Lead-Free Piezoelectric Materials

Review
JOURNAL OF ADVANCED DIELECTRICS

Vol. 5, No. 2 (2015) 1530002 (15 pages)
The Authors
DOI: 10.1142/S2010135X15300029
Lead-free piezoelectric materials and ultrasonic transducers for medical imaging

Elaheh Taghaddos, Mehdi Hejazi and Ahmad Safari*
Glenn Howatt Electroceramics Laboratories
Department of Materials Science and Engineering
Rutgers University, 607 Taylor Road, Piscataway, New Jersey 08854, USA
*safari@rci.rutgers.edu
J. Adv. Dielect. 2015.05. Downloaded from www.worldscientific.com

by UNIVERSITI KEBANGSAAN MALAYSIA on 12/08/15. For personal use only.
Received 2 March 2015; Revised 4 May 2015; Accepted 7 May 2015; Published 19 June 2015
Piezoelectric materials have been vastly used in ultrasonic transducers for medical imaging. In this paper, firstly, the most promising
lead-free compositions with perovskite structure for medical imaging applications have been reviewed. The electromechanical
properties of various lead-free ceramics, composites, and single crystals based on barium titanate, bismuth sodium titanate,
potassium sodium niobate, and lithium niobate are presented. Then, fundamental principles and design considerations of ultrasonic
transducers are briefly described. Finally, recent developments in lead-free ultrasonic probes are discussed and their acoustic
performance is compared to lead-based transducers. Focused transducers with different beam focusing methods such as lens
focusing and mechanical shaping are explained. Additionally, acoustic characteristics of lead-free probes including the pulse-echo
results as well as their imaging capabilities for various applications such as phantom imaging, in vitro intravascular ultrasound
imaging of swine aorta, and in vivo or ex vivo imaging of human eyes and skin are reviewed.
Keywords: Lead-free; piezoelectric; ultrasonic transducers; medical imaging.
1. Introduction
Piezoelectric materials generate polarization under application of a mechanical force. The generated polarization is
proportional to the applied force via a proportionality coefficient which is called the piezoelectric constant (dij ). Piezoelectric materials also exhibit a reverse piezoelectric effect
which is an electric field-induced displacement. The mechanical strain generated in these materials is also proportional to the applied electric field through the piezoelectric
constant.15
Ferroelectric materials are a subcategory of piezoelectrics
in which the direction of polarization can be switched by
application of an external electric field. Due to the internal
friction required to nucleate and switch ferroelectric domains
in different crystallographic orientation, ferroelectrics have a
characteristic hysteresis loop with a coercive field (the electric field required to switch the domains) and a remnant polarization. The remnant polarization in ferroelectrics is
permanent and does not disappear upon removing the electric
field. This is opposite to nonferroelectric piezoelectrics such
as ZnO, AlN, and quartz as well as anti-ferroelectrics which
do not possess a remnant polarization after the electric field is
removed.1,2,48
Due to their special characteristics, piezoelectric materials
have found hundreds of civil, military, and energy-related
applications. Automotive, computer, medical, and electronic
industries are the main customers of piezoelectric materials.
Disposable patient monitors, heart monitors, catheters, and
ultrasonic transducers for imaging and noninvasive therapy

are some of the medical applications of piezoelectrics.1,2,48
Materials used in aforementioned applications are mostly
based on lead-containing ferroelectric compositions such as
lead zirconate titanate PbZr0:5 Ti0:5 O3 (PZT), lead magnesium
niobatelead titanate Pb(Mg1=3 Nb2=3 )O3PbTiO3 (PMN
PT), and lead magnesium niobatelead indium niobate
lead titanate Pb(In1=2 Nb1=2 )O3Pb(Mg1=3 Nb2=3 )O3PbTiO3
(PINPMNPT).2,912 Lead is a volatile element with low
vapor pressure which can enter the atmosphere during high
temperature processing or recycling of piezoelectric ceramics. It can be directly (through inhalation) or indirectly
(contaminated food, rain, etc.) absorbed into the human body
and cause numerous side effects.1014 Some of the common
lead-poisoning symptoms with various degrees of severity are
mentioned in Table 1.
Therefore, in order to protect the environment and public
health, it is essential to explore new lead-free piezoelectrics
which can be used as alternatives for their lead-based counterparts. During last two decades, noticeable amount of research has been devoted to study lead-free piezoelectrics.
Although lead-free compositions in general show inferior
electromechanical properties compared to their Pb-based
counterparts, for some applications promising lead-free
ceramics have been introduced. There has been a remarkable
progress in development of lead-free piezoelectric ceramics
with improved electromechanical properties in the last decade. Soft lead-free piezoelectrics with high piezoelectric
This is an Open Access article published by World Scientific Publishing Company. It is distributed under the terms of the Creative Commons Attribution 3.0
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1530002-1
E. Taghaddos, M. Hejazi & A. Safari
J. Adv. Dielect. 5, 1530002 (2015)

