Journal of Alloys and Compounds 947 (2023) 169571

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Journal of Alloys and Compounds

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Optimization of magnetoelectric coupling in BiFeO3-BaTiO3-MnFe2O4 tri-

phase composites for ultra-sensitive devices ]]
]]]]]]
]]

Muhammad Ahmed Khan a, Kanwal Shahbaz b, Ghulam M. Mustafa c, Shahid M. Ramay d,

⁎
Shahzad Naseem a, Shahid Atiq a,
a
Centre of Excellence in Solid State Physics, University of the Punjab, Lahore, Pakistan
b
Department of Physics, University of the Punjab, Lahore, Pakistan
c
Department of Physics, Division of Science and Technology, University of Education, Lahore 54770, Pakistan
d
Department of Physics, College of Science, King Saud University, Riyadh, Saudi Arabia

a r t i cl e i nfo a bstr ac t

Article history: Multiferroic materials with coupled electric and magnetic orderings have astonished the scientific com­
Received 17 January 2023 munity by exhibiting magnetoelectric (ME) coupling, viable for multistate memory devices. Facile synthesis
Received in revised form 12 February 2023 of multiferroic composites have further triggered these delightful attributes. Here we present a series of tri-
Accepted 6 March 2023
phase composites of the form; (1–x)(0.7BiFeO3 + 0.3BaTiO3) + xMnFe2O4, synthesized by a facile two-step
Available online 7 March 2023
method. The phase-pure synthesis was confirmed using X-ray diffraction. For energy storage capability, a
composition with x = 0.02, reveals the recoverable energy density of ∼0.22 mJ/cm3 followed by the highest
Keywords:
Multiferroics efficiency of 64.02%, making such composition favourable for energy storage perspectives at minute in­
Perovskites clusion of the spinel phase. The characteristic I-V curves were used to explain the leakage current of BiFeO3
Ferroelectric nature (BFO). The positive up and negative down (PUND) sequence demonstrates the significant variation in
PUND sequence switching charge density. The gradual increase in grain size resulted in a lowering of the coercivity values
Magnetoelectric coupling up to 301 Oe at x = 0.10 having 6.31 emu/g as saturation magnetization (MS) value along with MR/MS ratio of
Ultra-sensitive devices 0.33. The linear response shown by ME coupling at x = 0.06 along with the afore mentioned attributes make
this composition a potential candidate for ultra-sensitive magnetoelectric devices.
© 2023 Published by Elsevier B.V.

1. Introduction earth metals and B-site as transition metals have gained much
attention owing to their cost effectiveness and superficial synth­
As the world was on the edge of the beholding energy crisis, esis. Moreover, these perovskites are highly in business because of
multiferroics a peculiar class of materials reduced this risk by their structural tunability and for some practical reasons, the
retrieving the energy storage devices through ME coupling [1]. compositional variations at A and B sites can also be made quite
Multiferroics exhibit the phenomenon of ME coupling which is easily [5]. Amongst the single phase ABO3 type perovskite oxides,
comprised of two exclusively coupled ferroic orders i.e., ferro­ the pristine BFO ceramic possesses a high Curie temperature of
electric and ferromagnetic orderings, simultaneously [2]. These ∼830 °C and Neel temperature of ∼370 °C that depicts highly
materials exhibit profound applications in spintronics, tempera­ ferroelectric and G-type anti-ferromagnetic behavior, simulta­
ture sensing devices, transducers, ultra-fast switching, and energy neously [6]. One of the promising features of BFO being the sole
harvesting devices [3]. Experimental verifications suggested that single-phase material is that it exhibits multiferroicity above
the single-phase multiferroic materials had depicted insignificant room temperature (RT) while other perovskites often show this
ME coupling because the electronic configuration that was quite feature well below RT. Apart from having such unique virtues, it
mandatory for ferroelectric and ferromagnetic nature (i.e., the d0 has encountered with some serious issues like high leakage cur­
vs dn) could not contest within the same phase simultaneously rent due to volatilization of Bi3+ ion when it is exposed to heat
[4]. The ABO3 type perovskites with A-site featuring alkali/rare treatment, whereas the cause of G- type anti-ferromagnetism
associated with cycloidal spin modulation is due to valency var­
iation of Fe ion [7,8]. In contrast, BFO has various merits such as
cost effectiveness, low energy band gap (Eg ∼2.2 eV), and high
⁎
Corresponding author. spontaneous polarization (PS ∼100 µC/cm2), but its moderate
E-mail address: [Link]@[Link] (S. Atiq).

[Link]
0925-8388/© 2023 Published by Elsevier B.V.
M.A. Khan, K. Shahbaz, G.M. Mustafa et al. Journal of Alloys and Compounds 947 (2023) 169571

Fig. 1. Schematic representation of the synthesis process.

