Journal of Materiomics 9 (2023) 261e268

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Journal of Materiomics
journal homepage: www.journals.elsevier.com/journal-of-materiomics/

Temperature-insensitive KNN-based ceramics by elevating O-T phase

transition temperature and crystal texture
Shuo Gao a, 1, Peng Li a, 1, Jiawei Qu a, Mingze Sun a, Jigong Hao a, Peng Fu a,
Zhongbin Pan b, Jiwei Zhai c, **, Wei Li a, *
a
School of Materials Science and Engineering, Liaocheng University, Liaocheng, 252059, China
b
School of Materials Science and Chemical Engineering, Ningbo University, Ningbo, 315211, China
c
School of Materials Science and Engineering, Tongji University, Shanghai, 201804, China

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

Article history: The inferior temperature stability of piezoelectric response is the main drawback of KNN-based ceramics.
Received 14 September 2022 Here, the Ba-doped 0.97(K0.48Na0.52)(Nb0.96Sb0.04)O3-0.03Bax(Bi0.5Ag0.5)1-xZrO3 (abbreviated as KNNS-
Received in revised form BxBAZ) textured ceramics were prepared by the template grain growth (TGG) method. Excellent
18 October 2022
comprehensive properties (d33¼(406 ± 15) pC/N, TC ¼ 274  C, strain is 0.17%) were achieved in KNNS-
Accepted 27 October 2022
Available online 15 November 2022
BxBAZ textured ceramics with x ¼ 0.2. Meanwhile, its piezoelectric and strain properties also show su-
perior temperature stability (d33 maintained within ±20% change in a wide temperature range from 25  C
to 200  C and strain variation was less than 5% in the temperature range from room temperature to
Keywords:
Textured ceramics
165  C). The high O-T phase transition temperature (TO-T is 110  C) induced by incorporating Ba ions
Ba modification accounts for the enhanced temperature stability of piezoelectric properties. In addition, the crystal
Piezoelectric properties texture always maintains the contribution of piezoelectric anisotropy to the piezoelectric properties
Temperature stability during elevated temperature, which significantly improved the temperature stability of piezoelectric
properties. This work provides an effective strategy for simultaneously achieving high piezoelectric
response and excellent temperature stability in KNN-based ceramics.
© 2022 The Authors. Published by Elsevier B.V. on behalf of The Chinese Ceramic Society. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction However, undoped KNN ceramics show low electrical properties.

Piezoelectric ceramics as a medium for the conversion between
electrical and mechanical energy, are widely used in sensors, actu-
ators and transducers [1,2]. Pb(Zr, Ti)O3 (PZT) based piezoelectric
ceramics have been the most important piezoelectric materials due
to their excellent electromechanical properties and low-cost pro-
cessing [3e5]. However, the toxicity of lead caused environmental
and health problems during both production and subsequent
disposal process. Consequently, researchers have made extensive
efforts to develop lead-free piezoelectric materials and tried to push
them to commercial applications [6e16]. In view of the balance
between non-toxicity and excellent properties, considerable atten-
tion has been focused on (K,Na)NbO3 (KNN)-based ceramics.
* Corresponding author.
** Corresponding author.
E-mail addresses: apzhai@tongji.edu.cn (J. Zhai), liwei@lcu.edu.cn (W. Li).
Peer review under responsibility of The Chinese Ceramic Society.
1
These authors contributed equally to this work.
Recently, the construction of polymorphic phase boundary (PPB) by
the addition of ions (e.g., Liþ, Agþ, Bi3þ, Sb5þ, Ta5þ, etc.) or second end
member have been accepted to boost the piezoelectric properties of
KNN-based ceramics [17]. Based on this strategy, a series of signifi-
cant progresses have been in KNN-based ceramics [18e21]. Wu and
Tao et al. reported that KNN-based piezoelectric ceramics with R-O-T
multiphase transition tailored by chemical modification have large
d33 value of (650 ± 20) pC/N [22]. In addition, the piezoelectric and
electromechanical coupling properties of KNN-based ceramics can
be improved by combining phase structure modification with
texturing technology [23e25]. Saito et al. reported that KNN-based
textured ceramics with a phase structure of O-T coexistence have a
good piezoelectric coefficient d33 of 416 pC/N [26], while we ach-
ieved an ultrahigh d33 of ~700 pC/N in <001>-oriented KNN-based
ceramics with eR-O coexisted phase structure [27].
However, the inferior temperature stability of KNN-based ce-
ramics is one of the main concerns meeting the requirement of de-
vice reliability. It should be noted that the piezoelectricity
temperature stability originating in the diffused polymorphic phase

