Journal of Alloys and Compounds 637 (2015) 137–142

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jalcom

Phase transition and enhanced electrical properties

in 0.725BiFeO3-0.275Ba0.85Ca0.15Ti0.9Zr0.1xSnxO3 multiferroic ceramics
Donghui Zhang, Yujie Gan, Tingkai Chen, Shenghong Yang, Yueli Zhang ⇑
State Key Laboratory of Optoelectronic Materials and Technologies, School of Physics & Engineering, Sun Yat-sen University, Guangzhou 510275, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Lead-free 0.725BiFeO3-0.275Ba0.85Ca0.15Ti0.9Zr0.1xSnxO3 (BF-BCTZS-1000x, x = 0, 0.025, 0.050, 0.075,

Received 18 December 2014 0.100) multiferroic ceramics were fabricated via a conventional solid-state reaction method. Effects of
Received in revised form 14 February 2015 Sn substitution on the structural, electrical and magnetic properties have been studied. The XRD patterns
Accepted 16 February 2015
reveal that the pseudocubic structure of the ceramics transforms into rhombohedral after Sn substitution
Available online 23 February 2015
for Zr. The SEM images show that Sn doping effectively facilitates the grain growth and densification of
the ceramics. Room-temperature dielectric properties are apparently improved. The temperature-depen-
Keywords:
dent dielectric results show that the Curie temperature of the BF-BCTZS-1000x increases almost linearly
Phase transition
Relaxor ferroelectrics
from 401.0 °C to 418.8 °C with the increasing Sn content, and the diffusivity c of the system decreases
Curie temperature from 1.958 to 1.361. Both remnant polarization and hysteresis loop squareness of BF-BCTZS-1000x
Sn doping ceramics are improved obviously after Sn substitution. Piezoelectric coefficient shows a sharp increase
after Sn substitution and decreases slightly with further increase of Sn content. Weak ferromagnetism
is revealed in all BF-BCTZS-1000x ceramics, but is weakened for Sn-doped samples.
Ó 2015 Elsevier B.V. All rights reserved.

1. Introduction antiferromagnetic canting structure of BF can be deteriorated in

As a single-phase multiferroic material, bismuth ferrite (BiFeO3,
BF) shows linear magnetoelectric effect at room temperature [1].
By the magnetoelectric effect, the magnetization of a material
can be manipulated through an applied electric field, and the
polarization of the material can be induced with an applied mag-
netic field [2]. The multiferroic materials have wide potential
applications in multifunctional instruments [2–5]. For instance,
they can be utilized to produce multistate memories that can be
electrically written and magnetically read, combining the advan-
tages of high-speed writing and nondestructive reading operations
[6–9].
Being the only room-temperature-stable single-phase multifer-
roic material, BF is antiferromagnetic below 370 °C and ferroelec-
tric below 830 °C [10]. BF faces several obstacles on its way of
application: instability during high-temperature processing, high
conductivity and weak magnetoelectric coupling [2,8,11].
To suppress the conductivity and impurity phases of BF, an
incorporation of BF with barium titanate- (BT-) based piezoelectric
materials is often used [12–14], and the resultant solid solutions
show improved resistivity and ferroelectric properties. The
⇑ Corresponding author. Tel.: +86 20 84113398; fax: +86 20 84113397.
E-mail address: stszyl@mail.sysu.edu.cn (Y. Zhang).
the solid solution, turning the materials into ferromagnetic.
Moreover, when a ferromagnetic material incorporates with a
ferroelectric material, a multiferroic composite will be formed,
whose magnetoelectric coefficient is larger than that of a single-
phase multiferroic material [2,15].
In the recent years, a new and highlighted member of BT-based
piezoelectrics, (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 (BCTZ), has attracted
much attention for its extraordinary piezoelectric properties
(d33 = 630 pC/N) [16–19]. The strong piezoelectric properties make
the BCTZ a perfect candidate as the ferroelectric component of a
multiferroic composite. In 2012, Wu et al. [20] fabricated
(1x)BCTZ-xBF ceramics at 0 6 x 6 1.0 mol% with a solid-state
reaction method, and obtained a high d33 of 405 pC/N at
x = 0.2 mol%. In 2014, Lin et al. [21] prepared (1x)BF-xBCTZ
ceramics at 0.15 6 x 6 0.35, and observed weak ferromag-
netism and enhanced ferroelectricity close to a rhombohedral–
pseudocubic morphotropic phase boundary (MPB) formed at
0.275 6 x 6 0.30.
It was reported that in BaTiO3–BaSnO3 [22] and BaTiO3–
x(0.4CaTiO3–0.6BaSnO3) [23], the Sn-containing ends stabilize the
rhombohedral phase from orthorhombic and tetragonal phases.
In Ba(Sn, Ti)O3-x(Ba, Ca)O3 (BST-BCT), the rhombohedral phase
transforms into tetragonal after BCT is introduced [24]. In these
cases, piezoelectric and ferroelectric properties are improved due

