Applied Physics A (2022) 128:576

https://doi.org/10.1007/s00339-022-05711-w

Crystal structure, magnetic and dielectric properties of Er‑doped

­BiFeO3 ceramics
Sonia Rani1,2 · Sujata Sanghi1 · Ashish Agarwal1 · Rohtash Kumar3 · Ompal Singh4

Received: 19 February 2022 / Accepted: 18 May 2022 / Published online: 13 June 2022
© The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature 2022

Abstract
Er-doped ­BiFeO3 (BFO) ceramics have been synthesized to investigate their improved physical properties. The analysis of
XRD patterns by Rietveld refinement revealed transformation in crystal structure from rhombohedral (x < 0.10, R3c) to mixed
rhombohedral and orthorhombic (0.10 ≤ x ≤ 0.20, R3c + Pnma) phases. Electron density contours confirm the stabilization
of the uniform and symmetric structures in the calculated profiles. Scanning electron microscopy (SEM) and transmission
electron microscopy (TEM) were used to examine the morphology of prepared ceramics. The presence of selective ele-
ments in prepared samples was confirmed by EDAX (Energy-dispersive analysis of X-ray). M-H loops depict significant
enhancement in magnetic properties with doping of Er, which is suggested to be evolved via suppression of spin cycloid and
reorientation of magnetic spins. The highest values of coercive field and remnant magnetization were observed for x = 0.20
(Hc = 0.35565 T, Mr = 0.39774 emu/g). Dielectric measurements of all the ceramics, recorded in the frequency range from
100 Hz to 7MHz follow Maxwell–Wagner type dispersive behaviour. The Nyquist plot characteristics of the prepared Er
doped BFO ceramics revealed non-Debye relaxation processes with negative (− ve) temperature coefficient of resistance
(NCTR). All the prepared ceramics show polarization hysteresis loops (P-E). The obtained results show that these ceramics
may be considered for designing novel smart systems.

Keywords  Multiferroics · Rietveld refinement · Structural distortion · Spin-reorientation · Electron density · VSM ·
Dielectric properties

1 Introduction (abbreviated as BFO) is a very interesting and unique inor-

In recent years, multiferroics have been studied widely
because, they exhibit multiple ferroic properties, viz., fer-
roelectricity, antiferromagnetism, and ferroelasticity, in a
single phase [1]. Multiferroic materials find potential appli-
cations in spintronics, data storage, sensors, high-density
ferroelectric random-access memory, multiple state memo-
ries, transducers, and microelectronic devices [2, 3]. ­BiFeO3
* Sujata Sanghi
sutkash@yahoo.com
1
Departmentof Physics, Guru Jambheshwar University
of Science and Technology, Hisar, Haryana 125001, India
2
Department of Physics, Government College, Hisar, Haryana,
India
3
Special Centre for Nano Sciences, Jawaharlal Nehru
University, New Delhi, India
4
Department of Physics, J.C. Bose University of Science
and Technology, YMCA, Faridabad, Haryana, India
ganic multiferroic material for research and innovation,
having a simultaneous occurrence of ferroelectricity (Curie
temperature is ­TC ~ 1103 K) and anti-ferromagnetism (Neel
temperature is ­TN ~ 643 K) in a wide temperature range
[4–6]. One of the main advantages of ­BiFeO3 is the exist-
ence of the Magnetoelectric (ME) coupling at room tempera-
ture, which enables its use in a large variety of electronic
devices [7]. BFO possesses a distorted perovskite structure
of ­ABO3 type with R3c space group in hexagonal setting [8,
9]. In pristine BFO, ferroelectricity and antiferromagnetism
originate in different sublattices:
(1) Ferroelectric instability arises from Bi–O orbital
hybridization due to ­6s2 lone pair electrons of Bi and,
(2) A complicated magnetic order (canted G-type antifer-
romagnetism) arises from Fe–O–Fe Dzyaloshinskii-
Moriya (DM) antisymmetric exchange interaction [10].