https://doi.org/10.1016/j.jmat.2022.10.008
2352-8478/© 2022 The Authors. Published by Elsevier B.V. on behalf of The Chinese Ceramic Society. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
S. Gao, P. Li, J. Qu et al.
transition (PPT) is essentially induced by the degraded singularity of
PPT effects, which comes at the expense of high piezoelectricity
[28,29]. Therefore, the temperature stability of KNN-based ceramics
should be improved on the premise of maintaining good piezo-
electric properties that has great significance to its practical appli-
cation. In the past decades, several strategies have been reported to
regulate the property variation with temperature [30e36]. Wu and
Zheng et al. successfully prepared KNN-based piezoelectric ceramics
with excellent temperature stability (d33 remains within 6% change
in the temperature range from 25  C to 100  C) by designing
compositionally graded multilayer composites with multiple suc-
cessive phase transitions under the cooperative contribution of the
continuous phase transitions, the strain gradient and the comple-
mentary effects of each component layer [37]. Li and Liu et al. re-
ported that piezoelectricity and thermal stability can be
simultaneously enhanced by incorporating perovskite compounds
with Zr ions at B-site, good piezoelectric properties (d33 of 450 pC/N)
and excellent thermal stability of d33 (variation less than 10% in the
temperature range of 22e80  C) and strain (fluctuation range less
than 0.13% in the temperature range from room temperature to
150  C) are achieved in the composition with x ¼ 0.25 [38].
In this work, the Ba-doped KNNS-BxBAZ textured ceramics were
prepared by the template grain growth (TGG) method. The effects
of the Ba-doped on the properties were investigated and high-
lighted. Good piezoelectric properties (d33 of (406 ± 15) pC/N) and
excellent temperature stability (d33 maintained within ±20%
change in a wide temperature range from 25  C to 200  C and strain
variation was less than 5% in the temperature range from room
temperature to 165  C) were simultaneously achieved in the
composition with x ¼ 0.2. We believed that this work will provide
new insights into improving the temperature stability of lead-free
piezoelectric ceramics by chemical composition engineering.
2. Experimental section
The <001> textured 0.97(K0.48Na0.52)(Nb0.96Sb0.04)O3-0.03Bax(-
Bi0.5Ag0.5)1-xZrO3 (abbreviated as KNNS-BxBAZ, x ¼ 0.1, 0.2, 0.3 and
0.4) ceramics were prepared by the template grain growth (TGG)
method. The raw materials, including K2CO3 (99%), Na2CO3 (99.95%),
Nb2O5 (99.98%), Sb2O3 (99.99%), BaCO3 (99.99%), Bi2O3 (99%), Ag2O
(99.7%), ZrO2 (99%) were weighed according to the stoichiometric
proportions, and then ball-milled for 16 h in ethanol solution. After
drying, the powders were calcined at 850  C for 5 h. Next, the
powders were secondly ball-milled for 50 h and sieved to obtain
fine-sized powder. To prepare tape-casting slurries, KNNS-BxBAZ
Fig. 1. (a) XRD patterns of KNNS-BxBAZ (x ¼ 0.1, 0.2, 0.3, 0.4) textured ceramics in the 2q range of 20 e60 ; (b) Rietveld refinement of the XRD profiles for the KNNS-BxBAZ (x ¼ 0.2)
textured ceramics.
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Journal of Materiomics 9 (2023) 261e268
matrix powders, 3% (in mole) NaNbO3 templates, 0.5% (in mass, the
same below) MnO2 (99.95%) and 40% binder were mixed in a solvent
70% alcohol and 30% toluene). Then, the slurries were tape-casted on
glass board to form tapes. The tapes were stacked and then pressed
at a pressure of 20 MPa and a temperature of 65  C for 20 min. After
removing organic binder, the samples were sintered firstly at a high
temperature of 1 190  C, and then rapidly cooled to a low tempera-
ture of 1 090  C, heating preservation for 6 h.
The crystal structure of the ceramics was determined by X-ray
diffraction characterization with Cu Ka radiation (XRD, D/MAX
2550 V, Rigaku, Japan). The microstructure was analyzed using
field-emission scanning electron microscope (FE-SEM, Carl Zeiss,
Merlin Compact). The temperature-dependent dielectric properties
were measured by LCR meter (E4980A, Agilent). The polarization
hysteresis (P-E), electric field-induced strain (S-E), and temperature
dependence of d33-E loops were tested by a ferroelectric test system
(aix-ACCT TF Analyzer 3000, Germany). After the ceramics were
poled under 20 kV/cm for 25 min, the d33 values were tested using a
quasi-static d33 m (YE2730A, China). The planar electromechanical
coupling factor (kp) was determined by the resonance and anti-
resonance frequencies collected using an impedance analyzer
(Agilent 4294A, USA). The domain structures were observed using
transmission electron microscopy (TEM, FEI Talos F200X, USA).
3. Results and discussion
Fig. 1a shows the XRD patterns of KNNS-BxBAZ textured ceramics.
The pristine perovskite structure of all ceramics proved that BxBAZ
and Sb diffused well into the ceramic matrix [39,40]. All the ceramics
exhibited crystal orientation along the <001> direction, being
confirmed by the (001)/(100) and (002)/(200) diffraction peaks in
the XRD pattern were significantly stronger than other peaks. The
phase structure of KNNS-BxBAZ textured ceramics was determined
by the Rietveld refinement. As shown in Fig. 1b, both the low Rp value
of 4.37% and the c2 value of 1.097 for the representative sample
x ¼ 0.2 prove high reliability of Rietveld refinement results. There-
fore, the sample with x ¼ 0.2 was determined to be orthorhombic
phase at room temperature. The εr-T curves measured in the tem-
perature range of 25e400  C were performed to further prove the
phase transition of KNNS-BxBAZ textured ceramics, as shown in
Fig. 2. For the Ba modified KNNS-BxBAZ textured ceramics with
x ¼ 0.1, 0.2, 0.3 and 0.4, the ferroelectric orthorhombic-tetragonal
phase transitions temperature (TO-T) was much higher than room
temperature, meaning that the crystal symmetry of KNNS-BxBAZ
textured ceramics was dominantly orthorhombic phase, which is
S. Gao, P. Li, J. Qu et al. Journal of Materiomics 9 (2023) 261e268

