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Unique dielectric tunability of
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Unique dielectric tunability of Pb0.99[(Zr0.6Sn0.4)0.94Ti0.06]0.98Nb0.02O3
antiferroelectric ceramics
Lei Li, Matjaž Spreitzer, Danilo Suvorov, and Xiang Ming Chen

Citation: Journal of Applied Physics 120, 074109 (2016); doi: 10.1063/1.4961424
View online: http://dx.doi.org/10.1063/1.4961424
View Table of Contents: http://scitation.aip.org/content/aip/journal/jap/120/7?ver=pdfcov
Published by the AIP Publishing

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Unique dielectric tunability of Pb 0.99[(Zr 0.6Sn0.4)0.94Ti0.06]0.98Nb0.02O3
antiferroelectric ceramics
LeiLi,1,a)Matja /C20zSpreitzer,2Danilo Suvorov,2and Xiang Ming Chen1
1Laboratory of Dielectric Materials, Department of Materials Science and Engineering, Zhejiang University,
Hangzhou 310027, China
2Jo/C20zef Stefan Institute, Jamova 39, SI-1000 Ljubljana, Slovenia
(Received 29 April 2016; accepted 8 August 2016; published online 19 August 2016)
The tunable dielectric properties of Pb 0.99[(Zr 0.6Sn0.4)0.94Ti0.06]0.98Nb0.02O3antiferroelectric
ceramics were investigated, and high relative tunability of 49% was obtained at 25/C14C under a low
bias electric field of 50 kV/cm. Abrupt changes and a significant hysteresis in dielectric constant
and dielectric loss against bias electric field were observed, which are very different from the
previously reported antiferroelectric materials. The unique dielectric tunability is attributed to thesquare-shaped double hysteresis loop and indicates the possible applications in some special tun-
able devices, such as an electrically-controlled switch. Pb
0.99[(Zr 0.6Sn0.4)0.94Ti0.06]0.98Nb0.02O3
ceramics also exhibit unique dielectric tunability at /C05/C14C. Abrupt changes in dielectric constant
and dielectric loss were observed when the bias electric field increased to 31 kV/cm for the fresh
sample, which is similar to the antiferroelectric-like dielectric tunability at 25/C14C. However, the
dielectric tunability was ferroelectric-like in the following measurement. This response is consis-tent with the hysteresis loop and can be explained by the electric field-assisted irreversible
antiferroelectric-ferroelectric phase transition. Published by AIP Publishing.
[http://dx.doi.org/10.1063/1.4961424 ]
I. INTRODUCTION
In the past decades, electrically tunable dielectric materi-
als have attracted much attention due to their potential appli-cations in various tunable devices, such as tunable oscillators
and filters, phase shifters, and varactors.
1–4Ferroelectric mate-
rials, which are characterized by the reversible spontaneouspolarization and polarization-electric field hysteresis loop,
5
are the most important tunable dielectric materials.1–4The
dielectric constant of a ferroelectric material usually decreaseswith increasing the bias electric field, as well as the dielectric
loss. Both the hysteresis loop and dielectric tunability of ferro-
electric materials have been understood deeply till now. As ananalogue of ferroelectrics, the antiferroelectric materials can
be switched between ferroelectric and antiferroelectric states
by applying and removing an electric field, so that a doublehysteresis loop can be observed.
5As the most important way
for judging the antiferroelectricity, the double hysteresis loop
has been measured extensively for antiferroelectric materials.
However, their dielectric tunability has not attracted enough
attention.
In the few references on the dielectric tunability of antifer-
roelectric materials, the dielectric constant and the dielectricloss increase with increasing the bias electric field when the
material is in antiferroelectric state, and they decrease gradu-
ally when the electric field exc eeds the antiferroelectric-
ferroelectric transition electric field.
6–12It should be noted that
all the reported antiferroelectric materials in these references
are of “slanted” double hysteresis loops.13So far the dielectric
tunable properties of antiferroel ectric materials with a “square”
double hysteresis loop have not been investigated yet,13forwhich quite different results are expected. In the present work,
therefore, Pb 0.99[(Zr 0.6Sn0.4)0.94Ti0.06]0.98Nb0.02O3antiferro-
electric ceramics with square double hysteresis loop at roomtemperature
14,15were prepared, and the dielectric tunable prop-
erties were characterized as well as the hysteresis loop.
