Article

Magnetoelectric Properties of Aurivillius-Layered Perovskites

Vadla Veenachary 1, Eskilla Venkata Ramana 2,*, Simhachalam Narendra Babu 1, Venkata Sreenivas Puli 3,
Sujoy Saha 4, Gopalan Srinivasan 4, G. Prasad 1 and N. V. Prasad 1,*

1 Materials Research Laboratory, Department of Physics, Osmania University, Hyderabad 500013, India;
[email protected] (V.V.); [email protected] (S.N.B.); [email protected] (G.P.)
2 I3N-Aveiro, Department of Physics, University of Aveiro, 3810 193 Aveiro, Portugal

3 Smart Nanomaterials Solutions, Orlando, FL 32707, USA; [email protected]

4 Physics Department, Oakland University, Rochester, MI 48307, USA; [email protected] (S.S.);

[email protected] (G.S.)
* Correspondence: [email protected] (E.V.R.); nvp1969@rediffmail.com (N.V.P.)

Abstract: In the present work, we have synthesized rare-earth ion modified Bi4−xRExTi2Fe0.7Co0.3O12−δ
(RE = Dy, Sm, La) multiferroic compounds by the conventional solid-state route. Analysis of X-ray
diffraction by Rietveld refinement confirmed the formation of a polycrystalline orthorhombic phase.
The morphological features revealed a non-uniform, randomly oriented, plate-like grain structure.
The peaks evident in the Raman spectra closely corresponded to those of orthorhombic Aurivillius
phases. Dielectric studies and impedance measurements were carried out. Asymmetric complex im-
pedance spectra suggested the relaxation of charge carriers belonging to the non-Debye type and
controlled by a thermally activated process. Temperature-dependent AC conductivity data showed
a change of slope in the vicinity of the phase transition temperature of both magnetic and electrical
coupling natures. Based on the universal law and its exponent nature, one can suppose that the
conduction process is governed by a small polaron hopping mechanism but significant distortion of
TiO6 octahedral. The doping of the A-sites with rare-earth element ions and changes in the concen-
trations of Fe and Co ions located on the B-sites manifested themselves in saturated magnetic hys-
teresis loops, indicating competitive interactions between ferroelectric and canted antiferromagnetic
spins. The magnetic order in the samples is attributed to pair-wise interactions between adjacent
Fe3+–O–Fe3+, Co2+/3+–O–Co3+/2+, and Co2+/3+–O–Fe3+ ions or Dzyaloshinskii–Moriya interactions among
Citation: Veenachary, V.; Ramana, magnetic ions in the adjacent sub-lattices. As a result, enhanced magnetoelectric coefficients of 42.4
E.V.; Narendra Babu, S.; Puli, V.S.; mV/cm-Oe, 30.3 mV/cm-Oe, and 21.6 mV/cm-Oe for Bi4−xDyxTi2Fe0.7Co0.3O12−δ (DBTFC),
Saha, S.; Srinivasan, G.; Prasad, G.; Bi4−xLaxTi2Fe0.7Co0.3O12−δ (LBTFC), and Bi4−xSmxTi2Fe0.7Co0.3O12−δ (SBTFC), respectively, have been
Prasad, N.V. Magnetoelectric obtained at lower magnetic fields (<3 kOe). The strong coupling of the Aurivillius compounds ob-
Properties of Aurivillius-Layered served in this study is beneficial to future multiferroic applications.
Perovskites. Crystals 2024, 14, 299.
https://doi.org/10.3390/cryst14040299 Keywords: multiferroic; Aurivillius; impedance spectra; magnetoelectric; dielectric studies;
Academic Editor: Zhonghua Yao magnetic studies; structural studies

Received: 18 February 2024

Revised: 10 March 2024
Accepted: 18 March 2024
Published: 22 March 2024
1. Introduction
Multiferroic compounds are a fascinating type of material that have garnered re-
markable attention in the realm of materials science. Multiferroics exhibit two or more
Copyright: © 2024 by the authors. orders of ferroelectric (FE), ferroelastic, and magnetic (ferromagnetism (FM)/anti-ferro-
Licensee MDPI, Basel, Switzerland. magnetism (AFM)) orders in the single phase. The present Aurivillius phase materials
This article is an open access article have shown their potential usage in many novel applications, like memory storage de-
distributed under the terms and vices, sensors, transducers, and actuators [1]. Multiferroics are promising materials due
conditions of the Creative Commons to their potential applications that exploit the combination of ferroelectric and magnetic
Attribution (CC BY) license orders [1,2]. The most fascinating prospect of research on these materials is tuning the
(https://creativecommons.org/license electric dipoles by applying magnetic fields under superimposed small AC magnetic
s/by/4.0/). fields [3–7]. The coupling between ferroelectric (FE) and ferromagnetic (FM) orders makes

Crystals 2024, 14, 299. https://doi.org/10.3390/cryst14040299 www.mdpi.com/journal/crystals