remanent polarization and un-stability at RT hindered its wide­ Bi0.9La0.1Fe0.9Mn0.1O3 + xMnFe2O4 at x = 0.10 [23]. The strong inter­
spread usage in multi-state device applications [9–11]. facial interactions between perovskite and spinel structures could
One of the convenient ways to avoid the phase transition (i.e., only be observed in composite form, providing some vast practical
secondary phases) of BFO ceramics is the composite formation applications with material’s controlled phase structures and com­
through the inclusion of some other ABO3-type structure [12]. BaTiO3 positional variations. In contrary strong interplay would not be
(BTO) is one of the famous and stable type-1 ferroelectric materials achievable if the phases were to be discussed individually [24].
having low leakage current compared to that of BFO and proved a Keeping in mind all the above-mentioned constraints, the cur­
vital option for composite making with BFO [13]. The significant rent project is designed to overcome these shortcomings. Thus the
piezoelectric nature of BFO-BTO composite with a high curie tem­ present work comprised of the synthesis of a novel tri-phase com­
perature of over ∼580 °C made it a substantial alternative to lead- posite that is primarily based upon two perovskite phases i.e., BFO
based ceramics such as PbZrTiO3 [14,15]. Consequently, BFO-BTO and BTO along with spinel phase of MFO having composite formula
ceramics showed better ferroelectric behavior. A similar attempt at (1–x)(0.7BFO + 0.3BTO) + xMFO (x = 0.00, 0.02, 0.04, 0.06, 0.08, and
composite synthesis was done by Ji et al., (2021) and they prepared 0.10). In this context, the BFO and MFO were synthesized through a
(1–x)BFO + xBTO (x = 0.2–0.4) composite aided by the microwave sol–gel auto-combustion method followed by a solid-state reaction
sintering (MWS) method and conventional sintering (CS) method method for synthesizing BTO and composite making. As many re­
and maximum value of remanent polarization (PR) for MWS and CS searchers have thoroughly discussed their individual electric polar­
was recorded as 2.22 µC/cm2 and 3.74 µC/cm2 at x = 0.35, respec­ ization and magnetic behaviour. Whilst, this study basically provides
tively [16]. But insufficient ferromagnetic behavior was also en­ a wide canvas to understand the coupling aspects between these
countered for this specific composite [17]. different phases so that they can be employed in various ME cou­
To enrich the ferromagnetism in this BFO-BTO composite, a third pling-based ultra-fast switching devices.
counterpart from the spinel family is selected. Spinel ferrites having
AB2O4 structure are the excellent magnetic counterpart where A 2. Experimental details
represents the di-valent ions (at tetrahedral sites) such as nickel,
calcium, cobalt, zinc, and manganese whereas B shows Fe3+ ions The schematic illustration for the synthesis of the composite
(octahedral sites) that can fluctuate the magnetic and electrical recipe (1–x)(0.7BFO + 0.3BTO) + xMFO (x = 0.00, 0.02, 0.04, 0.06,
properties quite significantly [18]. Besides cross-coupling between 0.08, and 0.10) can be observed in Fig. 1. Basically, the composite
different ferroic orders, the spinel ferrites hold better electric and recipe comprised of three individual phases having two perovskite
magnetic properties and had an opportunity of enhancing the ME phases: BFO and BTO and a spinel phase: MFO. Both BFO and MFO
effect in BFO-based composites [19]. Low electrical conductivity, low were prepared through the sol–gel auto-combustion technique be­
dielectric loss, high surface area, moderate magnetization, better cause of their bottom-up approach, cost-effectiveness, and better
mechanical stiffness, and high chemical stability has made spinel crystallinity results. For this purpose, the metal nitrates owing to
ferrites much more vibrant in multiferroic composites in uplifting their water solubility were preferred as precursors that include
the ME effect [20]. MnFe2O4 (MFO) a prominent spinel phase of a bismuth nitrate pentahydrate [Bi(NO3)3.5 H2O], iron nitrate non­
cubic crystal having Fd-3 m space group has gathered much interest ahydrate [Fe(NO3)3.9 H2O] and manganese nitrate tetra-hydrate [Mn
among several ferrites due to its soft magnetic behavior, easy fab­ (NO3)3.4 H2O] having 99% purity along with some fuelling agents
rication, and highly resistive nature [21]. Moreover, MFO has pro­ such as urea [CH4N2O] and glycine [C2H5NO2]. Whilst the overall
found applications in magnetic resonance imaging, hyperthermia metal nitrate to fuel ratio was taken as 1:2. All these chemical re­
cancer therapy, energy storage, and conversion gadgets [22]. Khan agents were of analytical grade and purchased from Sigma Aldrich.
et al., (2020) reported a significant value of saturation (MS) and re­ For making a homogeneous solution, the precursors were dissolved
manent magnetization (MR) of 37.676 emu/g and 16.248 emu/g along separately in two different beakers whereas a few drops of HNO3
with a coercivity value of 475.838 Oe in the composite recipe (1–x) have added to BFO beaker for better solubility. Furthermore, the

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M.A. Khan, K. Shahbaz, G.M. Mustafa et al. Journal of Alloys and Compounds 947 (2023) 169571

Fig. 2. (a) Diffraction patterns of the tri-phase composites (1–x)(0.7BFO + 0.3BTO) + xMFO (x = 0.00, 0.02, 0.04, 0.06, 0.08, and 0.10), (b) BFO twin peaks, (c) unit cell of BFO, (d) unit
cell of BTO, and (e) unit cell of MFO.

