Materials Letters
journal homepage: www.elsevier.com/locate/matlet
A R T I C L E I N F O A BS T RAC T
Keywords: We have successfully fabricated Mn-doped wide band gap lead-free ferroelectric Bi0.5Na0.5TiO3 by sol-gel
Sol-gel preparation technique. The band gap reduced from 3.12 to 1.71 eV as increasing doping Mn concentration level up to 9 mol
Lead-free ferroelectric %. The room temperature ferromagnetism in Mn-doped Bi0.5Na0.5TiO3 samples was observed. The magnetic
Ferromagnetism moment was around 2.69 B/Mn at 5 K. We expected that this work will open the new direction for advance
Multiferroics
function of lead-free ferroelectric materials.
Perovskites
Corresponding author.
E-mail address: dung.dangduc@hust.edu.vn (D.D. Dung).
http://dx.doi.org/10.1016/j.matlet.2016.09.105
Received 5 June 2016; Received in revised form 5 September 2016; Accepted 25 September 2016
Available online 26 September 2016
0167-577X/ 2016 Elsevier B.V. All rights reserved.
L.T.H. Thanh et al. Materials Letters 186 (2017) 239242
Fig. 1. (a) XRD pattern of Mn-doped Bi0.5Na0.5TiO3 as a function of Mn doping concentration and (b) a comparison of (003) diraction peak positions in 2 range of 45.548.5.
Mn-doped samples shifts toward a higher 2 values (Fig. 1(b)), spectroscopy in Mn-doped Bi0.5Na0.5TiO3 at TiO band is solid
indicated that Mn incorporated with lattice structure. Based on the evidence of Mn substitution at Ti site cause of the higher mass of the
Shannon reported, the ionic radii of Mn2+, Mn3+, Mn4+ and Ti4+ with Mn ion compared with Ti ions.
six coordination are 0.83, 0.645, 0.53 and 0.605 , respectively [12]. Fig. 3(a) shows the optical absorption spectra of Bi0.5Na0.5TiO3 and
The Mn states were reported from Mn2+ to Mn4+ which is depending Mn-doped Bi0.5Na0.5TiO3 samples. The appearance of multi absor-
on specially the materials and fabrication processing [13,14]. bance peaks (e.g. around 426 and 620 nm) suggested for multi local
Therefore, the present of valence state of ions Mn resulted in inuence states of Mn ion in forbiddance gap of Bi0.5Na0.5TiO3 materials. The
of distortion on lattice parameter which are very complicated. Our band gap (Eg) values reduced from 3.12 to 1.71 eV for un-doped and
results indicated that the peaks position shifted to higher 2 values for 9 mol% Mn-doped Bi0.5Na0.5TiO3, respectively (Fig. 3(b)). Recently,
doped samples; therefore, we suggest that the average ionic radius of theoretical calculation predicted that the Bi0.5Na0.5TiO3 compound has
Mn dopant is smaller than that of ionic Ti4+. conduction band mostly contains Bi-6p, Ti-4s, Na-3s and Na-2p
Fig. 2(a) shows the Raman spectra of pure Bi0.5Na0.5TiO3 and Mn- orbitals and the bottom of the valence band is constructed from Bi-
doped Bi0.5Na0.5TiO3 in the wave number range of 100700 cm1. The 6s and O-2p orbitals [16]. Our current work on Fe-doped Bi0.5K0.5TiO3
Raman spectra were relatively broad which resulted from disorder on materials also indicated that the presence of conduction bands of Fe
the A-site and from overlapping Raman modes. The eect of Mn ion resulted in reduction of band gap [11]. Thus, we suggested that the
substitution for Ti on the phonon vibration (Fig. 2(b)), where the high incorporation of Mn-d orbital electronics into the lattice reduced the
magnication Raman spectra of un-doped and Mn-doped band gap of Bi0.5Na0.5TiO3 materials, which result from the present of
Bi0.5Na0.5TiO3 in the wave number range of 150450 cm1. The new states in electronic structure of both the highest occupied
vibration modes for Bi0.5Na0.5TiO3 in the range of 109134 cm1 are molecular orbital and lowest unoccupied molecular orbital associated
dominated by displacement of Bi ions, and the modes in the frequency with the presence of Mn stabilized by an accompanying O-vacancy
range of 155187 cm1 and 246401 cm1 are dominated by Na-O and (Fig. 3(c)). Therefore, we suggested that the reduction of band gap in
TiO6 vibrations, respectively, while the modes in the range 413 transition metal doped lead-free ferroelectric materials results from
826 cm1 are primarily associated with the oxygen octahedral [15]. contribution of conduction bands of transition metal in total density of
The result indicated that the Ti-O bands shifted to lower frequency as state of lead-free ferroelectric materials.
the Mn concentration increased. The change frequencies of Raman Fig. 4(a) shows the magnetic hysteresis (M-H) loops of the undoped
Fig. 2. (a) Raman spectra of Mn-doped Bi0.5Na0.5TiO3 as a function of Mn doping concentration, and (b) a magnication of wave positions in range of 150400 cm1.
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L.T.H. Thanh et al. Materials Letters 186 (2017) 239242
Fig. 3. (a) UVvis absorption spectra and (b) the dependence of (h)2 on photon energy (h) of the pure and Mn-doped Bi0.5Na0.5TiO3 samples. (c) Schematic illustration of
mechanism for band-gap narrowing in the transition metal doped lead-free Bi0.5Na0.5TiO3 materials.
and Mn-doped Bi0.5Na0.5TiO3 samples at room temperatures. The anti- obtained in M-H curve for Mn concentration added Bi0.5Na0.5TiO3 over
S-shape is observed for undoped samples resulting from the competi- 5 mol% which resulted from compensation of ferromagnetic and
tion between ferromagnetic and diamagnetic. The origin of weak- paramagnetic of exchange interaction between magnetic ions and
ferromagnetism at room temperature of un-doped samples was pre- isolate magnetic ion in host lattice, respectively [10,11]. Fig. 4(b)
dicted from vacancy-induced magnetism via ab initio calculation [17]. shows the dependence of magnetization on temperature under an
By the incorporation of Mn in Bi0.5Na0.5TiO3 lattice, the weak applied eld of 1 kOe of Bi0.5Na0.5Ti0.99Mn0.01O3 samples. The inset of
diamagnetic signal has been converted to a feeble ferromagnetic loop Fig. 4(b) shows the M-H curve of Bi0.5Na0.5Ti0.99Mn0.01O3 samples
conrming ferromagnetism at room temperature. The coercive eld under magnetic up to 70 kOe at various temperatures. The maximum
and remanence magnetization were around 80 Oe and 0.5 memu/g, magnetization was ~0.71 emu/g at 5 K which was corresponded to
respectively, which were solidly evident for ferromagnetism behavior at 2.69 B/Mn. Therefore, we suggested that present of room temperature
room temperature. However, the unsaturation of magnetization was ferromagnetism in Mn-doped Bi0.5Na0.5TiO3 was possible due to
Fig. 4. (a) MH curves of the Bi0.5Na0.5TiO3 and Mn-doped Bi0.5Na0.5TiO3 samples, and (b) The MT curve at 1 kOe magnetic eld for Bi0.5Na0.5Ti0.99Mn0.01O3 samples. The inset of
Fig. 4(b) shows MH curve of Bi0.5Na0.5Ti0.99Mn0.01O3 samples at 5 K.
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