http://dx.doi.org/10.1016/j.jallcom.2015.02.127
0925-8388/Ó 2015 Elsevier B.V. All rights reserved.
138 D. Zhang et al. / Journal of Alloys and Compounds 637 (2015) 137–142
to phase transitions between the rhombohedral and other
ferroelectric phases. Accordingly, the addition of Sn into pseudocu-
bic 0.725BF-0.275BCTZ may also induce a rhombohedral phase,
and the ferroelectric and piezoelectric properties may be
enhanced.
In this work, 0.725BiFeO3-0.275Ba0.85Ca0.15Ti0.9Zr0.1xSnxO3
ceramics were fabricated with a conventional solid-state reaction
method. Before sintering, 1 mol% MnO2 was added as a sintering
aid to facilitate densification, maintain charge neutrality, and sup-
press impurity phases [11,25–27]. The structure of BF-BCTZS-
1000x ceramics was examined with XRD, and its dielectric,
ferroelectric, piezoelectric and magnetic properties were obtained.
2. Experimental procedure
Lead-free 0.725BiFeO3-0.275Ba0.85Ca0.15Ti0.9Zr0.1xSnxO3 (BF-BCTZS-1000x,
x = 0, 0.025, 0.050, 0.075, 0.100) ceramics were prepared by a conventional solid-
state reaction method. AR-grade BaCO3, CaCO3, TiO2, ZrO2, SnO2, Bi2O3, Fe2O3
reagents were used as starting materials, and were grinded with ethanol in stain-
less-steel jars for 10 h. The powders were dried and calcined at 800 °C for 4 h.
The calcined powders were mixed with 1 mol% MnO2 via ball milling, and then
the resultant mixtures were dried and pressed into tablets with diameters of
10 mm under 10 MPa. The tablets were sintered at 930 °C for 4 h in air. Mn is added
as a sintering aid before the sintering procedure. In our experiments, the same
amount of Mn is added in all samples, so the effect of Mn addition is the same to
all samples.
The structure of BF-BCTZS-1000x was examined by X-ray diffraction (XRD) (D-
MAX 2200VPC, RIGAKU, Japan) via Cu-a radiation (1.541 Å). Surface morphology of
the BF-BCTZS-1000x ceramics was obtained with scanning electron microscopy
(SEM) (Quanta 400F, FEI/OXFORD/HKL, the Netherlands). Sintered tablets were
grinded into powders in an agate mortar for magnetic measurements. Magnetic
field dependence of magnetization was recorded at room temperature with a physi-
cal property measurement system (PPMS, Quantum Design, America). Silver elec-
trodes were fired on both sides of the tablets for electrical measurements. The
frequency and temperature dependent dielectric response of the BF-BCTZS-1000x
ceramics was obtained with a precision LCR meter (E4980A, Agilent Inc.,
America). Ferroelectric properties were examined via a ferroelectric test system
(Precision Premier II, Radiant Technologies Inc., America). Before d33 measurements,
the electrode tablets were polarized under 7.0 kV/mm at 90 °C for 40 min in silicon
oil bath. The piezoelectric coefficient (d33) of the tablets was obtained with a d33
meter (ZJ-4AN, Institute of Acoustics, Academic Sinica, China).
3. Results and discussion
The XRD patterns of the BF-BCTZS-1000x ceramics are shown in
Fig. 1. A pure perovskite structure is revealed in all BF-BCTZS-
1000x samples, suggesting that the Sn ions have diffused into the
lattice of BF-BCTZ. Peaks of impurity phases were found existing
in calcined powders of BF-BCTZS-1000x but absent in sintered
tablets, indicating that the addition of MnO2 into the solid solu-
tions has suppressed the impurity phases. The XRD patterns of
undoped BF-BCTZ ceramics reveal a pseudocubic (referred to as
PC) structure, while the splitting of (1 1 1)PC into (0 0 6)R and
(2 0 2)R in the vicinity of 39° clearly shows that the Sn-doped sam-
ples are rhombohedral (R).
Fig. 1. XRD patterns of BF-BCTZS-1000x ceramics.
The SEM images of BF-BCTZS-1000x ceramics are shown in
Fig. 2(a)–(e), and the variation of average grain size with their error
bars is depicted in Fig. 2(f). The error bars indicate the 95% confi-