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Page 2 of 17
The antiferromagnetic ordering (G-type) in BFO is due
to the antiparallel alignment of ­Fe3+ ions. The magnetic
moments of the Fe3 + ions are antiferromagnetically cou-
pled between adjacent planes and ferromagnetically coupled
within the pseudocubic (111) planes [11].
The magnetic moments/spins are stretched in a spirally
spin modulated structure (SSMS) with a periodicity of about
620 Å, which results in the weakening of ferromagnetic
ordering [12–14] and this tends to lower magnetoelectric
(ME) coupling in BFO. The SSMS can be suppressed and
a strong ME coupling effect may be attained by decreas-
ing the dimensions of particle size below the periodicity of
the spiral order, i.e., 620 Å [5, 15]. Though this property
is favorable for practical purposes, bismuth ferrite also has
some inherent problems. The preparation of an ideal pure
phase of BFO is a very difficult task due to:
(i) Volatility of Bismuth
(ii) Formation of impurity phases as ­ B i 2 Fe 4 O 9 ,
­Bi25FeO40.
(iii) Instability of iron valence state ­(Fe3+–Fe2+) [2, 16–
18].
Also, BFO suffers from major leakage current problems.
These serious leakage current issues may be ascribed to the
presence of F ­ e2+ ions and oxygen vacancies in perovskite
­(ABO3 type) materials [19]. These issues prevent the appli-
cation of bismuth ferrite for multifunctional devices [20].
Various researchers made substantial efforts to dissolve
the problems associated with B ­ iFeO3 via doping elements
at A-site or B-site or both for improving the multiferroic
properties of BFO. From the available literature, it has been
found that doping of trivalent rare earth elements such as
­Eu3+, ­Dy3+, ­Ho3+, ­Nd3+etc. in place of A-site and C ­ r3+,
­Nb5+, ­Ti4+, or M ­ n4+ at B-site enhances the magnetic and
electrical properties of BFO [21–26]. Uniyal et al. synthe-
sized Eu doped ­BiFeO3 samples and reported enhancement
in multiferroic properties with Eu content [27]. Chowdhury
et al. synthesized Dy doped BFO in bulk ceramics and nano-
particles. The authors claimed better properties in bulk sam-
ples rather than nanoparticles [28]. Singh et al. prepared
Ho-doped ­BiFeO3 ceramic samples and reported better
conductivity as well as magnetic response in the prepared
samples as compared to pristine B ­ iFeO3 [29]. Singh et al.
synthesized Nd and Pr doped ­BiFeO3 with varying sintering
times and reported significant modifications in structural as
well as magnetic properties [30, 31]. Arnold et al. reviewed
the composition-driven structural transformation with dop-
ing of rare earth elements and briefed the effect of dopants
in phase formation [32]. Most of the reports specified the
doping of rare earth to be beneficial for improvement in
structural as well as other physical properties. Despite, the
significant research carried out in the field, more intriguing
13
S. Rani et al.
aspects, as well as the challenging physics behind the evo-
lution of crystal structure and the associated physical prop-
erties still need to be exposed. In this sense, Er has been
­ iFeO3 with
chosen to substitute at A-site (in place of Bi) of B
the aim that due to lower ionic radii of E­ r3+ as compared to
­Bi3+, Er ions can occupy the Bi-site and also Er–O bonds
have a higher bond energy than Bi–O bonds which in turn
may reduce oxygen vacancies [33]. Hence, in the present
work, the crystal structure, magnetic and dielectric proper-
ties of ­Bi1-xErxFeO3 for x = 0.05, 0.10, 0.15, and 0.20 have
been analysed.
2 Experimental procedure
2.1 Sample synthesis
In this report, ceramics were prepared by a rapid solid-state
sintering method to reduce impurity phases and oxygen
vacancies. This method is widely used in materials syn-
thesis with enormous advantages. It is one of the easiest
methods to procure ceramic samples without the require-
ment of any liquid reactant or any solvent. It is a flexible
method with multiple heat treatments with different treat-
ment temperatures/times to synthesize desired impurity-free
pure phase powder samples. Moreover, all reagents need not
necessarily be melted in reacting with each other, thereby
curbing the possibility of coagulation at a particular point.
Also, the solid-state reaction technique yields, nil or very
less side products which leads to a reduction in wastage of
chemicals. In the present study, High-quality raw materi-
als (@ Sigma-Aldrich) of ­Bi2O3 (Mol. Wt. 465.96 g/mol,
Purity-98%), ­Er2O3 (Mol. Wt. 382.52 g/mol, purity-99.99%),
­Fe2O3 (Mol. Wt. 159.69 g/mol, Purity-99%) were carefully
weighted in proper stoichiometric proportions. The stoichio-
metric weights of B ­ i2O3 and F
­ e2O3 for pristine B
­ iFeO3 were
calculated to be 7.46686 gm and 2.53313 gm respectively
for 10 g. The amount of stoichiometric weights were made
proportional accordingly with doping of Er in the composi-
tion ­Bi1-xErxFeO3 (x = 0.05, 0.10, 0.15 and 0.20). A total of
10 gm solid polycrystalline sample was prepared for each
composition. The raw mixtures were ground for 2 h in agate
mortar with a pestle. Calcination was done at 400 °C for 3 h
in an open-air furnace. The calcined powders were reground
for 1 h to obtain better homogeneity. Rapid liquid phase sin-
tering has been adopted for the second and final heat treat-
ment. The melting point of bismuth oxide is 820 °C. Hence
liquid phase is formed above 820 °C. This liquid phase may
minimize impurities evolving due to the volatility of Bi [33].
The samples were quenched after 1 h at 830 °C. For dielec-
tric characterization, the calcined powders were pressed
into disc-shaped pellets having a thickness of 1–2 mm and
a diameter of 10 mm using an organic binder (polyvinyl
Crystal structure, magnetic and dielectric properties of Er‑doped ­BiFeO3 ceramics Page 3 of 17  576

alcohol) by putting the pressure of 10 tons for one and half
minutes using a hydraulic press. Pellets of all ceramics were
quenched in rapid liquid phase sintering at 830 °C for 1 h.
The densities of pellets were determined by Archimedes’
principle. The pellet faces were polished with zero-sized
emery paper and the polished surfaces were coated with a
conductive silver paste to make electrodes. The ceramics
having composition B ­ i1-xErxFeO3 with x = 0.05, 0.10, 0.15,
and 0.20 have been labelled as BEFO5, BEFO10, BEFO15,
and BEFO20 respectively.
2.2 Crystal structure measurements
X-ray diffraction patterns were recorded for structural analy-
sis of synthesized samples. Rigaku MiniFlex-II X-Ray Dif-
fractometer equipped with radiation source of ­CuKα has
been used to record XRD patterns in scanning range 10°
to 80° at a scanning speed of 2°/minute with a step size of
0.02°. Rietveld refinement of the obtained XRD patterns
was carried out through FullProf software. The best possible
fit was obtained by minimizing the difference (∆) between
observed and simulated patterns. The function ∆ is given as:
∑ { }2
Δ= wi Iio − Iic (1)
i
where symbol wi is used for weight parameter which can be
further defined in terms of σi (standard deviation) as (1/wi
) = σi2; Iio and Iic are observed and simulated intensities
respectively [34, 35]. To compare the structural and areal
uniformity, electron density contour maps have also been
plotted with a calculated refined pattern. Surface microstruc-
tural analyses were performed with the help of the SEM-
assisted EDAX device (7610F Plus/JEOL). TEM images,
HRTEM (High Resolution) images, SAED pattern (JEOL
JEM 2100 plus) were obtained to determine average grain
size, d spacing and crystallinity of the ceramic samples.
2.5 Structural analysis
2.5.1 XRD analysis
Room temperature XRD patterns of Er substituted BFO
ceramics are shown in (Fig. 1). All the diffraction peaks
are obtained corresponding to reflections from (012), (104),
(110), (006), (202), (024), (116), (122), (018), (214)/(300)
planes of BFO, which are well-matched with the standard
described values (JCPDS File No. 86-1518). Pure BFO crys-
tallizes to rhombohedral symmetry that belongs to R3c space
group. The magnified view of X-ray diffraction patterns in
the vicinity of 2θ ~ 32° is shown in the inset of (Fig. 1). The
enlarged pattern represents the shifting of peaks towards
a larger diffraction angle. It is due to the incorporation of
smaller ionic radii ­Er3+ (0.881 Å) ions as compared to B ­ i3+
(1.03 Å). Er substitution in place of Bi is also found effec-
tive to reduce the formation of secondary phases during the
preparation of the sample.
2.5.2 Rietveld analysis
XRD patterns were further analyzed to estimate the crystal
structure and lattice parameters of prepared samples. These
patterns were simulated with Rietveld refinement using the
FullProf Suite. Rietveld refined X-ray diffraction patterns
for experimental, simulated and their difference are shown
in (Fig. 2 ) and the refined cell parameters (a, b, c), atomic
coordinates (x, y, z), Chi-square (χ2), weighted profile resid-
ual (Rwp), profile residual (Rp) factors are summarized in
(Table 1).