Table 1. Symptoms and signs of lead poisoning.13,18

Mild
Moderate
Severe
Lethargy
Anorexia
Abdominal discomfort
Arthralgia
Anemia
Headache
Abdominal cramps
Gingival lead line
Peripheral neuropathy
Convulsions
Coma
Encephalopathy
Renal failure
lead-free piezoelectrics. This ceramic also showed a remarkable clamped dielectric constant " S33 ="0 of about
2820. However, the low Curie temperature of BZT50BCT
ceramic (TC 93 C) restricts the application of this lead-free
piezoelectric ceramic.23,24
1.2. BNT-based ceramics
coefficient and low Curie temperature have been introduced

for actuator and ultrasonic transducer applications. On the
other hand, hard lead-free piezoelectrics with a high electromechanical quality factor have been developed for high
power devices where minimal heat dissipation and power
consumption is needed.5,911,1517
Ferroelectric materials with perovskite structure (ABO3)
such as BaTiO3 (BT), (Bi0:5 Na0:5 )TiO3 (BNT), KNbO3 (KN),
and (K0:5 Na0:5 )NbO3 (KNN) are the most significant leadfree piezoelectric materials. These compositions show relatively large piezoelectric and dielectric properties and can be
utilized as active elements of ultrasonic transducers. In the
following sections, viable lead-free compositions are briefly
reviewed. Then, the acoustic performance of lead-free ultrasonic transducers are discussed and compared to lead-based
probes used for medical imaging.
1.1. BaTiO3-based piezoelectrics
The first discovered ferroelectric oxide with perovskite
structure is barium titanate (BaTiO3).2 BT has relatively high
electromechanical properties, high dielectric constant, and
low Curie temperature (TC 120 C). BT-based ceramics
have been mainly used for capacitor applications. Their low
Curie temperature restricts the working temperature range in
which these materials can be used.11 Numerous investigations
have been devoted to increase the Curie temperature and
enhance the electromechanical properties of BT-based
ceramics. The binary system of 1 xBaTiO3x(Bi0:5 K0:5 )
TiO3 was studied by Sasaki et al.19 Introducing bismuth
potassium titanate in BT system increased the Curie temperature TC , however, it diluted the piezoelectric properties.11,13 Substitution of Ba and Ti by small amount of Sr and
Zr resulted in distortion of the tetragonal unit cell.20
Ba1x Srx TiO3 and BaZrx Ti1x O3 ceramics exhibited high
dielectric tunability and dielectric constant. A high clamped
permittivity " S33 ="0 of about 1350 and d33 of 300 pC/N were
reported for (Ba0:95 Sr0:05 )(Zr0:05 Ti0:95 )O3 composition.21,22
The binary system of Ba(Ti0:8 Zr0:2 )O3(Ba0:7 Ca0:3 )TiO3
(abbreviated as BZTxBCT) was investigated by Liu and
Ren.23 The highest electromechanical properties were
achieved at BZT50BCT composition around the morphotropic phase boundary (MPB). An outstanding piezoelectric
coefficient d33 of 560620 pC/N was attained for this
composition which was noticeably higher than that of other
BNT-based piezoelectrics with a high remnant polarization

38 C cm 2 and moderate depolarization temperature
( 200 C) are one of the promising lead-free materials.25,26
Pure BNT ceramics, however, suffer from high conductivity
and a large coercive ( 73 kV cm 1 ) field which makes the
poling process difficult. In order to enhance the electromechanical properties and decrease the coercive field, binary or ternary solid solutions in the vicinity of MPB have
been developed. BT, Bi0:5 K0:5 TiO3 (BKT), Bi0:5 Li0:5 TiO3
(BLT) are the most widely used materials which have been
added to BNT ceramics to improve the electrical properties.27,28 A-site substituted BNT-based ceramics exhibit a
lower coercive field, lower sintering temperature and higher
electrical resistivity compared to pure BNT. It has been
found that solid solutions of BNT with BKT, BLT, and
BT form an MPB between rhombohedral and tetragonal
phases.11,2933 The MPB compositions exhibit the highest
electromechanical properties which are suitable for soft
piezoelectric applications. On the other hand, the rhombohedral structure shows higher mechanical quality factor
which is desired for high power applications.26,34,35 Table 2
provides properties of several BNT-based ceramics with
different compositions.
1.3. K0.5 N0.5 NbO3-based ceramics
Another family of lead-free piezoelectrics with perovskite
structure is based on ANbO3 where A is an alkali metal. The
ferroelectricity in potassium niobate KNbO3 (KN) was discovered by Matthias.13,37 Sodium potassium niobate with the
general formula of K1x Nx NbO3 (KNN hereafter) is a solid
solution of ferroelectric KN and antiferroelectric NaNbO3
compounds which shows promising electromechanical
properties. KNN ceramics possess high Curie temperature
(TC 420 C) and noticeable ferroelectric properties (Pr
33 C/cm2).38 The phase transitions and variations of dielectric properties of KNN versus temperature are reminiscent
Table 2. Properties of BNT-based piezoelectric ceramics.
Ceramic composition " T33 ="0

0.88BNTBKTBT
0.94BNTBKTBT
BNT0.06BT
0.88BNTBKTBT
0.76BNTBKTBLT
1530002-2
1000
490
730
440
1160
Td ( C)
d33
(pC N 1 )
k33 (%)
Ref.
113
185
150
220
170
181
92
125
84
174
56
48
55
47
61
34
34
30
31, 34, 36
31, 34, 36
J. Adv. Dielect. 5, 1530002 (2015)
Table 3. Properties of KNN-based piezoelectric ceramics.40

Ceramic
composition
" T33 ="0
TC
( C)
d33
TtO
( C) (pC N 1 ) kp (%)
KNNBKT
1260
376
75
KNNLT
5401256
323
70
KNNLS
1380
368
35
KNNLTLS
6651865 265290 60
Ba-doped
1173
266
70
KNNLTLS
CuO-doped
1230
264
40
KNNLTLS
251
200230
265
315
210
260
1.4. LiNbO3 single crystals

Ref.
56
3651 41, 51
50
46, 52
48.4 57, 58
34.8
57
48
LiNbO3 single crystals possess very low clamped permittivity

(" S33 ="0 40), high sound velocity (7340 m/s), and very high
Curie temperature (TC 1150 C).59 These materials are
mostly used in fabrication of single element high frequency
transducer where a large aperture is required.63 LiNbO3 has
also been used in fabrication of non-destructive testing
(NDT) ultrasound transducers for high temperature applications because of their high Curie temperature nature.64,65
59