dence interval for all compositions. The error bar for BF-BCTZS-0
could not be seen since it is smaller than the size of the symbol.
It can be seen that Sn doping has significant influence on the mor-
phology: compared with the observed pores and relatively small
grain size in the undoped sample, dense micrographs are observed
in Sn-modified samples; moreover, an obvious grain growth is
manifested. According to the Ref. [28], some Sn ions serve as accep-
tors at the B sites of BaTiO3 in the form of Sn2+ and/or Sn3+.
Therefore, when Sn ions substitute for Zr ions in BF-BCTZS-
1000x, oxygen vacancies would be created. Oxygen vacancies can
promote grain growth due to an accelerated oxygen ion motion
[29,30], and this effect may explain the sharp increase of grain size
and the elimination of pores after Sn doping. These observed
results indicate that the addition of Sn is beneficial to the grain
growth and densification of the samples.
As shown in Fig. 3(a) and (b), obvious low-frequency dispersion
is revealed in BF-BCTZS-1000x ceramics. For all samples, dielectric
constant (er) decreases with increasing frequency, while dielectric
loss (tan d) increases with increasing frequency. Both the dielectric
constant and loss of BF-BCTZS-1000x ceramics are obviously
improved after Sn doping. The BF-BCTZS-75 shows the optimized
room-temperature dielectric performance (10 kHz): er = 407,
tan d = 0.030. The improvement of room-temperature dielectric
properties may be due to both intrinsic and extrinsic factors. The
pseudocubic–rhombohedral structural phase transition can induce
a striking change in dielectric properties, while the enlarged grain
size and decreased porosity may also be related.
The dielectric constant at 10 kHz of BF-BCTZS-1000x ceramics is
shown as a function of temperature in Fig. 3(c). The dielectric
anomaly revealed in the vicinity of 410 °C corresponds to the
Curie temperature, at which the ferroelectric–paraelectric phase
transition occurs, and the present observation is consistent with
previous report [21]. The dielectric anomaly is rather broad in
the case of the undoped BF-BCTZ samples, indicating the diffuse
nature of such phase transition [31]. This anomaly becomes much
more pronounced after the substitution of Sn. The diffuseness of
the phase transition can be quantitatively depicted with the
diffusivity c, which is defined in the modified Curie–Weiss law
[32]:
1=er  1=emax ¼ ðT  T C Þc =C ðT > T C Þ; ð1Þ
where c = 1 represents a normal ferroelectric material, and c = 2
represents a complete relaxor ferroelectric material. The c
decreases monotonically from 1.958 to 1.361 with x = 0 to 0.100,
revealing that the BF-BCTZS-1000x system undergoes a composi-
tional relaxor-to-ferroelectric phase transition with the increasing
Sn content. In BF-based ceramics, the TC usually increases with
the increase of the tolerance factor [33]. Accordingly, in the case
of BF-BCTZ whose tolerance factor is 0.988 < 1, the increase of the
tolerance factor resulting from the substitution of a smaller B-site
dopant will lead to an increase of the TC. As a B-site dopant, Sn4+
ion has a radius of 0.69 Å, smaller than 0.73 Å for Zr4+ [34], thus
the TC of BF-BCTZS-1000x increases as the Sn content increases.
The TC as a function of composition (x) is shown in the inset of
Fig. 3(c), and an almost linear increase from 401.0 °C to 418.8 °C
is revealed with the increasing Sn content, which is consistent with
the above analysis.
The dielectric loss vs. temperature curves at 10 kHz are shown
in Fig. 3(d). Concave segments can be recognized at temperatures
slightly lower than the Curie temperatures. The concave segment
of the undoped BF-BCTZ ceramic is much broader than those of
 D. Zhang et al. / Journal of Alloys and Compounds 637 (2015) 137–142 139

