J Mater Sci: Mater Electron
DOI 10.1007/s10854-016-4763-3
Scaling behavior of dynamic hysteresis in Bi3.15Nd0.85Ti3O12
ceramics
Peng Zhou1 • Zhiheng Mei1 • Chao Yang1 • Yajun Qi1 • Kun Liang1
Zhijun Ma1 • Tianjin Zhang1
Received: 15 December 2015 / Accepted: 31 March 2016
Ó Springer Science+Business Media New York 2016
Abstract The scaling behavior of dynamic hysteresis was
investigated in Bi3.15Nd0.85Ti3O12 bulk ceramics at a fre-
quency of 1–1000 Hz and an external electric field
amplitude of 79–221 kV/cm. The scaling behavior at low
amplitude (E0 B 114 kV/cm) takes the form of hAi /
f 0:013 E00:7 for low frequency (f B 200 Hz) and hAi /
f 0:013 E00:22 for high frequency (f [ 200 Hz), where hAi is
the area of hysteresis loop and f and E0 are frequency and
amplitude of external electric field, respectively. At high
amplitude (E0 [ 114 kV/cm), we obtain hAi / f 0:011 E01:163
at low frequency and hAi / f 0:015 E00:7 at high frequency.
At low E0, the contribution to the scaling relation mainly
results from reversible domain switching, while at high E0
reversible and irreversible domain switching concurrently
contribute to the scaling relation.
1 Introduction
Aurivillius bismuth-layered perovskites such as La- or Nd-
doped Bi4Ti3O12 have been widely studied, owing to their
lead-free composition, excellent retention, and fatigue free
behavior, making them excellent candidates for several
& Yajun Qi
yajun_qi@hotmail.com
& Tianjin Zhang
zhangtj@hubu.edu.cn
1
Hubei Collaborative Innovation Center for Advanced
Organic Chemical Materials, Key Laboratory of Green
Preparation and Application for Materials, Ministry of
Education, Department of Materials Science and
Engineering, Hubei University, Wuhan 430062,
People’s Republic of China
•
potential applications such as nonvolatile memory, electro-
optical devices, and microelectronic mechanical systems
[1]. The performance of ferroelectric materials employed
in these applications intrinsically relates to the dynamics of
domain reversal driven by a periodic electric field. There-
fore, it is of significant benefit to have a comprehensive
understanding of domain reversal dynamics in ferro-
electrics. The area of hysteresis loop of ferroelectric is the
energy dissipation during one cycle of the periodic electric
field. The shape and area of the loop have a good rela-
tionship with ferroelectric kinetics including domain
nucleation and growth, domain wall motion, and domain
rotation [2].
The scaling law hAi / f a E0b (where a and b are expo-
nents that depend on the dimensionality and symmetry of
system) of hysteresis loops in magnetic systems has been
intensively studied in the past several years. Rao et al. [3,
2 3
4] proposed the three-dimensional ð;2 Þ and ð;2 Þ models
with O(N) symmetry in the large N limit, and the scaling
law of low-f and high-f limits of the dynamic hysteresis can
be described for magnetic system as follows:
hAi / f 1=3 E0 ;
2=3
ð1Þ
hAi / f 1 E02 : ð2Þ
In fact, this model has been introduced to study ferro-
electric systems in detail [5–11]. Liu et al. [6] have
reported the scaling behavior in Bi3.15Nd0.85Ti3O12 (BNT)
2=3
thin film as hAi / f 1=3 E0 over the low frequency range
and hAi / f 2=3 E02 over the high frequency range, which is
close to the theoretical prediction [3]. However, BNT
ceramic is a three-dimensional bulk ferroelectric, and
several factors, such as the domain nucleation rate and the
velocity of domain wall motion, will result in different
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 J Mater Sci: Mater Electron

switching dynamics. Furthermore, depolarization effects,

such as domain walls, grain boundaries, space charges, and
immobile defects in bulk ceramics [5], will lead to some
differences in scaling behavior between thin films and bulk
ceramics. To the best of our knowledge, there is no report
of scaling behavior in bulk BNT ceramics. The purpose of
this work is to study the dynamic hysteresis behavior of
BNT ceramics.

