Ceramics International xxx (xxxx) xxx

Contents lists available at ScienceDirect

Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Fine grained textured BaTiO3-based piezoelectric ceramics with

outstanding strain properties for the lead-free multilayer actuator
Yingchun Liu a, Hongjun Zhang a, *, Chengyu Ma a, Kai Li b, **, Bin Yang a, Wenwu Cao c,
Jiubin Tan d
a
Functional Materials and Acoustooptic Instruments Institute, Harbin Institute of Technology, Harbin, 150080, China
b
Guangdong Provincial Key Laboratory of Electronic Functional Materials and Devices, Huizhou University, Huizhou, 516001, China
c
Department of Mathematics and Materials Research Institute, The Pennsylvania State University, University Park, PA, 16802, USA
d
Ultra-precision Optical & Electronic Instrument Engineering Center, Harbin Institute of Technology, Harbin, 150001, China

A R T I C L E I N F O A B S T R A C T

Keywords: Textured BaTiO3-based piezoelectric ceramics show the excellent application potential as their piezoelectric
Fine textured grain characteristics almost approach the commercial lead-based ceramics. Piezoelectric multilayer actuators (MLAs)
Partial RTGG with low driving voltages and compact structures are great in line with the equipment trend of miniaturization
Strain hysteresis
and functional integration. However, the coarse textured grains result in few grain layers in each thin ceramic
Lead-free actuator
layer of MLAs, hardly guaranteeing the electromechanical dependability. In this work, we combined the
composition regulation with a modified template grain growth (TGG) to prepare fine-grained textured ceramics.
The Zr4+ and Sn4+ co-substituted (Ba0.95Ca0.05)(Ti0.94Zr0.05Sn0.01)O3 (BCZTS) was chosen as the matrix
composition. Unreacted BaCO3 (BC, 7.3 % in content) was artificially introduced into matrix to realize the partial
reaction template grain growth (RTGG), reducing textured grains from 9.7 μm to 6.9 μm. Textured BCTZS-BC
MLAs achieved high texture degree of 92 % and further smaller grain size of 3.4 μm at 1300 ◦ C, due to inhi­
bition on mass transfer and improvement on thermal conductivity of Pt electrodes. The high strain of 0.12 % in
textured MLAs is almost 2.3 times enhancement compared to non-textured counterparts, and the ultralow strain
hysteresis Hs of 5.6 % at 30 kV/cm is equivalent to that in PZT MLAs. The microscopic coercive voltage is 3.1 V
with a maximum displacement of 210 p.m., which is mainly ascribed to the smaller domain sizes and the
favorable “4O” domain configuration in textured MLAs.

1. Introduction ceramic was as high as ~620 pC/N by designing a tricritical point

Piezoelectric multilayer actuators (MLAs) have unique advantages
such as the low driving voltage, the small structure size and the high
precision, which are well consistent with the trend of miniaturization
and functional integration of equipment [1,2]. Lead-based MLAs, con­
sisting of the most commercially available PZT and its derived ceramics,
exhibit superior electromechanical properties and great structural flex­
ibility. However, growing concerns over the lead toxicity to the envi­
ronmental security and the human health make lead-free piezoelectric
materials attract extensive attention. BaTiO3(BT)-based ceramics as the
most promising lead-free candidates have endured sustainable devel­
opment to improve piezoelectric characteristics for decades. The d33 of
A/B-site co-substituted (Ba0.85Ca0.15)(Ti0.90Zr0.10)O3 (BCT-50BZT)
(rhombohedral-tetragonal-cubic), which made a breakthrough in
lead-free ceramics [3]. Unfortunately, the substituted BT-based ceramics
typically have low Curie temperature (Tc) and exhibit high hysteresis Hs,
which seriously degrades the accuracy and the stability of actuators on
practices [3–7].
Textured piezoelectric ceramics enable to increase the piezoelectric
performance by orienting grains along a specific crystallographic di­
rection. And the templated grain growth (TGG) is a very effective
method to obtain the high texture quality [8]. For example, the d33 of Pb
(Mg1/3Nb2/3)-PbZrO3-PbTiO3 (PMN-PZT) ceramics textured by BT
templates was nearly 1100 pC/N, 4 times higher than that of
non-textured PMN-PZT ceramics [9]. A very high d33 ~ 700 pC/N was
achieved in modified K(Na,Nb)O3 (KNN)-based textured ceramics,

* Corresponding author.
