Materials Letters 59 (2005) 3471 3475

www.elsevier.com/locate/matlet

Piezoelectric materials for high power, high temperature applications

Shujun Zhang a,*, Ru Xia a, Laurent Lebrun b, Dean Anderson c, Thomas R. Shrout a
a
Material Research Institute, Pennsylvania State University, University Park, PA, 16802, USA
b
Laboratoire de Genie Electrique et Ferroelectricite, INSA de Lyon, 69621 Villeurbanne Cedex, France
c
TRS Ceramics, State College, PA, 16801, USA

Received 27 April 2005; accepted 10 June 2005

Available online 14 July 2005

Abstract

High intensity focused ultrasound (HIFU) and ultra sound-guided HIFU therapy require probes capable of both high quality diagnostic
imaging and radiating high acoustic power into tissue. Piezoelectric materials with high mechanical quality factor Q, large electromechanical
coupling (k ij) and high dielectric constant K T are desired to meet the demands of advanced high power electromechanical applications. In
addition, a high Curie temperature is desired because of wider temperature usage and improved temperature stability. Previous investigations
have shown that Q or k ij and K T can be enhanced only at the expense of each other. Also materials with higher Curie temperature were found
to possess lower dielectric and piezoelectric performance. Therefore, modified piezoelectric materials (including polycrystalline and single
crystals) were reviewed as a function of Curie temperature. Optimization of performance was exemplified with Pb(Sc1 / 2Nb1 / 2)O3 PbTiO3
(PSNT) compositions close to the morphotropic phase boundary (MPB) and the effect of manganese additions on Q, coupling k 33 and K T,
respectively.
D 2005 Elsevier B.V. All rights reserved.

Keywords: High power; PSNT; Piezoelectric; High temperature; Hard material

1. Introduction [1]. PbZr1 x Tix O3 (PZT) ceramics with morphotropic

The high power characteristics of piezoelectric materi-
als have been investigated for device applications includ-
ing ultrasonic motors, transformers and medical ultrasonics
applications, such as acoustic radiation force impulse
(ARFI) imaging and ultrasound-guided HIFU therapy.
Currently, high power applications are limited by the
internal power dissipation, which will generate heat and
increasing hysteretic effects resulting in thermal instability.
Thus, a piezoelectric material is desired which has a high
mechanical Q (low loss) to meet the requirement for
delivering higher power, in addition, materials with high
dielectric constant and electromechanical coupling are
required for improved imaging performance, e.g. sensitiv-
ity and/or bandwidth for medical ultrasonic transducers
* Corresponding author.
E-mail address: soz1@psu.edu (S. Zhang).
0167-577X/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2005.06.016
phase boundary (MPB) compositions have anomalously
high dielectric and piezoelectric properties as a result of
enhanced polarizability arising from the coupling between
two equivalent energy states, i.e., the tetragonal and
rhombohedral phases, allowing optimum domain reorien-
tation during the poling process. Further modifications
using acceptor and donor dopants give us the wide range
of piezoelectric compositions we have today. Generally,
acceptor dopants include lower valence additives (Fe3+,
Mn2+,3+, Ni3+, Co3+, K+), which play a hardening role in
the materials by pinning domain wall motion and
thus reducing internal loss and enhancing coercive field
EC, but at the expense of decreasing dielectric and
piezoelectric performance. In contrast, donor dopants,
which include higher valence additives (La3+, Sb5+, Bi3+,
W6+, Nb5+), generate lead vacancies and subsequent
enhancement of the dielectric and piezoelectric properties
[2 4]. However, to simultaneously achieve high values of
Q and good dielectric and piezoelectric behavior in one
3472 S. Zhang et al. / Materials Letters 59 (2005) 3471 3475