1.5. Piezoelectric composites

of BT, yet every transition occurs at a higher temperature.39,40
The highest piezoelectric properties in KNN system was
achieved in K0:5 Na0:5 NbO3 composition. The volatility of
alkaline elements and hygroscopic nature of potassium niobate are the obstacles associated with development of KNN.
Sodium potassium niobate ceramics have been chemically
modified to obtain enhanced piezoelectric response and
better processing repeatability. The effects of incorporation
of LiTaO3 (LT) and LiSbO3 (LS) on the structure, phase
transition, and electrical properties of the KNN ceramics
have been extensively investigated by several research
groups.4151 Ta addition enhanced the piezoelectric properties
due to the shifting of the transition temperatures.50 A dielectric constant of 1255, d33 of 230 pC/N, and kp of 50% was
reported for f(K0:5 Na0:5 )0:07 Li0:03 g(Nb0:8 Ta0:2 )O3 ceramics
reported by Saito et al.51 The simultaneous addition of Li and
Sb via LiSbO3 decreased the tetragonalorthorhombic phase
transition temperature TTO while not significantly affecting
the Curie temperature. Shifting TTO down to room temperature considerably improved the electromechanical properties. A dielectric constant of 1380 and piezoelectric
coefficient d33 of 265 pC/N were reported for KNNLS
ceramics.46,5254 The combination of KNNLT and KNN
LS systems resulted in advent of KNNLTLS ceramics
with remarkable dielectric and piezoelectric properties as
presented in Table 3.55
Besides piezoelectric ceramics and single crystals, piezoelectric/epoxy composites have also been used as the active
layer in ultrasonic transducers particularly in high frequency
probes for medical imaging. These composites offer several
advantages in comparison to monolithic piezoelectric ceramics or polymers. High coupling coefficient, low acoustic
impedance, better acoustic matching to the human body,
adjustable dielectric constant, and mechanical flexibility are
some of the benefits of piezoelectric composites.62 Composite materials show higher g33 coefficient (g33 d33 =" T33 )
than ceramics which results in a better sensitivity in the receiver mode.
Dice-and-fill method is a traditional technique for fabrication of 13 composites.60,62 Injection molding, lost mold,
tape lamination, relic processing, laser ultrasonic cutting, jet
machining, 3D printing and reticulation are some of the other
techniques used for fabrication of piezoelectric composite
with various structures.6466 Figure 1 illustrates a modified
dice-and-fill method to prepare 13 piezoelectric/epoxy
composites. Table 4 provides properties of several lead-free
composites used in fabrication of ultrasonic transducers.
1.6. Ultrasonic transducers
Ultrasonic transducers are composed of three main components: a piezoelectric material, a backing material and one or
Fig. 1. Schematic illustration of the modified dice-and-fill method used for fabrication of 13 composites.60
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J. Adv. Dielect. 5, 1530002 (2015)
Table 4. Properties of lead-free composites used in fabrication of ultrasonic

transducers.
Material

KNNLT composite
BNTBT composite
BNTBT fiber
composite
d33 (pC/N)
" T33 ="0
kt
Z (MRayl)
Ref.
140
360
72
300
600
588
0.65
0.73
0.71
6.6
16
61
60
62
multiple matching layers. Piezoelectric materials are the core

component of ultrasonic transducers for generating the ultrasound beam as well as receiving the echo signal. The
acoustic performance of transducers is prominently influenced by electromechanical and dielectric properties of the
piezoelectric layer. For medical imaging applications,
broadband transducers are required. The bandwidth (BW(%))
of the transducer is defined as57:
BW
fH fL
100;
fc
where fc is center frequency, and fL and fH are low and high

frequencies at 6 dB of the frequency response spectrum.
Broadband transducers can be operated at multiple
transmit/receive frequencies. Transmit at lower frequencies
followed by receiving the echo signal at higher frequencies
enhances the sensitivity and resolution during a medical
imaging event.69,70 Soft piezoelectric ceramics and single
crystals with high coupling coefficient and low mechanical
quality factor offer more efficiency in conversion of electricalacoustic signals which results in a broader bandwidth.69,70
The penetration depth of ultrasound beam in human body
is a function of frequency and acoustic output power. Ultrasound beams with high frequencies provide a better image
resolution but they are highly attenuated by human tissue and
as a result, the penetration depth is reduced. Usually piezoelectrics with a high dielectric constant suggest higher
acoustic output pressure. This is particularly important for
matrix arrays with small element size which demand high
permittivity materials for a better electrical impedance
matching. On the other hand, lower dielectric permittivity is
required in high frequency single element transducers to
improve the resolution and sensitivity of the transducer. The
frequency of the transducer is determined based on the
dimensions and characteristics of the tissue and the age of the
patient to be imaged.12,69,70
In order to decrease the reflection of acoustic wave at
the transducerbody interface, one or two matching layers are
employed on the front side of the transducer. To maximize
transmission of acoustic energy from transducer to the
medium (human body) and broaden the bandwidth, the
thickness of matching layers needs to be equal to =4
(where is the wavelength of acoustic wave in the matching
layer at the center frequency). The acoustic impedance of
the matching layer (ZM ) can be calculated either by Eq. (2) or
Eq. (3)36,7173:
p
Zwater ZCeramic ;
q
3
2
Zceramic :
ZM Z water
ZM
2
3
For a double matching layer design, the appropriate

acoustic impedance for the first and second layer can be
calculated through following equations36,7173:
q
7
3
4
Z Ceramic
;
4
ZM1 Z water
q
7
6
1
ZM2 Z water
Z Ceramic
:
5
The acoustic impedance of piezoelectric ceramics and
human body is about 2535 MRayls and 1.5 MRayls,
respectively. Materials such as silver-epoxy, Epotek epoxy,
graphite, and parylene with acoustic impedance of 37
MRayls are used as a matching layer.71
In ultrasonic transducers, a piezoelectric layer is bonded
on a backing material with relatively high acoustic attenuation to reduce the ringdown caused by the echo from backside
of the transducer. Mixture of epoxy with metallic/oxide particles (such as tungsten) and micro-bubbles are widely used
for the backing layers.71,74,75 The thickness of the backing
layer is chosen to provide an attenuation around 2030 dB.
The natural focal point (N) for flat transducers occurs at
the transition from near to far field region which can be
calculated by36
N
a2
f
a2 c ;