** Corresponding author.
E-mail addresses: zhanghj@hit.edu.cn (H. Zhang), kailics@hzu.edu.cn (K. Li).

https://doi.org/10.1016/j.ceramint.2024.04.343
Received 28 January 2024; Received in revised form 24 April 2024; Accepted 25 April 2024
Available online 26 April 2024
0272-8842/© 2024 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: Yingchun Liu et al., Ceramics International, https://doi.org/10.1016/j.ceramint.2024.04.343
Y. Liu et al.
which is comparable to commercial PZT ceramics [10]. In addition, we
have developed (Ba,Ca)(Zr,Ti)O3-based textured ceramics with the high
d33 ~750–780 pC/N and extremely low strain hysteresis Hs (< 6 %)
[11].
Despite the great success achieved in improving electromechanical
performances, current textured ceramics possess the abnormally coarse
grain size (Gavg) of 15–25 μm almost without exception [12–14]. How­
ever, the thickness of a single ceramic layer in MLAs is only around
50–100 μm. And at least ten grains are required to be uniformly ar­
ranged along the thickening direction in thin ceramic layers of MLAs to
ensure the sufficient electromechanical dependability. The large chunks
of textured grains make just 2–6 effective grain layers exist in the
ceramic layer with massive defects, which seriously weakens the
breakdown strength and restricts the actual applications of MLAs.
Therefore, to develop high-performance textured piezoelectric ceramics
with fine grains becomes quite critical, while current researches of the
texture engineering mainly focus on the improvement of the piezo­
electric properties. Very few studies have been carried out to address the
controllable growth process of grain refining and manage the textured
grain size.
The textured ceramic is a kind of core-shell structures formed by the
homo/hetero-epitaxial nucleation of templates via consuming nano
matrix grains. The rapid growth of templates and the abnormal growth
of matrix powder is accountable to the coarse textured grains. Therefore,
if matrix grains keep small during the sintering process, the finally
textured grain size will be reduced. Generally, regulating the composi­
tion of the matrix powder is one of the most important methods to obtain
smaller grains. In (K0.5Na0.5)NbO3-based ceramics sintered by a pres­
sureless solid-state method, the introduced end-member of SrTiO3 can
obviously reduced grain sizes to sub-micrometer (~300 nm) [15]. And
due to the replacement of Ti4+ by Sn4+ in B site, the average grain size of
(Ba0.9Ca0.1)TiO3-xBa(Sn0.2Ti0.8)O3 (BCT-xBST) decreases almost 75 %
from 27 μm at x = 0.20–7 μm at x = 0.60 [16]. Wu et al. also confirmed
that the grain sizes gradually decreased with increasing Ba(Sn0.2Ti0.8)O3
(BST) content [17]. Zhou et al. obtained the pristine (Ba0.95Ca0.05)
(Ti0.9Sn0.1)O3 ceramic with a relative density of 78 % and a uniform
grain size of 0.5–2 μm [18]. Du et al. achieved (Ba0.95Ca0.05)
(Ti0.94Sn0.06)O3 ceramics via the tape casting, exhibiting high relative
density of 99.5 % and small average grain size of 1.5 μm [19]. Such
publications imply that Sn4+ ions can inhibit the grain growth and lead
to BT-based ceramics with fine microstructures.