material is against the conventional concept of hard and
soft piezoelectric characteristics. So figure of merit
(product of Q, k ij and K T K T I k ij I Q) is an important
factor to value piezoelectric materials used in high power
applications.
PZT also offers the additional merit of a high T C (> 300
-C). High T C materials are desired owing to their expanded
operating temperature range, reduced properties temperature
dependence and enhanced acoustic power [5]. Recently,
new MPB compositions were identified in the perovskite
BiScO3 PbTiO3 (BSPT) system exhibiting a high T C > 450
-C with comparable piezoelectric properties to soft PZT [6].
It was reported when modified by Pb(Mn1 / 3Nb2 / 3)O3, this
material was found to possess Q values of 1000, but at the
cost of piezoelectric properties, which was found to be only
80 pC/N [7].
Ferroelectric perovskite single crystals, such as Pb(Zn1 / 3
Nb2 / 3)O3 PbTiO3 (PZNT) are promising for high per-
formance piezoelectric actuators and transducers because
of their ultrahigh piezoelectric coefficients (2000 pC/N),
dielectric constant (5000) and electromechanical cou-
pling factor (90%) [8]. However, the Q value for single
crystals is generally very low (< 100), which is similar
to soft PZT materials. It is proposed that hard single
crystals can be obtained by acceptor dopants, analogous
to hard PZT materials. PZNT single crystals with
rhombohedral and tetragonal phases were modified by
acceptor dopants, such as manganese or cobalt ions
and found to exhibit hard characteristics [9 12]. The Q
value was found to depend on the orientation of the
single crystal, in which the value for [110] direction is
much higher than that of [001] orientation, meanwhile
degrading the piezoelectric properties. As noted, the
above systems are limited by their inherently low T Cs
(< 200 -C).
In this paper, piezoelectric polycrystalline and single
crystal materials are surveyed; the mechanical quality factor
Q and electrical properties as a function of Curie temper-
atures are summarized. As an example, Pb(Sc1 / 2Nb1 / 2)O3
PbTiO3 (PSNT) materials with MPB compositions are

Table 1
Piezoelectric and dielectric properties for selected hard PZT, PMNT ceramics and single crystals
Material T C (-C) KT Loss Q k 33 kp d 33 (pC/N) Refs.
PZT4 328 1300 0.004 500 0.713 0.58 289 [2,3]
PZT8 300 1000 0.004 1000 0.64 0.51 225 [2,3]
PZ54 225 2500 0.004 1500 0.71 0.6 500 [21]
Fuji-C213 318 1500 0.003 2500 0.68 0.58 320 [22]
APC841 320 1350 0.004 1400 0.68 0.6 300 [23]
APC880 310 1000 0.004 1000 0.62 0.5 215 [24]
PZT-Mn,F 282 1600 0.002 1300 0.7 0.6 360 [15,16]
PZT 290 1000 0.002 1800 0.65 0.51 230 /
PZ52 250 1900 0.003 550 0.73 0.6 420 [21]
PZT-PSM-Yb 250 550 / 1350 0.61 0.46 160 [20]
PZT4 314 1650 0.003 750 0.74 0.62 460 [24]
PZT8 305 1200 0.004 600 0.71 0.60 360 [24]
K300 330 1450 0.004 900 0.7 0.6 350 [25]
PZT 217 2900 0.006 1000 / / 400 [25]
PMNT-Na 178 4100 / 150 / / 360 [19]
PMNT-Mn 175 2100 / 300 / / 350 [18]
PSNT-Fe 275 2500 0.005 300 0.55 0.58 320 [18]
HK1-Mna 155 2400 0.008 480 0.66 0.52 450 [24]
HK1-Mna 155 3300 0.006 420 0.62 0.51 510 [24]
610-Mnb 205 2530 0.004 150 0.72 0.59 505 [24]
610-Mnb 206 1560 0.004 310 0.58 0.45 300 [24]
BSPT-PMN 400 500 / 1000 / 0.22 80 [7]
BaTiO3 115 1700 / 300 0.5 / 190 [2,3]
PT-Lu,Mn 470 170 / 1100 0.46 / 51 [2]
KNbO3 417 48 / 7600 0.4 / 18.5 [2,3]
LiNbO3 1150 30 / 10000 0.16 / 6 [2,3]
PZNT8-Mn,F 180 6000 0.002 300 0.93 / 3500 [10]
PZNT12-Ce 180 1300 0.002 450 0.85 / 500 [9]
PZNT12-Mnc 180 5300 0.002 750 0.6 / 550 [9]
PZNT12-Mnc 180 5300 0.002 1900d 0.18d / 167d [9]
PYNT46 325 2500 0.01 70 90% / 2200 [13]
BSPT57 402 3000 0.04 70 90% / 1150 [14]
a
HK1: modified PMNT.
b
610: modified PLZT.
c
[110] orientation.
d
Lateral mode, k 31 and d 31.
 S. Zhang et al. / Materials Letters 59 (2005) 3471 3475 3473

12000 0.9 Single crystal

Electromechanical Coupling k33

LiNbO3 PSNT-Mn
Modified PSNT
10000 0.8
PZNT Crystal
Modified PLZT
Modified PZT
Mechanical Quality Q