Crystals 2024, 14, 299 2 of 20

it easier and faster to address a data bit in memory devices [2,8]. This could lead to the
development of magnetoelectric materials owing to their speed in read/write operations.
However, very few room-temperature magnetoelectric (ME) compounds have been re-
ported, due to the mutual exclusion nature of FM and FE in single-phase compounds.
Ferroelectricity is attributed to empty d-orbitals, while partially or half-filled d-orbitals
are responsible for magnetic nature [9]. In the path of searching for single-phase multifer-
roic compounds, Aurivillius phase multiferroics are a class of bismuth layer compound
that have been extensively investigated for their flexibility and the tunable nature of their
ferroelectric and magnetic properties [10–17].
The general formula of Aurivillius phase compounds can be expressed as
(Bi2O2)2+(Am−1BmO3n+1)2−, where m represents the dimensionality of perovskites
(Am−1BmO3n+1), which are sandwiched between fluorite-like (Bi2O2)2+ layers. Here, A is the
cuboctahedral site, which can be substituted by mono-, di-, or tri-valent elements and B is
the octahedral site (BO6), which can be substituted by di-, tri-, tetra-, or pentavalent ele-
ments [18]. The Aurivillius phase compounds were found to be familiar for their ferroe-
lectric/magnetoelectric behavior, high transition temperatures, and strong anisotropic na-
ture of spontaneous polarization [19]. Rare earth-modified A-site Aurivillius phases were
studied to explore the changes in structural and ferroelectric properties [20]. These mate-
rials are well-suited for non-volatile memory devices due to their fatigue-free nature. Re-
cently, many Aurivillius phase compounds have shown room temperature magnetoelec-
tric output when Fe/Co/Ni were placed in the B-sites. However, the origin of the combined
ferroelectric and magnetic and its coupling are still under discussion. Therefore, a strate-
gic way is required in choosing magnetic ions, which triggers the enhanced magnetoelec-
tric output in the materials. It is a known fact that the multiferroic properties can be altered
by the concentration of magnetic ions in the B-sites. From previous literature, iron-doped
Aurivillius phase compounds show strong multiferroic behavior at room temperature
[12,21]. These materials can be expressed as Bim+1Fem−3Ti3O3m+3 (BFTO-m). More interest-
ingly, the key factors of the Aurivillius phase materials are that: (i) the origin of ferroelec-
tricity is a combination of oxygen octahedral rotation and polar distortion; (ii) different
numbers of layers in perovskite plates show significant differences in physical and struc-
tural properties.
In the last decade, much research has been focused on different layered compounds,
such as Bi5FeTi3O15, Bi6Fe2Ti3O18, Bi7Fe3Ti3O21, etc. [22–28]. The reported study on the Au-
rivillius family embodies two main aspects: (i) aliovalent doping at A- and B-sites to en-
hance the multiferroic performance, and (ii) processing mediated structure-property cor-
relations in ceramics, thin films, single crystals, and intergrowths [29–36].
The three-layer structure of bismuth titanate (Bi4Ti3O12—BIT) has attracted research-
ers due to its high ferroelectric transition temperature (above 600 °C), low processing tem-
perature compared to higher-layer structured compounds, and its anisotropic ferroelec-
tric behavior [37–41]. However, these compounds possess high conductivity due to the
volatile nature of bismuth at higher temperatures. This results in leakage currents, which
deteriorate the ferroelectric nature [42–45]. The incorporation of rare-earth ions at the A-
site has been demonstrated as an effective approach to mitigate this trade-off [13,46,47]. A
noteworthy observation by Lu et al. is that Fe-doped BIT ceramics exhibit weak room-
temperature ferromagnetic behavior [48]. Shigyo et al. reported that the La-, Nd-, and Sm-
doped BIT samples show improved magnetic and ferroelectric properties due to con-
trolled oxygen vacancies [49]. According to Paul et al., Bi4−xSmxTi3−xCoxO12−δ at x = 0.07 has
shown that the coefficient of ME coupling is about 0.65 mVcm−1 [50]. In recent studies, Yu
et al. have reported an ME coefficient of 31.58 mVcm−1Oe−1 for Bi4LaTi3Co0.3Fe0.7O15 ceram-
ics [51]. Aurivillius phases possessing antiferromagnetic order or weak ferromagnetic or-
der have limitations for their practical use [52–54]. These defects can be controlled by RE
ions for the A-sites of Aurivillius phases. It should be remembered that the stoichiometry
and synthesis conditions play a vital role in optimizing the ME coupling.
Crystals 2024, 14, 299 3 of 20

The major endeavor of the present work was to diminish the leakage current by
introducing RE ions in the A-sites of perovskites and enhancing the cross coupling. We
prepared RE (Dy, Sm, La) ion-doped Bi4Ti2Fe0.7Co0.3O12−δ ceramics. Electrical, magnetic,
and ME measurements were carried out. The dispersion in AC-conductivity and
relaxations in the low-frequency range above 200 °C were explained in terms of Maxwell–
Wagner and multiple relaxations (non-Debye type). The presence of a small polaron
conduction mechanism played a vital role. The dielectric relaxations observed near 200 °C
can be attributed to the charge hopping of Ti3+ to Ti4+/Fe2+ to Fe3+ ions. The low
concentration doping of lanthanides enhanced the dielectric properties. Apart from the
above aspects, understanding structural evolution is interesting in Aurivillius phase
compounds. Systematic studies on X-ray, Raman, and impedance analysis confirm the
inherited magnetoelectric properties. Remarkably, the Dy-doped Bi4Ti2Fe0.7Co0.3O12−δ
(DBTFC) sample showed an ME coefficient of ~42.4 mV/cm-Oe at room temperature. Such
systematic studies have not been reported so far.

2. Materials and Methods

Aurivillius multiferroic ceramics Bi4-xRExTi2Fe0.7Co0.3O12−δ (RE = Dy, Sm, La) were
synthesized by conventional solid-state reaction method. For this purpose, stoichiometric
amounts of reagents (purity > 99.9%) Bi2O3, Sm2O3, Dy2O3, La2O3, TiO2, Fe2O3, and Co3O4
were milled in a planetary mill for 24 h using zirconia balls followed by calcination at 850
°C for 4 h. The calcined powder was again grounded with an agate mortar and pestle. The
powder mixed with 2 wt.% polyvinyl alcohol binder was pressed into circular pellets with
a thickness of around 1 mm and a diameter of 10 mm by a uniaxial hydraulic press. The
green pellets were sintered at 900 °C for 4 h to attain higher density. The RE (Dy, Sm, and
La) ion-doped Bi4Ti2Fe0.7Co0.3O12−δ compounds were named DBTFC, SBTFC, and LBTFC,
respectively.
Phase conformation of all the samples was performed by Powder X-ray diffraction
using a PAN analytic X’Pert diffractometer (Almelo, Netherlands). The sintered discs were
crushed into powders and annealed at 400 °C to relieve mechanical strain. Rietveld
refinement was also performed for all samples using Full-Prof Suit software (Version 3).
The phase of all samples was well matched with standard three-layered compounds of
XRD data (BIT, ICDD#00-008-0258). To study surface morphology and elemental analysis
(Energy Dispersive X-ray spectroscopy, EDAX)) the samples were analyzed using a
ZEISS-EVO185 SEM instrument (Oberkochen, Germany). Image J software was used to
calculate the average grain size of the sintered pellets, employing histograms with
Gaussian distribution. Raman spectra were measured using a Jobin Yvon spectrometer
(Horiba, Japan) with a 532 nm excitation laser. The magnetization–magnetic field
measurements were carried out using a vibrating sample magnetometer (VSM,
Cryogenic, London, UK). ME studies were performed using a micro-measurement Group
Strain Indicator, Model 3800, and a series WK strain gauge. The samples were electrically
and magnetically poled before ME was performed. Ferroelectric characterization was
carried out by measuring polarization–electric field hysteresis loops under various drive
voltages using a custom-made loop tracer. Before electrical measurements, the samples
were poled under an electric field of 20 kV/cm by placing them in a silicon oil bath at 120
°C and cooling them in the presence of the field. Magnetic poling was performed by
placing the samples in the magnetic field at 5 kOe at room temperature (RT).