precursor's solution was then mixed together in a single large beaker nanoparticles, the ball milled ground powder was then calcined at
and placed onto the hot plate with having magnetic stirrer inside for 800 °C for 2 h to achieve a proper phase development. Meanwhile,
providing a smooth stirring of the sol. The magnetic stirring rate for all three individual phases of the composites were then mixed to­
BFO and MFO was 350 rpm and 250 rpm at 110 °C, respectively. The gether according to specific stoichiometric ratios and then passed
beakers were then set aside for a few hours and after some time the through a ball milling chamber to make a composite by varying the
gel formation took place which was witnessed by the resistive mo­ value of x in (1–x)(0.7BFO + 0.3BTO) + xMFO as x = 0.00, 0.02, 0.04,
tion of the stirrer even at a high stirring rate. Ultimately, the mag­ 0.06, 0.08, and 0.10. Ultimately, the fine composite powder was
netic stirrer was removed and the gel was gradually heated up until pressed through an Apex hydraulic press by applying 30 kN force
the auto-combustion occurred with an energetic flame developing a onto a die of 10 mm thickness to achieve a proper pellet for various
better crystalline phase of the required samples. The auto-combus­ characterization purposes. A recent study done by Sahni et al., (2014)
tion for BFO and MFO took place at 250 °C and 230 °C, respectively showed the impact of Mn doping in (0.90)BFO + (0.10)BTO compo­
the former developed into dark brownish ash whereas the latter site. The presence of Mn2+ and Fe3+ ions at the same lattice sites has
formed a black suit-like ash. These were then ground into a fine surprisingly suppressed the spin cycloid of BFO which consequently
powder by mortar and pester. Moreover, for proper phase develop­ resulted in the enhancement of spontaneous magnetization in the
ment, both BFO and MFO were calcined at 600 °C and 800 °C, re­ composites [26].
spectively. A similar type of work is done by Augustine et al. (2021) The proper phase development of the individual phases of the
and they prepared a nanocomposite with recipe (1–x)BFO + xMFO tri-phase composites was analyzed using a Bruker D8-advanced, X-
(x = 10%, 30%, 50%, 70%) and observed that a maximum coupling ray diffractometer (XRD), that worked as a fingerprint to ascertain
coefficient (α) of 25.9 mV/cm Oe value was found for the specific the development of the crystalline phases. Morphological analysis of
nanocomposite having 70% BFO and 30% MFO [25]. the composite samples was performed using a Nova-Nano SEM-450,
The third counterpart BaTiO3 (BTO) is an eco-friendly and a field emission scanning electron microscopy (FESEM) and a Java-
better alternative to lead-based ceramics which have a negative based Image-J software was used to calculate the particle size and
impact on the environment due to their carcinogenic nature. Since distribution. For measuring the exact stoichiometric elemental
oxides are insoluble in water so the solid-state reaction was opted composition in the tri-phase composites, an Oxford instruments’
for synthesizing the BTO in which the precursors were in a solid energy dispersive X-ray (EDX) spectroscopy was utilized. The hys­
form that include barium nitrate [Ba(NO3)2 99%] and titanium oxide teresis loops of the samples for a magnetic response were de­
[TiO2 99%] and these precursors were thoroughly mixed in a ball termined using a DXV-9000 series vibrating sample magnetometer
milling chamber for about 9–10 h at 15 oscillations/sec. This ball (VSM). For measuring the ferroelectric nature of the samples along
milling method is a top-down approach providing better with the ME-coupling, the multiferroic tester of Radiant technology