Fig. 2. εr-T curves of KNNS-BxBAZ (x ¼ 0.1, 0.2, 0.3, 0.4) textured ceramics measured from 25  C to 400  C at varied frequencies.

consistent with the results revealed by XRD patterns.
Fig. 3 gives the cross-sectional SEM images of the polished and
thermally etched KNNS-BxBAZ textured ceramics, where the ho-
mogeneous microstructure and grain growth perpendicular to the
tape casting direction can be clearly observed. It is worth noting
that the textured ceramics with x ¼ 0.2 have larger grain size and
more orderly arrangement, showing excellent crystal orientation
characteristics, which is beneficial to the electromechanical prop-
erties and temperature stability of piezoelectric ceramics.
The polarization-electric field (P-E) hysteresis loops of KNNS-
BxBAZ textured ceramics are shown in Fig. 4a. Well-saturated
square P-E loops and large remnant polarization (Pr) for all

Fig. 3. Cross-sectional SEM images of KNNS-BxBAZ (x ¼ 0.1, 0.2, 0.3, 0.4) textured ceramics with (a) x ¼ 0.1, (b) x ¼ 0.2, (c) x ¼ 0.3, (d) x ¼ 0.4.

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S. Gao, P. Li, J. Qu et al. Journal of Materiomics 9 (2023) 261e268

Fig. 4. (a) Polarization hysteresis (PeE) loops. Electric field-induced bipolar strain curves (b) and unipolar strain curves (c) of KNNS-BxBAZ (x ¼ 0.1, 0.2, 0.3, 0.4) textured ceramics.
(d) d33 and kp values of KNNS-BxBAZ textured ceramics.

textured ceramics indicate excellent ferroelectric properties. The x ¼ 0.2 textured ceramics at an electric field of 40 kV/cm. Fig. 4d
bipolar and unipolar strains of KNNS-BxBAZ textured ceramics are shows the d33 and kp values of KNNS-BxBAZ textured ceramics. The
shown in Fig. 4b and c. Symmetric butterfly-like bipolar strain KNNS-BxBAZ textured ceramics with x ¼ 0.2 exhibit high piezo-
curves and large strain of ~0.17% were observed in x ¼ 0.1 and electric response with a longitudinal piezoelectric coefficient

Fig. 5. Bright-field TEM images (aec) and the corresponding SAED patterns (def) for the KNNS-BxBAZ textured ceramics with x ¼ 0.2.