3. Results and Discussions

3.1. Powder X-ray Diffraction and Morphological Studies
The powder X-ray diffraction patterns of DBTFC, SBTFC, and LBTFC were obtained
in the range of 20–80° at room temperature. The diffraction peaks of the compounds were
in good agreement with the standard XRD pattern of Bi4Ti3O12 (ICDD#00-008-0258) with
space group Fmmm as shown in Figure 1a–c [55,56]. The XRD data were fitted into Rietveld
Crystals 2024, 14, 299 4 of 20

refinement with Full-Prof software (version 3). The refining analysis revealed that all
samples consisted mainly of a single-phase structure with an admixture of another phase
of Bi12Fe0.5Ti0.5O20 belonging to the I23 space group. From the XRD studies, it could be
concluded that the pyrochlore (Bi12FeO20) formation was mainly due to the substitution of
heterovalent elements (Ti4+, Fe3+, and Co2+) in the B-site of the ABO3 perovskites of the
Aurivillius phases [55,57]. The reliability parameters (Rp, Rwp, and Rexp) and goodness of
fit (χ2) were within the specified range and well-matched between theoretical and
experimental diffraction patterns. The experimental and theoretical values of reliability
(R) factors revealed the quality of the phase formation of compounds and the observed
error was found to be less than 15% for higher present structured phases [58]. Here, the
pseudo-Voigt function was adopted to refine the XRD patterns (the original curve is a
combination of both Gaussian and Lorentzian).

DBTFC Yobs Yobs

Intensity (arb. units)

(a) (b) SBTFC

Intensity (arb. units)

Ycal Ycal
Yobs-Ycal Yobs-Ycal
Bragg positions Bragg positions

Rp = 8.15; Rwp = 12.1 Rp = 4.10; Rwp = 13.1

Rexp = 11.05; Rexp = 4.16;

20 30 40 50 60 70 80 20 30 40 50 60 70 80
2θ (Degree) 2θ(Degree)
(c) LBTFC Yobs τ
Intensity (arb. units)

Ycal
Tolarence factor(t)

0.945 La (d)
Yobs-Ycal
Bragg positions
0.938
Rp = 10.0; Rwp = 14.5
Rexp = 5.50;
0.931
Sm

0.924
Dy

20 30 40 50 60 70 80 1.00 1.04 1.08 1.12

2θ(Degree) RBi/RRE (RE=Dy,Sm,La)

Figure 1. (a–c) Rietveld refinement of XRD patterns of the DBTFC, SBTFC, and LBTFC ceramics; (d)
tolerance factor τ vs. RBi/RRE.

The tolerance factor (τ) explains the perovskite nature of the samples. It is reported
that τ < 1 indicates perovskite nature. From these values, one can understand the tilt of
TiO6 octahedral, which is mainly responsible for dielectric relaxations in the layered
perovskite compounds. The tolerance factor for the present compounds was calculated
using the following equation [59,60]:

τ= (1)
√ ( )

The terms RA, RB, and RO represent the ionic radii of A-site, B-site, and Oxygen ions
respectively. The variation of the tolerance factor with the ratio of 𝑅 ⁄𝑅 is shown in
Figure 1d. The size of the RE ionic radii is smaller than the Bi3+ (1.35 Å) and follows Hume–
Rothery conditions [59], and therefore it is reasonable to infer that RE ions can readily be
Crystals 2024, 14, 299 5 of 20

substituted with Bi3+ sites [60]. The changes observed in the tolerance factor are due to A-
O and B–O bond lengths, which would be reflected in the octahedral tilt. More aspects of
this are seen in the Raman spectra, near 800 cm−1 which corresponds to the stretching of
TiO6. The lattice parameters (a, b, c), volumes are given in Table 1 and structural
parameters are given in Table 2. The most intense peak was observed around 30° and
indexed as (117). The intensity of the peak associated with the (117) plane of Bi4Ti3O12 was
highest, indicating that the prepared ceramic composition conformed to the three-layered
structure (m = 3). The result is consistent with common reporting of the strongest
diffraction reflection, corresponding to (1, 1, 2m + 1) reflection in the Aurivillius phase
three-layered compound [56].

Table 1. Lattice and Rietveld refinement parameters of DBTFC, SBTFC, and LBTFC.

Sample Name DBTFC SBTFC LBTFC

Space group Fmmm I23 Fmmm I23 Fmmm I23
a = 5.415 a = 5.401 a = 5.401
Lattice parameters (Å) b = 5.381 a = 10.173 b = 5.400 a = 10.175 b = 5.399 a = 10.220
c = 32.231 c = 32.331 c = 32.291
Volume fraction (%) 82.300 17.700 79.78 20.22 99.70 0.300
Rp = 8.15; Rwp = 12.10; Rp = 4.10; Rwp = 13.10; Rp = 10.01; Rwp = 14.50;
Reliability factors (%)
Rexp = 11.05 Rexp = 4.16 Rexp = 5.50
Goodness of fit (χ2) 5.88 9.95 6.90

Table 2. Structural parameters of DBTFC, SBTFC, and LBTFC.

Sample Name DBTFC SBTFC LBTFC

Orthorhombic Distortion (b/a) 0.993 0.9998 0.9996
Tetragonal strain (c/a) 5.9521 5.9861 5.9787
Orthorhombicity (2(a − b)/(a + b) × 102) 0.629 0.018 0.003

3.2. Morphological Studies

The morphological images of the prepared ceramics were carried out by FESEM (field
emission scanning electron microscope) as shown in Figure 2. Randomly oriented plate-
like grains were observed in all ceramics. This kind of surface morphology is a
characteristic of Aurivillius phase ceramics [60]. It was also observed that all grains were
non-uniform and closely packed. The experimental densities of pellets were found to be
roughly 98%. Based on the mentioned values, the samples were found to be denser. The
histograms of grain sizes were drawn and well-fitted by the Gaussian distribution
function as shown in the inset of Figure 2. The mean grain sizes of the pellets were ob-
served to be ~0.492, 0.490, and 0.496 µm for DBTFC, SBTFC, and LBTFC, respectively.
Crystals 2024, 14, 299 6 of 20

30
Gaussian Fit B"Counts" Mean size of grains~0.492μm
20 Gaussian Fit B"Counts" Mean size of grains~0.496μm
25 DBTFC
Grains by Counts

SBTFC

Grains by Counts
20 15

15
10
10

5 5

0
0
0.0 0.2 0.4 0.6 0.8 1.0 1.2
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Grain size(μm) Grain size(μm)

25
Gaussian Fit B"Counts" Mean size of grains~0.490μm

LBTFC
20
Grains by Counts

15

10

0.0 0.2 0.4 0.6 0.8 1.0 1.2

Grain size(μm)

Figure 2. FESEM photographs of DBTFC, SBTFC, and LBTFC; Insets in figures: Histograms of the
samples. Inset: Histograms corresponding to grain sizes.

