Ferroelectrics

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Structure, dielectric and piezoelectric properties of

the BiScO3-PbTiO3-PbMg1/3Nb2/3O3 ceramics

M. V. Talanov, A. A. Bush, K. E. Kamentsev, V. P. Sirotinkin & A. G. Segalla

To cite this article: M. V. Talanov, A. A. Bush, K. E. Kamentsev, V. P. Sirotinkin & A. G. Segalla

(2019) Structure, dielectric and piezoelectric properties of the BiScO3-PbTiO3-PbMg1/3Nb2/3O3
ceramics, Ferroelectrics, 538:1, 105-112, DOI: 10.1080/00150193.2019.1569992

To link to this article: https://doi.org/10.1080/00150193.2019.1569992

Published online: 17 May 2019.

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FERROELECTRICS
2019, VOL. 538, 105–112
https://doi.org/10.1080/00150193.2019.1569992

Structure, dielectric and piezoelectric properties of the

BiScO3-PbTiO3-PbMg1/3Nb2/3O3 ceramics
M. V. Talanova
, A. A. Bushb, K. E. Kamentsevb, V. P. Sirotinkinb, and A. G. Segallac
a
Research Institute of Physics Southern Federal University, Rostov-on-Don, Russia; bResearch Institute of
Solid State Electronics Materials Moscow Technological University (MIREA), Moscow, Russia; cResearch
and Production Complex No 3 “ELPA” Research Institute, Zelenograd, Russia

ABSTRACT ARTICLE HISTORY

The structure, dielectric and piezoelectric properties of (1-2x) BiScO3- Received 14 May 2018
xPbTiO3-xPbMg1/3Nb2/3O3 ceramics with x ¼ 0.30-0.46 were investi- Accepted 31 October 2018
gated. A nonmonotonic U-shape behavior of the concentration
KEYWORDS
dependence of the Curie temperature was observed. It was shown that
Relaxor ferroelectrics;
the values of the piezoelectric coefficient d33 of the solid solution with morphotropic phase
x ¼ 0.42 exceed those for the known BiScO3-PbTiO3-based ceramics. A boundary; tricritical point;
conclusion was made about the possibility of application of these solid phase diagram;
solutions in piezoelectric devices which operate at room temperature. dielectric properties

1. Introduction
The relaxor ferroelectrics  PbTiO3 (PT) solid solutions are of interest for practical
applications in actuators, transducers and other piezoelectric devices due to their high
piezoelectric responses [1–5]. However the low Curie temperature (Tm 393-423 K) of
the relaxor-PT solid solutions seriously limits the range of their potential applications.
The solid solutions of the system (1-x)BiScO3(BS) xPT near the morphotropic phase
boundary (MPB) (x ¼ 0.64) [6] demonstrate a combination of high piezoelectric coeffi-
cients (d33>450 pC/N) and high Curie temperature (Tm > 723 K). Design of multicom-
ponent systems is the most effective way to connect the merits of various binary
systems, in particular, the highest piezoelectric response of relaxor-PT systems, and high
Tm of the BS-PT system. There are a lot of multicomponent solid solutions between BS,
PT and different relaxor ferroelectrics: PbZn1/3Nb2/3O3 [7, 8], Pb(Sc1/2Nb1/2)O3 [9], (Ba,
Sr)TiO3 [10], Pb(Ni1/3Nb2/3)O3 [11], (Na0.5Bi0.5)TiO3 [12], PbMg1/3Nb2/3O3(PMN)
[13–15]. In our last paper the structure-property relations were established in the
(1-2x) BS-xPT-xPMN system [15]. It was found the existence of the MPBs between the
rhombohedral and tetragonal phases at x ¼ 0.42 and a crossover from the nonergodic
relaxor state to the ferroelectric one at the same x value. In addition, high values of the
piezoelectric coefficients (d33¼509 pC/N, d31 ¼ -178 pC/N, dh ¼ 153 pC/N) were observed
near the MPB. Thus, the goal of this work was a detailed study of the dielectric and
piezoelectric properties of the (1-2x) BS-xPT-xPMN ceramics, as well as, their correlation
with the crystal structure.

Corresponding author. E-mail: tmikle-man@mail.ru

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106 M. TALANOV ET AL.

Figure 1. Concentration dependences of unit cell parameters in rhombohedral and tetragonal phases
(a) and the Goldschmidt tolerance factor of (1-2x) BS-xPT-xPMN solid solutions. MPB region is indi-
cated by a shaded area.

