J Mater Sci: Mater Electron
DOI 10.1007/s10854-015-3143-8
Double hysteresis loop in BaTi12xHfxO3 ferroelectric ceramics
S. K. Das1 • B. K. Roul1
Received: 13 March 2015 / Accepted: 28 April 2015
Ó Springer Science+Business Media New York 2015
Abstract Hafnium doped barium titanate ceramics were
prepared by the conventional solid-state reaction method.
The structural, microstructure and ferroelectric properties
were analyzed with varying Hf concentration. It is found
that the crystal structure of the solid solution remains in
tetragonal phase with the decrease of tetragonality by in-
creasing of Hf ion concentration. The grain growth habit is
significantly depending upon Hf ion concentration. The
remnant polarization and coercive field is decreased along
with narrowing of the central portion of the ferroelectric
hysteresis loop with the increasing of Hf ion concentration.
The double hysteresis loops are associated with the onset of
an antiferroelectric order and it is increased with increasing
of Hf ion concentration.
1 Introduction
The insistences of modern technology stimulate the pace of
research on functional materials with enhanced or novel
properties. Ferroelectrics are the classes of functional ma-
terials, which have been extensively investigated for their
potential applications in different fronts of modern tech-
nology for their intrinsic and extrinsic properties [1–3].
Among ferroelectrics, much interest has been paid to the
perovskite BaTiO3. The remarkable versatility of the
BaTiO3 (BTO) structure leads to a huge range of properties
with diversified applications [4]. It is also chemically and
mechanically very stable [4]. The functionality of BTO is
& S. K. Das
sangramdas.das722@gmail.com
1
Institute of Materials Science, Planetarium Building, Acharya
Vihar, Bhubaneswar, Odisha, India
significantly enhanced with induction of new properties by
substitution of different ions at Ba and Ti site [4–6]. Room
temperature ferromagnetism has been obtained success-
fully in Co, Mn, and Fe doped BTO systems [6–8]. BTO
doped with oxygen vacancies becomes metallic above a
critical electron concentration (nc) of 1 9 1020 cm-3 [5].
Double polarization hysteresis loops are an exceptional
phenomenon in ferroelectrics, which are often observed in
antiferroelectric materials. The double hysteresis loops
have enriched the functionality of ferroelectric materials
and enable them to be used in diversified applications in-
clude high-energy storage capacitors, electrocaloric re-
frigerators, high-strain actuators and transducers [8–10].
Hence, the research on the double loop ferroelectric ma-
terials has of great scientific and technological significance.
Such features are exhibited by multilayered or superlattice
thin films, such as (1 - x) PbMg1/3Nb2/3O3–xPbTiO3
multilayers, SrTiO3/BaZrO3 and KTaO3/KNbO3 superlat-
tices [11]. However, it has been known that after aging, Fe
doped BTO also exhibit a similar type of hysteresis loop
[12] and such loops are obtained due to constriction of the
polarization by defects. There is little work reporting
similar characteristics in other doped BTO.
In this work, ceramic compositions of BaTi1-xHfxO3
(with, x = 0.05, 0.1, 0.15) were prepared through solid state
reaction route and the ferroelectric properties of the compo-
sitions are studied. The related mechanism for the formation
of double polarization hysteresis loop was also investigated.
2 Experimental methods
Ceramic samples were prepared by traditional solid-state
reaction method from stoichiometric quantities of car-
bonates and oxides of different constituents according to
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 J Mater Sci: Mater Electron

the general formula BaTi1-xHfxO3, where x = 0, 0.05,

(110)
0.1, and 0.15. High-purity (99.99 %) BaCO3, TiO2, and

(211)
HfO2 powders were taken and mixed thoroughly using

(200)
(002)
(111)
(100)

(210)
(201)

(220)
(202)

(310)
(301)

(311)
(110)
x=0.15
agate mortar and pestle. Mixed powders were calcined in
air at 950 °C for 24 h. Calcined powders were
Intensity (a.u.)

(002)

(211)
(200)
(111)
pressed into pellets, and pellets were sintered at 1300 °C

(310)
(100)

(220)
(202)

(301)
(210)
(201)

(311)
x=0.1
for 5 h.
(110)

Phase composition and crystal structure were investi-

(211)
(002)
(111)

(200)

(220)
(100)

(202)

(310)
(210)

(301)
(201)

(311)
gated by Bruker (D8) X-ray diffractometer (XRD) with
x=0.05
(110)

Cu Ka (k—1.5406 Å) radiation. XRD data refinements

(111)

(211) were done using Full Prof software package. Mi-

(200)
(100)

(002)

(220)

(310)
(202)

(301)
(210)

(212)

(311)
crostructure was observed by EVO-60 (ZEISS) scanning

(221)
(201)

x=0
electron microscopy (SEM). Room temperature
20 30 40 50 60 70 80 ferroelectric characterizations were done at 1 kHz
2θ (degree) with ferroelectric loop tracer (Precision Premier-II,
Fig. 1 X-ray diffraction (XRD) patterns of BaTi1-xHfxO3 (with,
Radiant).
x = 0, 0.05, 0.1, and 0.15) ceramic samples

