Lecture 5: Piezoelectric Materials

• Piezoelectric ceramics
• Piezoelectric single crystals
• Piezoelectric polymer
 Piezoelectric Ceramics vs. Single Crystals
Polycrystalline ceramics Single Crystal

Piezo ceramics: polycrystalline aggregate,

grain boundary, isotropic, fabricated from
powders;
Single crystal: single crystal, no grain
boundary, anisotropic, crystal growth
Piezoelectric Materials
 Bulk Piezoelectric Ceramics
Pressing
Batch weighing
• Powder preparation
• Pressing
Bisque Firing &
Binder Burnout
Wet Blending &
• Powder calcining and sintering Milling
High Firing

• Mechanical machining
• Electroding Drying Machining

• Poling Electroding (Silk

• Test Calcining (PZT

Formation)
Screening)

Electrode Firing

Wet Milling &

Binder Addition
Poling

Spray Drying Electrical Testing

Inspection,
Packing & Shipping
 Soft and Hard Piezoelectric Ceramics
• PZT ceramics are usually prepared with dopants and so that
properties can be adjusted for specific applications.

• Soft PZT: addition of substitutions that produce Pb vacancies,,

small aging, higher piezoelectric coefficients, higher losses,
lower mechanical quality factor, low coercive field.

• Hard PZT: Ionic substitutions that produce oxygen vacancies,

lower permittivity, low dielectric loss, high mechanical quality
factor, high coercive field.

d33 (pC/N) kt Qm ε33 Tan δ

Soft 450 0.47 <100 1,800 > 0.02
Hard 290 0.47 >1,000 1,300 < 0.005
 Soft and Hard Piezoelectric Ceramics

Principal properties of various PZT based polycrystalline ceramics, compared to

BaTiO3 (BT), PbNb2O6 (PN) ceramics and LiNbO3 (LN) crystals. TC (C); d (pC/N); s
(pm2/N)
 Piezoelectric Ceramics
• PZT -2 may be used for requirements of low dielectric constant but it is
otherwise inferior in nearly all respects to PZT-4 or PZT-5A.
• PZT-4 is recommended for high power acoustic radiating transducers
because of Its high resistance to depolarization and low dielectric losses under
high electric drive. Its high resistance to depolarization under mechanical
stress makes it suitable for use in deep-submersion acoustic transducers and
as the active element in electrical power generating systems.
• PZT-5A is recommended for hydrophones or instrument applications
because of its high resistivity at elevated temperatures, high sensitivity, and
high time stability.
• PZT-5H has even higher sensitivity and permittivity than PZT-5A, and is in
most other respects similar to PZT-5A. Its markedly lower Curie point, however,
limits the working temperature range and leads to lower temperature stability.
• PZT-8 is similar to PZT-4, but has even lower dielectric and mechanical
losses under high electric drive. It is recommended for applications requiring
higher power handling capability than is suitable for PZT-4.

-- Morgan Technical Ceramics

 Piezoelectric Ceramics
Properties Symbol & unit NCE4 NCE4 NCE4 NCE51 NCE5 NCE55 NCE5 NCE5 NCE8
0 1 6 3 7 9 0

Dielectric Properties

Relative Dielectric constant ε33T/ε0 1250 1350 1300 1850 1600 5000 1800 2900 1050

Dielectric Loss Factor tgδ [10-4] 25 40 30 190 130 220 170 190 20

Dielectric Loss factor at 400V/mm tgδ [10-4] 140 200 100

Electromechanical Properties

Coupling Factors kp 0.58 0.57 0.57 0.65 0.56 0.62 0.59 0.64 0.55

k31 0.34 0.33 0.33 0.37 0.32 0.39 0.33 0.37 0.30

k33 0.70 0.68 0.68 0.72 0.65 0.72 0.70 0.75 0.68

kt 0.50 0.50 0.47 0.51 0.47 0.50 0.47 0.52 0.48

Piezoelectric Charge constants -d31 [10-12 C/N] 140 130 130 195 150 260 170 240 100