II. EXPERIMENTAL PROCEDURES
Pb0.99[(Zr 0.6Sn0.4)0.94Ti0.06]0.98Nb0.02O3ceramics were
prepared by a standard solid state reaction method. Raw
powders of PbO (99%), Nb 2O5(99.99%), ZrO 2(99%), SnO 2
(99.5%), and TiO 2(99.5%) were weighed and mixed by ball
milling in ethanol media, and then dried. The mixed powders
were calcined at 900/C14C for 3 h to synthesize the single-
phase powder. The powder was ball-milled again, mixed
with PVA solution, and pressed into pellets under the pres-
sure of 100 MPa. The pellets were sintered at 1325/C14C for 3 h
to obtain the dense ceramics. The crystal structure was iden-
tified by powder X-ray diffraction (XRD) with Cu Karadia-
tion (Rigaku D/max 2550/PC, Rigaku Co., Tokyo, Japan).
Scanning electron microscopy (SEM, S-3400, Hitachi,
Tokyo, Japan) was used to observe the microstructure on thefractured surface. Discs with the thickness of 0.5 mm were
sputtered with gold as electrodes. The dielectric tunable
properties were measured at 100 kHz by an LCR meter(4284A, Agilent Technologies, Inc., Santa Clara, CA) with a
10 kV amplifier and homemade high-voltage non-tunable
bias tees. The maximum bias electric field was 50 kV/cm,
and the dielectric tunability measurement was conducted
with three linear half cycles (0 !50!0, 0!/C0 50!0,
and 0!50!0 kV/cm). The hysteresis loops were mea-
sured at 1 Hz by a ferroelectric test system (RT Premier II,
Radiant Technology Inc., Albuquerque, NM) using a bipolar
a)Electronic mail: zjulilei@zju.edu.cn
0021-8979/2016/120(7)/074109/5/$30.00 Published by AIP Publishing. 120, 074109-1JOURNAL OF APPLIED PHYSICS 120, 074109 (2016)
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electric field with a triangular waveform and the maximum
value of 50 kV/cm. All the dielectric tunability and hystere-
sis loop measurements were conducted on the fresh samplesat 25 and /C05
/C14C.
III. RESULTS AND DISCUSSION
Figure 1shows the room-temperature XRD pattern of
Pb0.99[(Zr 0.6Sn0.4)0.94Ti0.06]0.98Nb0.02O3ceramics sintered
at 1325/C14C. The peaks are indexed according to Ref. 16,
and the antiferroelectric phase with tetragonal structure is
revealed.14,16The SEM image on the fractured surface is
shown in the inset of Fig. 1, indicating the dense and uniform
microstructure with the average grain size of several micro-
meters. The phase constitution, dielectric properties, and
hysteresis loop are insensitive to the sintering temperatureover the range of 1300–1350
/C14C, so only the properties of the
ceramics sintered at 1325/C14C with the highest density will be
discussed in the following.
Figure 2shows the dielectric constant and the dielectric
loss of Pb 0.99[(Zr 0.6Sn0.4)0.94Ti0.06]0.98Nb0.02O3ceramics at
25/C14C as functions of bias electric field. The properties show
very hysteretic curves against bias electric field. Withincreasing the bias electric field from 0 in step 1 of the firsthalf cycle, the dielectric constant and the dielectric loss first
increase gradually, which has been observed for the antiferro-
electric materials in the antiferroelectric state.
6–11However,
when the electric field reaches 35 kV/cm, the dielectric con-
stant drops, while the dielectric loss first increases rapidly and
then drops. The change can be explained by the electric field-induced antiferroelectric-ferroelectric phase transition, whichis also indicated from the polarization-electric field hysteresis
loop in Fig. 3. The sample is in ferroelectric state under higher
electric field, so the dielectric constant and the dielectric lossdecrease gradually with a further increase of the bias electric
field up to 50 kV/cm in step 1 of the first half cycle, just as
the ferroelectric materials behave.
1–3Pb0.99[(Zr 0.6Sn0.4)0.94
Ti0.06]0.98Nb0.02O3ceramics also exhibit similar tunable
dielectric properties to ferroelectric materials with decreasing
the bias electric field from 50 kV/cm down to 10 kV/cm instep 2 of the first half cycle (see Fig. 2), for which thedielectric constant and the dielectric loss increase gradually,
since the ferroelectricity is kept over this electric field range.
While a sudden increase in dielectric constant and a decrease
in dielectric loss are observed when the bias electric fielddecreases to about 7 kV/cm, which can be explained by
the phase transition from ferroelectric state back to antiferro-
electric state (see Fig. 3). In the following second and third
half cycles, the dielectric constant and the dielectric loss
exhibit a similar variation against bias electric field. The
antiferroelectric-ferroelectric transition fields in the second
FIG. 1. Room-temperature XRD pattern of Pb 0.99[(Zr 0.6Sn0.4)0.94Ti0.06]0.98
Nb0.02O3ceramics sintered at 1325/C14C. The inset shows the SEM image on
fractured surface.
FIG. 2. (a) Dielectric constant and (b) dielectric loss of Pb 0.99[(Zr 0.6Sn0.4)0.94
Ti0.06]0.98Nb0.02O3ceramics at 25/C14C as functions of bias electric field.