C
where a is the radius of the transducer, C is the sound velocity, and is the wavelength corresponding to the transducer center frequency ( fc ).
The lateral (Rlat ) and axial (Rax ) resolutions of the transducer can be calculated from Eqs. (7) and (8), respectively36:
F
;
2a
C
Rax
;
2f
Rlat
7
8
where the F is the focal length, 2a is the diameter of transducer, C is the sound velocity and f is the frequency width
( fhigh flow ).
Lens-focusing is the most common method to focus the
ultrasound beam and improve the resolution. Usually convex
lenses made of elastomers such as room temperature vulcanization (RTV) and Sylgard silicone with a sound velocity
less than the speed of sound in water ( 1480 m/s) are bonded
on top of outer matching layer. The focal length (F) of the
lens-focused transducers can be calculated by the following
equation76:

C 1
F R 1 2
;
9
C1
1530002-4

J. Adv. Dielect. 5, 1530002 (2015)
Fig. 2. Schematic structure of a single-element ultrasonic transducer

(not to scale).36
Fig. 3. The pulse-echo response and frequency spectrum of the

BZT50BCT transducer.24
where R is the radius of curvature of the lens, C1 is the sound

velocity in the lens, and C2 is the sound velocity in water.
Figure 2 shows a typical structure of a single element
ultrasonic transducer with backing layer, one matching layer,
and a focusing lens. In this particular case, a concave lens
design was used because the sound velocity in the lens material (Epotek epoxy) was higher than that of water.36
Insertion loss (IL) is one of other important characteristics
of transducers which is defined as the ratio of the output
power (Po ) to input power (Pi ).77 Low IL is desired for a
higher output pressure and less heat generation in the transducer.36

p
Vo
IL 10 log o 20 log
;
10
pi
Vi
2. Lead-Free Ultrasonic Transducers for Medical
Imaging
Fig. 4. An in vitro IVUS image acquired by the BZT50BCT

transducer.24
2.1. BT-based transducers
The BSZT ceramic has a piezoelectric constant of d33

300 pC/N and a thickness coupling coefficient of kt 0:45.
Figures 5(a) and 5(b) show the pulse echo response and
frequency spectrum of the transducer. The bandwidth of
76.4% with an IL of 26 dB was achieved in this lead-free
device. The axial and lateral resolutions were 22 mm
and 96 m, respectively. Broad bandwidth and high sensitivity were achieved due to high electromechanical coupling
coefficient of the ceramic.22
As mentioned in Sec. 1, an outstanding piezoelectric constant

(d33 600 pC/N) and high dielectric constant (" S33 ="0
2800) have been reported for lead-free BZT50BCT
ceramics.23,24 Yan et al. used this composition to fabricate a
30 MHz needle type transducer for intravascular imaging
application. The pulse-echo waveform and frequency spectrum of the probe exhibited a 6 dB bandwidth of 53%
(Fig. 3) with an insertion loss of 18.7 dB. The performance
of this lead-free transducer for biomedical applications was
evaluated by in vitro intravascular ultrasound (IVUS) imaging
of coronary artery. As illustrated in Fig. 4, adequate resolution and contrast to differentiate the vessel wall and fibrous
plaque were achieved.24
Lee et al. prepared a single element 40 MHz transducer
with (Ba0:95 Sr0:05 )(Zr0:05 Ti0:95 )O3 composition (BSZT).22
2.2. Bi0.5 Na0.5 TiO3-based transducers

Hejazi et al. designed and fabricated a high frequency
BNT-based transducer.36 A piezoelectric ceramic with composition of 0.88Bi0:5 Na0:5 TiO30.08Bi0:5 K0:5 TiO30.04Bi0:5 Li0:5 TiO3 (BNKLT88) was chosen as the active element of
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J. Adv. Dielect. 5, 1530002 (2015)
Normalized Amplitude
1.5
EXP
KLM
1
0.5
0
-0.5
-1
13.0
13.5
14.0
14.5
15.0
Time (s)
(a)
5
EXP
Magnitude (dB)

(a)
KLM
-5
-10
-15
-20
-25
-30
5
10
15
20
25
30
35
40
Frequency (MHz)
(b)
Fig. 5. (a) Pulse-echo waveform and (b) frequency spectrum of the
BSZT transducer.22
the transducer. This composition exhibited a thickness coupling coefficient (kt ) of 0.45 and clamped dielectric constant
of 350. Low dielectric constant is desired in single element
high frequency transducers for a better electrical matching
and improved lateral resolution (due to the larger aperture). In
addition, BNKLT88 ceramics possess a higher depolarization
temperature compared to other BNT-based compositions.36
The ceramic with thickness of 109 m was sandwiched between epoxy-tungsten backing and silver epoxy matching
layers to fabricate a single element transducer. The thickness
of backing layer was 1.3 mm to provide 30 dB round trip
acoustic attenuation around 20 MHz. The matching layer
thickness was determined based on the quarter wavelength
design rule. A curved Epotek epoxy lens was casted on the
matching layer to improve the acoustic performance.36
Figure 6 shows the pulse-echo waveform and frequency
spectrum of the focused transducer. The center frequency and
6 dB bandwidth were measured to be about 23 MHz and
55%, respectively.
Figure 7 illustrates an ultrasound image of a phantom
made of copper wires (30 m in diameter) acquired by a
BNT-based transducer. The results indicated that this
(b)
Fig. 6. Simulated (KLM model) and measured (a) pulse echo
responses and (b) frequency domains of a BNT-based lens-focused
transducer.36
transducer with a lateral resolution of 260 m could be