Aside from the matrix composition, morphologies of textured grains
are also directly influenced by the template crystals. Smaller templates
mean smaller texture grains. Nevertheless, because of the Brownian
motion of matrix particles in the tape-casting slurry, the directional
organization of templates will deteriorate with decreasing template di­
ameters, leading to the poor texture degree [20]. Hence, large templates
of 5–15 μm are regularly utilized in the tape casting process [12–14]. We
consider that original large templates may become tiny or even disap­
pear if they can take part in the reaction of matrix materials during the
sintering. Such method is referred to as reaction template grain growth
(RTGG), which uses original raw materials rather than calcined pure
powders in perovskite phases as matrix [21]. Raw materials can conduct
the in-situ reaction to produce matrix grains. On the one side, templates
are involved in the reaction, the grain nucleation occurs on template
surfaces via the sintering neck creation and particle rearrangement [22],
which would consume and break large templates into small pieces. On
the other side, textured grains in RTGG seldom grow larger at higher
temperature and for longer hold time due to the grain volume shrinking
brought on by the chemical reaction of raw materials [23]. For example,
Zhao et al. employed RTGG to produce BCT-50BZT ceramics with a high
texture degree f00l = 95 %, and quite small textured grains of 1 μm were
obtained using BT templates of 5–10 μm in diameter [24]. Wada et al.
prepared [110]-oriented BT textured ceramics by RTGG, possessing fll0
~ 80 % and textured grains <2 μm [25]. However, what is noteworthy is
that excessively fine grains in RTGG textured ceramics frequently have
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low relative densities <90 % and a high number of grain boundary de­
fects (e.g., pores). Naturally, how to combine the virtues of both RTGG
and TGG, and to synchronously reduce the grain size and maintain fewer
flaws in textured ceramics is worth considering.
In this work, we suggest combining the processes of composition
regulation with modified TGG as a synergistic design approach to pro­
duce fine-grained textured ceramics. For the obstruction effect of Sn4+
ions on the grain growth, (Ba0.95Ca0.05)(Ti0.94Zr0.05Sn0.01)O3 (BCZTS)
with Zr4+ and Sn4+ co-substituted in B-site was chosen as the matrix
composition. And [001]c-oriented BT platelets of 5–12 μm in diameter
and 0.5–1.2 μm in thickness were selected as texture templates. In the
modified TGG process, impure matrix powders containing deliberately
unreacted BaCO3 (BC) made textured grains drop from 9.7 μm to 6.9 μm
in comparison to the conventional TGG using the pure perovskite ma­
trix. Moreover, textured BCTZS-BC MLAs sintered at 1400 ◦ C for 6 h
simultaneously achieved high texture degree of ~92 % and small grain
size of ~3.4 μm in piezoelectric layers. The textured MLAs possessed a
high strain of 0.12 % at 30 kV/cm, which is almost 2.3 times enhance­
ment compared to randomly oriented counterparts. Such remarkable
property can be attributed to the piezoelectric anisotropy and the easier
polarization rotation owing to smaller domains. This study may pave a
new way to further develop high-performance lead-free MLAs.
2. Experimental procedures
The analytical grade raw materials of BaCO3 (BC, 99.95 %, aladdin),
CaCO3 (99.99 %, aladdin), TiO2 (99.8 %, aladdin), ZrO2 (99.9 %,
aladdin), and SnO2 (50–70 nm, 99.9 %, aladdin) were weighted ac­
cording to the stoichiometric ratio, and ball-milled for 24 h in alcohol,
then calcined at 890–1200 ◦ C for 2 h to form matrix powders. Non-
textured (Ba0.95Ca0.05)(Ti0.94Zr0.06)O3 (BCZT) and (Ba0.95Ca0.05)
(Ti0.94Zr0.05Sn0.01)O3 (BCZTS) ceramics were doped with 0.5 mol% CuO
and sintered at 1350oC for 4 h. All textured BCTZS ceramics were pre­
pared using 5 mol% BT templates with the thickness of 0.4–1.2 μm and
the diameter of 4–15 μm, shown in Fig. S1 (see Supplementary Mate­
rials, which also elaborates the tape casting procedure in more detail).
The fabrication of textured MLAs is similar to that of textured ceramics
but subjected to screen printing using the Pt electrode slurry after the
tape casting. Non-textured MLAs were obtained without any BT tem­
plates. The thickness of MLAs is about 0.43 mm, consisting of thin single
ceramic layers of 45 μm. Phase structures and the texture quality
quantified via the Lotgering factor f00l were determined using the X-ray
diffractometer (XRD, Empyrean, PANalytical, Almelo, Netherlands).
