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Acta Materialia 79 (2014) 84–92
www.elsevier.com/locate/actamat

Large piezoelectric properties induced by doping ionic pairs

in BaTiO3 ceramics
D. Xu a, W.L. Li a,b, L.D. Wang a, W. Wang a, W.P. Cao a, W.D. Fei a,⇑
a
School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, People’s Republic of China
b
National Key Laboratory of Science and Technology on Precision Heat Processing of Metals, Harbin Institute of Technology, Harbin 150001,
People’s Republic of China

Received 13 February 2014; received in revised form 15 June 2014; accepted 8 July 2014

Abstract

The high piezoelectric properties of piezoelectric ceramics are typically obtained by inducing a phase transition between two ferro-
electric phases, using either the morphotropic phase boundary (MPB) or the polymorphic phase transition (PPT). Here we demonstrate
that neither the MPB nor the PPT is necessary to achieve high piezoelectric properties. Our results show that the optimized distribution
of Li+–Al3+ pairs parallel to the [0 0 1] direction, as found in our xLiAlSiO4/BaTiO3 (xLAS/BT) lead-free piezoelectric ceramic system
prepared from ordinary raw materials by conventional solid-state reaction sintering, can generate a large piezoelectric constant (d33) of
378 pC/N when x = 7.5 mol.%. The d33 value of the 7.5 mol.% LAS/BT ceramic is more than three times that of the pure BT ceramic.
The distortion connected to the proposed Li+–Al3+ pairs locally creates unit cells of less than tetragonal symmetry, and these low-
symmetry cells can be responsible for the high piezoelectric response. The high-temperature stability testing reveals that these doped
ceramics are usable at temperatures as high as 120 °C. This piezoelectric mechanism coming from the doping ionic pairs provides a
new method to achieve large piezoelectric properties in a wide range of ABO3-type perovskite systems.
Ó 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Perovskites; Piezoelectricity; Lead-free; Doping ionic pairs

1. Introduction have prompted the extensive investigation of lead-free

Pb(Zr,Ti)O3 (PZT) ceramics have for many years repre-
sented one of the most commonly used piezoelectric mate-
rials and have played a vital role in various applications,
such as actuators, sensors, capacitors, resonators and
transducers. The exceptional piezoelectric properties of
these materials are achieved by using a composition
approximating Pb(Zr0.52Ti0.48)O3, which exhibits a compo-
sition-induced phase transition between two ferroelectric
phases known as a morphotropic phase boundary (MPB)
[1–4]. Recently, health and environmental considerations
⇑ Corresponding author. Tel./fax: +86 451 86413908.
E-mail address: wdfei@hit.edu.cn (W.D. Fei).
piezoelectric ceramics with excellent properties as replace-
ments for toxic PZT ceramics. The excellent piezoelectric
properties of PZT ceramics with MPB compositions have
led to interest in a variety of binary and ternary lead-free
piezoelectric ceramics with similar MPB compositions,
including Na0.5Bi0.5TiO3–BaTiO3 [5–7], BiFeO3–BaTiO3
[8,9], Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3–BaTiO3 [10–12], Na0.5
Bi0.5TiO3–K0.5Bi0.5TiO3–BiFeO [13] and Na0.5K0.5NbO3–
LiSbO3–BiFeO3 [14]. However, the piezoelectric perfor-
mance of existing lead-free ferroelectric systems still cannot
compete with that of PZT, especially with regard to the
performance of high-end PZT ceramics (those with a high
piezoelectric constant (d33) of 600 pC/N and a high depo-
larization temperature (Td) of 330 °C) [15–17]. Liu and

http://dx.doi.org/10.1016/j.actamat.2014.07.023
1359-6454/Ó 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
 D. Xu et al. / Acta Materialia 79 (2014) 84–92
Ren [18] have reported that the Ba(Ti0.8Zr0.2)O3–x(Ba0.7-
Ca0.3)TiO3 (BZT–BCT) ceramic system exhibits a very
large d33 value of 620 pC/N at an optimal composition.
Their work involved designing an MPB material analogous
to the PZT system and found that the high piezoelectricity
of the BZT–BCT system originates from the compositional
proximity of its MPB to the tricritical triple point (TCP)
formed from combined cubic paraelectric (C), ferroelectric
rhombohedral (R) and tetragonal (T) phases. Unfortu-
nately, its relatively low Curie temperature (TC) limits the
overall usefulness of the BZT–BCT system in practical
applications since the operational temperature of some pie-
zoelectric components is limited to half the TC value. More
effort is therefore required to further increase the TC of the
BZT–BCT system.