2.3 Magnetic measurements

The vibrating sample magnetometer (VSM) has been used

to record the magnetic properties of prepared samples up
to 2 Tesla at room temperature (PPMS, closed cycle-based
cryogen-free system-Cryogenics Limited, USA).

2.4 Dielectric measurements

Dielectric properties of all Er-doped BFO synthesized sam-

ples were measured in 100 Hz to 7 MHz frequency range
with an impedance gain-phase analyzer in the temperature
range from 313 to 623 K (Newton’s 4th Ltd., UK). The
variation of polarization vs. electric Field (P-E loops) was Fig. 1  Observed XRD spectra for all ­
Bi1-xErxFeO3 samples (Inset
recorded using High end PE loop tracer. shows a magnified view of XRD patterns around 2θ ~ 32°)

13
576 
Page 4 of 17 S. Rani et al.

Fig. 2  Rietveld refined
XRD patterns for a BEFO5,
b BEFO10, c BEFO15, d
BEFO20 samples

The residuals (Rp and Rwp) can be defined as: observation of XRD patterns of 0.10 ≤ x ≤ 0.20 samples, pre-
∑ � dict the evolution of the second structural phase. Initially
Iio − Iic �� for, 0.10 ≤ x ≤ 0.20 sample, refinement was carried out using
Rp = i �∑ (2)
i Iio space group R3c and Pnma separately. But no satisfactory
result was found. After that, refinement was performed by a
�∑ � �2 �1∕2 mixed (R3c + Pnma) space group. The best-fitting between
w I
i i io − Iic experimental and simulated values was found with low pro-
Rwp = (3)
∑ 2 file factor values. The structural trend evolved in the Er-
i wi Iio
doped samples is found to be analogous with reports con-
Rietveld refinement was started with zero-point shift and cerned with the substitution of Bi by other smaller rare-earth
scale factor. 12 coefficients Fourier cosine series polynomi- ions [32, 33]. The rare earth elements are reported to form
als were refined as the background parameters. Peak shapes greater bond strength with oxygen as compared to that of the
were modeled with pseudo-Voigt function. An approximate Bi–O bond which eventually tends to create inhomogene-
structural model similar to the actual structure was used ous strains in the host matrix. The replacement of Bi with
to initiate the procedure of refinement. All the observed smaller ions has been proved to boost chemical pressure and
peaks were reproduced as pristine ­BiFeO3 for the BEFO5 introduce heteronucleation in the compound, which eventu-
sample. Rietveld refinement of the x = 0.05 sample was ally leads to crystal structure transition [32]. Singh et al.
performed with the rhombohedral phase (R3c). The visual synthesized Nd-doped B ­ iFeO3 and suggested the smaller

13
Crystal structure, magnetic and dielectric properties of Er‑doped ­BiFeO3 ceramics Page 5 of 17  576

Table 1  The summary of various parameters obtained from Rietveld refinement; lattices parameters, atomic position, residual factors (Rp, Rwp),
Chi-square (χ2)
Composition Space group Lattices parameters Atomic position X, Y, Z ­ hi2Factor
R and C

