ferromagnetic properties of Bi1/2Na1/2TiO3 materials have been enhanced with the addition of
different types of ABO3-perovskite materials, such as SrMnO3-, CaFeO3-, or BaFeO3-, etc. [2,
4, 5]. Among Ln1/2Na1/2TiO3-perovskite family (Ln=La, Pr, Nd, Sm, Eu, Gd, and Tb),
Pr1/2Na1/2TiO3 materials were firstly fabricated by Sun et al., which exhibited an
orthorhombically distorted GdFeO3-type structure and quantum paraelectric behavior at 30-50 K
[13, 14]. Pr cations were suggested to active photoemission of Bi1/2Na1/2TiO3 when they were
randomly incorporated with the Bi1/2Na1/2TiO3 host lattices to form solid solutions.
In this work, (1-x)Bi1/2Na1/2TiO3+xPr1/2Na1/2TiO3 solid solutions were successfully synthesized
by the sol-gel method. The random incorporation of Pr3+ cations into Bi1/2Na1/2TiO3 host lattices
strongly induced red photoluminescence of the materials at room temperature.
II. Experimental
The solid solution (1-x)Bi1/2Na1/2TiO3+xPr1/2Na1/2TiO3 system (x=0, 0.5, 1, 3, 5, 7, and 9 mol.%,
named as BNT, BNT-xPr) were well synthesized by sol-gel technique. Firstly, suitable quantities
of raw materials, including Bi(NO3)3.5H2O, NaNO3, Pr(NO3)3.6H2O, were totally dissolved in an
acetic acid solution by magnetic stirring until the solution turned transparent. An amount of
acetylacetone was added to the solution before dropping C12H28O4Ti to prevent hydroxylation of

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Ti4+ cations in the aqueous solution. Subsequently, the solutions were kept on magnetic stirring
for about 3-5 hours before drying to form gels at 100C. Powder samples were obtained by
annealing the dry gels at 900C for 5 hours in the air. The chemical composition and surface
morphologies of as-prepared samples were studied by Energy Dispersive Spectroscopy (EDS)
and Scanning Electron Microscopy (SEM), as shown in Fig. 1S and Fig. 2S, respectively. The
composition of samples was further confirmed by an electron probe microanalyzer (EPMA).
The crystal structure and vibration modes were studied by X-ray diffraction (XRD) and Raman
scattering methods. The optical properties were investigated by Ultraviolet-visible (UV-Vis)
spectroscopy and photoluminescence (PL) spectroscopy. The detail of sample fabrication and
characterization was described in the supplementary.

III. Results and discussions

Fig. 1(a) showed the XRD patterns of the pure Bi1/2Na1/2TiO3 and Pr1/2Na1/2TiO3-modified
Bi1/2Na1/2TiO3 materials with various Pr1/2Na1/2TiO3 concentrations. The crystal structure of the
pure Bi1/2Na1/2TiO3 was indexed as rhombohedral symmetry (JCPDS card no.00-036-034, space
group ), agreeing with recent reports [2, 4, 5]. The addition of Pr1/2Na1/2TiO3 into the host
Bi1/2Na1/2TiO3 materials did not change the number of peaks and their relative intensity,
suggesting that the crystal symmetry of Pr1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 materials
followed the crystal structure of the host Bi1/2Na1/2TiO3 materials. No impurity or secondary
phases were observed in the XRD patterns, suggesting that Pr1/2Na1/2TiO3 were well-soluted into
the host Bi1/2Na1/2TiO3 materials. The effect of the Pr1/2Na1/2TiO3 impurity on the crystal
structure of the host Bi1/2Na1/2TiO3 was shown in Fig. 1(b) where the XRD patterns were
enlarged in the 2-range from 31.0° to 34.0°. The observed asymmetric peaks resulted from an
overlap of (012)/(110) coupling peaks. Each peak was distinguished by Lorentzian fittings with
r-square over 0.99, as shown in the blue lines in Fig. 1(b). The peaks shifted to higher diffraction
angles as the Pr1/2Na1/2TiO3 concentration in the solid solutions increased, indicating the
compression of lattice parameters. Furthermore, the lattice parameters a and c of the pure
Bi1/2Na1/2TiO3 and the Pr1/2Na1/2O3-modified Bi1/2Na1/2TiO3 as a function of
Pr1/2Na1/2TiO3 concentrations are shown in Fig. 3S. The results exhibited that the lattice
parameters of the Pr1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 compounds were complexly distorted.
The lattice parameter distortion by Pr1/2Na1/2TiO3 addition could be explained by considering the