In addition to the MPB, another means of achieving a
high level of piezoelectricity is polymorphic phase transi-
tion (PPT), which is mainly found in the (K,Na)NbO3
(KNN) system [19–22]. As an example, a piezoelectric coef-
ficient as high as 416 pC/N has been exhibited by a tex-
tured KNN-based ceramic with codopants of Li, Ta and
Sb [21], while the d33 values of non-textured KNN-based
ceramics are in the range of 200–300 pC/N. The enhanced
piezoelectric properties evident with the KNN system are
obtained owing to the coexistence of orthorhombic (O)
and T ferroelectric phases when the PPT temperature
(TO-T) is shifted downward to near room temperature,
and a temperature-driven ferroelectric–ferroelectric phase
transition such as this may provide an easy path for polar-
ization rotation. Although high piezoelectricity has been
reported in these KNN-based ceramics, the strong temper-
ature dependence of piezoelectric properties stemming
from associated PPTs means that they are unusable in
devices requiring high thermal stability. Zuo et al. [19],
for example, have found that the d33 values of Sb-doped
KNN ceramics decrease rapidly with increasing tempera-
ture. It is therefore worth noting that good piezoelectric
properties do not always equate to high performance in
piezoelectric ceramics, so there is an urgent need to develop
a lead-free candidate that also exhibits high performance.
Barium titanate (BT) ceramic was one of the most
widely used ferroelectric materials prior to the discovery
of high-performance PZT. Efforts have been devoted to
improving the piezoelectric properties of BT ceramic and
several effective approaches are explored. The addition of
some dopants into BT to replacing the A- and/or B-sites
is an effective means of enhancing the ceramic’s piezoelec-
tric properties [23–25]. In addition, the use of special fine
powders and unusual sintering techniques such as spark
plasma sintering (416 pC/N) [26], microwave sintering
(370 pC/N) [27] and two-step sintering (460 pC/N) [28]
have also resulted in a high d33. In such cases, the enhanced
d33 of the BT ceramic is the result of extrinsic contributions
to its polarizability, associated with submicron grain sizes
and nanodomain structures. A BT ceramic with high piezo-
electric properties (d33 > 300 pC/N), however, is difficult to
obtain using ordinary raw materials and a conventional
85
sintering method, so, unlike PZT, BT is used primarily as
a dielectric material rather than as a piezoelectric material.
The reason why good piezoelectric properties cannot be
obtained with ordinary BT ceramics remains a mystery.
To date, the basic approach to the design and optimiza-
tion of new ABO3-related piezoceramics has been to induce
a phase transition between two ferroelectric phases, as
exemplified by MPB and PPT. The question now arises
as to whether or not there is a new high piezoelectric mech-
anism waiting to be found, and the answer may involve
investigating piezoelectric ceramics with ABO3-type perov-
skite structures. Our recent work indicates that the addi-
tion of eucryptite (LiAlSiO4, LAS) can greatly enhance
the piezoelectric properties of BT ceramics prepared from
ordinary raw materials by conventional solid-state reaction
sintering. We have found that this high piezoelectricity is
dependent on a preferential distribution of Li+–Al3+ pairs
in the ABO3-type lattice and is not related to the MPB and
PPT effects, thus providing a new means of designing lead-
free piezoelectric materials. Moreover, the high depolariza-
tion temperature of these materials has encouraged us to
investigate xLAS/BT ceramic system for practical
applications.
2. Experimental procedure
xLAS/BT ceramics with LAS contents of 0, 4, 7.5 and
10 mol.% were prepared by conventional ceramic process-
ing techniques. Commercial BT (99.9%, Aladdin Chemistry
Co. Ltd, Shanghai, China) and LAS powders produced in
our laboratory [29] were used as the starting materials.
These compounds were weighed out in the desired ratios
and ball-milled for 6 h by planetary milling with zirconia
balls in alcohol. After ball-milling, the resulting slurries
were dried at 80 °C for 12 h, ground and sieved. The mixed
powders were subsequently pressed into pellets 10 mm in
diameter and 1 mm thick using a few drops of 5 wt.% poly-
vinyl alcohol (PVA) as a binder. After burning off the PVA,
the xLAS/BT pellets embedded in BT powder were sintered
in covered alumina crucibles, heating at a rate of
5 °C min1 to a final temperature of 1350 °C, which was
held for 2 h.
The crystalline structure of each sample was analyzed
using an Empyrean X-ray diffraction (XRD) system (PAN-
alytical) while in situ XRD measurements were carried out
on a Philips X’Pert diffractometer with Cu Ka radiation,
operating at 40 kV and 40 mA. The morphology, grain size
and local element occupancy were examined with a cold
field emission scanning electron microscope (Quanta
200F) equipped for energy-dispersive spectroscopy
(EDS). Platinum electrodes were evaporated onto the cera-
mic surfaces and annealed at 600 °C for 30 min to allow for
electrical properties characterization. The temperature
dependence of the dielectric constant of each sample was
measured at 1 kHz across the temperature range of
25–180 °C on a Novocontrol CONCEPT40 broadband
dielectric spectrometer. Polarization hysteresis and
86 D. Xu et al. / Acta Materialia 79 (2014) 84–92
strain–electric field curves were determined at different elec-
tric fields using a Radiant Technologies Precision worksta-
tion. The samples were poled at 80 °C in a silicone oil bath
under a DC field of 3 kV mm1 for 30 min. The piezoelec-
tric constant (d33) was measured employing a quasi-static
piezoelectric constant testing meter (ZJ-4AN, Institute of
Acoustics, Chinese Academy of Science).