2 Experimental methods

The BNT ceramic was fabricated by conventional solid-

state reaction. The detailed process has been reported
elsewhere [12]. The dynamic hysteresis (P–E) loops were
characterized at room temperature (*300 K) using a
standard ferroelectric test system (Radiant Premier II) with
f ranging from 1 to 1000 Hz and E0 from 79 to 221 kV/cm.
An electric field E(E0, f) with a standard bipolar triangular
waveform was applied to the sample using a Trek 609B
high voltage ac amplifier. The coercive field Ec and
remanent polarization Pr were obtained from the intersec-
tion with E-axis and P-axis of each hysteresis loop. The Ec
and Pr are defined [13] as Ec ¼ ðEcþ  Ec Þ=2 and
Fig. 1 Hysteresis loops at various E0 (a) and the dependence of loop
Pr ¼ ðPrþ  Pr Þ=2, where Ec?, Ec-, Pr?, Pr- are the area hAi on E0 at f = 200 Hz (b) (Color figure online)
positive coercive field, negative coercive field, positive
remanent polarization, and negative remanent polarization,
respectively.

3 Results and discussion

The hysteresis loops at different E0 with fixed f (200 Hz)

are shown in Fig. 1a. Clearly, at lower fields (79–114 kV/
cm), it exhibits slim loops. As E0 is increased, more elec-
tric field driving force is applied to electric dipoles in the
material [7], accompanied by an increase in hAi, Pr, and Ec
until well saturated loops are obtained. Figure 1b shows the
dependence of the loop area hAi on E0. The dotted lines
represent different linear relations at various E0 regions.
When E0 B 114 kV/cm, hAi increases faster than when
E0 [ 114 kV/cm, which implies that hAi is more sensitive
to E0 below 114 kV/cm. In fact, ln hAi - lnE0 curves at
different frequencies exhibit similar characteristics, as
shown in Fig. 1b, which implies that there may be different
scaling relations at lower and higher E0.
Figure 2 shows the hysteresis loops measured at various
f under a fixed E0 (121 kV/cm) and the dependence of loop
area hAi on f at low and high E0. It is evident that Pr
decreases while Ec increases as the frequency of the
Fig. 2 a Hysteresis loops at various f and E0 = 121 kV/cm, b the
applied electric field increases, as shown in Fig. 2a. It
dependence of loop area hAi on f at low field (E0 B 121 kV/cm, red
implies that as f increases, some ferroelectric domains arrow) and high field (E0 [ 121 kV/cm, black arrow) (Color
cannot catch up with the change of f, leading to the decline figure online)