Fig. 2 Rietveld refinement of a BaTiO3, b BaTi0.95Hf0.05O3, c BaTi0.9Hf0.1O3, and d BaTi0.85Hf0.15O3 ceramic samples

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J Mater Sci: Mater Electron

Table 1 Rietveld refinement results of BaTi1-xHfxO3 (with, x = 0, 0.05, 0.1, and 0.15) ceramic samples
Refined parameters BaTiO3 BaTi0.95Hf0.05O3 BaTi0.9Hf0.1O3 BaTi0.85Hf0.15O3

a (Å) 3.996 3.998 3.999 4.002

c (Å) 4.021 4.020 4.018 4.016
c/a 1.0062 1.0055 1.0047 1.0034
Space group P4mm P4mm P4mm P4mm
Volume (Å3) 64.207 64.255 64.256 64.32
R-pattern (Rp) 0.267 0.268 0.266 0.266
R-weighted pattern (Rwp) 0.273 0.274 0.272 0.271
Rwp expected (Rexp) 0.227 0.228 0.227 0.229
R-structure factor (RF) 0.0135 0.0138 0.0136 0.0134
Bragg R factor 0.0129 0.0131 0.013 0.0133
S (goodness-of-fit) 1.202 1.201 1.198 1.183
h i n o1=2
Here, Rp ¼ Rfyi ðoÞ  yi ðcÞg=Ryi ðoÞ, Rwp ¼ Rwi fyi ðoÞ  yi ðcÞg2 =Rwi yi ðoÞ2 , Rexp ¼ ðN  PÞ=Rwi yi ðoÞ2 ; S ¼ Rwp =Rexp . yi(o) and
yi(c) are observed and calculated intensities at profile point i, respectively and wi is the weight for each step i. N and P are number of
experimental observations and the number of fitting parameters

3 Results and discussion microstructure. The approximate grain size of BTO is in

The X-ray diffraction patterns of the composition
BaTi1-xHfxO3 (with, x = 0, 0.05, 0.1, and 0.15) are shown
in Fig. 1. All samples exhibit single tetragonal structure
(JCPDS file no. 83-1880) and no second phase is observed
within the apparatus resolution. However, a very weak
diffraction peak near 2H & 28° is also visible in Fig. 1. In
general, in X-ray diffraction patterns of BTO, the reflection
visible near 2H & 28° is corresponding to the reflection of
Ba2TiO4 [13]. As the intensity of the peak near 2H & 28°
is very feeble, there may be presence of very few fractions
of Ba2TiO4 in the composition BaTi1-xHfxO3 [13]. In ad-
dition to above, the diffraction peaks of doped samples are
also systematic shift to the lower angle side with increase
in Hf doping concentration. It implies that Hf ions have
entered the unit cell with maintaining the perovskite
structure. Figure 2 shows the Reitveld refinements of the
composition BaTi1-xHfxO3 (with, x = 0, 0.05, 0.1, and
0.15) and the results of refinements are shown in Table 1.
From Table 1, it is inferred that the degree of tetragonality
(c/a) is decreased with increasing of Hf concentration.
Hf4? ions are substituted for Ti4? ions on the B sites of the
BTO lattice and the ionic radius of Hf4? (0.079 nm) is
larger than that of Ti4? (0.068 nm) [14]. Hence, the te-
tragonality of BTO is decreased with increasing of Hf ions
concentration.
Figure 3 shows the SEM micrographs of the compo-
sitions BaTi1-xHfxO3 (with, x = 0, 0.05, 0.1, and 0.15)
sintered at the same conditions. It can be seen that the
grain size was decisively affected by the Hf concentration.
BTO sintered sample shows small grains with uniform
between 200 and 300 nm. On increasing the concentration
of Hf to 0.05, well developed grains are observed. In the
composition BaTi0.95Hf0.05O3, enlarged grain growth with
herribone and lamellar shaped grains can be clearly seen
from Fig. 3b. Spiral shaped grain growths are also ob-
served. Interlinking between grains is also noticed. The
average grain size is around 5–7 lm. It is known that
spiral growth usually takes place during solution growth
or melt growth of single crystal materials [15]. This is a
grain growth mechanism is related to the packing atoms
on the steps of a screw dislocation [15]. Mass transport for
such a step process cannot be accounted for the usual
mechanism of sintering by fusion of adjacent grains.
There should be an initial partial melting of the grains
where the nucleation occurs and consequently, mass
transport necessary for this process takes place by the
diffusion of ions to the growing steps through the fluid
phase and as a result of which such grain growth is oc-
curred. However, for the composition x = 0.1 (Fig. 3c),
non-uniform microstructure with bimodal grain distribu-
tions are observed. Larger grains coexist with the smaller
and with a certain amount of intergranular pores. In-
ter/transgranular fractures are also seen. The degree of
transgranular fracture tended to predominantly occur in
large grains (as shown in the inset of Fig. 3c). It indicates
that large grains were weaker than smaller ones [16].
Grain growth was inhibited as compared to x = 0.05. In
case of x = 0.15 composition, small grains were seen as
compared to other doped compositions. The diminishing
of grain growth for the compositions BaTi0.85Hf0.15O3
may be due to the reduction in the mobility of the grain