Microstructures and grain orientations of samples were investigated by
the field-emission scanning electron microscopy (FE-SEM, Quanta 200,
FEI, Hillsboro, OR, USA) combined with the electron backscatter
diffraction (EBSD) and the energy dispersive spectroscopy (EDS). All
grain size distributions were calculated from one hundred ceramic
grains randomly using the orthogonal dimensions measurement [26].
Dielectric constants were measured as a function of temperature through
the LCR meter (E4980A, Agilent, CA, USA). The polarization and uni­
polar strain hysteresis loops against electric fields were conducted by a
modified Sawyer-Tower circuit (Precision Premier II, Radiant Technol­
ogies Inc, NM). Domain structures and local electrical responses were
characterized by the piezoelectric force microscopy (PFM, MFP-3D,
Asylum Research, CA).
3. Results and discussion
Fig. 1 shows the SEM micrographs of non-textured BCZT and BCZTS
ceramics. Both non-textured ceramics presented typical equiaxed crys­
tals with clear grain boundaries and achieved high relative densities of
98.6 % for BCZT and 98.8 % for BCZTS. And their grain sizes coincided
with the symmetrical normal distributions, calculated via the open-
source software of ImageJ. As for the non-textured BCZT ceramic in
Fig. 1a, the grain size spans a wide range from 2 μm to 28 μm, and is
Y. Liu et al.
Fig. 1. SEM images and grain size distributions of BCZT (a, b) and BCZTS (c, d) ceramics sintered at 1350 ◦ C for 4 h.
mainly concentrated in 14–17 μm. As comparison, grains in the BCZTS
ceramic are 0.8–7 μm, and mainly concentrated in 1.5–2 μm. The
average grain size Gavg was estimated in the light of the grain size dis­
tribution. It can be found that Gavg (~2.0 μm) in BCZTS ceramic is much
smaller than that of BCZT ceramic (~16.2 μm), illustrating the signifi­
cant growth inhibition of Sn4+ ions, which agrees well with previous
reports [17–19].
Fig. 2a shows the XRD patterns of BCZT and BCZTS ceramics,
exhibiting pure perovskite phases within the precision of the instrument.
To analyse the phase formation, Rietveld refinement was used to refine
the XRD patterns by the GSAS-II software [27]. Original phase data were
from the corresponding CIF cards of tetragonal (T, PDF#05–0626) and
orthorhombic (O, PDF#81–2200) phases. Different strategies were
taken into account during refinements, such as possible phase forma­
tions, atomic occupancies and doping ratios. The final results indicated
that refinements got convincing reliability factors of Rwp = 9.83 % for
BCZT and Rwp = 9.05 % for BCZTS when both O and T phases were
considered. In the BCZT ceramic, the contents of O phase (54.9 %) and T
phase (45.1 %) were comparable. As to the BCZTS ceramic, the doping of
Sn4+ ions increased the T phase to 64.4 %, and decreased the R phase to
35.6 %. The phase characteristics in BCZT and BCZTS were further
confirmed by the temperature dependence of dielectric constant εr. In
Fig. 2. (a) Rietveld refinements of XRD data with phase contents, and (b) εr as a function of temperature measured at 1 kHz of BCZT and BCZTS ceramics.
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Fig. 2b, the εr-T curve of BCZTS was broader in contrast to BCZT,
meaning the increased structure inhomogeneity and more prominent
dielectric diffusion due to the Sn4+-doping. Such phenomenon is similar
to the Mn-doped Pb(In1/2Nb1/2)O3–Pb(Mg1/3Nb2/3)O3–PbTiO3 [28].
Two phase transitions were detected in BCZT and BCZTS, corresponding
to orthorhombic-tetragonal and tetragonal-cubic phase transitions (TO-T
and TC). The BCZT and BCZTS ceramics had the similar TO-T of 49 ◦ C and
50 ◦ C, respectively. While TC decreased from ~107 ◦ C for BCZT to
~97 ◦ C for BCZTS, which meant although the substitution of Sn4+ ions
weakened the upper limit temperature of BT-based ceramics, but barely
affected their RT applications. Wu et al. [29] reported that the substi­
tution of Sn4+ for Ti4+ decreased TC more rapidly comparing to the Zr4+
doping in (Ba0.94Ca0.06)TiO3 ceramics. To maintain the high Curie
temperature for wider practical applications, the relatively lower Sn4+
content of x = 0.01 was chosen in this study.