considered as a candidate for replacement of lead-based
ultrasonic transducers.36
Chen et al. developed a high frequency transducer based on
BNT-BT single crystals grown by top-seeded solution growth
(TSSG) technique.78 The clamped dielectric constant and
thickness coupling coefficient of the crystal were 80 and 0.52,
respectively. The crystal was polished down to 87 m to
achieve a center frequency of about 25 MHz. A thin layer of
Fig. 7. The image of a wire phantom (30 m diameter) formed by a

high frequency BNT-based transducer.36
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J. Adv. Dielect. 5, 1530002 (2015)

Fig. 8. Pulse-echo waveform and frequency spectrum of the BNT

BT single crystal transducer.78
Fig. 9. Scanning Electron Microscopy image of a BNTBT fiber/
epoxy 13 composite.62
parylene (20 m) was deposited on crystal as the matching

layer. Figure 8 shows the pulse-echo waveform and frequency
spectrum of the unfocused BNT-based transducer with a
6 dB bandwidth and IL of 46% and 31.9 dB, respectively.78
BNTepoxy composites have also been investigated for
ultrasonic imaging applications. Zhou et al. used a modified
dice-and-fill method to fabricate 13 BNT-based composites.60 BNTBT single crystal with a composition close to
the rhombohedraltetragonal MPB was grown by TSSG
technique. The width and height of diced elements in the
composite (52% crystal volume fraction) were 180 and
500 m, respectively. In order to minimize the cross-talk
between adjacent elements, an aspect ratio of higher than 2.5
was considered in the composite design.60 Table 5 provides
the properties of BNTBT single crystals and 13 composites. The composite showed lower acoustic impedance and
higher coupling coefficient than single crystal which would
improve the bandwidth and sensitivity of the ultrasonic
transducer.60
The BNT-based 13 composites reported by Zhou et al.
were used in fabrication of single element and linear array
transducers with center frequencies of about 34 MHz.60 A
mixture of Epotek 301 epoxy and alumina powder with
acoustic impedance of 3.9 MRayl was used as the matching
layer. An attenuative backing materials (15 dB/mm) was
prepared by mixing epoxy, tungsten powder, and microbubbles. To reduce the cross-talk between neighboring elements in the array, the dicing depth was extended into the
Table 5. Properties of monolithic BNTBT single crystal and BNTBT/

epoxy 13 composite.60
Material
d33 (pC/N)
" T33 ="0
kt
Qm
V(m/s)
Z(MRayl)
BNTBT single
crystal
BNTBT/epoxy
13 composite
430
1000
0.63
60
4800
29
360
600
0.73
4100
16
backing layer and the array kerf (70 m width) was filled
with an attenuative epoxy. The 6 dB bandwidth of both
single element and linear array transducers exceeded 100%.60
In order to image fine tissues for applications such as
ophthalmology and dermatology, high frequency transducers
with enhanced resolution are required.62 Traditional diceand-fill method has limitation for fabrication of composites
with very fine elements and small pitches. Fiberepoxy
composites can be regarded as an alternative method for
preparation of high frequency transducers.62 Using solgel
method, Wang et al. prepared BNTBT fibers with diameter
of about 150 m.62 13 composites were processed by
aligning fibers in a plastic tube followed by epoxy filling
(Fig. 9).
The ceramic volume fraction and thickness of the composite were 30% and 143 m, respectively. The thickness
coupling coefficient kt of the composites was 0.71 which
was considerably greater than that of monolithic ceramic
(kt 0:45). A 14 MHz focused transducer was fabricated by
forming a convex shape on the composite attached to silicone rubber as the backing material. The 6 dB bandwidth
and IL of the transducer were measured to be 80% and
34.8 dB.62
2.3. KNN-based transducers
KNN-based transducers for medical imaging application
were developed by Jadidian et al.55 The acoustic performance of a 25 MHz single element transducer with
(K0:44 Na0:52 Li0:04 )(Nb0:84 Ta0:10 Sb0:06 )O3 (abbreviated to
KNNLTLS) active element was compared to a PZT
fiber 13 composite transducer. The properties of KNNbased ceramics and 13 PZT composite are given in
Table 6. The KNNLTLS transducer exhibited a 6 dB
bandwidth of 70% and IL of 21 dB. The electrical impedance of KNN-based piezoceramic was close to 50 ,
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J. Adv. Dielect. 5, 1530002 (2015)

Table 6. Properties of KNNLTLS ceramic and 13 PZT fiber composite.55

Material
d33 (pC/N)
" T33 ="0
" S33 ="0
tan
kt
KNNLTLS
13 PZT fiber composite
175
400
644
541
506
296
0.022
0.013
0.39
0.64
which resulted in smaller IL compared to the lead-based

transducer. Pulse-echo responses and frequency spectra of
KNNLTLS and PZT-fiber composite transducers are illustrated in Fig. 10.55
Hagh et al.57 prepared Ba 2 -doped KNNLTLS ceramics for fabrication of a low frequency transducer with a
center frequency of 5.5 MHz. The transducer with a single
layer matching design (Zm 4:3 MRayl) showed a bandwidth of 50%. It was demonstrated that the acoustic
performance of Ba 2 -doped KNNLTLS transducer was
comparable to a PZT5H transducer.57
The (K0:5 Na0:5 )0:97 Li0:03 (Nb0:9 Ta0:1 )O3 (abbreviated to