3. Results and discussion
3.1. Phase and microstructure characterization
Fig. 1a shows XRD patterns of xLAS/BT ceramic pow-
ders with different LAS contents measured at room temper-
ature. The major diffraction peaks match well with the
ABO3-type perovskite phases. However, small additional
peaks indexed with an asterisk in the enlarged XRD pat-
terns are observed in those ceramics with added LAS, as
revealed in Fig. 1b, and their intensities increase with
Fig. 1. (a) XRD patterns of xLAS/BT ceramic powders measured at room
temperature and (b) the enlarged views of XRD patterns in the selected 2h
range showing the additional diffraction peaks on LAS doping.
increasing LAS content. The formation of secondary
phases may be associated with the low solubility limit of
LAS in the BT lattice. It is hard to determine the phase
type for these secondary phases due to the relatively low
intensities of their diffraction peaks.
In order to further identify the impurity phases, surface
scanning electron microscopy (SEM) micrographs of
xLAS/BT ceramics with different LAS contents sintered
at 1350 °C are displayed in Fig. 2. A remarkable effect of
the LAS addition on the microstructure of the ceramics is
obvious from Fig. 2b, c and d. Firstly, the densification
of the ceramic samples is improved to some extent, with
only a small number of surface pores. Secondly, the mor-
phologies of the ceramic samples are modified by the intro-
duction of LAS. For pure BT ceramic (Fig. 2a),
inhomogeneous but mostly spherical grains are found; in
contrast, a certain number of rod-shaped grains are
observed in the grain boundaries, e.g. in the red circular
regions in the SEM images (Fig. 2b, c and d). The excep-
tional rod-shaped grains are probably related to the impu-
rity phases. Finally, the average grain size is seen to initially
increase before reaching a maximum value of about 40 lm
(in the case of the 4 mol.% LAS/BT ceramic), then
decreases slightly with further increasing LAS content.
The large grain sizes suggest that the enhanced d33 of the
xLAS/BT ceramics is not the result of extrinsic contribu-
tions to the polarizability, which are typically associated
with fine grains (1 lm) [30,31].
Fig. 3 shows the EDS analysis of the 7.5 mol.% LAS/BT
sample. It is very hard to determine the respective Ba/Ti
compositions due to their overlapping spectrum peaks.
Hence, the composition table shown in the inset of Fig. 3
lists the sum of the Ba and Ti contents. The corresponding
EDS analysis shown in Fig. 3a reveals a composition close
to an Al:Si ratio of 1.69:1.95 for a normal spherical grain,
confirming that the LAS with such a content had doped the
BT lattice. The possible secondary phase was also analyzed
by EDS, with the result shown in Fig. 3b. Compared with
the matrix phase, the interfacial rod-shaped inclusion has
higher signal intensities in Al and Si, especially in Al. This
indicates that the secondary phases with an Al:Si ratio of
2 may be Al- and Li-enriched, though the Li content can-
not be detected by EDS due to its low element number. It is
clear that the presence of Al- and Li-enriched phases is
caused by the excess of A-site ions after Al3+ and Li+ ions
replacement for A-site Ba2+ ions. The identified impurities
phases confirm a low solubility limit of LAS in the BT lat-
tice, which is consistent with the XRD analysis above.
3.2. Lattice distortion and role of defects
As stated above, the LAS has doped the BT lattice and
the precipitated phases are Al-enriched due to the low sol-
ubility limit of LAS in BT. To analyze the influence of LAS
doping on the BT lattice distortion, fine scan XRD patterns
obtained at room temperature were performed, and these
are shown in Fig. 4a. The diffraction data confirms that
 D. Xu et al. / Acta Materialia 79 (2014) 84–92 87

Fig. 2. Surface SEM micrographs of xLAS/BT ceramics: (a) x = 0 mol.%, (b) x = 4 mol.%, (c) x = 7.5 mol.% and (d) x = 10 mol.%. The red circular
regions correspond to the secondary phases. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of
this article.)