To obtain textured ceramics with small crystal grains, the proper
matrix powder is one of the key factors. Fig. 3 illustrates XRD patterns of
BCZTS powders at various calcined temperature. The matrix powder
calcined at 890 ◦ C comprised the considerable amount of unreacted
BaCO3 (BC, PDF#44–1487) and the intermediate reaction product of
Ba2Ti9O20 (PDF#17–0662). Ba2Ti9O20 may be formed by the local
nonstoichiometric ratio of BC and TiO2. The content of BC was about
Y. Liu et al.
Fig. 3. (a) XRD patterns of BCZTS powders at various calcining temperatures. SEM images of BCZTS powders (b) uncalcined and calcined at (c) 890 ◦ C, (d) 900 ◦ C,
(e) 1200 ◦ C for 2 h.
13.5 % calculated through XRD data by the Reference Intensity Ratio
(RIR) [30]. By increasing temperature to 900 ◦ C, matrix powders were
still impure including BC and Ba2Ti9O20, but the BC concentration
decreased to 7.3 %. After calcination at 1200 ◦ C for 2h, matrix powders
showed the pure perovskite phase without any trace of impurities.
Fig. 3b-e show microstructures of BCZTS powders under selected
calcining conditions. In Fig. 3b, the uncalcined BCZTS shows the pri­
mary morphology of raw materials combined by ball-milling, including
a mass of rod-shaped powders which was still observed in matrix
calcined at 890 ◦ C (Fig. 3c). In comparison with pure BC powders in
Fig. S2a (see Supplementary Materials), the same long rod-shaped
morphology demonstrated that these rod-shaped powders marked by
red arrows can be identified as BC in Fig. 3b. In addition, other random
pictures arising from matrix powders calcined at 890 ◦ C contained
broken short rod-shaped powders. The short rod-shaped powders were
detected to have the higher Ba2+ content as shown in Figs. S2(b–d),
which further demonstrated the residual BC phase. Although BC still can
be detected by XRD in matrix calcined at 900 ◦ C, no evident rod-shaped
Fig. 4. SEM images and grain size distributions of cross-sectional textured BCZTS (a, b) and BCZTS-BC (c, d) ceramics. Insets are XRD patterns to calculate the
texture degrees.
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component was found in Fig. 3d, meaning that BC would break down
into smaller pieces first at higher temperature. The grain size was about
200 nm in the matrix at 900 ◦ C, and rose to approximately 300–500 nm
at 1200 ◦ C in Fig. 3e.
Two kinds of matrix powders were chosen to prepare the textured
piezoelectric ceramics, namely the pure perovskite matrix powder
calcined at 1200 ◦ C (BCZTS) and the matrix powder with 7.3 % BaCO3
calcined at 900 ◦ C (BCZTS-BC). All textured ceramics used 5 mol% BT
crystals as the template and 0.5 mol% CuO as the sintering aid. The
optimal sintering process was 1400 ◦ C, 9 h for the textured BCZTS and
1460 ◦ C, 9 h for the textured BCZTS-BC, respectively. As the residual BC
also reacted into the perovskite powder during the BT induced growth of
textured grains, which is similar to the RTGG process, the higher sin­
tering temperature was required for the textured BCZTS-BC [23]. Fig. 4
shows SEM images and grain size distributions of textured BCZTS and
BCZTS-BC ceramics. The textured BCZTS-BC ceramic possessed a high
texture degree f00l of 97 %, which is equivalent to that of 99 % in the
texture BCZTS, calculated by insets in Fig. 4a and c. The textured BCZTS
Y. Liu et al.
ceramic had large Gavg ~9.7 μm and abnormally coarse grains up to
~27 μm, as counted in Fig. 2b. However, much smaller grains (Gavg
~6.9 μm, Fig. 2d) with the narrower size distribution were achieved in
the textured BCZTS-BC ceramic. This phenomenon indicates that
although BT templates may react with the intermediate Ba2Ti9O20 phase
[31] and the residual BC phase with complex multiple-step reactions,
the grain growth can still be induced and do not suffer significant drop of
the texture degree. In addition, the high relative density reached 98.7 %
in textured BCZTS-BC, which was basically the same as that (98.5 %) in
the textured BCZTS, suggesting that trace amounts of unreacted BC in
the matrix not only benefits finer grains but also forms fewer defects.