x = 0.05 Rhombohedral a = 5.5686(2)Å Bi/Er(0,0,0.2217(4)) Rp = 4.22

R3c (100%) c = 13.8413(6)Å Fe(0,0,0) Rwp = 5.49
V = 371.70(2)Å3 O(0.8926(2),0.6449(2),0.4306(9)) χ2 = 2.78
x = 0.10 Rhombohedral a = 5.5655(19)Å
R3c (95.98%) c = 13.8370(5)Å
V = 371.45(2)Å3
Orthorhombic a = 5.6142(4)Å
Pnma (4.02%) b = 7.6514(4)Å Bi/Er (0,0,0.2201(4)) RP = 3.78
c = 5.3150(3)Å Fe (0,0,0) Rwp = 4.93
V = 228.35(2)Å3 O(0.7801(2),0.6684(2),0.4317(10)) χ2 = 2.95
Bi/Er(0.0591(4),0.25,0.9946(5))
Fe (0,0,0.5)
O1(0.365(14),0.25,0.1482(8))
O2(0.2122(3),0.4488(16),0.2309(16))
x = 0.15 Rhombohedral a = 5.5692(17)Å Bi/Er (0,0,0.2175(3)) Rp = 3.98
R3c (87.86%) c = 13.8434(5)Å Fe(0,0,0) Rwp = 5.04
V = 371.84(2)Å3 O (0.7685(2),0.6545(20),0.4302(9)) χ2 = 2.98
Orthorhombic a = 5.6099(3)Å Bi/Er(0.0570(15),0.25,0.9895(4))
Pnma (12.14%) b = 7.6599(3)Å Fe (0,0,0.5)
c = 5.3359(2)Å O1 (0.4965(13),0.25,0.1297(13))
V = 229.29(17)Å3 O2(0.3501(14),0.5689(9),0.2102(9))
x = 0.20 Rhombohedral a = 5.5648(2)Å Bi/Er(0,0,0.2207(5)) Rp = 3.75
R3c (80.11%) c = 13.8305(7)Å Fe(0,0,0) Rwp = 4.79
V = 370.92(3)Å3 O(0.7711(3),0.6541(2),0.4339(12)) χ2 = 2.87
Orthorhombic a = 5.6071(3)Å Bi/Er(0.05(2),0.25,0.9838(4))
Pnma (19.89%) b = 7.6787(2)Å Fe(0,0,0.5)
c = 5.3261(2)Å O1(0.4381(3),0.25,0.0553(3))
V = 229.32(17)Å3 O2(0.2986(15),0.5400(10),0.1820(11))

size of the dopant to be responsible for the structural trans-
formation from rhombohedral to orthorhombic phase [30].
The Emergence of orthorhombic nonpolar Pnma structure in
the present study may be suggested to evolve via the creation
of heteronucleation in the compound.
The values of bond length and bond angles between
atoms obtained from Rietveld’s analysis are listed in
(Table  2). The lower values of atomic parameters ‘a’
and ‘c’ as compared to that of pristine B ­ iFeO3, indicate
reduction in the volume of unit cell. This reduction may
be ascribed to the lower size of the dopant. It has been
established that pure BFO exhibit two different bond
lengths between Bismuth and Oxygen of dimensions ~ 2.17
and ~ 2.72 respectively. In the present study, it has been
found that these lengths are affected seriously, the lower
bond length increases and the larger one is reduced. This
notably indicates the distortion in the local setting of
­FeO6 octahedra arising from the substitution of Bi with
lower sized Er, which is consistence with the previous
reports concerning rare earth doped ­BiFeO3. The larger
bond strength between Er and O as compared to Bi and O
induces inhomogeneous strains in the compound. Also, the
Er-Fe interaction perturbs the Fe–O bond and thus gives
rise to an alteration in octahedra. The various obtained
bond lengths for the rhombohedral phase indicate the
formation of complex bonding and tilting of octahedral
to attain the least energy state. The rotation of octahedra
indeed insists on the structural transformation, which is
revealed in the present series. The schematic representa-
tion of the crystal structure of ­Bi0.8Er0.2FeO3 is displayed
in (Fig. 3). The three-dimensional view of the crystallo-
graphic structure of BEFO20 representing rhombohedral
and orthorhombic structure was generated from refined
phase parameters using the VESTA program. Goldschmidt
tolerance factor (t) has been calculated to predict distor-
tion and stability in ­ABO3 type perovskite oxides and is
given by [36].

13
576 
Page 6 of 17 S. Rani et al.

Table 2  The bond length and
bond angle obtained from
Rietveld refinement analysis of
prepared ceramics
Sample and model
BEFO5
Rhombohedral (R3c)
BEFO10
Rhombohedral(R3c)
Orthorhombic (Pnma)
BEFO15
Rhombohedral(R3c)
Orthorhombic(Pnma)
BEFO20
Rhombohedral(R3c)
Orthorhombic(Pnma)
Bond length (Å)
Bi/Er–O = 2.341, 2.476
Fe–O = 2.019, 2.023
Bi/Er–O = 2.292, 2.561
Fe–O = 1.915, 2.115
Bi/Er–O1 = 1.174, 2.957
Bi/Er–O2 = 2.755, 2.496
Fe–O1 = 2.463
Fe–O2 = 1.952, 2.022
Bi/Er–O = 2.332, 2.505
Fe–O = 1.895, 2.146
Bi/Er–O1 = 1.636
Bi/Er–O2 = 2.472, 2.249
Fe–O1 = 2.362
Fe-O2 = 2.375,1.648
Bi/Er–O = 2.324, 2.542
Fe–O = 1.893, 2.141
Bi/Er–O1 = 1.1470
Bi/Er–O2 = 2.100
Fe–O1 = 2.352
Fe–O2 = 1.985, 2.065
Bond angle (degree)
Bi/Er–O–Bi/Er = 110.46
Fe–O–Fe = 156.5
Bi/Er–O–Bi/Er = 109.05
Fe–O–Fe = 157.87
Bi/Er–O1–Bi/Er = 152.45
Bi/Er–O2–Bi/Er = 97.91
Fe–O1–Fe = 101.94
Fe–O2–Fe = 153.19
Bi/Er–O–Bi/Er = 109.75
Fe–O–Fe = 156.44
Bi/Er–O1–Bi/Er = 154.99
Bi/Er–O2–Bi/Er = 106.50
Fe–O1–Fe = 108.21
Fe–O2–Fe = 148.49
Bi/Er–O–Bi/Er = 108.78
Fe–O–Fe = 157.61
Bi/Er–O1–Bi/Er = 122
Bi/Er–O2–Bi/Er = 103.25
Fe–O1–Fe = 109.32
Fe–O2–Fe = 146.24