the xLAS/BT powders exhibit P4 mm symmetry (JCPDS tion- or internal stress-induced evolution can be ruled out
#83–1880), as evidenced by the relative intensity ratios of completely, since the XRD experiments were carried out
the 002/200 and 202/220 diffraction peaks and the existence on the powders of xLAS/BT ceramics. Moreover, the
of a single 111 peak at 2h  38.9°. The effect of the LAS observed variations in lattice parameters and I002/I200 with
content on the lattice parameters (a and c), as estimated LAS content cannot be explained solely by the random dis-
from XRD full pattern fitting by HighScore Plus software, tribution of Li+ and Al3+ ions. Assuming that Li+–Al3+
as well as the tetragonality (c/a) of the xLAS/BT ceramic ions randomly locate at A-sites, the same trend in the var-
powders, are shown in Fig. 4b. Both the lattice parameter iation of the diffraction intensity of the 002 and 200 peaks
c and the tetragonality are seen to decrease significantly would be evident, but reductions in the I002/I200 intensity
with increasing LAS content in spite of the slight reduction ratio with increasing LAS content would not occur since
in the lattice parameter a. the same effect would apply to the structure factor (F) asso-
The observed variations in lattice parameters are obvi- ciated with the 002 and 200 diffractions. It is therefore nec-
ously caused by the incorporation of LAS into the BT lat- essary to provide an alternative explanation for our
tice. Taking ionic valences into consideration, it is believed experimental results.
that Li+ and Al3+ ions, both of which have relatively small Since the average of the ionic radii of Li+ and Al3+ is
ionic radii, substitute the A-sites occupied by the Ba2+ ions less than the radius of Ba2+, the substitution of either
of the ABO3-type perovskite structure, while Si4+ ions Li+ or Al3+ for Ba2+ will induce lattice distortions in the
replace the B-sites occupied by Ti4+ [32]. In such cases, BT, reducing the XRD intensity [33]. In the case of the
the average A-site valence will be 2 + and hence the local (0 0 2), (0 2 0) and (2 0 0) planes, the effective structure fac-
charge neutrality is maintained. To thoroughly understand tors, F eff eff eff
002 , F 020 and F 200 ; adjusted for lattice distortions,
and identify the occupation behavior of Li+ and Al3+ ions, can be expressed as follows:
the relative intensity ratio of the 002/200 peaks (hereafter
8p2 sin2 h 2
referred to as I002/I200) was analyzed as a function of F eff
200 ¼ F 200 expð Dx Þ ¼ F 200 expðM 1 Þ ð1Þ
LAS content. Fig. 4c shows that the (I002/I200)x/(I002/ k2
I200)0 value (where the superscripts 0 and x denote pure 8p2 sin2 h 2
BT and LAS-doped BT ceramic powders, respectively) F eff
020 ¼ F 020 expð Dy Þ ¼ F 020 expðM 2 Þ ð2Þ
k2
tends to decrease with increasing LAS content. It should
8p2 sin2 h 2
be pointed out that the probability of preferred orienta- F eff
002 ¼ F 002 expð Dz Þ ¼ F 002 expðM 3 Þ ð3Þ
k2
88 D. Xu et al. / Acta Materialia 79 (2014) 84–92
Fig. 3. EDS analysis for (a) a normal spherical grain and (b) the
interfacial rod-shaped inclusion in the 7.5 mol.% LAS/BT ceramic.
where F 200 , F 020 and F 002 are the average structure factors
of the distortion-free crystal lattices, and Dx2 , Dy 2 and
Dz2 , which represent deviations from the ideal BT lattice
sites, are the mean square displacements in the [1 0 0],
[0 1 0] and [0 0 1] directions, respectively. Since the diffrac-
tion intensity (I) is proportional to the square of the mod-
ulus of the structure factor (|F|2), the following expression
can be obtained:
I i 1 expð2M i Þ ð4Þ
where the subscript i corresponds to the (2 0 0), (0 2 0) and
(0 0 2) planes. The 200 diffraction includes contributions
from the (2 0 0) and (0 2 0) planes.
From the above equations, it can be concluded that lat-
tice distortion is an important factor influencing the I002/
I200 intensity ratio. Based on the results of Fig. 4c, it is evi-
dent that the values of both M1 and M2 are much smaller
than M3, thus lattice distortion has little effect on the dif-
fraction intensity of the 200 peak but reduces the intensity
of the 002 peak with increasing LAS content, eventually
producing the changes in the I002/I200 ratio shown in
Fig. 4c. Based on the above analysis, it can be concluded
that Li+ and Al3+ ions may form Li+–Al3+ pairs within
the same cell in order to minimize electrostatic energy, as
indicated in Fig. 4b and c. In the case of A-site replace-
ment, the relatively large M3 value suggests that these
Li+–Al3+ pairs tend to adopt a preferential alignment such
that most of them are parallel to the [0 0 1] direction.