d33 [10-12 C/N] 320 310 290 460 360 670 425 575 240

Piezoelectric Voltage constants -g31 [10-3 Vm/N] 11 11 11 13 9 9 11 10 11

g33 [10-3 Vm/N] 27 25 28 27 23 19 27 23 27

Frequency constants NEp [m/s] 2160 2280 2230 1940 2180 1970 2010 1970 2270

NDt [m/s] 1980 2000 2040 2010 2040 1990 1950 1960 2050

NEt [m/s] 1470 1600 1500 1400 1400 1410 1610

ND 3 [m/s] 1340 1500 1800 1390 1500 1500 1500

Physical Properties

Mechanical Quality Factor QM 700 1400 >1000 80 80 70 80 90 1000

Density ρ [103 kg/m3] 7.75 7.90 7.70 7.80 7.60 8.00 7.70 7.45 7.80

Elastic compliances s11 E [10-12 m2/N] 13 13 13 16 16 17 17 17 11

s33E [10-12 m2/N] 17 16 20 19 18 21 23 23 14

Curie Temperature TC [°C] 325 290 330 340 340 170 350 235 305

-- Noliac Group
 Piezoelectric Ceramic Films

• Sputtering
• Sol-Gel
Piezo-film
• Screen printing
• Electrophoretic deposition
• Jet Printing
Substrate
• Laser ablation
• Soft-lithography
• Precision wafer lapping
• Wafer bonding
• 3D printing
•…
Piezoelectric Films

Coefficients ZnO AlN PZT

e31 (Cm-2) -1.0 -1.05 -8 - -12
d33 (pm/V) 5.9 3.9 60 - 130
ε33 10.9 10.5 300 - 1300
tan δ (@ 1 to 10 kHz, 105 0.01 - 0.1 0.003 0.01 - 0.03
V/m)
c33E (GPa) (PZT52/48 208 395 98
ceramic)
 Piezoelectric Single Crystals

• SiO2 (Quartz, hexagonal), AT cut

• LiNbO3 (Rhombohedral), 128˚-rotated Y-cut
• Relaxor lead based single crystals: PZN-PT, PMN-PT, PIN-
PMN-PT, …
 Growth of Relaxor Single Crystals

• Flux growth of PZN-PT

 Spontaneous nucleation
from a melt
 PbO flux used to lower
melt temperature and
stabilize perovskite phase
 Slow process (17 days)
 Irregularly shaped crystal
 Limited size
 No seed
 Growth of Relaxor Single Crystals

• Bridgman growth of PMN-PT

 Seeded melt growth
 No flux
 Sealed crucible pulled through
temperature gradient
 Large crystals (>1” dia. X 2– 4”
long)
 Fast; growth in 5-7 days
 Compositional gradient issues
Piezoelectric Single Crystals
 PMN-PT Single Crystal

Strain
1 2 3 4 5 6
1 LE TE TE LS TS TS
Polarization 2 TE LE TE TS LS TS
3 TE TE LE TS TS LS

LE: Longitudinal Extension

TE: Transverse extension
LS: Longitudinal Shear
TS: Transverse Shear
 PMN-PT Single Crystal
TE LE LS TS
d33
d31/d32
2000 ~ 3000 d36 d15, d24
<001> poling -800 ~ -1000
pC/N 0 < 100
pC/N
k33 > 0.90
d31
d15, d24
-1200 ~ -
d33 d36 2000 ~ 3500
<011> poling 1800 pC/N
< 500 pC/N 2500pc/N pC/N
k31 ~ 0.84 -
k15 > 0.9
0.90
d15/d24
d31, d32 d33 d36 4000 ~ 7000
<111> poling
< 150 pC/N < 200 pC/N 0 pC/N
k15 > 0.95
 PMN-PT Single Crystal vs PZT 5H