Furthermore, grains associated with impurity phases were found in all samples,
circled in the SEM pictures in Figure 2. The presence of an additional magnetic phase was
obvious due to heterovalent element substitution in the B-sites of perovskites [61]. EDAX
(energy dispersive X-ray analysis) studies were performed on all samples to calculate the
elemental composition. The experimental (measured) and theoretical (estimated)
percentage of elements are presented in the inserted table of Figure 3a–c. The measured
atomic percentages of the elements were consistent with the expected formula. Based on
the SEM photographs, one can speculate the formation of pyrochlore or secondary phase
or mixture of Fe2+/Co2+ (marked as red circle in Figure 2). Similar results were more
pronounced in the intergrowth Aurivillius phase compounds [62,63]. It was also observed
that grain size and uniformity were found to be greater in LBTFC. The appearance of
lamellar morphology along with the micro-pores could not be executed, which indicated
a low density (>97%) of the sample. As a result, the element composition in all samples
was found to be closer to the expected values, and it can be concluded that Fe3+ and Co2+
ions were segregated into the grain boundary region.
Crystals 2024, 14, 299 7 of 20

Theoretical Theoretical
Experimental Experimental
Theoretical Experimental atomic Theoretical Experimental atomic
atomic
atomic Element weight (%) weight (%) weight (%)
Element weight (%) weight (%) weight (%) weight (%)
weight (%)
Bi 56.520 52.520 15.789 14.231
Bi 55.910 52.320 15.789 14.630
Sm 12.420 10.380 5.260 5.821
Dy 11.290 17.210 5.260 6.190 Ti 8.600 9.330 10.526 10.125
Ti 9.980 9.180 10.526 11.080 Fe 3.510 3.162 3.680 3.121
Fe 3.470 3.120 3.680 3.090 Co 1.590 1.051 1.570 1.185
Co 1.570 1.140 1.570 1.240 O 17.280 17.680 63.157 68.330
O 17.050 17.550 63.157 63.157

Theoretical
Experimental
Theoretical Experimental atomic
atomic
Element weight (%) weight (%) weight (%)
weight (%)
Bi 56.520 52.520 15.789 14.231
Sm 12.420 10.380 5.260 5.821
Ti 8.600 9.330 10.526 10.125
Fe 3.510 3.162 3.680 3.121
Co 1.590 1.051 1.570 1.185
O 17.280 17.680 63.157 68.330

Figure 3. EDAX patterns of (a) DBTFC, (b) SBTFC, and (c) LBTFC: Insets in figures: Elemental
analysis of samples.

3.3. Raman Spectroscopic Studies

Raman scattering spectra of the prepared ceramics are shown in Figure 4a–c to
investigate lattice vibrational modes, lattice distortion, and occupancy of doped ions at
the specified A- and B-sites. All observed modes of the prepared samples showed similar
characteristic modes of the orthorhombic structure of three-layered Aurivillius
compounds [57,62,63]. The overlapped peaks were de-convoluted using Lorentzian peak
fittings, for better identification of peak positions. The Raman modes ν1, ν2, and ν3 below
200 cm−1 were attributed to the A-site of ABO3 perovskite blocks’ cation vibrations. Slight
changes observed for SBTFC, below 200 cm−1, were associated with the vibration of Bi3+
ions of (Bi2O2)2− layer slabs. Changes observed below 200 cm−1 for SBTFC were due to
strains caused in the layer-perovskite slabs. The phonon modes at high frequencies in the
range of 200–800 cm−1 were attributed to the vibrational modes of BO6 octahedral [64]. The
Raman modes ν4, ν5, and ν6 (around 225 cm−1, 260 cm−1, and 312 cm−1) demonstrated the
torsional bending of BO6 octahedral. The phonon modes ν7, ν8, and ν13 were ascribed to
the stretching of the O–Ti/O–Fe/O–Co bond. The broad peaks, namely ν7, ν8, and ν13, were
used to reveal the site occupancies of doped ions in the proposed sites. The broadening of
the peaks by merging ν8, and ν9 for the SBTFC sample was due to the inhomogeneous
distribution in the compositions of the A- and B-sites of perovskite blocks. Finally, this in
turn led to lattice distortion. From this, one can say that the RE and Co/Fe ions readily
occupy the A- and B-sites of perovskites [50,65]. The Raman modes ν4, ν5, and ν6 were
found to vary slightly depending on the RE ion. The same phenomenon was observed in
vibration modes above 200 cm−1 for SBTFC. This was once again attributed to the lattice
distortion caused by Fe and Co ion doping in Ti-sites of BO6 octahedral. The phonon
modes ν10 and ν11, around 730 cm−1 in all samples, were attributed to the FeO6 and CoO6
Crystals 2024, 14, 299 8 of 20

octahedral. Based on this, one can say that the Fe and Co ions are partially occupied by
the Ti-sites of the perovskite blocks.

υ1 υ5
υ2 υ3 υ4
Experimental
Fitting
DBTFC
υ6 υ10 υ11

Intensity (arb.units)
υ8 υ9 υ12 υ13 (a)
υ7

SBTFC
(b)

LBTFC
(c)

100 200 300 400 500 600 700 800 900 1000
-1
Raman Shift (cm )
Figure 4. Raman spectra of (a) DBTFC, (b) SBTFC, and (c) LBTFC with peak fitting.

3.4. Dielectric Studies

The dielectric measurements of all compounds were carried out on the three samples
at different frequencies and shown in Figure 5a–c. The variation of dielectric loss (tan δ)
with the temperature in the range of 30 to 500 °C at 10 kHz, 20 kHz, 30 kHz, 50 kHz, and
100 kHz frequencies are shown in the inset of Figure 5a–c. The higher the temperature
was, the greater the dielectric constant. A notable dielectric dispersion observed with
frequency at high temperatures was due to the presence of thermally activated
polarization of charge species such as space charges, charge defects, and oxygen
vacancies. A slow increase of dielectric nature especially in the DBTFC sample indicated
the presence of oxygen vacancies, as pointed out by many researchers. Temperature
independent of the dielectric constant up to 250 °C was attributed to the hopping
conduction mechanism in between the neighboring sites of Ti3+ and Ti4+ or Fe2+ and Fe3+.
Typically, the formation of dipoles with doubly ionized oxygen vacancies (𝑉 ) is less
likely than singly ionized oxygen vacancy (𝑉 ). The doubly ionized oxygen vacancies
(V″O) and electrons together create defective or complex dipoles, such as Fe3+ − V″O, Co3+ −
V″O, and Ti4+ − V″O. The doubly ionized oxygen vacancies predominate in the conduction
process over mono ionized oxygen vacancies [66–68]. Generally, the dielectric transition
temperature of ceramics depends on complex or defective ions. Since the measurements
were carried out in the range of 30 to 500 °C, the transition temperatures (TC) of all samples
could not be observed. It was observed that Fe-/Co-doped Bi4Ti3O12 compounds showed
transition temperatures [67–70]. In the present analysis, SBTFC compounds showed a
higher dielectric constant than DBTFC and LBTFC. This may be due to an increase in the
interfacial or space charge polarization. This increase in the interfacial polarization was
observed in the FESEM images (Figure 3). This reveals a decrease in grain size in SBTFC.
The decrement in grain size led to an increase in the interfacial charges due to an
increment in the volume fraction of grain boundaries. The same phenomenon was also
applicable to the DBTFC and LBTFC samples. A similar conclusion can be inferred from
Crystals 2024, 14, 299 9 of 20

the variation of dielectric loss as a function of temperature, as shown in the inset of Figure
5a–c.