The polarization-electric field (P-E) loops of non-textured/textured
BCZTS and textured BCZTS-BC ceramics are shown in Fig. 5a, exhibit­
ing well saturated P-E hysteresis with almost the same maximum po­
larization Pmax ~18 μC/cm2 at 30 kV/cm. Compared to the non-textured
BCZTS, lower coercive fields (Ec) but higher remanent polarization (Pr)
were obtained in textured ceramics as shown in Fig. 5b. Due to effects of
fine grains, the textured BCZTS-BC ceramics further decreased Ec to 1.7
kV/cm, and the corresponding Pr also became lower than that in
textured BCZTS ceramics, indicating easier switchings and motions of
polarization and domain walls due to fine textured grains. Finer grains
commonly lead to smaller domain sizes and decreased domain-wall
energy [32,33]. In addtion, the piezoelectric coefficients (d33) of
textured ceramics were about twice as high as that in non-textured
BCZTS. As a whole, the texture BCZTS-BC ceramics with fine grains
simultaneously possessed higher d33, εr, kp, but lower dielectric loss,
which would be beneficial to practical applications.
To further reveal the effect of Pt electrode layers on grain size, cross-
sectional microstructures and grain size distributions in MLAs of non-
textured and textured BCZTS-BC are displayed in Fig. 6. In Fig. 6a, it
can be found that the non-textured MLAs got densified ceramic layers
(45 μm in thickness) with uniform equiaxed grains at 1300 ◦ C. The grain
size distribution was concentrated in a range of 0.8–2.7 μm, and the Gavg
of these equiaxed grains was about 0.9 μm (Fig. 6b), both of which were
much smaller than that in ceramic monoliths in Fig. 1. This phenomenon
may be contributed to two possible reasons. On the one side, Pt electrode
layers would obstruct the mass transfer and slow down the grain growth
rate. On the other side, the metal Pt has much greater thermal con­
ductivity and made thin ceramic layers reach sintering temperature
much faster and more evenly, which increased nucleation sites of the
grain growth and inhibited the abnormal grain growth.
Such effects of Pt electric layers were also effective to the textured
BCZTS sintered at 1300 ◦ C for 6 h and textured BCZTS-BC MLAs sintered
at 1400 ◦ C for 6 h. The textured BCZTS MLAs in Fig. 6c still presented
coarse grains with Gavg ~9.5 μm in Fig. 6d, which were indeed smaller
than that in textured BCZTS ceramics in Fig. 4a-b. No miniature matrix
grains existed in textured BCZTS MLAs, resulting in large voids at grain
boundaries. As to the textured BCZTS-BC MLAs with ceramic layers of
45 μm in thickness, the Gavg was about 3.4 μm in Fig. 6f, which
decreased up to 50.7 % in comparison to the textured BCZTS-BC ce­
ramics in Fig. 4c-d. When ceramic layers became thicker to 60 μm in
Fig. 6g, the heating effect and the obstruction of mass transfer of Pt
layers would be weaker, thus the Gavg increased slightly to 4.3 μm in
Fig. 5. (a) P-E hysteresis loops and (b) piezoelectric properties of non-textured/textured BCZTS and textured BCZTS-BC ceramics.
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Fig. 6h. In addition, some smaller matrix grains (~0.8–2.5 μm) were not
consumed to generate textured grains as shown in Fig. 6e and g, which
effectively filled voids left by large textured grains and eliminated de­
fects among textured grain boundaries. The small grains in textured
BCZTS-BC MLAs further revealed the inhibition of grain growth via the
existence of BC and the partial RTGG process, which would enhance the
reliability of piezoelectric actuators.