8000 KNbO3
Non-perovskite 0.7
materials
6000
0.6
Modified
PSNT-Fe
PMNT
4000 PMnN-PZT-Yb
0.5 Modified PMNT
Modified PZT PT-Lu, Mn
BaTiO3 ceramic
2000
0.4 nonlead
material KN crystal
PT-Mn,Lu
0
0.3
0 200 400 600 800 1000 1200 100 200 300 400 500
o
Curie Temperature Curie Temperature ( C)

Fig. 1. Mechanical quality factor Q as a function of Curie temperature Fig. 3. Electromechanical coupling factor k 33 as a function of Curie
various for hard piezoelectric materials. temperature various for hard piezoelectric materials.

modified to demonstrate the hardening effect in poly-
crystalline ceramics.
2. Survey of the hard materials
The dielectric and piezoelectric properties of various
commercial and reported hard piezoelectrics are summar-
ized in Table 1 with various trends in properties depicted in
Figs. 1 6. The survey includes hard PZT4 and PZT8,
relaxor-PT based MPBs ceramics and single crystal
relaxors. In addition, non-perovskite systems are also
included. From Fig. 1, the relationship of Q and T C is
clearly noted with the highest Qs reported with materials
with high T C. Furthermore, perovskites are limited to
T C < 330 -C for PZTs, with a higher T C in the new BSPT
system. The trends of dielectric constant and piezoelectric
properties are opposite to the Q relationship with T C (Figs. 2
and 4) with the highest values reported with low T C
materials. Fig. 3 depicts the electromechanical coupling
against T C, with the highest values for polycrystalline
materials corresponding to MPB compositions (T C inde-
pendent). For the case of single crystals, ultrahigh coupling
coefficients (> 90%) are noted even for the high T C systems,
such as Pb(Yb1 / 2Nb1 / 2)O3 PbTiO3 (PYNT) [13] and
BSPT [14] single crystals.
Fig. 5 shows the mechanical quality factor Q as a
function of dielectric constant, demonstrating that both high
Q and K T are incompatible, except in the case for various
orientations in single crystals [9].
Fig. 6 summarizes the figure of merit of commercial hard
PZT materials, single crystals, modified PMNT and PLZT
materials, manganese modified PSNT materials as a
function of Curie temperature. It was found that the
modified PZNT12 single crystals possess high value about
2.5  106, but low Curie temperature at 180 -C. Most of
the modified hard PZT materials exhibit figure of merit
range from 1 105 to 2.5  106, with the exception of PZ54,

PZNT crystal 2400 PZNT crystal

5000
PYNT crystal
2000
Dielectric Constant

4000
Piezoelectric d33

Modified PMNT PSNT-Mn

ceramic 1600
BSPT crystal
3000 BSPT crystal
PYNT crystal 1200
Modified PZT Modified Modified
2000
PMNT PLZT
BaTiO3
800
PSNT-Mn
Modified PZT
1000
PMnN-BSPT 400
KN crystal PT-Lu,Mn BaTiO3 PMnN-BSPT PT-Lu, Mn
0 KN
0
100 200 300 400 500 100 200 300 400 500
o o
Curie Temperature ( C) Curie Temperature ( C)
T
Fig. 2. Dielectric constant K as a function of Curie temperature various for Fig. 4. Piezoelectric coefficient d 33 as a function of Curie temperature
hard piezoelectric materials. various for hard piezoelectric materials.
3474 S. Zhang et al. / Materials Letters 59 (2005) 3471 3475

12000 Table 2
Piezoelectric properties for PSNT and manganese modified PSNT ceramics
Non-perovskite
10000 Material TC KT Loss Q k 33 kp d 33 EC
Materials
(-C) (pC/N) (kV/cm)
Mechanical Quality Q

8000 PSNT41 263 1790 0.013 50 0.8 0.71 530 6.38

PSNT42 266 2000 0.014 70 0.8 0.69 540 7.68
PSNT43 270 3400 0.016 50 0.75 0.67 660 8.57
6000
PSNT43.5 272 3500 0.016 50 0.72 0.64 620 9.34
PSNT44 276 3200 0.014 60 0.76 0.64 550 10
4000 Perovskite MPB PSNT41-Mn 260 900 0.002 960 0.77 0.63 325 10
Systems PSNT42-Mn 263 1150 0.003 1100 0.76 0.64 356 11
Relaxor PZNT PSNT43-Mn 265 2500 0.002 1400 0.74 0.64 500 11.7
2000
Crystal PSNT43.5-Mn 268 2750 0.002 830 0.73 0.63 505 9.6
PSNT44-Mn 271 2200 0.003 720 0.73 0.62 450 10.3
0
0 1000 2000 3000 4000 5000
Dielectric Constant 263 -C for PSNT41, increasing to 276 -C for PSNT44
ceramics. The highest dielectric constant was found to be
Fig. 5. Mechanical quality factor as a function of dielectric constant various 3500 for PSNT43.5, while the highest piezoelectric
for piezoelectric materials.
coefficient was found to be 660 pC/N for the PSNT43
material. The largest electromechanical coupling factor k 33
showing value of 2.7  106 at the cost of Curie temperature
was found to be 80% for PSNT41 and PSNT42 ceramics.
about 225 -C. In Fig. 6, the manganese modified PSNT
materials were found to show good figure of merit,
indicating modified PSNT also a very promising material (a)
for high power applications. 40 Q=250 Q=1200