2. Experimental Methods
Based on the results of preliminary studies [15–17], we used the
(1-2x)BiScO3 - xPbTiO3 - xPb(Mg1/3Nb2/3)O3 ((1-2x)BS - xPT - xPMN) solid solutions
with 0.30  x  0.46 for detailed study. Ceramic samples were obtained by solid-phase
synthesis and they were sintered according to the traditional ceramic technology.
Technical details of sample preparation are described in [15]. The relative density of
sintered ceramics was more than 95% of the x-ray density. Samples as disks with a
diameter of 10 mm and a thickness of 0.5 mm were formed. A silver paste was deposited
on their surfaces. The polarization of the samples was performed in polyethyl siloxane
liquid at 373 K under applied electric field (E ¼ 25 kV/cm, exposure of 15 min) with
subsequent cooling to room temperature under the electric field.
The crystal structure of sintered simples was analyzed by X-ray diffraction technique
using DRON-3 and Rigaku Ultima IV diffractometers with a D/teX detector and Cu Ka
radiation. Relative dielectric permittivity (e/e0) and loss tangent (tan d) were measured
with a help of the Motech MT-4090 LCR meter at temperatures 300-700 K and frequen-
cies (f) 0.1-1000 kHz of the measuring field with the amplitude 1 V. The piezoelectric
coefficient d33 was measured by a Berlincourt-type d33 meter.

3. Results and Discussion

Figure 1a shows the concentration dependences of the unit cell parameters of the solid
solutions under study. At x > 0.38 a morphotropic phase transition from the rhombohe-
dral phase to the tetragonal phase takes place. In the simplest way, similar structural
changes can be described using the Goldschmidt tolerance factor (t) (Fig. 1b). It is
believed that cubic or tetragonal symmetry takes place at t > 1, and rhombohedral,
monoclinic or orthorhombic distortions take place when t < 1. Both the replacement of
Pb2þ ions by Bi3þ ions in the A perovskite sublattice, and the substitution of Ti4þ,
Mg2þ, Nb5þ ions by Sc3þ ions in B-sublattice leads to a decrease in t.
A detailed study of the X-ray diffraction patterns by the Rietveld method was carried
out in order to establish the symmetry of the phases near the MPB [15, 18]. The best
quality agreement between observed and calculated profiles was achieved when
 FERROELECTRICS 107

considering model with the coexistence of monoclinic Cm and cubic Pm-3m phases. It
should be noted that the monoclinic phase with space group Cm was previously
detected both in PMN-PT solid solutions [19–21] and in BS-PT solid solutions [22, 23].
Therefore, the existence of this phase in ternary solid solutions near the MPB was quite
expected. It is believed that the intermediate monoclinic phases favor the polarization
rotation mechanism and, as a consequence, enhance the piezoelectric properties [24].
The e/e0 (T) and tan d(T) dependences of the studied ceramics measured on cooling
at various f are shown in Fig. 2. As x increases, the shape of the e/e0 and tan d tempera-
ture dependences varies from diffused to sharp (at x ¼ 0.46). Earlier, we estimated the
diffusion degree of the ferroelectric phase transition and carried out a fitting of Tm (f)
dependences using the Vogel-Fulcher law [15]. As a result, it was established that for
x > 0.42 a crossover between the relaxor ferroelectric and the normal ferroelec-
tric occurs.
The behavior of the Tm(x) dependence, which undergoes a diffuse minimum at x 
0.34, is unusual (Fig. 3). The nonmonotonic U-shape behavior of the dependences
Tm(x) was observed previously for Bi/Pb-containing compounds, in particular, for BS-
PT solid solutions [25, 26]. Using density functional theory, it was shown that the Tm
value of such materials is well correlated with computed polarization magnitudes [27].
In addition, the correlation between Tm value and calculated (from neutron powder dif-
fraction data) spontaneous polarization was experimentally detected in BS-PT solid solu-
tions [26]. It should be noted that in this work only tetragonal solid solutions were
considered. The minimum of the Tm(x) dependence is formed in the rhombohedral
region of the phase diagram in the case of solid solutions under study. Another example
of the similar Tm(x) dependence is (1-x)Pb(Sc2/3W1/3)O3 (PSW) -xPbTiO3 solid solu-
tions [28]. Based on the results of complex experimental and theoretical studies, the
authors conclude that the order-disorder processes play a key role in the formation of
the Tm minimum with increasing PT concentration. The contribution of ferroelectrically
active Ti4þ and W6þ cations to the dielectric response may depends on the degree of
ordering in the B sublattice, that affects the Tm(x) dependence. In the case of the cer-
amic under study, the B-position of the perovskite structure is occupied by heterovalent
ions with a significant size mismatch: Sc3þ¼0.745 Å, Nb5þ¼0.640 Å, Ti4þ¼0.605 Å,
Mg2þ¼0.720 Å, which, in principle, could contribute to the emergence of an ordered
(or partially ordered state) [29–32]. It is interesting to note the observed correlation
between the concentration dependences of Tm and inverse D parameter (D ¼ Tm2-Tm1
where Tm1, Tm2 are the Tm obtained at f1¼1 kHz and f2 ¼100 kHz) (Fig. 3), which char-
acterizes the degree of the system heterogeneity. A detailed diffraction study of solid
solutions from the rhombohedral region of the phase diagram is required to establish
the origin of the unusual Tm(x) behavior.
Figure 4 shows a d33-Tm diagram constructed from the literature data on the best
compositions of BS-PT based systems [6–12, 15, 33–38]. It is evident that in most cases
a decrease in the d33 and/or Tm values is observed with addition of new components.
The overall trend is a decrease in the d33 with an increase in the Tm within one ceram-
ics system, although there are exceptions (BS-PT-BST, BS-PT-PSN and some others).
The maximum values of the d33 (509 pC/N) were found in studied solid solutions near
MPB with x ¼ 0.42 [15]. The reasons for the amplification of the piezoelectric response
108 M. TALANOV ET AL.