Fig. 3  The schematic dia-

gram of the BEFO20 sample
represents a rhombohedral
structure with R3c space group
b orthorhombic structure with
Pnma space group

concentration. In each case, the value of the tolerance fac-

��
1 − x)RBi3+ + xREr 3+ ] + RO2−
t= √ (4) tor is found to be less than one. For the t < 1, octahedral
2[RFe3+ + RO2− ] distortion occurs to fit into the unit cell [37]. The toler-
ance factor decreases with Er concentration which shows
Here RBi3+ , REr 3+ , RO2− and RFe3+ are effective ionic radii
an increase in driven forces which indeed shrink oxygen
of ­B i 3+,Er 3+ , ­O 2−and Fe3+ respectively. The calculated
octahedral to fit into the unit cell [34]. Plot between toler-
values of tolerance factor are found to be 0.8837, 0.8788,
ance factor and concentration of Er (x = 0.05, 0.10, 0.15
0.8738, 0.8687 for x = 0.05, 0.10, 0.15, 0.20, respectively.
and 0.20) is displayed in (Fig. 4).
The tolerance factor (t) decreases with the increase of Er

13
Crystal structure, magnetic and dielectric properties of Er‑doped ­BiFeO3 ceramics Page 7 of 17  576

0.884 In an X-Rays diffraction, electrons act as the scattering

0.882
t
centers/scatterers, therefore 𝜌(x, y, z) will denote the number
0.880 of electrons per unit volume or more specifically the electron
Tolerance factor (t)

0.878 density.
0.876 The electron density, ρ(x, y, z) can be deduced by taking
0.874 the inverse Fourier transform of Eq. (5), as given below [39]:
0.872
1∑
0.870 𝜌(x, y, z) = Fhkl e−2i𝜋(hx+ky+lz) (6)
V
0.868
0.866 The electron density at various lattice points in the
4 6 8 10 12 14 16 18 20 22
crystal can be calculated using Eq. (6). Three dimensional
Concentration (x%)
(3D) Fourier map for measurement of electron density of
­Bi0.95Er0.05FeO3 and two dimensional (2D) contour pro-
Fig. 4  The variation of tolerance factor (t) with the concentration of
Er in BFO files for all B
­ i1-xErxFeO3 prepared ceramics are displayed
in (Figs. 5, 6), respectively. The three-dimensional Fourier
maps were obtained by the G Fourier program in the Full-
The electron density variation is useful to analyse the Prof Suite. All the 3D Fourier maps of prepared samples
uniformity in structure and the physical properties associ- were found to be similar. Hence, it would be very difficult
ated with the same. An appropriate localization scheme is to obtain the structural differences among the prepared sam-
required to see the variation in the crystal structure. Atomic ples. So, the two-dimensional electron density contour for
structure factor Fhkl for a diffraction pattern is defined as all the samples was plotted through OriginPro software with
[38]: a refinement pattern to check the uniformity in each sam-
a b c
ple and variation of electron density in comparison to other
samples. There is overlapping of electron density gradient of
∫ ∫ ∫
Fhkl = 𝜌(x, y, z)exp{2𝜋i(hx + ky + lz)}dxdydz (5) lower and upper bounds over one another confirms that crys-
0 0 0 tal structure obtained from Rietveld refinement is symmetric
where 𝜌(x, y, z) represents the density of scatterers, hkl in space. An intense change in the mid-region of electron
denotes the miller indices and dxdydz is the small volume density patterns is observed from x = 0.05 to x = 0.10 sample,
element. which indicates a change in the formulated structure. With

Fig. 5  Three-dimensional
Fourier map for B
­ i0.95Er0.05FeO3 67.20
ceramic 70 59.70

52.20
60
44.70
50
E le ctr o n d e n sit y (n

37.20

40 29.70

22.20
30
14.70

20 7.200
/Å 3 )

10 -0.3000

-7.800
0
1 .0
-10 0 .0 0 .8
0 .2 0 .6
0 .4
z/c
0 .4 x/a
0.6 0 .2
0.8
0 .0
1.0

13
576 
Page 8 of 17 S. Rani et al.

Fig. 6  Two-dimensional electron density contour maps for all ­Bi1-xErxFeO3 ceramics