In summary, it appears that no one piezoelectric material 20

can exhibit a combination of a high Q, high K T and coupling
Polarization (C/cm2)

0
k ij while exhibiting a high T C.
-20

-40
3. PSNT based hard ceramics 40 Q=800 Q=1000

20
From all the trends presented above (polycrystalline
only), it was deemed that a compromise in Q, K T, k ij, 0
while maintaining a relatively high T C could be achieved -20
within the relaxor-PT perovskite system PSNT, whose -40
MPB composition was found to be at 43% PT with a Curie -20 -10 0 10 20 -20 -10 0 10 20
temperature around 270 -C. As listed in Table 2, PSNT Electric Field (kV/cm)
materials with compositions close to the MPB were (b)
studied, in which the Curie temperature was found to be
0.2
Q=250 Q=1200
0.1
3.0x106 PZ54
0.0
PSNT-Mn
Modified PZNT12
Figure of Merit (K . kij . Q)

crystal -0.1
2.5x106
Strain (%)

-0.2
2.0x106
T

Modified
PZNT8 crystal
-0.3
0.2
Q=800 Q=1000
Modified PZT
1.5x106 0.1
Modified
PZNT4.5 0.0
1.0x106 crystal
Modified -0.1
HK1
5.0x105 -0.2
PT-Lu,Mn
BaTiO3
0.0 crystal Modified
Modified KNbO3 -0.3
PMNT
PLZT crystal -20 -10 0 10 20 -20 -10 0 10 20
100 200 300 400 500 Electric Field (kV/cm)
o
Curie Temperature ( C)
Fig. 7. Bipolar polarization versus electric fields hysteresis (a) and strain
Fig. 6. Figure of merit as a function of Curie temperature various for loops (b) for PSNT43 materials with different manganese doped level,
piezoelectric materials. exhibiting asymmetric shapes.
 S. Zhang et al. / Materials Letters 59 (2005) 3471 3475
The Q value of PSNT system was increased when
modified with manganese, analogous to PZT and PMNT
materials [15 19], the manganese ions enter into B site,
which will generate oxygen vacancies, consequently
pinning the domain wall motion, producing a hardening
effect in PSNT system. As listed in Table 2, the modified
PSNT materials exhibited somewhat reduced dielectric
constants, lower dielectric loss and piezoelectric coeffi-
cients, while showing larger coercive fields and much
higher mechanical quality factors, indicating an evident
hardening effect by the manganese additive. It was found
that the Q value increased from 250 to 1400 with different
manganese doped levels. Bipolar polarization and strain
hysteresis were measured at 20 kV/cm field and 1 Hz
frequency for PSNT43 materials with different levels of
manganese dopant, as presented in Fig. 7. The bipolar
polarization loops were found to be asymmetric due to an
internal bias, where the internal bias was only 4 kV/cm for
the material with low Q value at 250, while the internal
bias was found to increase to 8 kV/cm for the material
with higher Q value about 1200, showing the similar
tendency as other hard PZT materials.
4. Summary
Piezoelectric materials for potential use in high power
ultrasonic and imaging applications based on PZT and
PMNT ceramics, single crystals and PSNT ceramics were
surveyed and summarized. It was observed that generally,
materials with higher Curie temperature possess lower
dielectric constant, lower piezoelectric coefficient, but
higher Q values. Relaxor-PT single crystals with low Curie
temperature were found to possess ultrahigh K T and k ij, but
low Q value, while non-perovskite crystals with high Curie
temperature were found to possess very high Q value but
very low dielectric constant. No one system offered high Q,
high K T and coupling with a high T C > 200 -C. As a
compromise, manganese modified PSNT ceramics were
found to be promising materials for high temperature, high
power applications.
3475
Acknowledgment
The work was supported by NIH under grant # P41-RR
11795 and ONR.
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