Fig. 2. SEM images of BF-BCTZS-1000x ceramics: (a) BF-BCTZS-0, (b) BF-BCTZS-25, (c) BF-BCTZS-50, (d) BF-BCTZS-75 and (e) BF-BCTZS-100; (f) average grain size as a function
of composition (x).

the Sn-doped samples. The evolution can be regarded as another
sign of the decrease of the diffusivity.
The ferroelectric properties of BCTZS ceramics are illustrated in
Fig. 4. Apparent improvements after Sn doping can be seen by com-
paring the P–E loops of undoped BF-BCTZ (Fig. 4(a)) with that of
BF-BCTZS-25 (Fig. 4(b)). The slim relaxor-like hysteresis loop of
the undoped BF-BCTZ sample is quite different from those of the
Sn-doped ceramics, which are closer to the square-like hysteresis
loops of normal ferroelectrics. The remnant polarization (Pr)
increases obviously after the substitution of Sn for Zr, and the
squareness of the hysteresis is also improved, indicating an
enhanced ferroelectricity. The Rsq = Pr/Ps can be utilized as a mea-
surement of the squareness of the P–E loops, where Ps is the satu-
rated polarization [35]. The Rsq value of undoped BF-BCTZ ceramics
is only 0.24, while those of the Sn-doped ceramics are all around or
above 0.50. To be noticed, during the removal of the positive
external electric field (segment AB in Fig. 4(a) and (b)), the polar-
ization of undoped BF-BCTZ declines apparently faster when the
maximum applied field (Em) increases, while the slope of the P–E
curves of BF-BCTZS-25 is almost independent of Em. This phe-
nomenon can be attributed to the knowledge that the polar
nanoregions in relaxor ferroelectrics usually exhibit field-depen-
dent magnitude and are inhomogeneously poled, while normal fer-
roelectrics possess uniform and homogeneously poled domains
[36,37]. The prominent difference suggests that a compositional
relaxor-to-ferroelectric phase transition is undergoing with the
Sn modification, which agrees with the dielectric results in this
work. The P–E loops for BF-BCTZS-1000x samples with different
Sn contents under an Em of 5.5 kV/mm are displayed in Fig. 4(c),
and the evolutions of Pr and coercive field (Ec) are illustrated in
Fig. 4(d). The Pr and Ec behave alike with the increasing Sn content.
When a maximum electric field of 5.5 kV/mm is applied, a
140 D. Zhang et al. / Journal of Alloys and Compounds 637 (2015) 137–142

Fig. 3. Dielectric properties of BF-BCTZS-1000x ceramics: room-temperature frequency dependences of (a) dielectric constant and (b) dielectric loss, temperature
dependences of (c) dielectric constant and (d) dielectric loss at 10 kHz. Inset of (c): TC as a function of composition (x).