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J Mater Sci: Mater Electron
of Pr. Furthermore, it has been reported that Ec can be
interpreted as an effective field necessary to overcome
restoring force (FR) and viscous force (FV) during domain
wall motions [14]. At lower f, the Ec will be small because
the velocity of domain wall motions is low and Fv can be
neglected. On the other hand, with increasing f, the speed
of domain wall movement increases, which will result in
the material becoming more viscous. Therefore, Fv and the
effective field needed to overcome the resistance of domain
switching will increase. As a consequence, the Ec will
increase though the amount of domain switching declines.
Figure 2b shows that hAi decreases as f increases at lower
E0 (E0 B 114 kV/cm), while there is a single peak at
higher E0 (E0 [ 114 kV/cm). Furthermore, the slopes for
the region of low E0 are different at low and high fre-
quency, which implies that there are different scaling
relations for distinct frequency range.
According to the above discussion, BNT bulk ceramic
exhibits different scaling behaviors at various electric field
ranges. As shown in Fig. 1b, the critical value that divides
the range into low and high E0 is determined to be 114 kV/
cm. To further investigate the scaling behavior of the bulk
ceramics, the data can be fitted with hAi / f a E0b , where
exponent a and b can be directly obtained from experi-
mental data [5]. By plotting hAi against f at fixed E0, we
obtain the exponent a, and exponent b can be obtained by
plotting hAi against E0 at fixed f. The results are shown in
Fig. 3 Scaling behavior of the
loop area hAi against f and E0
for BNT ceramics at room
temperature (300 K), a low
f and low E0, b low f and high
E0, c high f and low E0, and
d high f and high E0. The
dashed lines denote linear
relations fitted to the data in
each regime (Color
figure online)
Fig. 3 and the scaling relations were determined to be as
follows:
hAi / f 0:013 E00:7 for low f and low E0 ; ð3Þ
hAi / f 0:011 E01:163 for low f and high E0 ; ð4Þ
hAi / f 0:013 E00:22 for high f and low E0 ; ð5Þ
hAi / f 0:015 E00:7 for high f and high E0 : ð6Þ
The dotted lines in Fig. 3 represent linear fitting in terms of
hAi / f a E0b . All the data can be fitted within the measured
uncertainty (with R2 [ 0.98).
In the lower E0 region (E0 B 114 kV/cm), correspond-
ing to Eqs. (3), (5) and Fig. 3a, c, respectively, one can see
that the exponents of f for the low and high f range are the
same, while the exponent of E0 for the low f range is larger
than that of the high f range. The identical negative
exponents of f for the low and high f range indicate that the
domain reversal exhibits the same dependence on fre-
quency at low electric field range (E0 B 114 kV/cm). This
can be attributed to the reversible polarization process.
According to Bolten et al. [15, 16], ferroelectric hysteresis
is the consequence of reversible and irreversible polariza-
tion processes in response to an external periodic oscillat-
ing electric field. When the domain wall is moving inside a
local minimum of the random potential, there are only
reversible domain wall motions. Therefore, at lower
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electric fields (E0 B 114 kV/cm), most domain switching
is reversible and can catch up with the change of external
field, therefore, their dynamic behavior is not sensitive to
frequency. Hence, the f exponents are the same. The E0
exponent at low frequency is larger than that at high fre-
quency, which means that hAi grows more quickly with E0
at a low- than at a high-frequency range. It is easy to
understand that the amount of polarization flip that can
catch up with the varying of the external field at low fre-
quency is more than that at high frequency [7]. In other
words, there are more domain reversals at low than at high
frequency, which means there is more energy dissipation at
low frequency, therefore the exponent value of E0 for the
low frequency is larger than that for the high frequency.
In the high E0 region, the scaling behaviors correspond
to Eqs. (4), (6) and Fig. 3b, d, respectively. The depen-
dence of hAi on f shows a single peak pattern at a certain
value of E0 (E0 = 143 kV/cm), as shown in Fig. 2b. The
peak position shifts to high frequency with the increase of
E0 (not shown here). Many researchers have paid attention
to this interesting phenomenon [2, 6, 8–11, 17–19]. It is
believed that the frequency corresponding to the peak in
Fig. 2b is characteristic frequency, the reciprocal of which
is the characteristic time for domain switching [9]. When
the flip time of external field is larger than the character-
istic time, the process of domain switching can be com-
pleted. If the flip time is close to the characteristic time,
almost all domains can be reversed and the hysteresis area
reaches its maximum. Once the flip time is smaller than the
characteristic time, the velocity of domain switching can-
not catch up with the flip of external field. Consequently,
the area of hysteresis declines. One can see that the f ex-