3
M.A. Khan, K. Shahbaz, G.M. Mustafa et al. Journal of Alloys and Compounds 947 (2023) 169571

Inc. (USA) was utilized. All these characterization techniques provide process such as weighted R-profile (Rwp), R-profile factor (Rp), and R-
an insightful vision of the tri-phase composites to validate which expected (Rexp), whereas by taking the ratio of (Rwp/ Rexp) we get the
composition is highly feasible for multi-state applications. value of goodness of fit (χ2) that validates whether the phase has
properly developed or not [30]. It was analyzed that the χ2 value for
3. Results and discussion all the samples seemed quite similar with the least variation that
assured the exact phase development of the tri-phase composites as
The crystalline structure of various phases present within the shown in Fig. 3(a-f). All the values of χ2 for all the samples are quite
composites were determined using XRD patterns which were in­ consistent whereas at x = 0.10 the value of χ2= 1.14 showed that the
dexed by an analytical method proposed by B.D Cullity, as shown in tri-phase composite has developed quite properly. All the above-
Fig. 2(a) [27]. This indexing method explicitly showed that the peaks mentioned Rietveld’s refined factors are mentioned in Table 2.
at 22.44°, 31.80°, 32.20°, 39.65°, 45.87°, 51.57°, 52.16°, 57.52°, 66.73°, The microstructural analysis of the tri-phase composites (1–x)
67.24° 2θ values correspond to the Bragg’s planes (i.e., hkl values) (0.7BFO + 0.3BTO) + xMFO (x = 0.00, 0.02, 0.04, 0.06, 0.08, and 0.10)
(100), (110), (1−10), (1−11), (200), (210), (2−10), (1−21), (220), (2−20), was carried out using FESEM images taken at 100,000x magnifica­
respectively and these peaks were matched with ICSD card no. tion as shown in Fig. 4(a-f). These FESEM images were analysed to
01–072–2035 which assured the formation of rhombohedral type investigate the grain size, grain size distribution, and porosity of the
crystal structure of BFO having R3m space group symmetry [28]. composite samples. The bi-phase composition at x = 0.00 as shown
These peaks are represented by phi (Ф) sign as shown in Fig. 2(a). An in Fig. 4(a) depicts an average grain size of ∼ 200 nm. It was observed
explicit depiction of BFO twin peaks can be visualized in Fig. 2(b) that after the inclusion of MFO, a slight variation in the grain size
whereas the unit cell of BFO is illustrated in Fig. 2(c). In addition, the was observed and its value is noted around ∼ 250 nm at x = 0.02 as
peaks positioned at 2θ values of 38.94°, 55.96°, and 56.60° corre­ shown in Fig. 4(b). Since this synthesis approach does not yield a
spond to the diffraction planes (111), (112), (211) and matched with uniform grain size therefore it is preferable to mention the average
ICSD card no. 00–005–0626, confirming a tetragonal phase devel­ grain size [31]. So, the average grain size is preferred over the single
opment of BTO with P4mm space group symmetry. The peaks be­ grain which is provided by the formulation of the histogram as an
longing to the tetragonal structure of BTO were symbolized by a inset of the corresponding FESEM image that was determined using
delta (Δ) sign and its unit cell arrangement was illustrated in Image-J software. As the MFO contents are increased to x = 0.04, the
Fig. 2(d). Meanwhile, some new peaks were seen to appear at 2θ surface inspection suggested that cubical and rectangular shaped
values of 29.90°, 35.35°, and 62.30° that belonged to Miller’s indices grains were grown having minimal voids in between the clusters
such as (220), (311), and (440) and matched with ICSD card no. with average grain size around ∼220 nm in the tri-phase composites
00–010–0319 and thus assured the formation of cubic spinel struc­ as depicted in Fig. 4(c). For x = 0.06 composition, the average grain
ture of MFO having Fd-3 m space group symmetry. The corre­ size was enhanced to ∼310 nm and the grains seemed to be em­
sponding peaks of MFO are represented with a psi (Ψ) sign and its bedded into each other which resulted in significant intergranular
corresponding unit cell arrangement is depicted in Fig. 2(e). It was voids formation shown in Fig. 4(d). As the MFO contents enhanced
observed that the composition with x = 0.00, comprised a bi-phase up to x = 0.08 as provided in the FESEM image in Fig. 4(e), the dif­
composition (BFO-BTO) with exclusion of MFO contents. As the MFO fusive nature of the grains becomes more prominent consequently
concentration is introduced to x = 0.02, the extra peaks corre­ showing variation in the porosity of the sample having a grain size of
sponding to MFO appeared which showed maximum peak intensity ∼301 nm. The last composition, x = 0.10 vividly depicted that this tri-
at x = 0.10 confirming the presence of the desired tri-phasic com­ phase composite was comprised of an average grain size of ∼305 nm.
posite. The crystallite size of different phases was calculated by The variation in grain size may be associated with Fe3+ ions at grain
using Scherrer’s formula as given in Eq. (1) [29]. boundaries which might have restricted the growth of the grains at
different compositions [32]. The variation in the crystallite size and
0.9 grain size basically alters the mean free path of the electrons which
D=
cos (1) consequently varies the resistivity of the sample under consideration
Here D is the crystallite size, k = 0.9 is the Scherrer’s constant, λ is [33]. These variations can be manipulated by optimizing the heat
the wavelength of Cu-Kα radiation (1.5404 Å), whereas β is the full treatment conditions for the desired growth of nano-structured
width at half maximum, and θ is Bragg’s angle, respectively. The composites as it plays a key role in ME-coupled device application.
average crystallite size of BFO, BTO, and MFO was approximately 28, The distinct atomic structure of every individual element can be
18 and 19 nm, respectively. The bulk density of the composite distinguished based on the specific energy of X-rays emitted while
samples was calculated by the relation: ρB= m where m is the mass of subjecting it to an electron beam provides EDX spectra as shown in
V
the pellet, and V is the volume of the pellet. Volume V is calculated Fig. 5(a) [34]. This EDX spectrum comprised peaks belonging to Bi,
2
by the following relation: V = πr h, here r and h represent the radius Fe, Mn, Ba, Ti, and O along with Au as a constituent element of the
and thickness of the pellets. For calculating the X-ray density, the as-synthesized tri-phase composite. The concerned EDX spectra as­
following relation was utilized: ρx = NM , where N, M, V, and NA re­ sured the exact stoichiometric formulation of (1–x)(0.7BFO +
VNA
0.3BTO) + xMFO (x = 0.00, 0.02, 0.04, 0.06, 0.08, and 0.10) tri-phase
present the number of formula units, molecular weight, the volume
composite as it was expected based upon its empirical formula. The
of the unit cell, and Avogadro’s number, respectively. Furthermore,
peaks of C were related to the sticky tape used for sample holding;
for finding the porosity of the as-synthesized samples the following
whilst the conductive coatings Au were done onto the composite
relation has been used;
sample to avoid the charging phenomenon [35]. Moreover, no un­
B
desirable peak in the EDX spectra validates the exact formulation of
%Porosity = 1 × 100 the composite recipe. It was observed that at x = 0.00 the intensity
x (2)
peak of BFO is at maximum extent whereas on increasing the MFO
All the concerned structural data of the composite samples that contents the BFO intensity peaks get shorter whilst the Fe and Mn
are measured through the above relations are enlisted in Table 1. peaks got enhanced. All the weight % values of the elements present
Furthermore, for confirming the phase identification of the compo­ in the composite are enlisted in Table 3.
site samples, Rietveld’s refinement was carried out for the quanti­ Whilst performing the FESEM and EDX analysis, a small portion
tative phase analysis obtained through X′pert HighScore Plus of the composite sample at x = 0.10 was scanned to investigate the
software. It provided the major R-factors involved in the refinement elemental mapping as illustrated in Fig. 5(b). The coloured spectrum

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M.A. Khan, K. Shahbaz, G.M. Mustafa et al. Journal of Alloys and Compounds 947 (2023) 169571

Table 1
Lattice constants with average crystallite size attained through Scherrer’s formula, bulk density, X-rays density and porosity of the tri-phase composites (1–x)(0.7BFO + 0.3BTO)
+ xMFO (x = 0.00, 0.02, 0.04, 0.06, 0.08, and 0.10).