264
S. Gao, P. Li, J. Qu et al.
d33¼(406 ± 15) pC/N and excellent electromechanical coupling
performance with a planar electromechanical coupling factor
kp ¼ 63%. The excellent piezoelectric properties can be interpreted
by engineered domain configuration. Engineered domain configu-
rations “4O” can be formed when poled along <001> directions for
the orthorhombic mm2 crystals with the spontaneous polarization
direction of <00l>. The favorable “4O” engineered domain config-
uration facilitates polarization rotation and thus enhances the
Fig. 6. Temperature dependence of in-situ d33 values of KNNS-BxBAZ (x ¼ 0.1, 0.2, 0.3,
0.4) textured ceramics.
Fig. 7. d33-E loops and d33,T/d33,RT of KNNS-BxBAZ (x ¼ 0.1, 0.2, 0.3, 0.4) textured ceramics (aed) as a function of temperature.
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Journal of Materiomics 9 (2023) 261e268
piezoelectric activity in the textured ceramics [41e43].
It is well known that the piezoelectric response is closely related
to the domain morphologies. In order to analyze the domain
structures, the TEM images of the x ¼ 0.2 sample as representative
are depicted in Fig. 5a-c. The stripe-like domains with a width of
(59 ± 12) nm observed inside the grains. These nano-sized domains
are readily to response under the external excitation due to the
decreased domain wall energy, and boost the piezoelectric prop-
erties [44]. Furthermore, the smaller domain structures were
observed in Fig. 5b. These nanodomains exhibit lower domain wall
energy and more flexible features under the external excitation,
which is conducive to the improvement of piezoelectric perfor-
mance [45e47]. Fig. 5d-f illustrate the SAED patterns collected from
the same grain (Fig. 5c) along the [0_1 1], [1_1_1] and [_11_2] zone
axes, which is well matched with the standard card of ortho-
rhombic phase. These results further prove that the x ¼ 0.2 sample
shows an orthorhombic phase structure at room temperature [27].
It is important to significantly improve the temperature stability
of piezoelectric ceramics to meet the requirements of their appli-
cations in devices. Therefore, the temperature stability of piezo-
electric properties for the KNNS-BxBAZ textured ceramics has been
systematically evaluated. Fig. 6 shows the temperature dependence
of the in-situ d33 value of KNNS-BxBAZ (x ¼ 0.1e0.4) textured ce-
ramics. One can see that with the increase of temperature, the d33
values of all samples increased at first and then decreased. It is
worth noting that the d33 variation of x ¼ 0.2 sample is less than
±20% in the temperature range from room temperature to 200  C,
demonstrating excellent thermal stability of piezoelectric perfor-
mance. Fig. 7 shows the d33-E loops and normalized d33 (d33,T/
d33,RT) of KNNS-BxBAZ (x ¼ 0.1, 0.2, 0.3, 0.4) textured ceramics (a-d)
S. Gao, P. Li, J. Qu et al.
Fig. 8. XRD patterns of KNNS-BxBAZ ceramics with x ¼ 0.2 at different temperatures.
as a function of temperature from room temperature to 165  C. The
small signal piezoelectric coefficient d33 can also be approximately
extracted from the d33(E) loops when E ¼ 0. Obviously, the d33
values of KNNS-BxBAZ textured ceramics with x ¼ 0.1, 0.3 and 0.4
show dramatic change with the increase of temperature, while for
the x ¼ 0.2 sample the fluctuation range of d33 is within ±16% from
room temperature to 165  C.
Fig. 9. Polarization hysteresis (PeE) loops and Pr,T/Pr,RT of KNNS-BxBAZ (x ¼ 0.1, 0.2, 0.3, 0.4) textured ceramics (aed) as a function of temperature.
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Journal of Materiomics 9 (2023) 261e268
The results of Figs. 6 and 7 demonstrate KNNS-BxBAZ textured
ceramics with x ¼ 0.2 have outstanding temperature stability,
which may be related to the phase structure of ceramics at room
temperature or the evolution characteristics of phase structure
with temperature. Fig. 8 shows the temperature dependence of the
XRD pattern of KNNS-BxBAZ textured ceramics with x ¼ 0.2. In the
temperature range from room temperature to 110  C, the diffraction
peaks remain stable, indicating that the phase structure exists
stably in this temperature range, which is also proved by the εr-T
curves. The O-T phase transition temperature TO-T is much higher
than room temperature, indicating pure orthorhombic phase can
persist over a wide temperature range around room temperature.
The almost unchanged phase structure with respect to temperature
contributed to the thermally stable piezoelectric properties for the
KNNS-BxBAZ textured ceramics with x ¼ 0.2 [48]. The results in this
work prove that postponing the phase transition temperature far
away from room temperature by chemical composition engineer-
ing is an effective strategy to improve the thermal stability of
piezoelectric properties in KNN-based ceramics.
Piezoelectric response is closely related to dielectric and ferro-
electric properties. The P-E loops and normalized remnant polari-
zations (Pr,T/Pr,RT) of KNNS-BxBAZ (x ¼ 0.1, 0.2, 0.3, 0.4) textured