13
Crystal structure, magnetic and dielectric properties of Er‑doped ­BiFeO3 ceramics Page 9 of 17  576
an increase in the concentration of Er, the structure stabilizes
and enhancement in uniformity is observed.
2.6 Morphological analysis
The surface morphology of Er-doped BFO ceramics meas-
ured with a scanning electron microscope (SEM) are shown
in (Fig. 7a–d). It is observed that grains are nearly spherical
in shape with homogeneous grain distribution. SEM analysis
clearly indicates that the grain size of all synthesized sam-
ples is almost of the same size and shape having grain size
around 190–210 nm. Hence Er doping was not observed to
alter the morphology of B ­ iFeO3 samples significantly and
well in agreement with previously reported work [40, 41].
Often, the density of the sintered pellets is used for dielec-
tric, impedance spectroscopy, and ferroelectric justification
as it can be well correlated with the presence of voids and
pellet interior. Hence, it is important to determine the densi-
ties of the pellets for better interpretation of the dielectric
and ferroelectric analysis. The experimental densities of
all the synthesized samples were calculated by Archime-
des’ principle and observed to increase with increasing Er
concentration up to 15% then decreases for 20% Er-doped
samples (5.0639 g/cm3, 5.1628 g/cm3, 5.2210 g/cm3, and
5.0122 g/cm3 respectively).
2.7 TEM analysis
Figure 8a–d exhibits TEM, HRTEM and SAED images of all
Er doped B ­ iFeO3 samples. The grain size shown in the inset
(Fig. 8) reveals no significant variation in size with doping
of ­Er3+ ions, which is in agreement with results obtained by
SEM (scanning electron microscope) images. Lattice fringes
can be clearly seen in the high-resolution TEM image inset
(Fig. 8a–d) which suggests good crystallinity of the sam-
ples. The lattice spacing of the typical crystalline region for
BEFO5, BEFO10, BEFO15, and BEFO20 is about 0.409,
0.392, 0.384, and 0.389 nm respectively, which is consist-
ent with the (012) lattice plane of pure BFO (#71-2494) and
that calculated from Rietveld refinement. The selected area
electron diffraction (SAED) pattern (Fig. 8a–d) shows the
diffraction rings corresponding to 012, 104, 202/022 lattice
planes for doped ­BiFeO3 ceramics.
2.8 Magnetic analysis
Figure 9 depicts a variation of magnetization (M) with an
applied magnetic field (H) (measured at room temperature)
for all B
­ i1-xErxFeO3 ceramics. The basic structure of BFO
shows G-type anti-ferromagnetic ordering accompanying
spin cycloidal structure periodicity with 62 nm long-wave-
length, which hinders net magnetization on a macroscopic
scale [34, 42, 43]. The M-H hysteresis loops of prepared
samples were found to be unsaturated even up to a magnetic
field of 2 T which confirms the presence of basic antifer-
romagnetism in these samples [8]. The substitution of Er at
A-site in BFO changes anti-ferromagnetic BFO into weak
ferromagnetic, which could be attributed to phase transfor-
mation from the rhombohedral phase (R3c) to a combined
phase of rhombohedral and orthorhombic phase (Pnma)
(x ≥ 0.10). There is a larger distortion of lattice due to the
suppression of the spin cycloidal structure and ferromagnetic
interaction between ­Fe3+ and ­Er3+ ions. Bond angles and
bond distances between atoms change abruptly throughout
phase boundaries which results in alteration of the anti-
parallel spin structure. The robust rise in magnetization
may be suggested to be caused via canting of spins along
with the distortion of a spin cycloid. The rare earth doping
in ­BiFeO3 has been proved to distort the incommensurate
spin modulated spiral structure and hence able to release the
restricted magnetization in the compound. Table 3 presents
the values of remnant magnetization (Mr) and coercivity (Hc)
corresponding to each sample. It has been noticed that the
5 mol% Er doped sample exhibits a nice weak ferromag-
netic like M-H loop which indicates the distortion of the
spin modulated spiral structure present in pristine BiFeO3
ceramic. In the next sample, with x = 0.10, the magnetisation
has been observed to reduce along with the increasing non
saturation in the loop in the equipment magnetic field range.
This reduction in Magnetic parameters may be attributed to
the evolution of non-polar Pnma symmetry in subtle frac-
tion which in turn lead to reduce magnetisation. The gradual
enhancement in the next samples (x = 0.15 and x = 0.20) is
suggested to occur via still continue destruction of the spiral
structure with concentration. The remnant magnetization is
maximum (0.39774 emu/g) with 20 mol% doping in BFO.
2.9 Dielectric analysis
2.9.1 Frequency dependence of complex dielectric
permittivity
Figure 10a–d shows the variation of dielectric constant (ε′)
and loss tangent (tan δ) with frequency of all ­Bi1-xErxFeO3
prepared ceramics at different temperatures 373 K, 393 K,
413 K, 433 K, 453 K and 473 K. Dielectric constant behav-
iour is suppressed at higher frequencies and exhibits more
dispersion at low frequencies for all prepared ceramic sam-
ples. The tangent loss (tan δ) also shows similar behaviour.
Indeed, dispersion in ε′ and tan δ is an extrinsic property of
almost dielectric materials [44]. The dispersion behaviour
at low frequencies can be described based on the interfacial
polarization model of Maxwell–Wagner (MW) [45, 46].
According to the M-W model, the dielectric material with
a heterogeneous structure can be considered as a structure
consisting of well-conducting grains that are well separated
13
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Page 10 of 17 S. Rani et al.