260 1400
10

DBTFC (a) (b)

Dielectric constant(ε)

12

Dielectric constant (ε)

240 SBTFC
Dielectric loss(tanδ)

1200

Dielectric loss(tanδ)
10 8
220 8

200 6
1000 6

4 4
180 800
2
160 2
0 600
140 0 100 200 300 400 500 0
0 100 200 300 400 500
120 Temperature(oC) 400 Temperature (oC) 10k Hz
10k Hz
100 20k Hz 20k Hz
30k Hz 200 30k Hz
80 50k Hz 50k Hz
100k Hz 100k Hz
60 0
0 100 200 300 400 500 0 100 200 300 400 500
Temperature ( C) o Temperature (oC)
700 21

LBTFC (c)
Dielectric constant(ε)

18
Dielectric loss(tanδ)

600 15

12

9
500 6

400 0
0 100 200 300 400 500 600

Temperature (oC)
300 10k Hz
20k Hz
30k Hz
200 50k Hz
100k Hz

0 100 200 300 400 500

o
Temperature ( C)
Figure 5. Variation of dielectric constant with temperature of (a) DBTFC, (b) SBTFC, and (c) LBTFC;
Insets in figures: dielectric loss vs. temperature.

3.5. Electrical Studies

AC-conductivity analysis was performed for a better understanding of the transport
mechanism in the samples. Figure 6a–c depicts the AC-conductivity (σac) as a function of
frequency plots (f) at various temperatures. The AC-conductivity data were obtained by
considering the following expression [69].
Crystals 2024, 14, 299 10 of 20

10-2
10-2
(a) DBTFC Region I Region II
500 oC (b) SBTFC
Region I Region II
500 oC
σ ac (Ω -1.m -1)

σ ac (Ω -1.m -1)
10-3 10-3

325 oC 325 oC
10-4 10-4

Fitting Fitting
-5 10-5
10
102 103 104 105 106
102 103 104 105 106
Frequency (Hz) Frequency (Hz)
10-2
1.8
(c) LBTFC Region I
500 oC
Region II
DBTFC
(d) SBTFC

Exponent value (n 1, n 2)
1.5 LBTFC
σ ac (Ω -1.m -1)

10-3 1.2

Region II (n2)
0.9
Region I (n1)
10-4 325 oC 0.6

0.3 DBTFC
Fitting SBTFC
LBTFC
10-5 0.0
102 103 104 105 106 300 330 360 390 420 450 480 510
Frequency (Hz) Temperature ( C) o

Figure 6. Variation of AC-conductivity with the frequency of (a) DBTFC, (b) SBTFC, and (c) LBTFC;
(d) exponent values (n1, n2) vs. temperature. Slopes measured in region-I (lower) and region-II
(upper) are marked as dotted circles.

𝑍 𝑑
𝜎 = (2)
𝑍 +𝑍 𝑆
where σac is AC-conductivity, and Z′ and Z″ are real and imaginary values of impedance.
The terms d and S denote the thickness and area of the sample respectively. The AC-
conductivity data were found to obey the following Jonscher’s power law [69]

𝜎 =𝜎 + 𝐴(𝑇)𝜔 (3)
where σac is ac conductivity, σdc is DC-conductivity, A(T) is temperature dependent
coefficient, and the exponent n represents slope. The term 𝐴(𝑇)𝜔 characterizes the
dispersion phenomena observed in the sample, and 𝜔 is the angular frequency. The
exponent n is a dimensionless quantity that generally lies between 0 and 1. This quantity
depicts the degree of interaction between mobile ions and the surrounding lattice.
Attempts were made to fit the AC-conductivity data with Equation (2), but no data were
found to fit successfully throughout the frequency region. From the AC-conductivity
plots, we can observe two regions, namely high-frequency and intermediate-frequency
regions, as shown in Figure 6a–c. The AC-conductivity in the low frequency (region-I) is
merely independent of frequency. To account for better fitting, the experimental data have
been fitted with the following relation [69]:

𝜎 =𝜎 + 𝐴(𝑇)𝜔 + 𝐵(𝑇)𝜔 (4)

Crystals 2024, 14, 299 11 of 20

where n1 (0 < n1 < 1) and n2 (1< n2 < 2) are frequency exponents, which give slopes of
corresponding regions. The exponent n1 depicts the intermediate-frequency dispersion
attributing to the ion hopping mechanism. The exponent n2 describes high-frequency
dispersion, attributing to the localized relaxation process [70–72]. The experimental data
were in good agreement with fitting data using Equation (4) as shown in Figure 6a–c. The
AC-conductivity of all samples was strongly independent of frequencies above 400 °C.
The AC-conductivity ≤104 Hz was independent of frequency (ω) at all temperatures and
provided DC-conductivity. At a temperature below 400 °C, the AC-conductivity became
strongly dependent on frequency for all samples. Strong coalitions or merging into a
single curve at higher frequencies for all samples indicated the migration of oxygen
vacancies. The exponent values n1 and n2 were plotted against temperature (Figure 6d).
The frequency-independent conductivity at lower frequencies for all samples can be
illustrated using the ion-jump relaxation model [73,74]. The defective ions, which were
oxygen vacancies, hopped between their neighborhood vacant sites of Ti3+ and Ti4+. This
hoping of ions may take a long time and results in a long-range transitional motion of
ions. This process is called the DC-conductivity of the samples. The correlated barrier
hopping model can generally explain the frequency-dependent conductivity. It was
deduced from the fitting, shown in Figure 6d, that the frequency exponent n1 decreased
with increasing temperature. A cation in the lattice was hopping either a forward or
backward vacant site. Thermally active oxygen vacancies yield to more dispersive nature
at lower frequencies [75]. Frequency exponent n illustrates the motion or localization of
charge carriers in the samples. In region-I (R1), where 0 < n1 < 1, the charge carriers can
have translation motion and a sudden long-hop takes place, whereas 1 < n2 < 2 illustrates
a localized relaxation or hopping mechanism in the vicinity of lattice sites. Here, exponent
n1 values are less than 1, so the charge carriers have translational ion hopping within the
ceramics [71,76,77]. On the other side, the values of n2 are greater than 1 at a higher
frequency range, which illustrates the existence of a localized relaxation process. From
this analysis, one can speculate that the conductivity is mainly due to short-range hopping
or a kind of competitive interaction via doubly ionized oxygen vacancies.
The DC-conductivity of the samples was calculated from AC-conductivity plots by
extrapolating the frequency-independent term to 1 Hz. Figure 7 shows DC-conductivity
as a function of temperature. The increase in conductivity with increasing temperature
indicates the negative temperature coefficient of resistance behavior. The variation of DC-
conductivity with temperature can explain the overall conduction (bulk) of the samples.
The activation energies were calculated using the following Arrhenius relation:

-2.7
DBTFC
-3.0 SBTFC
LBTFC
-3.3
σdc (Ω-1.m-1)

-3.6

-3.9

-4.2

-4.5

-4.8
1.30 1.35 1.40 1.45 1.50 1.55 1.60 1.65 1.70
1000/T (K-1)

Figure 7. Variation of DC-conductivity with 1000/Temperature (°C) of DBTFC, SBTFC, and LBTFC.
Crystals 2024, 14, 299 12 of 20

/
𝜎 = 𝜎𝑒 (5)
where σdc is DC-conductivity, Ea is activation energy, T is temperature, and K is Boltzmann
constant. The variation of DC-conductivity plots reveals the conduction of a thermally
activated rotation of dipoles. From the plots, activation energies were observed to be 0.931,
0.828, and 0.807 eV for DBTFC, SBTFC, and LBTFC, respectively. From the previous
reports, the activation energies of Aurivillius compounds were observed to lie in the order
of 0.87–1.4 eV. The present activation energy values were in good agreement with
previous reports [78]. Aurivillius phase compounds have the volatile nature of bismuth
during high sintering temperatures. To conserve charge neutrality, certain oxygen loss
occurs, as per the following Kroger–Vink notations:
Bi2O3 → 2Bi + 3/2 O2 + 2𝑉 + 3𝑉
𝑉 → 𝑉 + e’ (6)
𝑉 → 𝑉 + e’
Where, 𝑉 is doubly ionized bismuth vacancy, e’ is electron released, and 𝑉 and 𝑉
are singly and doubly ionized oxygen vacancies, respectively. The overall conductivity
can be attributed to oxygen vacancies and ion charge fluctuations. The ion charge
fluctuations in the present samples can be explained as follows:
Fe3+ + e' ↔ Fe2+

Co3+ + e' ↔ Co2+

(7)

Ti4+ + e' ↔ Ti3+

From the above equations, Fe2+ and Ti4+ sites form dipoles with vacant defects (oxygen
vacancy). These dipoles try to orient themselves using an electron-hopping mechanism.
The charge carriers get trapped near localized sites and may form large polarons. The
same phenomenon can apply to the Fe2+ ions, where the conduction mechanism is
attributed to small polarons.
Another aspect of the above defect mechanism can be illustrated by complex
impedance curves (Cole–Cole) as shown in Figure 8a–c. The first big and second small
semi-circles represent the grain (g) and grain boundary (gb) contribution of the samples.
Large grain resistance (Rg) indicates defects such as oxygen vacancies and complex
dipoles at grain interfaces. This interim affects the single domain or ferroelectric nature of
the samples. All fitting parameters are depicted in Table 3. The inset of Figure 8a–c exhibits
the room temperature hysteresis (polarization vs. electric field) loops of the DBTFC,
SBTFC, and LBTFC samples under the applied strengths of 500 V/cm, 750 V/cm, and 1000
V/cm with a constant frequency of 50 Hz. The unsaturated loops revealed very high
coercive and saturation fields. Generally, the Aurivillius phase compounds showed low
remanent polarization and high coercive and saturation fields. In addition, the
polarization of Aurivillius phase compounds depended on factors such as crystal
symmetry, strain effects, phase transitions, and the competition of dopants. The
Aurivillius phase compounds caused lattice distortion in the BO6 octahedron, which
affected the electric dipole moments [57]. The asymmetric and unsaturated ferroelectric
hysteresis (P-E) loops illustrated the leaky nature or accounted for the presence of a
greater number of oxygen vacancies or defective charge carriers. It is a known fact that
ferroelectric (hysteresis) nature is considered as a collective nature rather than a single
ionic migration. Since the overall conductivity was due to the migration of oxygen
vacancies or complex defect dipoles at lower temperatures, a saturated hysteresis loop
could not be obtained. This result was an enhancement of the magnetic nature of the
samples. From this Bi3.25La0.75Ti3O12 impedance data observation, it is evident that complex-
defect dipoles, which were accumulated at the grain interfaces, became relaxed easily
during the conduction mechanism. Therefore, similar compound Sm0.75Bi3.25Ti2.9625V0.03O12
Crystals 2024, 14, 299 13 of 20

(SBVT), rare-earth doped Aurivillius multiferroics showed well-saturated P-E loops

[59,79]. This suggests that when Ti4+ ions were replaced by Fe3+ or Co3+, these defective
charge complexes were trapped by the oxygen vacancies, so higher electric fields were
required to activate these trapped charges to acquire saturated P-E hysteresis loops.
Within the applied electric fields, all samples showed less loss nature.

60k 1.8
(a) DBTFC 500V
100k (b) SBTFC
2.4

Polarization (μC/cm2)
750V

Polarization (μC/cm2)
1.2 1.8
1000V
50k 0.6
1.2
0.6
0.0 80k 0.0
40k 400 oC -0.6
400 oC
Z''(Ω)

425 oC -0.6
-1.2 500V
425 oC

Z''(Ω)
450 oC 750V
30k 475 oC
-1.2
60k 450 oC -1.8
1000V
500 oC -1.8
475 oC -2.4
fit -15 -10 -5 0 5 10 15 500 oC -20 -10 0 10 20
20k Electric Field (kV/cm) Fit Electric Field (kV/cm)
40k

10k
20k
0
0 10k 20k 30k 40k 50k 60k 0
Z'(Ω) 0 20k 40k 60k 80k 100k
Z'(Ω)
70k (c) LBTFC 3.6
Polarization (μC/cm2)

2.4
60k 1.2

0.0
50k
400 oC -1.2
425 oC
Z''(Ω)

500V
40k 450 oC
-2.4
750V
475 oC -3.6 1000V

500 oC
30k Fit
-20 -10 0 10 20
Electric Field (kV/cm)

20k

10k

0
0 10k 20k 30k 40k 50k 60k 70k
Z'(Ω)

Figure 8. Complex impedance (Cole–Cole) plots of (a) DBTFC, (b) SBTFC, and (c) LBTFC; Insets in
figures: P vs. E loops.

Table 3. Complex impedance fitting parameters of the DBTFC, SBTFC, and LBTFC sample.