ceramics (a-d) as a function of temperature from room temperature
to 165  C are shown in Fig. 9. The temperature dependence of Pr for
the samples with difference x was compared and the x ¼ 0.2 sample
exhibits the best temperature stability (the Pr variation is less than
12%) in the measured temperature range. The results demonstrated
that incorporating with Ba ions can enhance temperature stability
of KNN-based ceramics. Based on the above analysis, we believed
S. Gao, P. Li, J. Qu et al.
Fig. 10. Unipolar strain curves (a) and ST/SRT (b) of KNNS-BxBAZ (x ¼ 0.2) textured ceramics as a function of temperature.
that the good temperature stability of KNNS-BxBAZ textured ce-
ramics with x ¼ 0.2 mainly comes from three aspects. Firstly, the
ceramics maintain a stable orthorhombic phase structure in a wide
temperature range (25e110  C), which reduces the influence of
phase structure transformation on piezoelectric properties. Sec-
ondly, the temperature insensitivity of crystal orientation also
significantly improved the temperature stability of piezoelectric
properties. Finally, the decreasing trend of the piezoelectric
response caused by the deteriorating ferroelectricity can be
compensated by the enhanced dielectric property, contributing to
the good temperature stability [38,49].
Fig. 10 shows the unipolar strain curves and normalized strain
(ST/SRT) of KNNS-BxBAZ (x ¼ 0.2) textured ceramic as a function of
temperature from room temperature to 165  C. The x ¼ 0.2 sample
still exhibits the outstanding temperature stability. As shown in
Fig. 10a, the unipolar strain for the x ¼ 0.2 sample reaches ~0.17% at
40 kV/cm, and is insensitive to temperature variation. To further
intuitively observe the variation of unipolar strains of the x ¼ 0.2
sample, the ratio of strain values between the strain values at
different temperatures and room temperature were calculated, as
shown in Fig. 10b. One can see that with the increase of tempera-
ture, the strain values of x ¼ 0.2 sample fluctuated around 0.17% and
the strain variation is less than 5% in the temperature range from
room temperature to 165  C. The results demonstrate that syner-
gistic effect of crystal orientation and chemical composition engi-
neering is an effective strategy to boost the temperature stability of
strain properties in KNN-based ceramics.
4. Conclusions
In this paper, the effect of incorporating with Ba ions on the
piezoelectric properties and temperature stability was investigated
in KNN-based textured ceramics. Excellent temperature stability of
piezoelectric properties (d33 maintained within ±20% change in a
wide temperature range from 25  C to 200  C) and strain properties
(strain variation was less than 5% in the temperature range from
room temperature to 165  C) was achieved in KNNS-BxBAZ textured
ceramics with x ¼ 0.2. The high phase transition temperature (TO-
 [10] Yang W, Wang Y, Li P, Wu S, Wang F, Shen B, Zhai J. Improving electrome-
T~110 C) evoked by Ba-doping accounts for the enhancement of
the temperature stability. In addition, the temperature insensitivity
of crystal orientation also significantly improved the temperature
stability of piezoelectric properties. This study provides a new idea
and solution for chemical composition engineering to improve
temperature stability.
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Journal of Materiomics 9 (2023) 261e268
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.
Acknowledgement
This work was supported by the National Natural Science
Foundation of China (No. 52102132), Natural Science Foundation of
Shandong Province of China (Nos. ZR2020QE043, ZR2020ME031
and ZR2020ME033), Innovation Team of Higher Educational Sci-
ence and Technology Program of Shandong Province (No.
2019KJA025), and Research Foundation for the Doctoral Program of
Liaocheng University (No. 318051932).
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Shuo Gao is currently pursuing his M.S. degree in the
school of Materials science and engineering, Liaocheng
University. His research interest is mainly on lead-free
ferroelectric/piezoelectric ceramics.
Peng Li received his Ph.D. degree from Tongji University in
2019. He has been a lecture of School of Materials Science
and Engineering at Liaocheng University, since 2019. His
research interests include synthesis and characterization
of lead-free ferroelectric/piezoelectric ceramics and thin
films.
Dr. Wei Li received his B.S. degree in inorganic non-
metallic materials from Jiangsu University in 2004, M.S.
degree in materials science from Nanjing University of Sci-
ence & Technology in 2006 and Ph.D. degree in materials
science & engineering from Tongji University in 2015. He
has worked at the School of Materials Science and Engi-
neering, Liaocheng University since 2006. He was a
visiting scholar at University of Wollongong in Australia
from 2018 to 2019. His main research interest is composi-
tion design and property modification of ferroelectric/
piezoelectric materials.