KNNLT) composition with clamped dielectric constant of
" S33 ="0 890, piezoelectric coefficient of d33 245 pC/N,
electromechanical coupling factor of kt 0:42, and Curie
temperature of TC 320 C was also used to fabricate a high
frequency transducer by Wu et al.79 The design parameters
used for an unfocused 40 MHz transducer are summarized in
Table 7. The 6 dB bandwidth (Fig. 11) and two-way insertion loss were 45% and 18 dB, respectively. The lensfocused transducer demonstrated axial and lateral resolutions
of 32 m and 102 m, respectively.79
Za , Zm1 , Zm2 and Zb are acoustic impedance (in MRayl); ta ,
tm1 , tm2 and tb are thickness (in m, except tb ).
Mechanical dimpling technique has been employed to
fabricate focused transducers with wide bandwidth for applications such as IVUS. Dimpled ceramics have a continuous
change in thickness which produces multi-resonance frequencies and as a result, boarder bandwidth could be
(a)
(b)
(c)
(d)
Fig. 10. The time and frequency domain spectra of (a)-(b) the 13 PZT fiber/polymer composite and (c)-(d) KNNLSLT transducer.55
1530002-8
J. Adv. Dielect. 5, 1530002 (2015)
Table 7. Acoustic impedance and thickness of materials used in KNN-LT

high frequency transducer.

Piezoceramic
First matching
silver epoxy
Second matching
silver epoxy
Backing material
Za
ta
Zm1
tm1
Zm2
tm2
Zb
tb
31
75
7.3
8.4
2.5
13.0
5.9
> 3 mm
(a)
Fig. 11. The pulse-echo characteristics of a 40 MHz KNNLT

transducer.79
achieved.8082 A lead-free focused probe with MnO-doped

0.97(K0:5 Na0:5 NbO30.03(B0:5 K0:5 TiO3 ceramic (KNN
BKT) was fabricated and characterized by Chen et al.82
Table 8 compares the performance of dimpled KNNBKT,
dimpled PMNPT and plane PMNPT transducers. Assessing
the ultrasound images of the swine aorta revealed that the
artery wall and fatty tissues were discernable as depicted in
Fig. 12. However, the KNNBKT probe showed lower sensitivity and higher IL compared to its lead-based counterpart.82
Table 8. Summary of results obtained by dimpled and plane transducers.82
Material
Dimpled KNNBKT
ceramic
Dimpled PMN0.28PT
single crystal
Plane PMN0.28PT
ceramic
Fc
(MHz)
6 dB
BW%
IL
(dB)
Axial
resolution
(m)
Lateral
resolution
(m)
40
72
28.8
44
125
34
75
22.9
58
131
29
30
21.8
(b)
Fig. 12. In vitro imaging of swine aorta acquired by (a) a dimpled
PMNPT and (b) a dimpled KNN-based probes.82
Shen et al. developed a broadband transducer using a 13

KNNLT composite.61 First, the (Na0:535 K0:485 )0:95 Li0:05
(Nb0:8 Ta0:2 )O3 ceramics were prepared by spark plasma
sintering technique. Then, KNLNT/epoxy composite with
50 m element width and pitch size of 100 m was fabricated
by modified dice-fill method. In order to achieve broader
bandwidth and higher sensitivity two matching layers
were used. The center frequency, 6 dB bandwidth, and
two way IL of the transducer were 29 MHz, 90% and 25 dB,
respectively.61
Bantignies et al. reported acoustic performance of a
30 MHz linear array transducer based on potassium niobate
(KN) 13 composites.83 The linear array contained 128 elements with 100 m pitch size. It was validated that 30 MHz
lead-free transducer with 59% bandwidth was suitable for
skin imaging due to its high sensitivity and large depth of
1530002-9
J. Adv. Dielect. 5, 1530002 (2015)
(a)
(b)

(a)
Fig. 14. High resolution in-vivo images of (a) a nail finger and
(b) naevus of human forearm skin.
film. The lead-free transducer with a center frequency of

12 MHz showed a wide bandwidth of 93% and illustrated
acceptable image quality for human forearm skin and finger
nail imaging (Fig. 14).
2.4. LiNbO3-based transducers
(b)
Fig. 13. In vivo images of a naevus of human forearm acquired by
(a) a 30 MHz lead-free probe and (b) a 20 MHz PZT-based probe.83
field. However, KN 13 piezocomposite had low dielectric

constant of 14 which led to a high impedance mismatch.
Figure 13 illustrates the in vivo skin images acquired by
KNN- and PZT-based probes. The boundaries of naevus
were perfectly distinguishable in both images. The 30 MHz
lead-free transducer showed a better clarity for skin structure
at depth of 3 mm under the naevus.83
Pad-printing process is one of the other techniques
for fabrication of ultrasonic transducers.84 Levassort et al.
employed this method to prepare a curved high frequency
KNN-based transducer.85 In this process, a machined KNN
porous cylinder with radius curvature of 5 mm was used as
the backing material. Then a KNN-based piezoelectric thick
film was deposited by pad-printing technique. Table 9 provides the electromechanical properties of KNN-based thick
Due to their high electromechanical coupling coefficient,

low relative clamp dielectric constant (" S33 ="0 39),
and high Curie temperature, LiNbO3 single crystals are
interesting candidates for large aperture single element
transducers.8688
A 50 MHz transducer utilizing LiNbO3 crystal was fabricated and characterized by Snook et al.85 In addition, its
performance was compared to other transducers based on 13
PZT fiber composite, PVDF, and PbTiO3. Tables 10 and 11
present a summary of design parameters and the measured
acoustic results for these transducers.
The images acquired by LiNbO3- and PbTiO3-based
transducers (not shown here) had better sensitivity and contrast compared to PVDF and fiber composite transducers.
Although the PVDF transducer showed the largest bandwidth,
it demonstrated a poor sensitivity. Medium sensitivity and
bandwidth were observed in the fiber composite transducer.86
Canatta et al. fabricated LiNbO3 single crystal-based
transducers with center frequencies ranging from 20 to
80 MHz.87 Lens-focusing and press-focusing techniques were
Table 10. Design parameters used in four different transducers reported by
Snook et al.86
Material
Table 9. Physical and electromechanical properties of a KNN-based thick
films prepared by pad-printing method.
Material
KNN-based film
t (m) l (m/s) fa (MHz) " S33 ="0 kt (%) Z (MRayl)