Fig. 4d presents a diagram of the lattice distortion induced
by the preferential distribution of Li+–Al3+ pairs parallel
to the [0 0 1] direction. Here the lattice distortion induced
by doped Li+–Al3+ pairs with a small average ionic radius
occurs primarily along the [0 0 1] direction. As can be seen
in Fig. 4b, the (0 0 2) interplanar spacing (d002) is obviously
decreased because of the lattice distortion induced by the
preferential substitution of Li+–Al3+ pairs parallel to the
[0 0 1] direction. A decrease in the (2 0 0) and (0 2 0) interpla-
nar spacings (referred as d200 and d020, respectively), how-
ever, does not occur since the lattice distortion has
minimal influence on these spacings. The value of d002 thus
decreases more rapidly than the value of d200 with increas-
ing LAS content. In addition, the rate of reduction of the
(I002/I200)x/(I002/I200)0 ratio tends to slow at an LAS con-
tent above x = 7.5 mol.% (as in Fig. 4c), demonstrating
that the number of [1 0 0]- and [0 1 0]-oriented Li+–Al3+
pairs begins to increase as a result of elastic energy
limitations.
According to the chemical formula of LiAlSiO4, how-
ever, for such a replacement of Li+–Al3+ pairs for Ba2+
and Si4+ for Ti4+, if the excess Li and Al cannot be precip-
itated fully in the grain boundaries, there will be either an
excess of A-site ions or a deficiency of B-site ions, accom-
panied by the formation of oxygen vacancies to keep
charge neutrality. As a consequence, the occurrence of oxy-
gen vacancies and Si4+ replacement for Ti4+, which has a
larger radius, can reduce the elastic energy induced by
the lattice distortion stemming from the preferential distri-
bution of Li+–Al3+ pairs. In particular, the elastic energy
can be decreased more effectively when the smaller Si4+
ions and oxygen vacancies are distributed in the vicinity
of Li+–Al3+ pairs. Furthermore, the substitution of Ti4+
with the smaller Si4+ is very beneficial for enhancing the
solubility of LAS in BT.
As shown in Fig. 4d, the preferential distribution of
Li+–Al3+ pairs along the [0 0 1] direction may be caused
by the effect of the electric field formed from Li+–Al3+
pairs upon C–T phase transition. The detailed discussions
are as follows. Firstly, the paraelectric–ferroelectric phase
transition of BT ceramics with ABO3-type perovskite struc-
ture is a first-order transition, which includes the nucle-
ation and growth of the tetragonal ferroelectric phase.
The c-axis orientation of the tetragonal ferroelectric phase
is determined by the nucleus orientation. Secondly, the
nucleation process can be adjusted by changing the electric
field, and it is energetically favorable for the spontaneous
polarization (PS) of ferroelectric nuclei parallel to the elec-
tric field. Finally, Li+–Al3+ pairs can create an electric
dipole moment PD, the local electric fields (ED) formed
by the dipole at the head and tail of the pairs are nearly
parallel to PD, and the ED in the middle and at the sides
around the dipole are nearly antiparallel to PD. The former
ED can lead to a ferroelectric phase nucleus with PS
nearly parallel to PD, whereas the latter ED can induce a
 D. Xu et al. / Acta Materialia 79 (2014) 84–92 89

Fig. 4. (a) Fine-scan XRD patterns in the 2h ranges of 38.3–39.3o, 43.7–46.3 o and 65.0–66.7o, (b) lattice constants (a and c) and tetragonality (c/a) as a
function of LAS content x, (c) (I(002)/I(200))x/(I(002)/I(200))0 intensity ratio and (d) schematic illustration of the preferential distribution of Li+–Al3+ pairs
parallel to the [0 0 1] direction. The error bars in (b) are a few tenths of the whole.

ferroelectric phase nucleus with PS nearly antiparallel to
PD. Therefore, the nucleation of the tetragonal phase in
the vicinity of Li+–Al3+ dipole causes the coexistence of
PS nearly parallel (PS//PD) and nearly antiparallel to PD
(-PS//PD) in the xLAS/BT ceramics, which is in good agree-
ment with the observed symmetric hysteresis loops (see the
next section and Fig. 5b).
3.3. Electrical properties
The temperature dependence of the dielectric constant
(e), as measured at 1 kHz for xLAS/BT ceramics with com-
positions of x = 0, 4, 7.5 and 10 mol.%, are shown in
Fig. 5a. The dielectric curves of these ceramics only exhibit
one dielectric anomaly, characterized by a phase transition
from the ferroelectric phase (T) to paraelectric phase (C).
The O–T phase transition cannot be observed in the dielec-
tric–temperature curves within the measuring temperature.
The dielectric constant (em) at TC first increases, reaching a
maximum value of 6245 at x = 7.5 mol.%, then decreases
with increasing LAS content. In addition, the LAS doping
has little impact on TC, as evident in Fig. 5a.