13
 Crystal structure, magnetic and dielectric properties of Er‑doped ­BiFeO3 ceramics Page 11 of 17  576
◂Fig. 7  a–d Scanning electron microscopy (SEM) images of
­Bi1-xErxFeO3 (x = 0.05, 0.10, 0.15 and 0.20) multiferroics. The pres-
ence of different elements in synthesized compositions was confirmed
by SEM/EDS (EDX) spectra shown in (Fig.  7e–h). The presence of
Er was confirmed in all synthesized samples by detecting the Er peak
in BDFO5, BDFO10, BDFO15, and BDFO20 sample with increas-
ing Er concentration. (e–h) EDS micrograph of all ­Bi1-xErxFeO3 e
x = 0.05, (f) x = 0.10, g x = 0.15, and h x = 0.20 ceramic samples at
room temperature
by high resistance grain boundaries. As the electric field
is applied, space charge polarization is built up at grain
boundaries. The element which exists in more than one
valance state provides electrons for the polarization mech-
anism to exchange [47]. The exchange of electrons takes
place between ­Fe3+–Fe2+ions in these samples. During the
exchange, the electrons could have crossed the grains and
grain boundaries but due to the highly resistive nature of
grain boundaries, these electrons gather at grain boundaries
resulting in the build-up of space charge polarization.
According to Koop’s theory, grain boundaries have a
strong effect at low frequencies while grains have a strong
effect at high frequencies [48]. Hence, the dielectric con-
stant increases rapidly in the low-frequency region due to
the accumulation of charge and becomes low at high fre-
quency as charges do not have enough time to accumulate
at the borders of conducting regions resulting in lower space
charge polarization. Hence the net capacitance or dielec-
tric constant is decreased. At low frequencies, the dielectric
loss factor (tanẟ) is higher, whereas at high frequencies, it
is lower because the grain boundaries offer high resistance
at low frequencies and extra energy is required for drifting
the charge carriers which results in high energy loss in this
region. But at a higher frequency, grains offer low resistance
and hence less energy is needed for drifting the charge car-
riers with low loss.
Debye proposed the following model of dielectric
response with applied frequency and the equation of this
model may be written as follows [44, 49]:
(∈s + ∈∞ )
∈∗ (𝜔)=∈∞ +
1 + i𝜏𝜔
where ω is the angular frequency (2πf), τ is the relaxation
time, ε∞ is dielectric permittivity at very high frequencies,
and εs is static dielectric constant. The relaxation time (τ) is
inversely proportional to the relaxation frequency (ω) and
is related through the relation: τ ∝ 1/ω. The real (ɛʹ) and
imaginary (ɛʹʹ) parts of complex dielectric permittivity can
be calculated using Eqs. (8), (9) as:
� ∈s + ∈∞ (𝜏𝜔)2
∈ (𝜔) =
1 + (𝜏𝜔)2
(∈s + ∈∞ )𝜏𝜔
∈ε (𝜔) = (9)
1 + (𝜏𝜔)2
��
( )
∈ (𝜔) ∈s + ∈∞ 𝜏𝜔
Tan𝛿 = � = (10)
∈ (𝜔) ∈s + ∈∞ (𝜏𝜔)2
These equations are known as Debye relations for
dynamic polarization with only one relaxation time (τ). In
general, the bigger molecule has a higher relaxation time
than smaller ones resulting in less mobility.
2.10 Temperature dependence of complex
dielectric permittivity
Temperature dependence of dielectric permittivity (Ɛ ʹ)
and loss tangent factor (tan δ) of prepared ­Bi1-xEr xFeO3
(x = 0.05, 0.1, 0.15 and 0.20) ceramics at various frequen-
cies are shown in (Fig. 11a–d). The temperature-dependent
dielectric properties have been measured in the temperature
range of 323 K to 623 K using a programmable temperature
controller. The dielectric properties are strongly dependent
on the frequency of the ac field. It can be seen from the
plot (Fig. 11) that the behaviour of dielectric constant and
dielectric loss is similar for all ceramic samples. The value
of dielectric constant (Ɛʹ) and tan δ increase gradually with
the rise in temperature and reaches a maximum value at a
certain temperature. This can be explained as follows: at
the low-temperature side, the electric dipoles cannot align
themselves in the direction of the applied ac field, and hence
weak polarization results in the low value of the dielectric
constant. In contrast, with a temperature rise, the electric
dipoles are aligning themselves in the direction of the
applied ac field due to enough thermal energy and this leads
to enhanced space charge polarization and hence improved
the dielectric properties [50, 51]. An anomalous peak is
detected in the range of 400–550 K (Fig. 11a–d) for all Er-
doped ­Bi1-xErxFeO3 ceramic samples. The anomalous peak
is prominent at low frequency (1 kHz) and disappears with
(7) an increase in frequency. This type of dielectric anomaly in
the vicinity of the Neel temperature has been reported by
many researchers for ­BiFeO3 ceramics. This anomaly can
be induced with a transient interaction between ­Fe+3 / ­Fe+2
and oxygen ion vacancies [8, 52, 53].
The value of dielectric loss increases at around 600 K at
1 kHz for all-ceramic samples. The maximum value of the
dielectric constant for the x = 0.15 sample is observed to be
3700 at a frequency of 1 kHz. The value of the dielectric
constant falls as frequency increases from 1 kHz to 1 MHz
(Fig. 11c). At low frequencies, both dipolar and interfacial
(8)
polarisation contribute to the improved dielectric constant,
whereas at higher frequencies, only electronic polarisation
contributes to the dielectric constant [50, 51]. This indicates,
13
576 
Page 12 of 17 S. Rani et al.

Fig. 8  (a–d) TEM images of Er doped B

­ iFeO3 ceramics at low and high resolution, and corresponding SAED patterns

Table 3  The summary of M-H loop parameters; residual magnetism

(Mr), coercive Force (Hc)
BEFO5 1.40 Sample Remanent magnetisation Coercive force
BEFO10
1.05 X Mr (emu/g) Hc (Tesla)
Magnetic Moment/Mass (emu/g)

BEFO15
BEFO20
0.70 0.05 0.36181 0.35502
0.10 0.29766 0.29109
0.35
0.15 0.34410 0.32548
0.00 0.20 0.39774 0.35565
-2.25 -1.50 -0.75 0.00 0.75 1.50 2.25
-0.35

-0.70 the dielectric properties are improved with substitution of

-1.05
­Bi3+ with ­Er3+ concentration in ­BiFeO3 may be attributed to
lower leakage current due to decrease of oxygen vacancies
-1.40 originated by the valence fluctuation of Fe ions [40, 54–56].
Magnetic Field (Tesla) Although for 20% Er-doped BFO, the decrease in dielec-
tric constant may be due to a decrease in pellet density and
Fig. 9  Magnetic hysteresis loops for all ­Bi1-xErxFeO3 ceramics increased voids in the interior of the pellet. The variation in