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Fig. 3 SEM images of BaTi1-xHfxO3 (where, x = 0, 0.05, 0.1, and 0.15) ceramic samples sintered at 1300 °C for 5 h
boundary. Thus, the mass transportation was weakened
after the addition of Hf.
Figure 4 shows the P–E loops the composition
BaTi1-xHfxO3 (with, x = 0, 0.05, 0.1, and 0.15) at room
temperature. BTO shows the typical ferroelectric hysteresis
loop with remnant polarization (Pr) value of 5.1 lC/cm2
and coercive field (Ec) of 2.1 kV/cm. However, in case of
Hf doped BTO, pinched double hysteresis loop has been
observed, in spite of the obvious remnant polarization. In
general, a pinched double hysteresis loop is a typical
characteristic of antiferroelectric materials [17]. With in-
creasing of Hf doping concentration, narrower P–E loop
with further decreased Pr and Ec is observed. It means that
the ferroelectric order tends to disappear and the antifer-
roelectric order tends to appear [10]. In other words, the
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J Mater Sci: Mater Electron
ferroelectric and antiferroelectric orders coexist on this
system [10]. The reduced Pr values also indicated the
higher abundance of the antiferroelectric state as a result of
the relative decrease in the volume fraction of the ferro-
electric state [10]. Increasing of Hf concentration leads to
the weakening of ferroelectric order and enhanced anti-
ferroelectric order.
In general, a bulk ferroelectric material with a low-en-
ergy alternative antipolar phase could be driven to anti-
ferroelectric order [18] in which the depolarization field
associated with any uncompensated polarization along the
normal would tend to suppress the formation of a single-
domain [18] and the gradual change of domain wall con-
figuration towards more energetically stable equilibrium
states [19]. This process is also affected by mechanical and
J Mater Sci: Mater Electron

Fig. 4 Room temperature P*E 8

loops of a BaTiO3, 20 (a) (b)
b BaTi0.95Hf0.05O3, 6
c BaTi0.9Hf0.1O3, and 15
d BaTi0.85Hf0.15O3 ceramic 4
samples 10

Polarization ( C/cm )

Polarization ( C/cm )
2

2
2
5

0 0

-5 -2

-10 -4

-15
-6
-20
-8
-15 -10 -5 0 5 10 15 -20 -15 -10 -5 0 5 10 15 20
Electric field (kV/cm) Electric field (kV/cm)

10
(c) 8 (d)
8
6
6

4 4
Polarization ( C/cm )
2

Polarization ( C/cm )
2
2 2

0 0

-2 -2

-4
-4
-6
-6
-8
-8
-10
-30 -20 -10 0 10 20 30 -20 -15 -10 -5 0 5 10 15 20
Electric field (kV/cm) Electric field (kV/cm)

electrical stresses, electric and anisotropic elastic defects
(associated with lattice distortions due to the presence of
vacancies or substitutions with atoms of different size)
[19]. For domain wall stabilization, an internal bias field is
built-up and it acts as additional coercive fields in ceramics
[19]. As a result of which an energy lowering antiferro-
electric order is obtained.
In our case, Hf is substituted at Ti site and the ionic
radius of Hf is larger than Ti. This tends to elongate the
distance between off center Ti–O dipoles and thus weak-
ening the correlation between them [20]. In addition to the
above, the mismatch in the size of Ti and Hf ions causes
substitutional distortion of the oxygen octahedral and it
also leads to give raise a local electric and strain field [20].
These local fields are usually random in nature and the
coupling between this local field and oxygen octahedron
tend to decrease the long-range ferroelectric domains and
the stability of the ferroelectric domain. It is likely to re-
duce the degree of ferroelectric order and thereby inducing
the transformation of the ferroelectric to the antiferro-
electric state.
4 Conclusions
In summary, we investigated the change in properties of
BaTi1-xHfxO3 ceramics with different concentrations of Hf.
From XRD, it is inferred that the degree of tetragonality (c/
a) is decreased with increasing of Hf concentration. The
addition of hafnium can significantly influence the grain
growth in the BTO ceramics and the grain size begins to
increase and then decrease with increasing of Hf ion con-
centration. The remnant polarization and coercive field is
decreased simultaneously along with the arising of the

123

pinched double hysteresis loop with the increasing of Hf ion
concentration. The obtaining of pinched double hysteresis
loop indicates the appearance of antiferroelectric order and
that antiferroelectric order is enhanced with increasing of Hf
ion concentration. This work may provide a new insight for
obtaining of energy storage devices.
Acknowledgments Author S.K. Das acknowledges to the Director,
Institute of Materials Science, Bhubaneswar for providing ex-
perimental facilities to carry out this research work and CRF, IIT-
Kharagpur for SEM measurements. The authors also acknowledge to
Department of Physics, Utkal University, Bhubaneswar for carrying
out XRD measurements.
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