Fig. 5b shows the room-temperature polarization hys-
teresis loops of xLAS/BT ceramics with compositions of
x = 0, 4, 7.5 and 10 mol.%. A well-saturated ferroelectric
loop is observed for pure BT ceramic under an electric field
of 40 kV cm1. After adding LAS, good ferroelectric loops
of the resulting xLAS/BT ceramics, which do not exhibit
any obvious signs of leakage, are observed under a higher
electric field of 50 kV cm1. The offset behavior in the coer-
cive field reflecting the level of internal bias, which gener-
ally occurs in acceptor-doped ferroelectrics [16,34–36], is
not observed in the polarization vs. electric field curves of
xLAS/BT ceramics measured at room temperature. This
can be attributed to the coexistence of PS//PD and -PS//
PD in the xLAS/BT ceramics, and PD is distributed ran-
domly in space. Consequently, the total net electric field
from PD is zero, giving rise to the relatively symmetric
and no internal-bias P–E loops. The situation is different
from that in the aged acceptor-doped ferroelectrics with a
severely constricted hysteresis loop and a notable bias field,
where there is a defect dipole moment PD oriented along
the PS (along the crystallographic c-axis), as noted in the
previous reports [34–36].
The polarization hysteresis loop of the pure BT ceramic
exhibits typical ferroelectric behavior, with a remnant
polarization (2Pr) of 25 lC cm2, while the xLAS/BT
ceramics show a relatively low 2Pr value of 17 lC cm2
at x = 4 and x = 7.5 mol.% (Fig. 5c). As the LAS content
increases to 10 mol.%, the hysteresis loop becomes more
slanted in comparison with those obtained from the 4
and 7.5 mol.% samples, accompanied by a further decrease
in 2Pr to approximately 13 lC cm2 at x = 10 mol.%
(Fig. 5c). The reduced 2Pr values can be accounted for
90 D. Xu et al. / Acta Materialia 79 (2014) 84–92
Fig. 5. (a) Temperature dependence of the dielectric constant at 1 kHz for xLAS/BT ceramics, in which the highest permittivity peak appears for the
composition of x = 7.5 mol.%, (b) hysteresis loops of xLAS/BT ceramics measured at room temperature and (c) 2Pr values with different LAS contents.
by the decreased tetragonality (c/a) (Fig. 4b) [37,38] and
Li+–Al3+ pairs oriented antiparallel to c-axis because the
orientation of these dipole moments cannot be changed
by an external electric field.
Fig. 6a presents unipolar strain (S)–electric field (E)
curves obtained for poled xLAS/BT ceramics with various
LAS contents at room temperature. In the case of the
xLAS/BT ceramics, a curve close to saturation at
E P 3.5 kV mm1 and characteristic nonlinearity of unipo-
lar strain are observed, compared with the results obtained
for the pure BT ceramic. The maximum converse piezoelec-
tric coefficient (dS/dE), calculated from the slope of the
unipolar S–E plot, achieves an optimum value of
540 pm V1 at x = 7.5 mol.%, comparable to the reported
high d33 values of the BT ceramics prepared by microwave
sintering [27] and two-step sintering [28].
For comparison purposes, the maximum converse pie-
zoelectric coefficient and the piezoelectric constant mea-
sured using a quasi-static d33 meter are shown together in
Fig. 6b. When increasing the LAS content, the d33 initially
increases, reaches its highest value of 378 pC/N at the com-
position of x = 7.5 mol.%, then declines at x = 10 mol.%.
The d33 value (378 pC/N) associated with the 7.5 mol.%
LAS/BT is very difficult to achieve for BT-based ceramics
prepared from ordinary raw materials by a conventional
sintering method, and is much higher than the values exhib-
ited by existing lead-free piezoelectrics with TC
P 120 °C, which primarily show d33 values of 200 pC/N
[16,17]. In addition, the high d33 value of the 7.5 mol.%
LAS/BT is on a par with that of 300 pC/N reported for a
non-textured KNN-based ceramic [21]. This is indeed an
exciting result, but the question still remains as to why
these xLAS/BT ceramics have such high piezoelectric con-
stants compared with the pure BT ceramic.
To clarify the origin of the high piezoelectricity in BT
ceramics doped with Li+–Al3+ pairs, a possible piezoelec-
tric mechanism is proposed here. The Li+ and Al3+ ions,
substituting Ba2+ sites, locate at the interstices formed
from four immediately neighbouring BO2- 6 octahedras.
The replacements of Li+ and Al3+ with small radii for
the large Ba2+ will lead to two important consequences.
On the one hand, a large lattice distortion can be generated
in the vicinity of Li+–Al3+ pairs, as revealed in Fig. 4d, and
this distortion can induce a deviation of spontaneous
polarization direction from the c-axis near Li+–Al3+ pairs.
Most of all, the distortion connected to the Li+–Al3+
dipoles locally creates unit cells of less than tetragonal sym-
metry, and these low-symmetry cells can be responsible for
the high piezoelectric response, in analogy to the local
monoclinic phase at the MPB in PZT [39]. On the other
hand, because their radii are smaller than that of Ba2+,
Li+ and Al3+ ions, with their relatively high mobility, can
respond immediately to the external fields, which contrib-
utes to the piezoelectric properties of xLAS/BT ceramics.