ponent is positive at low frequency while negative at high
frequency, but in both cases the absolute values are almost
the same. This means that hAi decreases at high frequency
and increases at low frequency under a high electric field.
In this situation, for a certain value of E0 the domain
reversal can catch up with the varying of external electric
field at a lower frequency but not at a higher frequency;
hence the sign for the f exponent is different.
For the E0 exponent, the value is larger at low f than that
at high f, which indicates that the increase of E0 affects the
domain reversal less at high frequency than that at low
frequency. As discussed above, when E0 is above the
critical value, the polarization is a combination of rever-
sible and irreversible polarization processes in the BNT
ceramics [15, 16]. With increasing E0, more domains will
reverse and Pr and Ec will increase at the same time, as will
the loop area hAi, as depicted in Fig. 1. Hence, the E0
exponent is larger in Eq. (4) than in Eq. (3). Moreover, in
ceramics, domain walls, grain boundaries, space charges,
and immobile defects will lead to depolarizing effects [5].
Under a high electric field, as f increases continuously,
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J Mater Sci: Mater Electron
these depolarizing effects and the fact that some domains
cannot catch up with varying of the external field will lead
to a decrease of the E0 exponent, as described in Eqs. (4)
and (6).
It is noted that the scaling relations of BNT ceramic
deviate substantially from theoretical predictions [3, 4].
The above results give a relatively small value for the f
exponents, which reveals that the BNT ceramic is not
sensitive to the frequency of external field within the
measured frequency range and the main contribution to
different scaling relations comes from E0. In fact, the
scaling relations in ceramic are extremely different from its
1=3
thin film counterpart [6] (hAi / f 1=3 E0 over the low-fre-
quency range and hAi / f 2=3 E02 over the high-frequency
range). The different scaling behavior between thin films
and ceramics could be because of dimension dependence,
and more importantly, because of the size effects, the dif-
ferences of domain nucleation rate, and the velocity of
domain wall motion, which will result in different
switching dynamics.
There are three types of domain structures in bismuth-
layered perovskites, including the 180° and 90° domains
and the anti-phase boundary [20]. Different domain walls
are activated at different electric fields [21]. The 90°
domain switching needs a higher E0 field than the 180°
domain reversal does, because the 90° domain switching is
normally accompanied with mechanical strain [5, 22].
Therefore, in the low E0 region, the main contribution to
domain switching comes from the 180° domain reversal.
This may be the reason why the exponent E0 for Eqs. (3)
and (5) are smaller than for Eqs. (4) and (6), respectively. It
has been reported that the non-180° domain wall motion is
typically very heavily clamped in thin films [5, 21]. Hence,
the main switching contribution for BNT thin film comes
from 180° domain reversal, and the bulk and thin film BNTs
should theoretically have similar scaling behavior in the low
E0 region. In fact, the E0 exponent in the low f region for
BNT thin film [6] is close to the bulk in the low f and low E0
region. There are many depolarization effects in ceramics,
including domain walls, grain boundaries, space charges,
and immobile defects, which may act as a barrier to the
external field [5]. As a result of the depolarization field, the
hysteresis area must show a relatively weaker dependence
on the amplitude of E0 [5]. Therefore, the E0 exponent for
the BNT ceramic is much smaller than that of its thin film
counterpart in the high f region. Moreover, the depolariza-
tion effects act as a buffer to the polarization reversal
mechanism, and this type of buffer is stronger in bulk than
in thin film [5]. As a consequence, the dependence of hys-
teresis area on f will be weaker in bulk than that observed in
thin film, i.e., the absolute values of f exponents are smaller
in bulk than in thin film.
J Mater Sci: Mater Electron
4 Conclusions
In summary, dynamic hysteresis loops in BNT bulk
ceramics at low E0 can be described by hAi / f 0:013 E00:7 at
low frequency and hAi / f 0:013 E00:22 at high frequency,
while at high E0 they take the form of hAi / f 0:011 E01:163 at
low frequency and hAi / f 0:015 E00:7 at high frequency. The
scaling relations in BNT bulk ceramic are different from
the results in thin film counterpart and theoretical studies.
Such differences at low E0 cases can be partially ascribed
to the contributions from reversible domain switching. At a
higher frequency, the depolarization field is another
important factor influencing the frequency exponents in
ferroelectric ceramics.
Acknowledgments This work was supported by the National Sci-
ence Foundation of China (11204069, 51472078 and 11574073), and
the Science Foundation of the Education Bureau of Hubei Province,
China.
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