d31 d33 d36 d15

4000 - 7000
-1200 - 1800 2000 - 3000 2000 - 2500
pC/N
PMN-PT pC/N pC/N pC/N
k15 > 0.95
Crystals k31 : 0.84 - 0.90 k33 > 0.90 k36 > 0.90
xzt - 22.5
zxt - 0 cut zxt - 0 cut zxt - 45 cut
cut
PZT-5H -274 pC/N 593 pC/N 0 741 pC/N
Ceramics k31 : 0.39 k33 : 0.75 0 k15 : 0.68
Piezoelectric Single Crystals

PMN-PT
Single
crystal
 Piezoelectric Single Crystals
Crystal Tc(°C) TRT(°C) Ec(kV/cm) Eint(kV/cm) 𝑲𝑻𝟑𝟑 d33(pC/N) k33 Qm
PMN-0.29PT
135 96 2.3 0 5400 1700 0.91 150
(Gen I)
PMN-PT (MPB)
155 65 2.8 0 8200 2800 0.95 100
(Gen I)
PIN-PMN-PT
191 125 5.0 0 4400 1500 0.92 180
(Gen II)
PIN-PMN-PT
197 96 5.5 0 7200 2700 0.95 120
(MPB) (Gen II)
Mn: PIN-PMN-PT
193 119 6.0 1.0 3700 1100 0.90 800
(Gen III)
Mn: PMN-PZT
203 141 6.3 1.6 3400 1100 0.92 1050
(Gen III)
 Composition Change for Property
Enhancement

MPB Doping

Composition-Change

Morphotropic phase boundary

(MPB) determination

Doping
Acceptor dopants – “Hard”
Donor dopants – “Soft”T (°C)
Crystal c TRT(°C) Ec(kV/cm)
CrystalEint(kV/cm) 𝑲C)𝑻𝟑𝟑
Tc(° TRT
d33(°C)
(pC/N)
Ec(kV/cm)
k33 Eint
Qm (kV/cm) 𝑲𝑻𝟑𝟑 Dielectric
d33(pC/N)k 33 Qand piezoelectric
m

PMN-0.29PT
135 96 2.3
PMN-0.29PT
0 135
5400 961700 2.30.91 150
0 5400 coefficients
1700 0.91of samarium-doping
150 Sm:
(Gen I) (Gen I)
PMN-PT
PMN-PT (MPB) PMN-PT (MPB)
155 65 2.8 0 155
8200 652800 2.80.95 100
0 8200 2800 0.95 100
(Gen I) (Gen I)
F. Li, et al., Science 364, 264 (2019).
PIN-PMN-PT PIN-PMN-PT
S. Zhang, et al. Prog. Mater. Sci. 68, 1 (2015).
(Gen II)
191 125 5.0
(Gen II)
0 191
4400 125
1500 5.00.92 180
0 4400 1500 0.92 180

PIN-PMN-PT PIN-PMN-PT
197 96 5.5 0 197
7200 962700 5.50.95 120
0 7200 2700 0.95 120
(MPB) (Gen II) (MPB) (Gen II)
Mn: PIN-PMN-PT Mn: PIN-PMN-PT
193 119 6.0 1.0 193
3700 119
1100 6.00.90 800
1.0 3700 1100 0.90 800
(Gen III) (Gen III)
Mn: PMN-PZT Mn: PMN-PZT
203 141 6.3 1.6 203
3400 141
1100 6.30.92 1050
1.6 3400 1100 0.92 1050
(Gen III) (Gen III)
 Domain Engineering

• Domain engineering on BaTiO3

Domain Engineering
Relationship between piezoelectric
properties and domain sizes (WD)
Methods used to engineer the
( (
domain structures and to obtain a) b)
enhanced properties.