The piezoelectric mechanism proposed in the present
work is different from any of the effects previously noted
 D. Xu et al. / Acta Materialia 79 (2014) 84–92
Fig. 6. (a) Unipolar strain–electric field curves measured on poled xLAS/
BT ceramics, and (b) piezoelectric constant (d33) and maximum converse
piezoelectric coefficient (dS/dE) with different LAS contents.
in the PZT and BZT–BCT systems exhibiting high piezo-
electricity. The piezoelectric mechanism of the xLAS/BT
ceramics is different from that of the BZT–BCT system,
as reported by Liu and Ren [18], the decreased energy bar-
rier is realized by a TCP in the BZT–BCT system and only
those ceramics with compositions near the MPB show large
piezoelectric coefficients. This mechanism is also different
from the high piezoelectricity of the PZT system associated
with the MPB effect. Our work indicates that, if a suitable
preferential distribution of ion pairs is designed (such as
occurred with Li+ and Al3+ in our case), lead-free ceramic
systems prepared from ordinary raw materials by a conven-
tional sintering method have a high probability of exhibit-
ing excellent piezoelectric properties.
3.4. Piezoelectric thermal stability
With regard to the development of piezoelectric ceram-
ics, one of the most serious challenges is to improve their
stability and reliability. To allow piezoelectric ceramics to
function properly under high-temperature conditions, min-
imal piezoelectric temperature dependence is vitally impor-
tant if these devices are to have practical applications.
Fig. 7 shows the temperature dependence of the normalized
d33 values of poled xLAS/BT ceramics measured ex situ.
The depolarization temperature (Td) was determined from
91
the temperature dependence of d33 measured at room tem-
perature after annealing the poled samples at various tem-
peratures for 30 min. It is evident that, while the d33 value
of the pure BT ceramic begins to decrease remarkably
above 50 °C, this is not the case for the xLAS/BT ceramics.
As the temperature increases, the d33 values of these ceram-
ics remain almost unchanged and then drop dramatically
above a critical temperature (Td) of approximately
120 °C, which is very close to the Curie temperature of
these ceramics. Thus the piezoelectric temperature stability
of the BT ceramic can be greatly improved by adding a
small amount of LAS. More importantly, the large temper-
ature dependence and considerable degradation typically
exhibited by KNN-based ceramics are not observed in
our xLAS/BT ceramics, as shown in Fig. 7. Their high-
temperature stability demonstrates that xLAS/BT ceramics
may be used at temperatures as high as 120 °C, a range
which is very hard for pure BT ceramics to reach.
Recent studies on lead-free piezoelectric ceramics have
primarily involved three ABO3-type perovskite systems:
KNN-based, NBT-based and BT-based. In the case of
KNN-based systems, although non-textured KNN ceram-
ics have a relatively high d33 of 200–300 pC/N, their most
significant disadvantage is the large temperature depen-
dence of their piezoelectric properties, such that degrada-
tion occurs through thermal cycling between the two
distinct ferroelectric domain states. In the case of NBT-
based systems, the inherently low d33 of 200 pC/N is only
halfway to the desired piezoelectric value, even though they
have a moderate depolarization temperature in the range of
100–200 °C [16]. In the case of BT-based systems, much
effort is still required to enhance the low TC so as to
improve their overall usefulness. In fact, in most cases, high
values of d33 and Td appear to be mutually exclusive when
dealing with lead-free piezoelectric ceramics such as KNN-,
NBT- and BT-based systems. From the above analysis, the
current piezoelectric properties of xLAS/BT ceramics are
Fig. 7. Temperature dependence of the normalized d33 values of the poled
xLAS/BT ceramics measured ex situ. Each datum point in Fig. 7 is the
average value of several tests.
92 D. Xu et al. / Acta Materialia 79 (2014) 84–92
superior to those of non-textured KNN-based ceramics.
Furthermore, the d33 value (378 pC/N) of the 7.5 mol.%
LAS/BT ceramic is obviously higher than the values
obtained with NBT-based ceramics with similar depolar-
ization temperatures (Td  120 °C). These results indicate
that there is a real possibility that the xLAS/BT system
may represent a good lead-free piezoelectric ceramic
material.
4. Conclusions
xLAS/BT lead-free piezoelectric ceramics were prepared
using ordinary raw materials and a conventional sintering
method. The 7.5 mol.% LAS/BT ceramic exhibits a very
high piezoelectric constant (d33) of 378 pC/N, a converse
piezoelectric coefficient (dS/dE) of 540 pm V1 and a depo-
larization temperature (Td) of 120 °C. The high piezoelec-
tricity of these LAS-doped BT ceramics primarily
originates from the unit cells of less than tetragonal sym-
metry created by the local distortion connected to the pref-
erential [0 0 1]-distributed Li+–Al3+ pairs. These properties
indicate that this system represents a promising lead-free
piezoelectric candidate material worthy of further study.