FIG. 3. Hysteresis loop of Pb 0.99[(Zr 0.6Sn0.4)0.94Ti0.06]0.98Nb0.02O3ceramics
at 25/C14C.074109-2 Li et al. J. Appl. Phys. 120, 074109 (2016)
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and third half cycles are almost the same (30 kV/cm), but they
are lower than that in the first half cycle, and this is also indi-
cated by the hysteresis loops with two cycles in Fig. 3.
Pb0.99[(Zr 0.6Sn0.4)0.94Ti0.06]0.98Nb0.02O3antiferroelectric
ceramics exhibit high relative dielectric tunability of 49% at
25/C14C when the bias electric field is only 50 kV/cm (from the
second and third half cycles in Fig. 2(a)). More importantly,
the above dielectric tunable properties are very different
from the reported antiferroelectric materials. The curves ofdielectric constant and dielectric loss against bias electric
field are very hysteretic for the present Pb
0.99[(Zr 0.6Sn0.4)0.94
Ti0.06]0.98Nb0.02O3antiferroelectric ceramics, and the abrupt
changes in dielectric constant and dielectric loss can be
observed when the bias electric field changes to certain val-
ues. In comparison, the dielectric properties change moregradually with bias electric field, and the hysteresis is not
significant for the previously reported antiferroelectric mate-
rials.
6–11The differences can be related to the different
shapes of the polarization-electric field double hysteresis
loops. As shown in Fig. 3, the double hysteresis loop of the
present Pb 0.99[(Zr 0.6Sn0.4)0.94Ti0.06]0.98Nb0.02O3antiferro-
electric ceramics is square-shaped, for which a large differ-
ence between antiferroelectric-ferroelectric and ferroelectric-
antiferroelectric transition electric fields can be observed, aswell as the rapid changes of polarization near the transition
electric fields. It means that the antiferroelectric-ferroelectric
and ferroelectric-antiferroelectric phase transitions are suddenprocesses that occur under quite different electric fields,
which lead to the significant hysteresis and abrupt changes in
dielectric properties against bias electric field. In case the dou-ble hysteresis loop is slanted and slimmer for the previously
reported antiferroelectric materials, the antiferroelectric-
ferroelectric and ferroelectric-antiferroelectric transition elec-tric fields are nearer, and the electric field-induced transitions
are gradual rather than sudden processes,
6–11so that the
dielectric properties show less hysteresis and change gradu-ally with bias electric field. It should be noted that not the
rapid changes of polarization but the sudden electric field-
induced phase transitions between antiferroelectric and ferro-electric states are responsible for the abrupt changes in dielec-
tric constant and dielectric loss against bias electric field. In
fact, the abrupt change in dielectric constant has not beenobserved in the ferroelectric materials with square-shape hys-
teresis loop, for which the polarization changes rapidly when
the electric field is near to the coercive electric field.
1–4
Figure 4shows the details of the significant hysteresis
and abrupt change in dielectric constant for the Pb 0.99
[(Zr 0.6Sn0.4)0.94Ti0.06]0.98Nb0.02O3antiferroelectric ceramics
at 25/C14C (taken from steps 5 and 6 of the third half cycle in
Fig.2(a)). The dielectric constant drops from 646 at 29 kV/
cm (spot A in Fig. 4) to 363 at 30 kV/cm (spot B) in step 5
and increases from 431 at 8 kV/cm (spot C) to 588 at 6 kV/
cm (spot D) in step 6. The relative changes in dielectric con-
stant are as high as /C043.8% and 36.4% when the changes in
electric field are only 1 and /C02 kV/cm, respectively. This
characteristic has not been observed for other tunable materi-
als and is not suitable for normal practical applications, sincethe dielectric constant under a certain electric field is
strongly dependent on the electric field application history.However, it offers the possibility to tune the capacitance of
an electrically-tunable device greatly with a small change in
bias electric field. The unique tunable properties can also be
used for a special electrically-controlled capacitive switch.
The dielectric constants higher than 588.1 (spot D) and lower
than 430.7 (spot C) can be assumed as states 0 and 1 of the
switch, respectively. The switch is in state 0 initially with
zero bias electric field. When a bias electric field higher than
30 kV/cm (spot B) is applied, the state is switched into 1.
After that, only a much lower bias electric field slightly
higher than 8 kV/cm (spot C) is needed to keep state 1. This
advantage cannot be realized with other tunable materials
due to the absence of the abrupt changes and significant hys-
teresis in dielectric constant. The state can be switched backto 0 by removing the electric field.
It is reported that the antiferroelectric phase converts
to the ferroelectric phase when the temperature decreases
to about 0
/C14C for Pb 0.99[(Zr 0.6Sn0.4)0.94Ti0.06]0.98Nb0.02O3
ceramics,14so the dielectric tunability and the hysteresis
loop were also characterized at /C05/C14C for comparison.