Poling along different directions

Surface condition modification:

Nano-composite electrodes

Lower domain width

Poling condition modification: or Higher piezoelectric property
Alternating current poling(ACP) Higher domain wall density

S. Wada, Handbook of Advanced Dielectric, Piezoelectric and Ferroelectric Materials, Edited By Z.G. Ye, CRC Press, pp. 266-303, 2008.
 Domain Engineering via Nano-electrodes

10000

Before poling 2500

9000
After poling

Piezoelectric constant (pm/V)

8000
2000
Dielectric constant

7000
1500
6000

5000 1000

4000
500
3000

2000 0
Planar 200 nm 500 nm 800 nm 1000 nm Planar 200 nm 500 nm 800 nm 1000 nm
Samples with different pattern period Samples with different pattern period

P=200 nm P=500 nm P=800 nm P=1000 nm

Y. Yamashita, et al., Japanese J. of Appl Phys. 50(2011), 09NC05; W. Chang, et al., Acta Materialia 143 (2018): 166-173;22
C. Luo, et al., Acta Materialia 182 (2020):10-
17.
 ACP Introduction
ACP vs. DCP

ACP
Electric field

Electric field
DCP

time
time

Y. Yamashita, et al., U.S. patent 2015/0372219 A1, 2015.

 ACP Effectiveness
[001] PMN-0.3PT [001] PMN-0.25PT

DCP 10 kV/cm 30 min DCP /

ACP 1 Hz, 20 cycles ACP 30 Hz, >20 cycle

W. Chang, et al. Mater. Res. Lett. 6, 537 (2018). J. Xu, et al., Appl. Phys. Lett. 112, 182901 (2018).
 ACP of PMN-xPT Single Crystals

PT content
0.28 (132 °C) 0.29 (136 °C) 0.30 (140 °C) 0.31 (146 °C)
x (Tc)
High-PT Poling DCP ACP DCP ACP DCP ACP DCP ACP
(T Phase) 8900 8840 8840 5480
0.33 εT33/ε0 7000 7740 7740 4770
MPB (+ 27%) (+ 14%) (+ 14%) (+ 15%)
0.30
tan δ (%) 0.35 0.65 0.6 0.98 0.6 0.98 0.65 0.49
Low-PT k33 92.7 93.5 95 93.9 95 93.9 94.7 94.63
(R Phase)
2650 2850 2850 2100
PT content x =
d33 (pC/N) 1940 2030 2030 1880
(+ 37%) (+ 40%) (+ 13%) (+ 12%)

• Effects of ACP on PMN-xPT with different PT contents are different.

• Enhancement on the low-PT side (R phase) is higher than high-PT side.

Y. Sun, et al., Jpn. J. Appl. Phys. 58, SLLC06 (2019).

 Strain vs. E for ACP Samples

Courtesy of Dr. H. Luo from SICCAS

 ACP of PIN-PMN-PT Single Crystal

4 x 4 x 12 mm bars

d33 (pC/N) d33 (pC/N)

Field Frequency d33
(after 90 (after one
(kV/cm) (Hz) (pC/N)
days) year)
7.5 2.5 1825 1819 1815
7.5 5 1684 1683 1660

A. Heitmann, et al., ONR International Symposium on Piezocrystals and their Applications, Lausanne, Switzerland - July 14, 2019.
 ACP Induced Optical Property Changes

• ACP could be used to enhance the transmittance of rhombohedral PMN-0.28PT single crystals
C. Qiu, et al., Nature 577, 350 (2020).
 Piezoelectric Polymer