DBTFC
Temperature
No. R1 (Ω) R2 (Ω) CPE-1 n R3 (Ω) CPE-2 n
(°C)
1 400 200 92,000 5.200 × 10−10 0.885 7000 3.40 × 10−4 1
2 425 240 84,000 7.500 × 10−10 0.87 6500 4.20 × 10−4 1
3 450 320 36,000 6.200 × 10−10 0.875 3600 4.60 × 10−4 1
4 475 340 17,200 4.9 × 10−10 0.88 2200 4.65 × 10−4 1
5 500 360 9500 7.80 × 10−10 0.86 1050 5.20 × 10−4 1
SBTFC
Temperature
No. R1 (Ω) R2 (Ω) CPE-1 n R3 (Ω) CPE-2 n
(°C)
1 400 100 51,000 6.100 × 10−10 0.877 4800 9.9 × 10−4 1
2 425 180 26,000 5.700 × 10−10 0.882 3000 9.1 × 10−4 1
3 450 250 18,400 5.500 × 10−10 0.885 1300 8.2 × 10−4 1
4 475 350 10,100 4.400 × 10−10 0.895 950 7.9 × 10−4 1
5 500 380 6041 5.300 × 10−10 0.90 480 7.8 × 10−4 1
LBTFC
Temperature
No. R1 (Ω) R2 (Ω) CPE-1 n R3 (Ω) CPE-2 n
(°C)
Crystals 2024, 14, 299 14 of 20

1 400 150 59,800 9.900 × 10−10 0.862 6000 5.0 × 10−4 1

2 425 280 33,284 6.400 × 10−10 0.880 5000 4.1 × 10−4 1
3 450 300 21,200 6.200 × 10−10 0.89 3600 4.5 × 10−4 1
4 475 320 12,400 6.1 × 10−10 0.886 1600 4.7 × 10−4 1
5 500 350 7100 9.50 × 10−10 0.86 800 5.2 × 10−4 1

3.6. Magnetic Studies

Figure 9a–c shows the variation of magnetization with the applied magnetic field (M-
H loops) for all DBTFC, SBTFC, and LBTFC samples obtained at room temperature. Small
hysteresis loop areas indicate a canted antiferromagnetic (AFM) nature. This nature
correlates to the tilt-canted magnetic dipole moments. It should be noted that the canted
nature of two sub-lattices yields a small hysteresis loop area. These materials consist of
spontaneous magnetized domains. These materials possess low retentively and coercivity
values even at high magnetic fields. The introduction of magnetic ions Ni/Fe/Co in the B-
site of Aurivillius phases raised the spontaneous magnetization [80]. The magnetization
in the Co-/Fe-doped Aurivillius phase compounds main contributions, viz (i) exchange
interactions between the neighboring ions like Fe3+−O—Co2+ or Fe3+−O—Co3+ in iron-rich
regions, and (ii) tilt-canted spins or antisymmetric DM (Dzyaloshinskii–Moriya)
interactions. Three-layered single-phase Aurivillius compounds with orthorhombic
Fmmm structure exhibited AFM or weak ferromagnetism, which emerged from the
localized magnetic (Fe/Co) rich regions. This suggests a super-exchange interaction
between neighboring Fe and Co ions via oxygen vacancies [81,82]. This can also be due to
the long-range magnetic order in the ceramics. The structure evolution and Fe/Co—O—
Co/Fe bond angles in ABO3 perovskites in the layered compounds also affect the
magnetization of the ceramics. To understand more about FM nature, the following law
of approach is used [79,80]:

3
dM/dH(emu.g-1.Oe-1.10-4)

3
Magnetization (emu/g)

dM/dH(emu.g-1.Oe-1.10-4)

20
15
2 15
Magnetization (emu/g)

10 2 10

(b)
5
1 0
-20 -10 0 10 20 1 0
(a)
μoH (kOe) SBTFC -20 -10 0 10
μoH (kOe)
20

0 DBTFC
2.4 0
M (emu/g)

2.0
-1 2.0
M (emu/g)

-1 1.6
1.6 SBTFC
MS = 2.441 emu/g 1.2 DBTFC
-2 M=MS[1-(a/H)-(b/H2)] + kH
MS = 1.481 emu/g
1.2 -2 0.8 M=MS[1-(a/H)-(b/H2)] + kH
0 5 10 15 20
0 5 10 15 20
μoH (kOe)
μoH (kOe)
-3
-3
-20 -10 0 10 20 -20 -10 0 10 20
Magnetic Field (kOe) Magnetic Field (kOe)
dM/dH(emu.g-1.Oe-1.10-4)

1.2
Magnetization (emu/g)

12

4
0.6
0
(c)
-20 -10

μoH (kOe)
0 10 20
LBTFC
0.0 1.2
M (emu/g)

-0.6 0.9
LBTFC
MS = 1.066 emu/g
M=MS[1-(a/H)-(b/H2)] + kH
0.6
-1.2 0 5 10 15 20
μoH (kOe)

-20 -10 0 10 20
Magnetic field (kOe)

Figure 9. Room-temperature magnetic hysteresis loops of (a) DBTFC, (b) SBTFC, and (c) LBTFC;
Insets in figures (left): derivation of magnetization (dM/dH) vs. applied magnetic field; Insets in
Crystals 2024, 14, 299 15 of 20

figures (right): law of approach to saturation fittings M vs. H curves of DTFCS, SBTFC, and LBTFC
samples.

𝐴 𝐵
𝑀=𝑀 1− − +𝜒 𝐻 (8)
𝐻 𝐻
The term represents the inhomogeneity of magnetization; 𝜒 𝐻 is the forced
field-induced magnetization; and parameters explain magneto-anisotropic nature. By
considering the importance of the above LAS, Equation (8) is fitted in the low magnetic
field regions and shown in the inset of Figure 9a–c. By using Equation (8), the output of
fitting curves (R2) was found to be ~0.99 and thus the results of fitting were highly reliable.
In the present investigation, the DBTFC sample showed an unsaturated hysteresis
nature, indicating a combination of both FM and AFM [83]. The formation of Bi–O–Dy
bonds enhances magnetization. The Sm3+-doped REBTFC sample showed a higher value
of magnetization. The results are consistent with our recent work on rare-earth modified
Aurivillius intergrowths whose magnetization follows the similar rare-earth dependence
[57]. The magnetic moment per formula unit (𝜇 . . ) in the Bohr Magnetron is calculated
using the following formula:
∗ . ∗
𝜇 . . (in μB) = (9)
∗

where M (emu/g) is measured magnetization from the fitting of the law of saturation
(shown in the 4th quadrant of Figure 9); mol. weight (g) is the molecular weight of the
formula; 𝜇 . is the Bohr magnetron; 9.274 × 10−24 J/T, 𝑁 is Avogadro’s number = 6.023 ×
1023; and the conversion factor is 10−3 J/T. The magnetic moment per formula units (in µB)
for DBTFC, SBTFC, and LBTFC were found to be 0.30, 0.49, and 0.21 µB, respectively. The
SBTFC sample exhibited remanent magnetization (2Mr) of about 550 × 10−3 emu/g at room
temperature, which was bigger than the earlier reported value [84,85]. The inset of Figure
9a–c (left) illustrates the plots of the derivation of magnetization (dM/dH) as a function of
the applied magnetic field. It can be noticed that a single sharp peak is observed in all
curves. This can be attributed to the behavior of soft kind magnetism and uniform
magnetic grain nature. A single sharp peak is observed in the left side inset of Figure 9a–
c. From this, one can anticipate that all prepared samples were of a soft magnet.