Fig. 7a shows the XRD patterns of non-textured and textured BCTZS-
BC MLAs. Apart from diffraction of Pt electrodes, the (110)C diffraction
as the main peak in the perovskite dominated the XRD pattern of the
non-textured sample, whereas only (00l)C peaks can be detected for the
textured MLAs. Even though some matrix grains still existed, textured
BCTZS-BC MLAs exhibited a high f00l value of ~92 %. In Fig. 7b, the
surface EBSD map directly demonstrated the strong [001]C-preferred
orientation of textured grains in MLAs. Cross-sectional EBSD maps and
(001) pole figures for non-textured and textured MLAs are given in
Fig. 7c and d, respectively. Black strips are Pt electrodes. Different from
the completely random distribution of non-textured MLAs in Fig. 7c,
grains concentrated along the [100] or [110] orientations slightly in the
cross-section of textured MLAs, which resulted in the green ribbon of the
(001) pole figure in Fig. 7d. The contrast of the orientation distribution
further confirmed the strong effect of interior (001) texture in textured
BCTZS-BC MLAs.
The electric field induced unipolar strain (S-E) curves of non-
textured/textured BCTZS-BC MLAs and textured BCTZS MLAs are
shown in Fig. 8a. As the thickness of ceramic layers was ~45 μm, the
electric field of S-E curves reached 30 kV/cm when the driving voltage
was as low as 135 V. For the textured BCTZS MLAs with coarse grains,
the electrostrain Smax reached a relatively high value of 0.10 % due to
the texture engineering, but the strain hysteresis (Hs) was over 18.9 %.
In contrast, the textured BCTZS-BC MLAs with fine grains generated Smax
of 0.12 %, nearly 2.3 times higher than that in non-textured ones.
Moreover, the textured BCTZS-BC MLAs possessed the ultralow Hs of 5.6
%, which was almost 70 % reduction relative to that of the textured
BCTZS MLAs. In comparison with lead-based MLAs, the higher Smax and
the lower Hs achieved in textured BCTZS-BC MLAs were equivalent to
that in commercial PZT MLAs (e.g. P-885.51), but superior to that in
BiScO3-PbTiO3 (BS-PT) or Pb(Sb, Nb)O3–Pb(Zr, Ti)O3 (PSN-PZT) MLAs
in Fig. 8b. The ceramic thickness of PSN-PZT, BS-PT and P-885.51 MLAs
is 44, 62 and 50 μm [34–36], respectively, also similar to the textured
BCTZS-BC MLAs. Such synergistic improvement on Smax and Hs in
textured BCTZS-BC MLAs might be attributed to the fine textured grains
and their more reversible ferroelectric domains.
The PFM amplitude and phase images along surfaces of non-
textured/textured BCTZS MLAs and textured BCTZS-BC MLAs were
investigated to reveal the microscopic origin of the high strain and low
hysteresis in Fig. 9. For the non-textured samples, domains like islands
and watermarks were about 0.10–0.80 μm in width and irregularly
distributed in Fig. 9a and b. However, the domain morphology in the
textured MLAs exhibited much smaller stripe patterns with widths of
0.10–0.55 μm for BCTZS in Fig. 9c-d and 0.10–0.40 μm for BCTZS-BC in
Fig. 9e-f. It can be found that the textured BCTZS-BC MLAs with fine
grains had the smallest dominans. Furthermore, local switching
Y. Liu et al. Ceramics International xxx (xxxx) xxx

Fig. 6. Cross-sectional SEM images and grain size distributions of non-textured (a, b) and textured (c, d) BCZTS MLAs, and textured BCZTS-BC MLAs with ceramic
thickness of (e, f) 45 μm and (g, h) 60 μm.

Fig. 7. (a) XRD patterns and (b) surface-sectional EBSD maps and (001) pole figure of textured BCTZS-BC MLAs. Cross-sectional EBSD maps and (001) pole figure of
(c) non-textured and (d) textured BCTZS-BC MLAs.

Fig. 8. (a) Electric field induced unipolar strain (S-E) of non-textured and textured BCZTS MLAs, and textured BCZTS-BC MLAs, (b) S-E curves of textured BCTZS-BC
and other well-known lead-based MLAs [34–36].