50
3140
31.4
90
34
11.3
LiNbO3 crystal
13 PZT Fiber
composite
PVDF
PbTiO3 ceramic
1530002-10
Thickness
(m)
Zbacking
(MRayl)
Zmatching
(MRayl)
Focusing
technique
60
32
5.9
1
7.3
3
Epotek 301 lens

Spherical shaping
9
32
3.15
5.9
No
3
Spherical shaping
Spherical shaping
J. Adv. Dielect. 5, 1530002 (2015)
Table 11. Acoustic properties of several lead-free and lead-based high

frequency transducers.86
Material
Fc (MHz)
BW (%)
IL (dB)
Pulse
length (ns)
44.5
53.6
48.1
45.1
74
47
118
47
21.3
34.4
45.6
23.7
56
67
44
74

LiNbO3 crystal
13 PZT Fiber composite
PVDF
PbTiO3 ceramic
employed to enhance the lateral resolution and performance

of the transducers. Lens thickness nonuniformity and processing flaws resulted in degradation of sensitivity of the
lens-focused transducer. On the other hand, the press-focused
transducer produced higher sensitivity and lower incretion
loss. Table 12 summarizes the acoustic characteristics of
LiNbO3-based transducers. Figure 15 depicts in vivo and ex
vivo ultrasound biomicroscopy (UBM) images of human eye.
The images exhibit outstanding signal-to-noise ratio, penetration depth, and appropriate contrast.87
Inversion layer design could be applied to fabricate
broadband transducers.8890 The sign of the piezoelectric
constant and generated strain in the ferroelectric inversion
layer are opposite to those of the regular layer.8891
Nakamura et al. have shown that the transducer performance
depends on the location of inversion layer.89 The inversion
layer ratio is another key parameter in designing these devices which can be controlled by annealing temperature, heating time, or via mechanical bonding. It has been
demonstrated that by increasing the thickness of the inversion
layer to half thickness, most of the energy was transferred to
the second harmonic.88,89 Zhou utilized LiNbO3 single
crystals to develop half-thickness inversion layer highfrequency ultrasonic transducer. The results showed that the
center frequency of the transducer was increased to twice as
large as the original frequency. The center frequency, 6 dB
bandwidth, and two way IL were 60 MHz, 80%, and 28 dB,
respectively. The pulse echo characteristics of this transducer
are depicted in Fig. 16.88
The concept of dual frequency transducers have
been demonstrated by several researchers.9295 In regular
Table 12. Acoustic characteristics of LiNbO3-based high frequency transducers.87
Fc (MHz)
Focusing
technique
Aperture
size (mm)
6 dB
BW (%)
IL
(dB)
Pulse
length (ns)
22
23
45
50
73
78
Lens
Spherical shaping
Lens
Spherical shaping
Lens
Spherical shaping
10
12
3.0
6.0
1.8
3.0
72
60
74
60
57
73
19.5
13.4
21.3
9.6
20.3
13.5
145
140
56
54
40
36
(a)
(b)
Fig. 15. (a) An UBM image of the anterior portion of an excised
human eye acquired by 40 MHz LiNbO3 transducer. (b) A wideangle view of a normal anterior human eye segment taken in vivo by
a 50 MHz transducer.87
transducers there is always a trade-off between the ultrasound

beam penetration depth and image resolution. On the other
hand, in dual frequency transducers, the low frequency
transmit element provides a deep penetration while the high
frequency receive element creates an image with enhanced
resolution. Kim et al. fabricated annular dual element arrays
for high frequency ophthalmic imaging.92 The outer ring
element (12 mm in diameter) was designed to transmit at
20 MHz while the inner circular element (5 mm in diameter)
received the second harmonic signal at 40 MHz. The thickness of LiNbO3 single crystals for transmit and receive
elements were 150 and 77 m, respectively. Press-focusing
technique was used to create a radius of curvature of 30 mm
to place the focal point at the retina. A double matching layer
design (Insulcast silver epoxy and parylene) was used to
further improve the bandwidth and resolution of the transducers. The backing material was a centrifuged E-solder
silver epoxy. Figure 17 compares the images of the posterior
segment of an excised pig eye acquired by single element
(fundamental imaging) and dual element (harmonic imaging)
transducers. It was clearly observed that the harmonic image
1530002-11
J. Adv. Dielect. 5, 1530002 (2015)