3.7. Magnetoelectric Studies

The variation of the magnetoelectric (ME) coefficient with the applied magnetic field
of prepared samples is shown in Figure 10. The values of the magnetoelectric coefficient
were found to be 42.4 mV/cm-Oe, 30.3 mV/cm-Oe, and 21.6 mV/cm-Oe for DBTFC,
LBTFC, and SBTFC, respectively.

40
α(mV/cm.Oe)

20

-20
DBTFC
-40 SBTFC
LBTFC

-3 -2 -1 0 1 2 3
μoH (kOe)

Figure 10. ME coefficient vs. applied magnetic field plots of DBTFC, SBTFC, and LBTFC samples.
Crystals 2024, 14, 299 16 of 20

It is observed from the previous reports that the Bi4Ti3Fe0.7Co0.3O15 (BFTO) sample
showed an ME coefficient of 16.45 mV cm−1Oe−1 [64,86]. The obtained ME values of the
prepared samples were found to be higher compared to the other Aurivillius compounds.
Furthermore, the high ME coefficient was obtained at lower magnetic fields (3 kOe), as
shown in Figure 10. The ME coupling mainly arises from two aspects, namely, (i) spin-
exchange or spin–orbit interactions, driven by inverse DM interaction, and (ii) spin–lattice
interaction. The contribution of spin–orbit or spin–exchange interaction via inverse DM
interactions is smaller than the spin–lattice interactions [87]. In particular, the magnetic
ions in BO6 octahedral sites are slightly shifted from their regular sites under the
application of a magnetic field. This induces a strain in the lattice structure and develops
the voltage via ferroelectric accumulated changes. However, further studies are needed to
establish the plausible reason for obtaining a high ME coefficient. As it is reported, the
impurity phases of Co/Fe compositions influence the ME nature in Aurivillius compounds
[57]. The presence of circled regions of SEM micrograph dots (nanoregions) represents a
Co/Fe-rich magnetic phase. Based on these observations, such Co/Fe-rich phases could
contribute partly to the enhanced ME properties of the prepared samples.
In particular, when an external magnetic field is applied, the magnetic ions are
slightly displaced from their normal octahedral position, which induces a voltage in the
lattice, resulting in ferroelectric and ferroelastic changes, and finally producing an output
voltage. The parameters of orthorhombic distortion, tetragonal stain, and orthorhombicity
play a significant role in ME properties [88]. In our study, the DBTFC sample showed
higher ME coefficients. This is in good agreement with the lattice structure of the prepared
samples. Higher orthorhombicity and lower orthorhombic distortion values were
observed for the Dy-doped sample (DBTFC), which are favorable to enhancing the ME
coefficient under magnetic fields. In this study, the RE (Dy, La, and Sm) element
substitution in the A-site of Aurivillius compounds induced lattice distortion, and it led to
accompanying electric polarization under magnetic fields. It can be concluded that the
RE-doped three-layered Aurivillius phase compounds show strong ME coupling. These
multiferroic materials are useful for understanding the ME phenomenon.

4. Conclusions
In summary, we investigated the structural, morphological, electrical, magnetic, and
magnetoelectric properties of the RE-doped (Dy, Sm, and La) Bi3RETi2Fe0.7Co0.3O12−δ
Aurivillius multiferroic compounds. The XRD and Raman spectroscopic studies revealed
that the prepared samples were formed in single phase and orthorhombic structure with
space group Fmmm. This revealed that the ions were properly substituted into lattice cells.
The plate-like, anisotropic, randomly orientated grains were observed in FESEM studies,
which is a characteristic feature of Aurivillius phase ceramics. The substitution of RE
significantly enhanced the dielectric and ferroelectric properties with improved dielectric
constants in the frequency range, and reduced dielectric loss values were found at lower
frequency ranges. Improved remanent polarization was observed in all samples at room
temperature. This is attributed to the reduction in the oxygen vacancies by doping RE in
the Bi-sites of the samples. Ferroelectric and magnetic studies revealed good multiferroic
behavior in the samples. The M-H loops of the samples suggested an exchange interaction
between adjacent ions or DM interactions among magnetic ions. Strong ferroelectric-
magnetic coupling accompanied by a high coefficient of magnetoelectric coupling of 42.4
mV/cm-Oe was exhibited by the DBTFC sample. This strong ME coefficient in a single
phase may be applicable in multiferroic devices and can be interpreted from the
perspective of previous studies and of the working hypotheses.

Author Contributions: Conceptualization: V.V., N.V.P. and E.V.R.; Methodology: V.V. Data curation,
V.V., V.S.P., S.S. and S.N.B.: Writing—original draft preparation V.V.; writing and reviewed work:
N.V.P., E.V.R., G.S. and G.P.; Supervision: N.V.P., E.V.R. and G.P. All authors have read and agreed
to the published version of the manuscript.
Crystals 2024, 14, 299 17 of 20

Funding: This work was partially supported by OU-DST PURSUE-II/80/2021, project

ARDB/01/2032004 and CSIR-HRDG, No: 09/132(0875)/2018-EMR-I, New Delhi for providing
fellowship. National Science Foundation (NSF) (ECCS-1923732, ECCS-EAGER-2236879, DMR-
1808892) and the Air Force Office of Scientific Research (AFOSR) Award No. FA9550-20-1-0114
Data Availability Statement: Data is contained within the article.
Acknowledgments: One of the authors (V.V) is thankful to CSIR-HRDG, New Delhi for providing
JRF/SRF (File No: 09/132(0875)/2018-EMR-I). One of the authors (N.V.P) acknowledges the funding
by ARDB/01/2032004, OU-DST PURSUE-II/80/2021, SIR-HRDG and 09/132(0875)/2018-EMR-I, New
Delhi. EVR (032-88-ARH/2018) acknowledges the Portuguese Foundation for science and
Technology (FCT) for financial assistance through national funds (OE), in the scope of the
framework contract foreseen in the numbers 4, 5, and 6 of article 23 of the Decree-Law 57/2016, of
August 29, changed by Law 57/2017, of July 19. The research at Oakland University was supported
by grants from the National Science Foundation (NSF) (ECCS-1923732, ECCS-EAGER-2236879,
DMR-1808892) and the Air Force Office of Scientific Research (AFOSR) Award No. FA9550-20-1-
0114.
Conflicts of Interest: The authors declare no conflicts of interest.

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