Composition Lattice constants (nm) Average crystallite size (nm) Bulk density X-ray density Porosity
(x) by Scherrer’s formula (gcm−3) (gcm−3) (%)
BFO BTO MFO

a=b=c a=b c a=b=c BFO BTO MFO

0.00 0.394 0.397 0.403 0.848 25 19 - 3.72 6.12 40

0.02 0.394 0.397 0.403 0.848 22 16 13 3.61 6.32 43
0.04 0.394 0.397 0.403 0.848 34 14 20 3.40 6.55 49
0.06 0.394 0.397 0.403 0.848 25 16 15 3.22 6.70 52
0.08 0.394 0.397 0.403 0.848 29 18 24 3.12 7.11 56
0.10 0.394 0.397 0.403 0.848 32 24 21 3.04 7.25 58

Fig. 3. Rietveld’s refined XRD patterns of (1–x)(0.7BFO + 0.3BT0) + xMFO tri-phase composites with (a) x = 0.00, (b) x = 0.02, (c) x = 0.04, (d) x = 0.06, (e) x = 0.08, and (f) x = 0.10,
respectively along with their corresponding phase quantification.

the radiated X-rays which corresponds to the electronic transition of

Table 2
Rietveld’s refined factors of (1–x)(0.7BFO + 0.3BTO) + xMFO at various contents that certain element. So, the X-rays associated with Bi and Au were
(x = 0.00, 0.02, 0.04, 0.06, 0.08, and 0.10) for tri-phase composites. obtained through M-shell transition, whilst Fe, O, Ti and Mn were
R-factors attained through Rietveld’s refinement
attained through K-shell transitions and Ba was the sole element
that showcased the L-shell transitions [36].
MFO contents (x)
The bipolar P-E hysteresis loops obtained under an applied
electric field (Ef) of ± 800 V/cm manifested an insightful idea about
x 0.00 0.02 0.04 0.06 0.08 0.10
the ferroelectric behaviour of the as-synthesized tri-phase compo­
Rexp 8.30 8.31 7.92 8.31 6.44 19.89
Rp 6.55 6.71 5.69 5.57 4.65 7.24 sites as shown in Fig. 6(a). The systematic behaviour of the P-E loops
Rwp 10.59 10.99 9.99 9.13 7.49 20.89 about the origin could be visualized which depicts the linear re­
DStatistics 0.03 0.04 0.03 0.03 0.06 23.34 sponse of the composites under Ef. The ferroelectric materials are
[Link] 4.05 3.69 5.10 4.05 11.21 19.80 mainly linked with some attributes like maximum polarization (PM)
χ2 1.27 1.32 1.26 1.09 1.16 1.14
and remanent polarization (PR) and coercive filed (EC), depending
upon these computed values, the device performance can be pre­
indicates the presence of Bi, Fe, Mn, Ba, Ti, and O along with Au dicted before fabrication. This is because the Ef dependency can
which could be visualized as provided in Fig. 5(c-i) which re-assured greatly influence the polarization switching capability in ferro­
the formulation of the desirable composite recipe. The contrast of electric materials [37]. The unipolar P-E loops having charge-dis­
the coloured spectrum is subjected to two basic entities; firstly, the charge curve is plotted in 1st quadrant to study the ferroelectric
brighter regions depict the highest probability of a certain element properties as shown in Fig. 6(b) [38]. For visualizing the increasing
in that specific region, whereas the darker region indicates the ab­ trend of polarization by enhancing the Ef the unipolar graph for
sence of that certain element. Since the elements are associated with x = 0.10 is plotted for various voltages as shown in Fig. 6(c). The P-E

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M.A. Khan, K. Shahbaz, G.M. Mustafa et al. Journal of Alloys and Compounds 947 (2023) 169571

Fig. 4. FESEM images of (1–x)(0.7BFO + 0.3BTO) + xMFO tri-phase composites with (a) x = 0.00, (b) x = 0.02, (c) x = 0.04, (d) x = 0.06, (e) x = 0.08 and, (f) x = 0.10, respectively
captured at 100,000x.

loop does not seem saturated at x = 0.00 because of the highest % plotted for x = 0.08 and x = 0.10 for better visualization amongst
percentage of BFO depicted by an oval-shaped leaky loop as shown different compositions. The systematic suppression in the leakage
in Fig. 6(a), this bi-phase composite at x = 0.00 showed PM, PR, and EC current of BFO composite is mainly due to BTO contents that have
values to be 8.87 × 10−4 µC/cm2, 5.05 × 10−4 µC/cm2 and 446 V/cm, provided insulation to the samples as observed at x = 0.00 [39]. All
respectively. While doing so, at x = 0.10, the maximum recorded values of PM, PR, and EC are provided in Table 4. Moreover, a prime
values of PM, PR, and EC were 2.6 × 10−3 µC/cm2, 2.1 × 10−3 µC/cm2, and objective of analysing the ferroelectric behaviour is to ensure its
540 V/cm, respectively as shown in Fig. 6(d) with an inset of PE loop energy storage capability and for this purpose, the recorded values of

Fig. 5. (a) EDX spectra of (1–x)(0.7BFO + 0.3BTO) + xMFO at various contents (x), whilst (b) indicates the small scanned area, (c) depicts Bi mapping, (d) Fe, (e) O, (f) Ba, (g) Ti, (h)
Au, (i) Mn elemental mapping with various shell transitions.