spectroscopies of various MLAs were employed to evaluate the piezor­
esponse via phase-voltage hysteresis loops and amplitude-voltage but­
terfly curves in Fig. 9g-i. All curves were obtained using the contact
mode by applying a DC voltage superimposed 500 mV AC signal to the
AFM Pt/r-coating probe. Both textured MLAs showed smaller coercive
voltages of 3.1 V in comparison with 4.5 V in the non-textured MLAs,
indicating the easier polarization switching due to the smaller stripe
patterns. Moreover, the average maximum displacement was about 178
p.m. in the textured BCTZS MLAs, and increased to nearly 210 p.m. in
the textured BCTZS-BC MLAs, which was almost 2 times higher than that

6
Y. Liu et al.
Fig. 9. PFM amplitude and phase images of non-textured (a, b), textured (c, d) BCTZS MLAs, and (e, f) textured BCTZS-BC MLAs. (g–i) The corresponding phase-
voltage hysteresis loops and amplitude-voltage butterfly curves.
of non-textured ones. Such improvement on piezoresponse characteris­
tics may be mainly ascribed to the smaller domain sizes and the corre­
sponding lower strain energy in textured MLAs. As the domain size is
proportional to the domain wall energy, smaller domains in textured
MLAs could reduce the domain wall energy and make domain switch­
ings easier [37–39], which demonstrated the best comprehensive per­
formance in the textured BCTZS-BC MLAs with fine grains. Otherwise,
textured ceramics poled along [001]C consisted of the orthorhombic
phase and formed the favorable “4O” domain configuration (Fig. S3, see
Supplementary Materials), which enhanced the piezoelectric response
due to the coexistence of four equally favored domain states, reducing
the driving force for extensive domain wall motion.
4. Conclusions
In summary, (001)C-oriented BCTZS-BC MLAs were prepared using
the modified TGG method combined with 5 mol% BT templates. The
Zr4+ and Sn4+ co-substituted (Ba0.95Ca0.05)(Ti0.94Zr0.05Sn0.01)O3
(BCZTS) was chosen as the matrix composition. The Sn4+ doping
reduced the grain size of BT-based ceramics from 2.0 μm to 16.2 μm,
falling by over 87 %. Unreacted BaCO3 (BC) was artificially introduced
into matrix with the content of 7.3 %, which realized the partial RTGG to
reduce the textured grain size from 9.7 μm to 6.9 μm. Textured BCZTS
and BCZTS-BC ceramics exhibited the same maximum polarization Pmax
of 18 μC/cm2 at 30 kV/cm, while the textured BCZTS-BC had lower
coercive fields. Pt electrode layers inhibited the mass transfer but
improved the thermal conductivity, which made textured BCTZS-BC
7
Ceramics International xxx (xxxx) xxx
MLAs achieve high f00l of 92 % and smaller grains of 3.4 μm at
1300 ◦ C. The textured MLAs possessed high strain of 0.12 % and ultra­
low strain hysteresis Hs of 5.6 % at 30 kV/cm, equivalent to the com­
mercial PZT MLAs. Smaller stripe patterns with widths of 0.1–0.4 μm
were observed by PFM in textured BCTZS-BC MLAs. And their lower
microscopic coercive voltage and higher maximum displacement are
mainly arising from the smaller domain sizes and the favorable “4O”
domain configuration.
CRediT authorship contribution statement
Yingchun Liu: Writing – original draft, Funding acquisition, Data
curation, Conceptualization. Hongjun Zhang: Writing – review &
editing, Writing – original draft, Methodology, Funding acquisition,
Conceptualization. Chengyu Ma: Data curation. Kai Li: Resources,
Investigation. Bin Yang: Supervision, Project administration, Funding
acquisition. Wenwu Cao: Supervision, Resources, Methodology. Jiubin
Tan: Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Y. Liu et al.
Acknowledgments
This work was supported by Natural Science Foundation of Hei­
longjiang Province (LH2022E049, LH2021E052), National Natural Sci­
ence Foundation of China (Grant no. 52202131, 52002093), and the
Fundamental Research Funds for the Central Universities (HIT.
NSRIF202313, HIT.NSRIF202214), National Key Research and Devel­
opment Program of China (No. 2022YFB3403902).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.ceramint.2024.04.343.
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