• PVDF, Poly(vinylidene fluoride), beta phase

 Piezoelectric Polymer
Symbol Parameter PVDF Copolymer Units
t Thickness 9,28, 52, < 1 to 1200 μm
110
d31 Piezo strain constant 23 11 10-12 C/N
d33 -33 -38
g31 Piezo stress constant 216 162 10-3 Vm/N
g33 -330 -542
k31 Electromechanical 12 % 20 %
coupling factor
kt 14 % 25-29%
Y Young’s modulus 2-4 3-5 109 N/m2
ε/ε0 Relative permittivity 12-13 7-8
ρm Mass density 1.78 1.82 103 kg/m
ρe Volume resistivity > 1013 > 1014 Ohm meters
tan δ Loss tangent 0.02 0.015 @ 1 kHZ
Yield strength 45-55 20-30 106 N/m2
(stretch axis)
Temperature range -40 to -40 to °C
80...100 115...145

-Measurement Specialty
 Piezoelectric Materials

Piezoelectric Piezoelectric Young’s Electro-mechanical

materials coefficient Modulus Coupling
(pC/N) (GPa)
AlN (film) d31 ~-2 330 kt ~0.24
ZnO (film) d31 ~-5 210 kt ~0.27
PZT (sol-gel, d31 ~-100 40 kt ~0.39
sputtering)
PVDF d33: ~ -30 3.5 kt ~ 0.15
d31: ~ 11
PZT (Bulk) d33, ~600 70 kt~0.5
d31 ~-300 k33 ~0.7
Quartz d33: ~ 2 76-97 -
LiNbO3 d33: ~ 6 200 -
PMN-PT (bulk) d33 ~2000 12 kt~0.6
d31 ~-1000 k33 ~0.93
 Piezoelectric Materials

Using the parameters given below, answer the questions regarding the PMN-PT single
crystal plate below (the electrode is on the top and bottom surfaces)
1. What is the charge generated if a pressure of 1 MPa is applied onto the surface?
2. What is the vertical and horizontal displacement if 100 V is applied across the plate
along the poling direction?
3. Calculate the capacitance if relative dielectric constant is 4000.

P
d33: 2000 pm/V (or pC/N)
d31: -1000 pm/V (or PC/N)
ε0 = 8.85 x 10-12 farad /meter

1 mm
S = 𝑠 𝐸 T+dE
D=dT+𝑇 𝐸 5 mm
 Piezo Material Selection Guidelines

Hard PZT ceramics High power piezo devices: high power

ultrasound transducers, piezo motors,
transformers
Soft PZT ceramics Non-resonant actuators, low power ultrasound
transducers, piezo sensors (not high
temperature)
Quartz/Lithium Niobate Resonators, high temperature sensors
Relaxor SC High end ultrasound transducers, sensors
Polymer Receiving transducers, sensors
Films Integrated piezo sensors, actuators
 Piezoelectric Composite Materials

• 2-2 composite • 1-3 composite

• Optimized electromechanical coupling

• Acoustic impedance matching
• Flexibility
 References
• http://www.noliac.com/Default.aspx?ID=141
• http://www.morganelectroceramics.com/materials/piezoelectric/
• D. Damjanovic, “Lead-based piezoelectric materials”, (Piezoelectric and Acoustic
Materials for Transducer Applications”, edited by A. Safari, E. Akdogan, Springer,
2008)
• T. Shrout, T. Ritter, and K. Shung, “Piezoelectric Materials and Fabrication”, NIH
Resource on Medical Ultrasonic Transducer Technology, 2002.
• S. TROLIER-MCKINSTRY and P. MURALT, “Thin Film Piezoelectrics for MEMS”,
Journal of Electroceramics, 12, 7–17, 2004.
• Measurement Specialties, Inc., Piezo Film Sensors Technical Manual.
• http://www.physics.montana.edu/eam/polymers/piezopoly.htm
• http://www.hcmat.com/Pmn_Opportunities.html
• http://www.trstechnologies.com/Materials/single_crystals.php
• Zhang, S., F. Li, X. Jiang, J. Kim, J. Luo, and X. Geng, "Advantages and
Challenges of Relaxor-PbTiO3 Ferroelectric Crystals for Electroacoustic
Transducers-A Review," Progress in Materials Science, (2015).