Figure 2. e/e0 (T) and tan d(T) dependences measured at various f on cooling of (1-2x) BS-xPT-xPMN
ceramics. The Vogel-Fulcher temperature is shown in dotted lines.
 FERROELECTRICS 109

Figure 3. Concentration dependences of D and Tm of (1-2x) BS-xPT-xPMN ceramics. MPB region is

indicated by a shaded area.

Figure 4. d33-Tm diagram constructed from the literature data on the best compositions of BS-PT
based systems [6–12, 15, 33–38]. The composition of the BS-PT with x ¼ 0.64 [6] is indicated by dot-
ted lines. The following abbreviations are used: Pb(Ni1/3Nb2/3)O3 (PNN), (K0.5Bi0.5)TiO3 (KBT),
(K0.5Na0.5)NbO3 (KNN), (Ba,Sr)TiO3 (BST), Pb(Zn1/3Nb2/3)O3 (PZN), Bi(Mg1/2Ti1/2)O3 (BMT), Pb(Mn1/3Nb2/
3)O3 (PMnN), Pb(Sc1/2Nb1/2)O3 (PSN), (Na0.5Bi0.5)TiO3 (NBT).

of these solid solutions can be related both with extrinsic contributions (increasing the
number of domain configurations, minimizing the domain structure, etc.) and with
intrinsic contributions (polarization rotation, proximity of the assumed tricritical point,
etc.). As a result, the studied solid solution studied is superior to the BS-PT ceramics in
the value of d33, but inferior to them in Tm. Thus, it can be concluded that solid solu-
tions with x ¼ 0.42 can be effectively used in piezoelectric devices which operate at
room temperatures.
110 M. TALANOV ET AL.

4. Conclusions
A complex study of the structure, dielectric and piezoelectric properties of
(1-2x)BiScO3-xPbTiO3-xPbMg1/3Nb2/3O3 (x ¼ 0.30-0.46) ceramics was carried out. As
the concentration x increases (at x > 0.42), the structural phase transition from the
rhombohedral phase to the tetragonal one as well as the crossover from relaxor ferro-
electric to normal ferroelectric occur simultaneously. An unusual U-shape dependence
of the Tm(x), which was previously observed in some Bi/Pb-containing compounds, was
detected. In particular, it was noted that there is a correlation between the concentration
dependences of Tm and the inverse D parameter. An analysis of the d33-Tm diagram of
solid solutions based on BS-PT was carried out. The conclusion was made about the
possibility of application ceramics with x ¼ 0.42 in piezoelectric devices which operate
at room temperatures.

Funding
The reported study was funded by RFBR - research projects no.16-32-60025 mol_a_dk
(Talanov M. V.) and RF Ministry of Education and Science –research project no. @
3.1099.2017/PS (Bush A.A.).

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