Acknowledgements
This work was financially supported by the National
Nature Science Foundation of China (Grant No.
11272102). D.X. and W.L.L. contributed equally to this
work.
References
[1] Noheda B, Gonzalo JA. Phys Rev B 2000;61:8687.
[2] Asada T, Koyama Y. Phys Rev B 2007;75:214111.
[3] Schhierholz R, Fuess H. Phys Rev B 2011;84:064122.
[4] Cordero F, Trequattrini F, Craciun F, Galassi C. Phys Rev B
2013;87:094108.
[5] Babu JB. Appl Phys Lett 2007;90:102901.
[6] Cernea M, Vasile BS, Capiani C, Ioncea A, Galassi C. J Eur Ceram
Soc 2012;32:133.
[7] Cernea M, Galassi C, Vasile BS, Capiani C, Berbecaru C, Pintilie I,
et al. J Eur Ceram Soc 2012;32:2389.
[8] Yang HB, Zhou CR, Liu XY, Zhou Q, Chen GH, Li WZ, et al. J Eur
Ceram Soc 2013;33:1177.
[9] Zhou CR, Feteira A, Shan X, Yang HB, Zhou Q, Cheng J, et al. Appl
Phys Lett 2012;101:032901.
[10] Li YM, Chen W, Xu Q, Zhou J, Gu XY, Fang SQ. Mater Chem Phys
2005;943:28.
[11] Dai YJ, Zhang SJ, Shrout TR, Zhang XW. J Am Ceram Soc
2010;93:1108.
[12] Shieh J, Wu KC, Chen CS. Acta Mater 2007;55:3081.
[13] Zhou CR, Liu XY, Li WZ, Yuan CL. Mater Chem Phys
2009;114:832.
[14] Jiang MH, Liu XY, Chen GH. Scr Mater 2009;60:909.
[15] Liu W, Xu J, Wang YZ, Xu H, Xi XQ, Yang JL. J Am Ceram Soc
2013;96:1827.
[16] Shrout TR, Zhang SJ. J Electroceram 2007;19:111.
[17] Takenaka T, Nagata H. J Eur Ceram Soc 2005;25:2693.
[18] Liu WF, Ren XB. Phys Rev Lett 2009;103:257602.
[19] Zuo RZ, Fu J, Lv DY, Liu Y. J Am Ceram Soc 2010;93:2783.
[20] Shen ZY, Li YM, Jiang L, Li RR, Wang ZM, Hong Y, et al. J Mater
Sci: Mater Electron 2011;22:1071.
[21] Saito Y, Takao H, Tani T, Nonoyama T, Tajatiri K, Homma T, et al.
Nature 2004;432:84.
[22] Wang K, Li JF. Adv Funct Mater 2010;20:1924.
[23] Ang C, Yu Z, Jing Z, Guo RY, Bhalla AS, Cross LE. Appl Phys Lett
2002;80:3424.
[24] Sharma S, Kumar P, Palei P. Ceram Int 2012;38:5597.
[25] Yang WG, Zhang BP, Ma N, Zhao L. J Eur Ceram Soc 2012;32:899.
[26] Shen ZY, Li JF. J Ceram Soc Jpn 2010;118:940.
[27] Takahashi H, Numamoto Y, Tani J, Tsurekawa S. Jpn J Appl Phys
2008;47:8468.
[28] Moon SM, Wang XH, Cho NH. J Ceram Soc Jpn 2009;117:729.
[29] Wang LD, Fei WD, Hu M, Jiang LS, Yao CK. Mater Lett
2002;53:20.
[30] Zhao Z, Buscaglia V, Viviani M, Buscaglia MT, Mitoseriu L, Testino
A, et al. Phys Rev B 2004;70:024107.
[31] Ghosh D, Sakata A, Carter J, Thomas PA, Han H, Nino JC, et al.
Adv Funct Mater 2013. http://dx.doi.org/10.1002/adfm.201301913.
[32] Shannon RD. Acta Cryst 1976;A32:751.
[33] Wang YM. X-ray Diffraction of noncrystal and crystal with defects.
1st ed. Beijing: Science Press; 1988 [in Chinese].
[34] Ren XB. Nature Mater 2004;3:91.
[35] Zhang LX, Erdem E, Ren XB, Eichel R-A. Appl Phys Lett
2008;93:202901.
[36] Robels U, Arlt G. J Appl Phys 1993;73:3454.
[37] Ullah A, Ahn CW, Hussain A, Lee SY, Kim IW. J Am Ceram Soc
2011;94:3915.
[38] Fan LL, Chen J, Li S, Kang HJ, Liu LJ, Fang L, et al. Appl Phys Lett
2013;102:022905.
[39] Guo R, Cross LE, Park SE, Noheda B, Cox DE, Shirane G. Phys Rev
Lett 2000;84:5423.