Fig. 4. Ferroelectric properties of BF-BCTZS-1000x ceramics: P–E hysteresis loops of with (a) x = 0 and (b) x = 0.025; (c) P–E loops with different Sn contents at an maximum
applied voltage of 5.5 kV/mm; (d) Pr and Ec as functions of composition (x).

maximum remnant polarization Pr (5.15 lC/cm2) is obtained in at The composition dependence of piezoelectric coefficient (d33) of
x = 0.050 with Ec = 3.50 kV/mm. For BF-BCTZS-75 (not shown), the BF-BCTZS-1000x ceramics is shown in Fig. 5. The substitution of Sn
breakdown field is so low that the regular P–E loop is not leads to obvious enhancement of piezoelectricity, which can be
accessible. attributed to the pseudocubic–rhombohedral phase transition,
 D. Zhang et al. / Journal of Alloys and Compounds 637 (2015) 137–142
Fig. 5. Piezoelectric coefficient (d33) of BF-BCTZS-1000x ceramics as a function of
composition (x).
Fig. 6. Magnetic hysteresis loops of BF-BCTZS-1000x ceramics. Inset: composition
dependences of Mr and Hc.
the decrease of diffusivity and the improved densification. The d33
of BF-BCTZS-1000x ceramics reaches a maximum of 91 pC/N at
x = 0.025, and then decreases as the Sn content increases further.
The M–H loops of BF-BCTZS-1000x were investigated via a
physical property measurement system at room temperature with
a magnetic peak field of 20 kOe, as shown in Fig. 6. Typical mag-
netic hysteresis loops are obtained, suggesting that the materials
all possess weak ferromagnetism. While BF is antiferromagnetic,
the weak ferromagnetism of BF-BCTZS-1000x indicates that the
G-type antiferromagnetic spin cycloid structure in BF is deterio-
rated by Ba/Ca ions at the A sites and Ti/Zr/Sn ions at the B sites
[38,39]. After the substitution of Sn, an increase in the coercivity
(Hc) and a decrease in the remnant magnetization (Mr) appear as
depicted in the inset, suggesting that the ferromagnetism is weak-
ened. Of all Sn-doped BF-BCTZS-1000x ceramics, BF-BCTZS-75
shows a maximum remnant magnetization of 0.361 emu/g.
4. Conclusion
Pure perovskite BF-BCTZS-1000x ceramics were fabricated with
a solid-state reaction method. A phase transition from pseudocubic
to rhombohedral after the substitution of Sn is revealed by the
clear splitting of the (1 1 1)PC peak in the XRD patterns. The SEM
images reveal that the substitution of Sn for Zr effectively
141
facilitates the grain growth and the densification of the ceramics
by eliminating the pores. Dielectric, ferroelectric and piezoelectric
properties are enhanced by the addition of Sn, accompanied by a
transition from relaxor to normal ferroelectrics. Room-tempera-
ture dielectric constant increases and dielectric loss decreases
apparently after Sn doping. The Curie temperature increases lin-
early with the increasing Sn content, while the diffusivity dimin-
ishes monotonically. After Sn doping, the slim relaxor-like
ferroelectric hysteresis loop of BF-BCTZ is replaced by more
square-like ones, and the ferroelectricity is improved. Obvious
enhancement of the piezoelectric coefficient d33 is observed. The
BF-BCTZS-1000x ceramics show weak ferromagnetism, but the
remnant magnetization decreases slightly when Sn is added.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China under Grant Nos. 61176010 and 61172027,
Guangdong Natural Science Foundation under Grant No.
1414050000317, the Research Foundation of IARC-SYSU under
Grant No. IARC 2014-09.
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