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M.A. Khan, K. Shahbaz, G.M. Mustafa et al. Journal of Alloys and Compounds 947 (2023) 169571

Table 3 Table 4
Weight percentage of various elements in (1–x)(0.7BFO + 0.3BTO) + xMFO (x = 0.00, Quantified values of maximum polarization (PM), remanent polarization (PR) and
0.02, 0.04, 0.06, 0.08, and 0.10) tri-phase composites. variation in coercive field (EC) in tri-phase composites (1–x)(0.7BFO + 0.3BTO) + xMFO
at various contents (x = 0.00, 0.02, 0.04, 0.06, 0.08, and 0.10).
x Bi% Fe% Ba% Ti% Mn% Au% C% O%
MFO contents (x) PM PR EC
0.00 35.44 12.32 16.30 5.93 - 0.35 5.30 24.36
(µC/cm2) (µC/cm2) (V/cm)
0.02 32.64 14.52 15.12 4.45 3.23 0.74 5.50 23.80
0.04 30.96 16.87 14.44 3.67 3.92 0.90 5.98 23.26 0 0.00087 0.00050 446
0.06 28.98 18.40 12.99 3.12 4.07 1.05 7.82 23.57 0.02 0.00082 0.00031 229
0.08 25.93 19.35 11.04 2.42 4.23 1.32 9.75 25.96 0.04 0.00098 0.00054 443
0.10 24.03 21.29 9.23 2.12 5.92 2.06 9.30 26.05 0.06 0.0011 0.00058 396
0.08 0.0018 0.0015 600
0.1 0.0026 0.0021 540
PM, and PR, were utilized to calculate the recoverable energy density
(WR) and energy loss density (WL) values for various compositions as
Table 5
shown in Fig. 6(e). An inset of x = 0.08 and 0.10 composition is Evaluating total energy density (WT), recoverable energy density (WR), energy loss
provided within Fig. 6(e) to investigate the extent of the charge- density (WL) and % efficiency (%ɳ) for (1–x)(0.7BFO + 0.3BTO) + xMFO at various
discharge trend for measuring the material’s energy densities, ex­ contents (x = 0.00, 0.02, 0.04, 0.06, 0.08, and 0.10) tri-phase composites.
plicitly. The value of WR is the measure of the area outside the P-E MFO contents WT WR WL % Efficiency
hysteresis loop which is basically calculated through the following (x) (mJ/cm3) (mJ/cm3) (mJ/cm3)
P
relation: WR = P M EdP where E is the applied external field and dP is 0.00 0.34 0.15 0.19 44.48
R
the change in polarization i.e., PM -PR. In addition, the total energy 0.02 0.32 0.22 0.11 64.02
1 0.04 0.39 0.18 0.21 44.89
density (WT) that’s is calculated through the relation: WT = 2 PM *E
0.06 0.44 0.20 0.23 47.72
and with the help of the aforementioned relations the value of WL 0.08 0.72 0.12 0.60 16.61
(WL= WT - WR) was calculated [40]. Similarly, for calculating the 0.10 1.04 0.20 0.84 19.23
energy storage capability of the samples, the % efficiency (%ɳ) can be
W
achieved through the following prescribed relation: %ɳ = W RW x100
R+ L current phenomenon of the as-synthesized composites. It is notified
[41]. It was observed that the maximum value of WR was recorded as that on increasing the MFO contents, the leakage current was in­
0.22 mJ/cm3 at x = 0.02, whereas the maximum WL having 0.84 mJ/ creased and a maximum leakage current of 1.8 × 10−3 A was recorded
cm3 value was observed at x = 0.10 as shown in Fig. 6(e). It was de­ for x = 0.06. Variation in the current leakage was observed from 10−5
duced through the plot given in Fig. 6(f) that x = 0.02 showed the A to 1.8 × 10−3 A as shown in Fig. 7(a). It was observed that the
highest ɳ of 64.02% making this composition quite preferable conductivity remained consistent for x = 0.00 to x = 0.04 whereas the
amongst others in this series of tri-phase composites. Since in lead- highest value of conductivity was observed for x = 0.10 of about ∼
free ceramics, it is quite a difficult task to achieve a high value of WR 10−7 (Ωcm)−1 which is illustrated in Fig. 7(b). For a better under­
and a high %ɳ, simultaneously [42]. All values of WT, WR, WL, and EC standing of ferroelectric behaviour, PUND (positive up and negative
are mentioned in Table 5. down sequence) method was first examined by Scott to determine
The I-V curve analysis was carried out while subjecting the the remanent polarization that provides switched charge density
composite samples to an applied voltage ranging between − 80–80 V (Qsw) [43]. For this purpose, an electric field of 10 V/cm was provided
provided by a multiferroic tester machine to visualize the leakage by a multiferroic tester machine having a pulse width of 1 ms along

Fig. 6. (a) Polarization (P) vs electric field (Ef), (b) charge discharge region for estimating energy storage, (c) energy storage capability observed through charge-discharge at
various field, (d) maximum polarization (PM)and remanent polarization (PR) at various contents of (x), (e) variation in recoverable energy density (WR) and energy loss density
(WL) at various contents (x), (f) % efficiency of energy storage against MFO concentration.