Unique dielectric tunability was observed in step 1 of the
first half cycle, as shown in Fig. 5. With increasing the bias
electric field from 0, the dielectric constant and the dielectric
loss first increase gradually. When the electric field increases
to about 30 kV/cm, the dielectric constant drops, while the
dielectric loss increases dramatically and then drops. Such
behavior is similar to that at 25/C14C (see Fig. 2), indicating the
initial antiferroelectric state and the electric field-induced
antiferroelectric-ferroelectr ic phase transition. However, the
abrupt changes in dielectric constant and dielectric loss cannot
be observed again in the follo wing measurements, and the
dielectric tunability becomes typi cally ferroelectric-like rather
than antiferroelectric-like. The polarization-electric field mea-
surement at /C05/C14Ci nF i g . 6also indicates the antiferroelectric-
like hysteresis loop with the antife rroelectric-ferroelectric phase
transition in the first quarter cycle and the ferroele ctric-like hys-
teresis loop in the following measurement. The unique dielec-
tric tunability and the hysteresis loop of Pb 0.99[(Zr 0.6Sn0.4)0.94
Ti0.06]0.98Nb0.02O3ceramics at /C05/C14C can be explained by the
electric field-assisted antiferroel ectric-ferroelectric phase transi-
tion. According to Refs. 16and17, the electric field-induced
FIG. 4. Dielectric constant of Pb 0.99[(Zr 0.6Sn0.4)0.94Ti0.06]0.98Nb0.02O3
ceramics at 25/C14C as a function of bias electric field (taken from the third
half cycle of Fig. 2(a)).074109-3 Li et al. J. Appl. Phys. 120, 074109 (2016)
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antiferroelectric-ferroelectric phase transition can be divided
into electric field-forced and electric field-assisted transi-
tions, which are reversible and irreversible, respectively.For the first kind of phase transition, the antiferroelectric
phase is the stable phase in the initial state without applied
electric field. When the electric field is high enough, theferroelectric phase becomes the stable phase instead of the
antiferroelectric phase, so the electric field-forced antiferro-
electric-ferroelectric phase transition occurs. When the elec-tric field is removed, the antiferroelectric phase becomes the
stable phase again, so that the double hysteresis loop and the
antiferroelectric-like dielectric tunability can be observedduring the whole measurement, just as Pb
0.99[(Zr 0.6Sn0.4)0.94
Ti0.06]0.98Nb0.02O3ceramics behave at 25/C14C. For the elec-
tric field-assisted antiferroelectric-ferroelectric phase transi-tion, however, the antiferroelectric and the ferroelectricphases are the thermodynamically meta-stable and stablephases in the initial state, respectively. With the aid ofenough high electric field to overcome the thermodynamic
barrier, the meta-stable antiferroelectric phase converts to
the stable ferroelectric phase, so the antiferroelectric-likedielectric tunability and the hysteresis loop can be observedin the first step of the measurements only. However, whenthe electric field is removed, the reversed ferroelectric-antiferroelectric phase transition does not occur since theferroelectric phase is the stable phase in the initial state, sothat the ferroelectric-like rather than antiferroelectric-likedielectric tunability and hysteresis loop are observed in thefollowing measurements, as Pb
0.99[(Zr 0.6Sn0.4)0.94Ti0.06]0.98
Nb0.02O3ceramics behave at /C05/C14C.
IV. CONCLUSION
In summary, Pb 0.99[(Zr 0.6Sn0.4)0.94Ti0.06]0.98Nb0.02O3
antiferroelectric ceramics exhibit unique tunable dielectric
properties at 25/C14C comparing with other antiferroelectric
materials. High relative tunability of 49% was obtainedunder a low bias electric field of 50 kV/cm, indicating theapplicability of this material in electrically tunable devices,
especially for low-voltage operation. Abrupt changes and the
significant hysteresis in dielectric constant and dielectric lossagainst bias electric field were observed, which are attributedto the square-shaped double hysteresis loop. The uniquedielectric tunability makes it possible to tune the capacitanceof a tunable device greatly with a small change in electricfield, and also indicates the great potential of the antiferro-electric materials with square-shaped double hysteresis loopfor some special tunable applications, such as an electrically-controlled switch. Furthermore, antiferroelectric-like dielec-tric tunability and hysteresis loop were observed at /C05
/C14C
only in the first step, while they were ferroelectric-like inthe following measurements, which are due to the electricfield-assisted irreversible antiferroelectric-ferroelectric phasetransition.
ACKNOWLEDGMENTS
The present work was supported by National Natural
Science Foundation of China under Grant Nos. 51332006and 11274270, and Slovenian Research Agency throughProgramme No. P2-0091.
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