13
Crystal structure, magnetic and dielectric properties of Er‑doped ­BiFeO3 ceramics Page 13 of 17  576
(a)
(c)
Fig. 10  a–d Frequency dependence of dielectric constant and dielectric loss of prepared samples
the dielectric loss in the low-temperature region is smaller
as compared to the high-temperature region. This behaviour
is the similar for all Er-doped B­ iFeO3 samples at various
frequencies. There is an abrupt increase in dielectric loss
with the increasing temperature that could be attributed to
the direct consequence of higher electrical conductivity of
samples [57].
2.11 Impedance spectroscopy
The complex impedance spectroscopy technique is used to
determine the contribution of grains and grain boundaries in
the material system. The plots between impedance Zʹ (real
part) and Zʹʹ (imaginary part), known as Nyquist plots for
prepared samples at different temperatures: 533 K, 543 K,
(b)
(d)
553 K, and 563 K are shown in (Fig. 12). The Nyquist plot,
is typically obtained in the shape of a semicircle. In poly-
crystalline materials, conducting grains are separated by
insulating grain boundaries. The number of semicircular arcs
in the plots shows contribution of grain and grain boundary
effect in the electrical process. The evolution of semicir-
cle at lower frequency indicates grain boundary relaxation
mechanism; whereas the emergence of semi-circular arcs at
higher frequency shows grain relaxation in polycrystalline
ceramics. Similar behaviour was reported by Sindhu et al.
for the ­Ba0.9Ca0.1Ti1-xZrxO3 (x = 0.05) sample [58].
In the present study, all prepared ceramic samples exhibit
the evolution of the second semicircle which could be attrib-
uted to the beginning of the grain boundary effect in the
samples.
13
576 
Page 14 of 17
(a)
(c)
Fig. 11  (a–d) Temperature dielectric constant and dielectric loss tangent with temperature for all-ceramic samples
In the Nyquist plot, the intercept at the real axis of a semi-
circular arc indicates the resistance of the prepared sample.
As the temperature increases from 533 to 563 K, the inter-
cept position for all samples shifts toward the origin which
exhibits a decrease in resistivity. This reduction in resistivity
could be due to the thermally excited conduction mechanism
which is evidence of the NCTR behaviour of the material
[59].
The centre of these arcs lies below the real impedance
axis because of the statistical distribution of relaxation
times. The depression of the semicircle further can be cor-
related with the non-Debye type of relaxation. The semi-cir-
cular arc of the Nyquist plot indicates type of the relaxation
process and hence total time, the relaxation process time is
13
S. Rani et al.
(b)
(d)
more if the arc is fully semicircle. Hence, the impedance of
BFO was observed to reduce with increasing doping concen-
tration of Er (x = 0.10 to x = 0.20) which may be attributed
to grain orientation, grain boundary, atomic defects and Er
induced structural distortions. The maximum value of imagi-
nary part of impedance (Z") is 0.45MΩ for x = 0.10 sample
(Fig. 12b) which leads to a low leakage current [60].
2.12 Ferroelectric properties
Figure 13 depicts the variation of polarization with electric
field at room temperature for all ­Bi1-xErxFeO3 samples, at a
frequency of 50 Hz. The improvement in remnant polariza-
tion with Er-doped ­BiFeO3 ceramics could be attributed to
Crystal structure, magnetic and dielectric properties of Er‑doped ­BiFeO3 ceramics Page 15 of 17  576
(a)
(c)
Fig. 12  (a–d) Nyquist plots for Er-doped B
­ iFeO3 prepared samples at different temperatures
an increase in stereochemical activity of the Bi lone pair
caused by hybridization between the ­6s2 lone pair of elec-
trons and the 6p unoccupied orbital of ­Bi3+ ions, resulting
in a disturbance of the electron cloud and enhanced electric
polarization [61]. Despite the fact that the observed loops
were not saturated due to the presence of defects (oxygen-
related defect, leakage current defect, etc.). The calculated
values of remnant polarization for x = 0.05, 0.10, 0.15 and
0.20 are 0.013, 0.068, 0.041 and 0.007 μC/cm2, respectively.
Maximum polarization is observed for x = 0.10 in modified
bismuth ferrite ­Bi1-xErxFeO3. With the further addition of Er
content, polarization gets reduced which may be attributed
to structural transitions from rhombohedral to mixed phase
(rhombohedral plus orthorhombic).The addition of Er at the
Bi site suppresses defects due to the larger bond dissociation
(b)
(d)
energy of the Er-O bond as compared to the Bi–O bond,
resulting in an increase in polarisation in the doped sam-
ples [62]. Hence, the doping of Er at A-site significantly
improves ferroelectric properties.
3 Conclusions
Er-doped BFO ceramics have been successfully prepared
using a conventional solid-state reaction route. Structural,
magnetic, dielectric and ferroelectric analyses of synthesized
ceramics have been systematically investigated. The Riet-
veld refinement of XRD data of prepared samples confirmed
structural transformation from rhombohedral (R3c) to mixed
(R3c + Pnma) phase with 10 mol% Er-doping in ­BiFeO3.
13
576 
Page 16 of 17
Fig. 13  The variation of ferroe-
lectric polarization with electric
field for all ­Bi1-xErxFeO3 ceram-
ics, at a frequency of 50 Hz, at
room temperature
Morphological analysis shows that grains are nearly spheri-
cal in shape with homogeneous grain distribution. The crys-
talline nature of the prepared samples is confirmed by SAED
pattern. The investigation of Magnetic properties reveals a
significant improvement in remanent magnetization, which
facilitates Er substitution in the distortion of spin cycloid
structure along with an increase in the canting of spins of
­BiFeO3 and issued net magnetization by transforming anti-
ferromagnetic (Basic nature of BFO) to weak ferromagnetic
behaviour. Dielectric constant and dielectric loss follow
Maxwell–Wagner type dispersive behaviour. Impedance
spectroscopy indicates that Er substitution at Bi site in BFO,
enhanced the impedance in the sample (x = 0.10) which will
lead to a low leakage current. The prepared ceramics have
a negative temperature coefficient of resistance and non-
Debye relaxation behaviour. A well-developed P-E loop
for the Er doped samples shows the improvement of leak-
age behaviour in BFO which is attributed to a decrease of
oxygen vacancy and leakage current. Er, doping improves
magnetic and dielectric properties of pristine BFO, which
13
S. Rani et al.
indicated that these samples are promising candidates for
capacitive applications and data storage media.
Acknowledgements  The authors are grateful to DST, New Delhi for
providing XRD facility under FIST scheme (Grant No. SR/FST/PSI-
089/2005). One of the authors (Sonia Rani) is thankful to Haryana
State Council for Science and Technology (HSCST), Panchkula for
financial assistance. Authors thanks AIRF, Jawaharlal Nehru Univer-
sity, New Delhi, for access to the VSM facility.
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