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difference in radius between the impurity cations and the host cations. Based on Shannon’s
report, Bi3+ and Na+ cations located at A-sites had a radius of 1.17 Å (Bi3+ in the coordination of
VIII) and 1.39 Å (Na+ in the coordination of XII), respectively, while the radius of Pr3+ cations
(in the coordination of VIII) was 1.126 Å [15]. As a result, the complex distortion of lattice
parameters was predicted as randomly incorporating Pr3+ cations with Bi3+- or Na+-sites: The
random substitution of Pr3+ cations for Bi3+-sites resulted in lattice expansion, while the
incorporation of Pr3+ cations in Na+-sites exhibited lattice compression. However, according to
Sung et al., the difference in valence states of Pr3+ cations and Na+ cations created Na vacancies,
leading to a distortion of lattice parameters [16]. The role of random incorporation of Pr3+ cations
in the host lattices on phonon vibration modes had been studied by the Raman spectra, as shown
in Fig. 1(c). The Raman spectrum of the pure Bi1/2Na1/2TiO3 material exhibited three main
scattering peaks which were overlapped together because of the random distribution of Bi3+ and
Na+ cations in rhombohedral structures, according to Niranjan et al., [17]. The Raman spectra of
Pr1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 were complicately dependent on the Pr1/2Na1/2TiO3
concentrations. As increasing the Pr1/2Na1/2TiO3 amounts, the intensity of modes in the range
150-680 cm-1 were suppressed, while the intensity of the hump in the range of 680-1700 cm-1
increased, which were suggested the contribution of Pr3+photoluminescence in the Bi1/2Na1/2TiO3
host lattices. The presence of Pr3+ cations influenced the Raman vibration modes of
Bi1/2Na1/2TiO3 crystals, as illustrated in Fig. 1(d) for low-frequency modes after normalizing the
intensity of TiO6 vibration modes at about 322 cm-1. The figure clearly demonstrated that the
peak position of TiO6 vibration modes tended to shift to higher frequencies by increasing the
Pr1/2Na1/2TiO3 amounts. This result indicates that the TiO6 vibrations were distorted, being well
consistent with the distortion of lattice parameters via our XRD study.
In the next step, we’ll discuss in more detail the UV-Vis and Raman results. Fig. 2(a) shows the
absorption spectra of the pure Bi1/2Na1/2TiO3 and Pr1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3
materials depending on the Pr1/2Na1/2TiO3 concentrations. For the pure Bi1/2Na1/2TiO3 sample,
only one single absorption edge tailored with a slight tail was observed. The single absorption
edge is caused by self-defects and/or surface effects, according to Sun et al., and Hung et al. [2,
4]. The addition of Pr1/2Na1/2TiO3 into the host Bi1/2Na1/2TiO3 crystal as solid solutions exhibited
a slight shift of the absorption slope edges and the appearance of the multi-absorption peaks with
increased intensities as increasing the Pr1/2Na1/2TiO3 amounts. The magnified absorption spectra

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shown in the inset of Fig. 2(a) indicated multi-emission levels of Pr3+ cations, including
transitions from the 3H4 level to 3P2, 3P1+1I6, 3P0, and 1D2 levels. The optical bandgap Eg was
estimated by linear extrapolation to zero of Tauc plots (h)2 vs. (h), as shown in Fig. 2(b) [2, 4,
5]. The estimated Eg value was 3.04 eV for the pure Bi1/2Na1/2TiO3 and decreased to 2.95 eV as
increasing the Pr1/2Na1/2TiO3 concentration up to 9 mol.%. Detailed Eg values were given as a
function of Pr1/2Na1/2TiO3 concentrations in the inset of Fig. 2(b). The reduction of the optical
bandgap of Bi1/2Na1/2TiO3 materials via the Pr1/2Na1/2TiO3 addition might be linked to the
emergence of new local states of impurity cations in the host Bi1/2Na1/2TiO3 structure.
Fig. 3(a) showed significant observations of strong red photoemission of Pr1/2Na1/2TiO3-modified
Bi1/2Na1/2TiO3 materials. The main peak at approximately 610 nm was attributed to electron
transitions from 3P0 to 3H6 levels of Pr3+ cations. Besides the main peak, multi-emissions of
electron transitions from 3P0 to 3H4, 3H5, 3F2, 3F4, 1G4, and 3P1 to 3F3, 3F4, and 3P2 to 3H6 levels
had also been indexed. Based on the comparison of main emission intensity, it pointed out that
the PL intensity of Pr1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 samples reached a maximum for the
BNT-1Pr sample (containing 1 mol.% Pr1/2Na1/2TiO3), and quickly reduced as increasing the
Pr1/2Na1/2TiO3 concentration up to 9 mol.%. This observation was consistent with recent reports
on the quenching effect in Pr-doped lead-free ferroelectric materials because Pr3+ emission
photons in red wavelength were self-absorbed and excited the deeper level electrons [3, 6]. In
other words, the strong red photoemission of Bi1/2Na1/2TiO3 materials was successfully obtained
by doping Pr1/2Na1/2TiO3 in the host Bi1/2Na1/2TiO3 crystals.

IV. Conclusion
The Pr1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 materials were successfully synthesized by a simple
chemical method. Pr1/2Na1/2TiO3 was found to be well dissolved into the host Bi1/2Na1/2TiO3
material, resulting in the reduction of the optical bandgap and a strong influence on the red
photoemission at room temperature. Our work was important in opening a new simple way to
incorporate photoluminescence properties in lead-free ferroelectric materials for smart
electronic-device applications.

V. Acknowledgment

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This research is funded by Vietnam National Foundation for Science and Technology
Development (NAFOSTED) under grant number 103.02-2019.366.

Figure captions
Fig. 1 XRD patterns of Pr1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 system with 2-theta (a) in the
range of 20.0°70.0, (b) magnification from 31.0° to 34.0. The Raman scattering spectra of
Pr1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 system in (c) the wavenumber range of 150-1750 cm-1,
and (d) comparing the peak position in the wavenumber range from 150 to 550 cm-1.
Fig. 2 (a) UV-Vis spectra and (b) plots of (h)2 as a function of photon energy (h) of
Pr1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 materials. The inset in Fig 2(b) shows the dependence of
Eg values on Pr1/2Na1/2TiO3 concentrations.
Fig. 3 (a) PL spectra of Pr1/2Na1/2TiO3-modified Bi1/2Na1/2TiO3 materials, and (b) the dependence
of PL intensity as a function of Pr1/2Na1/2TiO3 concentrations in the solid solutions.

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Dung et al. Fig. 1

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Dung et al. Fig. 3

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