High Performance, High Temperature Perovskite
Piezoelectrics
T.R. Shrout, S.J. Zhang, R. Eitel, C. Stringer, and C.A. Randall
Materials Research Institute, The Pennsylvania State University,
University Park, PA 16802 USA
Phone: (814) 865-1645; Fax: (814) 865-2326; e-mail: tshrout@psu.edu
Abstract: The industrial and scientific communities have
expressed the need for sensing and actuation over a broad
temperature range. This review presents high temperature
piezoelectric materials that are commercially available and
those that are under development. Key materials, in order of
increasing Curie Temperature (Tc), are Pb(Zr,TiO)3 (PZT),
PbTiO3, (Pb,Ba)Nb2O6, Na0.5Bi4.5Ti4O15, and LiNbO3. The
maximum operation temperature is limited by Tc and
dielectric loss combined with the level of electrical resistivity.
With increased Tc also comes the expense of reduced
piezoelectric coefficient (d), being further reduced in non-
morphotropic phase boundary (MPB) systems. Recently new
high Tc systems with MPBs analogous to PZT have been
developed. Predicted by a perovskite crystal structure
tolerance factor relationship, compositions based on
Bi(Me)O3–PbTiO3, where Me=Sc+3,(Mg+2,Ti+4), etc., exhibit
piezoelectric activity compared to PZT, with Tcs greater than
100˚C higher, making them promising candidates for high
temperature applications.
I. INTRODUCTION
New application areas for actuator and transducer
design continue to be the driving force for the innovation of
new piezoelectric materials. The piezoelectric coefficient
(dijk), electromechanical coupling (kij), and dielectric
permittivity (εij) are the most important parameters that
determine device performance. Most piezoelectric ceramics
are based on the perovskite Pb(Zr1-xTix)O3 (PZT), offering
high piezoelectric activity and coupling, a range of
dielectric permittivity, and low dielectric loss.[1] The high
performance piezoelectric ceramics are based around a
specific set of compositions that have two ferroelectric
phases in equilibrium over a relatively temperature-
independent range. These compositions correspond to a
morphotropic phase boundary (MPB), as shown in Figure
1.[2, 3] The high piezoelectric properties translate into
actuator and transducer performance in the form of high
strain, sensitivity, and bandwidth.
Recently, the automotive and aerospace industries have
both expressed the need for actuation and sensing over a
broader temperature range than currently available. In
automotive electronics, under-hood applications, such as
pre-ignition knock sensors and fuel injection nozzles for
diesel engines, result in reduced emissions and improved
engine efficiency. Environments of 150˚C with repeated
thermal cycles are at present considered the automotive
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norm, with higher temperatures projected in the near
future.[4-7] In particular, the aerospace and aircraft
industries have especially difficult high temperature
requirements. With space and weight at a premium, engine
designers and builders find it difficult to protect sensitive
electronic systems in a cool, remote place. Electronic
controls are to be placed directly inside jet engines because
of reliability and noise requirements. Sensor devices for
such systems need to be built that can withstand
temperatures ≥ 300˚C while allowing long service lifetimes.
In the following section, new materials that target high
temperature piezoelectric applications in both
polycrystalline and single crystal forms will be reviewed in
contrast to current state-of-the-art materials.
II. BACKGROUND
Piezoelectric materials commonly found in commercial
sensors and actuators are listed in Table I as a function of
increasing transition temperature.[1, 8-14] In addition to
ferroelectrics, of which piezoelectric activity is limited to
below Tc, non-ferroelectric piezoelectrics, such as quartz,
are also included.
From this table, it is clear that both the dielectric ( )
and piezoelectric activity (d) falls off dramatically for
materials with increasing Tc. It is evident that the existence
of a morphotropic phase boundary (MPB) is essential to
achieve high levels of dielectric and piezoelectric activity.
Specifically, perovskite MPBs, such as PZT, exhibit nearly
an order of magnitude higher levels of piezoelectric activity
(d33) as compared to non-MPB systems and nearly two
orders of magnitude higher than that of non-ferroelectric
piezoelectrics, such as quartz, langasites, and GaPO4, the
latter two not listed. Furthermore, it appears that a
perovskite MPB is also essential, exhibiting higher levels of
piezoelectric activity than MPBs found in non-perovskite
systems, such as the tungsten bronze family.
In summary, perovskite materials with MPBs
exhibiting Tcs significantly higher than that of PZT are
desired for high performance, high temperature
piezoelectric applications.
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 Fig. 1(b). Enhanced dielectric and piezoelectric properties for
Fig. 1(a). PbZrO3–PbTiO3 (PZT) phase diagram showing the morphotropic
compositions near the MPB in PZT.[2]
phase boundary (MPB) at ~48% PbTiO3.[2, 15]

Table I. Room Temperature Electrical Properties of High Temperature Piezoelectric Materials

Piezoelectric Piezoelectric Electromech-

strain constant voltage constant anical coupling
(10-12 C/N) (10-3 Vm/N)
Material Structure Curie point Dielectric d33 d15 g33 g15 k33 k15
Tc (˚C) Permittivity ( r)
Pb(Zr,Ti)O3[1] Perovskite (MPB) 190 3400 593 741 20 27 0.75 0.68
DoD Type VI Perovskite (MPB) 330 1800 417 584 25 41 0.73 0.77
DoD Type II
[8, 16]
(BaPb)Nb2O6 Tungsten bronze 400 300 85 100 32 46 0.30 —
(BPN) [9]
PbTiO3 Perovskite 470 190 56 68 33 32 0.45 —
(PT) [10, 11]
Na0.5Bi4.5Ti4O15 Bismuth Layer ~600 140 18 15 0.15 —
(NBT) [12]
LiNbO3 Corundum 1150 25 6 69 23 91 0.23 0.60
(LN) [13]
SiO2 [14] α-Quartz N/A 4.5 2(d11) 50