7
M.A. Khan, K. Shahbaz, G.M. Mustafa et al. Journal of Alloys and Compounds 947 (2023) 169571

Fig. 7. (a) Current vs voltage plot for visualizing the leakage behaviour of composites, and (b) conductivity behaviour of the tri-phase composites (1–x)(0.7BFO + 0.3BTO) + xMFO
at different substitution contents (x).

Fig. 8. PUND sequence for observing impact of polarization on switching density for tri-phase composites (1–x)(0.7BFO + 0.3BTO) + xMFO with several compositions (a) x = 0.00,
(b) x = 0.02, (c) x = 0.04, (d) x = 0.06, (e) x = 0.08, and (f) x = 0.10.

with a 100 ms delay period to analyse the Qsw at RT. Categorically, For investigating the magnetic properties of the composite
the PUND sequence is comprised of two main varieties; firstly P* samples, the magnetic hysteresis (M-H) loops were achieved
signifies total polarization of the material with leakage current through VSM operated at ± 15 kOe magnetic field as shown in
phenomenon and switching polarization [44]. Secondly, P^ demon­ Fig. 9(a). This study comprised a detailed analysis that notified the
strates the total polarization of the composite samples without the values of saturation magnetization (MS), remanent magnetization
involvement of Qsw for attaining remanent polarization. The pulse (MR) and coercivity (HC) attained through the M-H loops. All the
sequence depicted the remanent polarizations of both P*r and -P*r individual M-H loops for all the composites are provided in Fig. 9(b-
for switching and P^r and -P^r without switching. It was explored g) indicating a quite similar hysteresis loop. But particularly, for bi-
while PUND analysis that the maximum remanent polarization value phase composite, (x = 0.00) which mainly comprised of BFO and BTO
for P* with switching was comparatively higher than P^ without somehow showed a very narrow loop with MS, MR, and HC values
switching. A significant variation in the Qsw values for the composite approximately to be 0.015 emu/g, 0.001 emu/g, and 414 Oe, respec­
samples could be visualized in Fig. 8(a-f). The study suggests that tively as shown in Fig. 9(b) [45]. The reason behind the small value of
x = 0.10 composition showed some prominent variational changes in MS is the suppression of oxygen vacancies, and lattice distortion
Qsw making this specific composition considerable for ME-coupled caused by the influence of Ti4+ with Fe3+ ions at the B-site [46]. With
ultra-fast switching applications. the inclusion of MFO contents, when x = 0.02, the value of MS, MR,

8
M.A. Khan, K. Shahbaz, G.M. Mustafa et al. Journal of Alloys and Compounds 947 (2023) 169571

Fig. 9. (a) M-H hysteresis loops, M-H loops of x = (b) 0.00, (c) 0.02, (d) 0.04, (e) 0.06, (f) 0.08, (g) 0.10), respectively, and (h) saturation magnetization (MS), remanent magnetization
(MR) and coercivity (HC) for (1–x)(0.7BFO + 0.3BTO) + xMFO tri-phase composite at various contents (x).