(a)
(b)
Fig. 16. (a) Pulse-echo waveform and (b) frequency spectrum for LiNbO3 half-thickness inversion layer transducer.88
(a)
(b)
Fig. 17. Images of the posterior segment of an excised pig eye (a) fundamental imaging using the single element transducer and (b) harmonic
imaging using the dual element transducer.92
produced by dual element probe had better resolution than the

image formed by a single element transducer.92
have been developed. In last decade, a remarkable progress in

enhancement of electromechanical properties of lead-free
ceramics was made and as a result, ultrasonic transducers
with a performance level comparable to PZT-based probes
3. Conclusions
In this paper, the current state of lead-free ultrasonic transducers for medical imaging applications was reviewed.
Electromechanical properties of lead-free ceramics, single
crystals, and composites were summarized and promising
candidates with enhanced properties were identified. The
characteristics of the most encouraging lead-free transducers
along with the properties of their piezoelectric layer are
provided in Table 13.
Lead-free piezoelectrics have been successfully used in
fabrication of single element transducers, linear arrays, dual
frequency annular arrays, and inversion-layer transducers.
LiNbO3 single crystals are suitable for fabrication of single
element transducers with a large aperture. Depending on their
dielectric and electromechanical properties, BNT and KNNbased ceramics and single crystals could be utilized in single
element or array transducers. Transducers with wide range of
frequencies (3 to 80 MHz) for variety of imaging applications
Table 13. Properties of lead-free and lead-based piezoelectrics along with

characteristics of their ultrasonic transducers.
Material
d33
" S33 ="0 (pC/N)
BSZT
1346
BZTBCT
2817
39
LiNbO3 crystal
KNNLTLS
506
(1173)
Ba 2 doped
KNNLTLS
KNNLT
890
BNTBT crystal
80
BNTBKTBLT
353
KNNBKT
730
PMN0.33PT
797
(Pb-based)
PbTiO3 (Pb-based) 200
1530002-12
kt
Fc
6 dB
(MHz) BW (%)
IL
(dB)
26
19
21
21
Ref.
300
597
35
175
210
0.45
0.41
0.49
0.39
0.37
42
30
45
26
5.5
76
53
54
72
50.5
22
22, 24
87
55
96
245
210
84
189
1430
0.42
0.52
0.45
0.50
0.58
40
25
22
40
44
45
46
61
72
45
18
32
28.6
28.8
15
79
78
36
82
97
50
0.49
45
47
24
86
J. Adv. Dielect. 5, 1530002 (2015)
have been introduced. The bandwidth of lead-free transducers

is in the range of 4576% with IL of 1829% at different
frequencies.
Acknowledgments
The authors would like to appreciate the financial support of
Glenn Howatt foundation for continuous support of research
on lead-free piezoelectrics.
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Review

JOURNAL OF ADVANCED DIELECTRICS

Lead-free piezoelectric materials and ultrasonic transducers for medical imaging

J. Adv. Dielect. 2015.05. Downloaded from www.worldscientific.com

ultrasonic transducers for imaging and noninvasive therapy

E. Taghaddos, M. Hejazi & A. Safari

J. Adv. Dielect. 5, 1530002 (2015)

J. Adv. Dielect. 2015.05. Downloaded from www.worldscientific.com

Table 1. Symptoms and signs of lead poisoning.13,18

coefficient and low Curie temperature have been introduced

BNT-based piezoelectrics with a high remnant polarization

Ceramic composition " T33 ="0

E. Taghaddos, M. Hejazi & A. Safari

J. Adv. Dielect. 5, 1530002 (2015)

Table 3. Properties of KNN-based piezoelectric ceramics.40

" T33 ="0

1.4. LiNbO3 single crystals

LiNbO3 single crystals possess very low clamped permittivity

J. Adv. Dielect. 2015.05. Downloaded from www.worldscientific.com

1.5. Piezoelectric composites

E. Taghaddos, M. Hejazi & A. Safari

J. Adv. Dielect. 5, 1530002 (2015)

Table 4. Properties of lead-free composites used in fabrication of ultrasonic

J. Adv. Dielect. 2015.05. Downloaded from www.worldscientific.com

" T33 ="0

multiple matching layers. Piezoelectric materials are the core

where fc is center frequency, and fL and fH are low and high

For a double matching layer design, the appropriate

J. Adv. Dielect. 2015.05. Downloaded from www.worldscientific.com

E. Taghaddos, M. Hejazi & A. Safari

J. Adv. Dielect. 5, 1530002 (2015)

Fig. 2. Schematic structure of a single-element ultrasonic transducer

Fig. 3. The pulse-echo response and frequency spectrum of the

where R is the radius of curvature of the lens, C1 is the sound

Fig. 4. An in vitro IVUS image acquired by the BZT50BCT

2.1. BT-based transducers

The BSZT ceramic has a piezoelectric constant of d33

As mentioned in Sec. 1, an outstanding piezoelectric constant

2.2. Bi0.5 Na0.5 TiO3-based transducers

E. Taghaddos, M. Hejazi & A. Safari

J. Adv. Dielect. 5, 1530002 (2015)

J. Adv. Dielect. 2015.05. Downloaded from www.worldscientific.com

transducer with a lateral resolution of 260 m could be

Fig. 7. The image of a wire phantom (30 m diameter) formed by a

E. Taghaddos, M. Hejazi & A. Safari

J. Adv. Dielect. 5, 1530002 (2015)

J. Adv. Dielect. 2015.05. Downloaded from www.worldscientific.com

Fig. 8. Pulse-echo waveform and frequency spectrum of the BNT

parylene (20 m) was deposited on crystal as the matching

Table 5. Properties of monolithic BNTBT single crystal and BNTBT/

" T33 ="0

E. Taghaddos, M. Hejazi & A. Safari

J. Adv. Dielect. 5, 1530002 (2015)

J. Adv. Dielect. 2015.05. Downloaded from www.worldscientific.com

Table 6. Properties of KNNLTLS ceramic and 13 PZT fiber composite.55

" T33 ="0

" S33 ="0

which resulted in smaller IL compared to the lead-based

The (K0:5 Na0:5 )0:97 Li0:03 (Nb0:9 Ta0:1 )O3 (abbreviated to

E. Taghaddos, M. Hejazi & A. Safari

J. Adv. Dielect. 5, 1530002 (2015)

Table 7. Acoustic impedance and thickness of materials used in KNN-LT

J. Adv. Dielect. 2015.05. Downloaded from www.worldscientific.com