III. NEW HIGH TEMPERATURE (TC) MORPHOTROPIC properties of BS –PT and BMT-PT systems, as contrasted to
PHASE BOUNDARY PEROVSKITES selected PZT compositions.
Since the discovery of PZT in the 1950s, researchers
have yet to discover alternative MPB systems with Tcs
higher than that of PZT. Recently, new high Tc MPB
systems have been projected and experimentally confirmed
in the perovskite Bi(Me)O3–PbTiO3 family of solid
solutions.[17, 18] Specific examples include Bi(Sc)O3–
xPbTiO3 and Bi(Mg,Ti)O3–PbTiO3, which exhibit MPBs
with Tcs of 440˚C and 480˚C, respectively.[18, 19] The
high temperature phase diagram for the solid solution
system (1-x)BiScO3–PbTiO3 is given in Figure 2.[20] It is
interesting to point out that the Curie temperatures (Tc) for
compositions in the tetragonal phase field (0.7 = x ≤ 95
mol%) exhibit Tcs greater than the end member PbTiO3.
This behavior has also been observed in the Bi(Mg,Ti)O3–
PbTiO3 and also by Nomura et al. in the PbTiO3–
Bi(Zn2/3Nb1/3)O3 system.[19, 21] Analogous to PZT, these Figure 2. Phase diagram for the system BiScO3–PbTiO3 (x > 0.5) showing
systems exhibit enhanced dielectric and piezoelectric a MPB @ ~ 0.64 PT.[20]
activity for MPB compositions. Table II summarizes the

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 As reported in Table II, the new MPB systems exhibit
comparable dielectric and piezoelectric properties to PZT
with Tcs > 100˚C higher. Furthermore, it is important to
point out that the data given for the new systems are for
undoped compositions.
The higher Tc of the new perovskite systems translates
into corresponding higher temperature range of operation,
as shown in Figure 3. As presented, the piezoelectric
activity of the BS-PT system extends out more than 100˚C
than that of PZT-5 (DoD Type II).

Figure 3. Temperature dependence of electromechanical coupling

coefficient k31 for BS-PT (MPB) and PZT-5 (DoD Type II).

Table II. Piezoelectric properties of novel perovskite systems and PZT.[1, 19, 22]

Composition Structure Tc (˚C) ε33T d33 (pC/N)

PZT DoD Type VI MPB 190 3400 593
DoD Type II MPB 330 1800 417
Undoped MPB 386 730 229
Current Work
BS-xPT x=0.62 Rhombohedral 440 900 280
x=0.64 MPB 450 2000 460
x=0.66 Tetragonal 460 1400 260
B(MgTi)–xPT x=0.36 MPB 480 1000 280

IV. NEW HIGH TEMPERATURE, HIGH STRAIN

PIEZOELECTRIC SINGLE CRYSTALS
Recently, domain engineered single crystals in the
perovskite system Pb(Zn1/3Nb2/3)O3–PbTiO3 (PZN-PT) and
Pb(Mg1/3Nb2/3)O3–PbTiO3 (PMN-PT) MPB system have
revealed piezoelectric activity far superior to that found in
polycrystalline ceramics with coupling coefficients > 90%
and piezoelectric d33 values exceeding 2000 pC/N.[23]
However, despite this technological breakthrough, these
materials offer relatively low TCs, being further limited by
the low temperature phase transitions (~100˚C) between
rhombohedral and tetragonal phases associated with a
strongly curved MPB boundary. Unlike PZT, single
crystals in the new system BS-PT could be readily grown
using the high temperature flux technology.[24-26] As Figure 4. High temperature piezoelectric properties for BS –PT crystal
(x=0.57) in the [001] direction.
expected, high piezoelectric properties were observed, as
shown in Figure 4, for a rhombohedral composition @
In polycrystalline form, BS-PT demonstrates a
x=0.57, with d33 > 1000 pC/N and k33 ~ 90%, with Tc >
high transition temperature Tc ≈ 450˚C at the MPB. The
400˚C.
piezoelectric properties d33 ≈ 500 pC/N, at room
temperature, are competitive with state-of-the-art PZTs,
V. SUMMARY which exhibit lower transition temperatures.
High temperature piezoelectrics are of interest for Through flux grown crystals of BiScO3–PbTiO3 in
future actuators, sensors, and more temperature stable the rhombohedral ferroelectric phase and in the <001>
piezoelectric devices. BiMeO3–PbTiO3 solid solutions are orientation, high k33 ~ 0.90, combined with high transition
an extremely promising family of materials to fulfill these temperature is possible. From these observations, it is clear
needs and possess higher electromechanical performance that there is a large body of work remaining to optimize
than traditional complex lead-based perovskite solid high temperature piezoelectric materials.
solutions, such as PZT.

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 ACKNOWLEDGMENTS Perovskite. The Structure of PbZr0.52Ti0.48O3," Physical
This work was sponsored, in part, by ONR, Review B, Vol. 61, No. 13, pp. 8687-8695, 2000.
DARPA, and NIH. Thanks also to Joanne Aller for typing [16] MIL-1376B(SH), "MIL-STD-1376B(SH)," in
this manuscript. Finally, thanks to Dr. Wada. Piezoelectric Ceramic Material and Measurements
Guidlines for Sonar Transducers. Department of
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