and HC is increased to 1.218 emu/g, 0.34 emu/g, and 315 Oe, respec­ The exclusive interphase coupling between the individual
tively. The remaining compositions showed an organized increasing electric and magnetic phases in the tri-phase composite resulted
trend of magnetization with increasing MFO contents until it reaches in ME coupling. The extent of the exchange interaction between
to MS value of 6.31 emu/g at x = 0.10, whereas some drastic variation the phases justifies the strength of coupling amongst them. The
of MR was observed from 0.001 to 2.10 emu/g as demonstrated in ME-coupled devices can induce spontaneous magnetization
Fig. 9(h). This is because the asymmetrical spins located in the spinel through the application of the electric field and vice versa owing to
ferrites resulted in the enhancement of spontaneous magnetization the presence of two ferroic orders simultaneously within the same
in the composites [47]. The coercivity has an indirect relevance with material. This virtue of ME coupling provides much ease in de­
the average grain size of the composite samples (i.e., HC 1/D) veloping ultra-fast switching devices subjective to electric and
where D is the diameter of the grains [48]. The M-H loops indicated magnetic response, simultaneously. Although one of the pioneers
an abrupt decrease in coercivity of the composites sample from of multiferroic materials BFO possessed ME coupling but it’s not
414 Oe (at x = 0.00) to 301 Oe (at x = 0.10) as the average grain size significant enough to be employed in multistate devices. So, the
increased from 202 nm for x = 0.00–305 nm for x = 0.10. It was ob­ inclusion of spinel phase MFO in this composite provides some
served through the M-H loops that all the composites possessed a better spin dynamics at ambient temperature which could be re­
certain magnetic domain structure that validates the extent of ex­ sulted in the enhancement of ME coupling phenomena between
change coupling interaction between the perovskite structure of BFO the different phases of the tri-phase composites. The linearity of
and spinel structure of MFO; enhancing the probability of better ME ME-coupled phases depends upon the extent of variation in po­
coupling in tri-phase composites. The ratio MR/MS provides the ex­ larization and magnetic field [50]. Therefore, the strain-mediated
tent of spin-spin interaction between the composites. The lower ME effect could be attained through the following relation as
values of MR/MS ratio for the composite samples provide a significant provided in Eq. (3) [51];
interparticle dipolar interface in the nanostructured composites
with favoured anisotropy that consequently resulted in an en­ Magnetic Mechanical
ME effect = ×
hancement of coercivity of the composites [49]. It was observed that Mechanical Electrical (3)
for x = 0.00, the MR/MS ratio is quite low indicating no significant
coupling. Meanwhile, increasing the MFO contents MR/MS ratio en­ This attribute of multiferroic materials in a composite form
hanced up to 0.33 for x = 0.10. All the computed values of MS, MR, HC, significantly enhances their viability in device fabrication. For the
and MR/MS are reported in Table 6. as-synthesized samples, a linear response of polarization sub­
jective to the magnetic field could be viewed in Fig. 10(a-f). The
Table 6 significant linear behaviour of the composite sample was observed
Determined values of saturation magnetization (MS), remanent magnetization (MR) at x = 0.06. The peculiar noisy behaviour could be seen at x = 0.08
and coercive field (HC) values with remanent ratio (MR:MS) for the tri-phase compo­ and x = 0.10 as these compositions have the highest % of MFO
sites (1–x)(0.7BFO + 0.3BTO) + xMFO (x = 0.00, 0.02, 0.04, 0.06, 0.08, and 0.10). contents in the composites. The variation observed in the ME loops
MFO Saturation Remanent Coercive field MR:MS might have occurred because of some interfacial defects in the
contents (x) magnetization magnetization (HC) in Oe crystal structures. Meanwhile, by enhancing the strain-mediated
(MS) (MR)
coupling a significant ME coupling in the materials could be in­
(emu/g) (emu/g)
duced [52]. By taking into account all the aforementioned dis­
0 0.01 0.001 414 0.13 cussion it can be concluded that the as-synthesized composite has
0.02 1.21 0.34 315 0.20
the virtue of better ME coupling between perovskites and minimal
0.04 2.49 0.72 309 0.15
0.06 4.59 1.41 297 0.25 spinel contents and thus has significant potential for its applic­
0.08 5.28 1.45 303 0.27 ability in highly sensitive devices subjective to electric and mag­
0.1 6.31 2.10 301 0.29 netic response, simultaneously.

9
M.A. Khan, K. Shahbaz, G.M. Mustafa et al. Journal of Alloys and Compounds 947 (2023) 169571

Fig. 10. ME coupling in composite samples with (a) x = 0.00, (b) x = 0.02, (c) x = 0.04, (d) x = 0.06, (e) x = 0.08, and (f) x = 0.10.

4. Conclusion CRediT authorship contribution statement

This study comprised the structural, surface, elemental and Muhammad Ahmed Khan: Conceptualization, Data curation,
multiferroic characteristics of the tri-phase composites (1–x)(0.7BFO Formal analysis, Writing − original draft. Kanwal Shahbaz: Software,
+ 0.3BTO) + xMFO (x = 0.00, 0.02, 0.04, 0.06, 0.08, and 0.10) synthe­ Resources. Ghulam M. Mustafa: Data curation, Formal analysis,
sized by sol–gel auto-combustion technique followed by the solid- Methodology. Shahid M. Ramay: Software, Data curation. Shahzad
state ball-milling method. The XRD patterns confirmed the for­ Naseem: Resources, Formal analysis. Shahid Atiq: Methodology,
mulation of the tri-phase composite consisting of BFO exhibiting Project administration, Supervision, Final proof reading.
rhombohedral type crystalline phase with R3m space group sym­
metry and BTO with tetragonal phase having P4mm space group Data availability
symmetry. In addition, a spinel cubic phase of MFO having Fd-3 m
space group symmetry was confirmed. The average crystallite size of Data will be made available on request.
BFO, BTO, and MFO were approximately 28 nm, 18 nm, and 19 nm,
respectively. The maximum increase in % porosity of 58% was ob­ Declaration of Competing Interest
served at x = 0.10 having maximum spinel phase contents. Rietveld’s
refinement was carried out for phase quantification and it was de­ The authors declare that they have no known competing fi­
duced that χ2 values were quite consistent showing exact phase nancial interests or personal relationships that could have appeared
development. The FESEM images captured at 100,000x magnifica­ to influence the work reported in this paper.
tion verified the gradual increase in grain size resulting in a lowering
of the value of materials coercivity from 414 Oe (x = 0.00) to 301 Oe Acknowledgement
(x = 0.01), respectively. Through EDX and elemental mapping, the
stoichiometric ratios of the elements were confirmed. For energy The authors would like to acknowledge the Researchers
storage capability the ferroelectric analysis confirmed the highest Supporting Project number (RSP2023R71), King Saud University,
value of WR (0.22 mJ/cm3) at x = 0.02 followed by ɳ of 64.02% that Riyadh, Saudi Arabia.
was observed with a maximum value of WL (0.84 mJ/cm3) at x = 0.10.
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