Ferroelectric

Devices
Second Edition
Ferroelectric
Devices
Second Edition

Kenji Uchino

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Library of Congress Cataloging-in-Publication Data

Uchino, Kenji, 1950-

Ferroelectric devices / Kenji Uchino. -- 2nd ed.
p. cm.
Includes bibliographical references and index.
ISBN 978-1-4398-0375-2 (hardcover : alk. paper)
1. Ferroelectric devices. I. Title.

TK7872.F44U24 2010
537’.244--dc22 2009030733

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Contents
Preface...............................................................................................................................................xi
Suggested Teaching Schedule ........................................................................................................ xiii
Prerequisite Knowledge ................................................................................................................... xv
Author ............................................................................................................................................xvii
List of Symbols ...............................................................................................................................xix

Chapter 1 General View of Ferroelectrics ....................................................................................1

1.1 Crystal Structure and Ferroelectricity .................................................................1
1.2 Origin of Spontaneous Polarization ....................................................................4
1.3 Origin of Field-Induced Strain ............................................................................7
1.4 Electro-Optic Effect .......................................................................................... 11
1.5 Example of Ferroelectrics ................................................................................. 17
1.5.1 Barium Titanate ..................................................................................... 17
1.5.2 PZT ........................................................................................................ 18
1.5.3 Polyvinylidene Difluoride (PVDF) ........................................................ 19
1.5.4 Pb-Free Piezoceramics ..........................................................................20
1.6 Applications of Ferroelectrics ...........................................................................20
References .................................................................................................................. 23

Chapter 2 Mathematical Treatment of Ferroelectrics .................................................................25

2.1 Tensor Representation of Physical Properties ...................................................25
2.1.1 Fundamentals of Tensor .........................................................................25
2.1.2 Tensor Representation ............................................................................26
2.1.3 Crystal Symmetry and Tensor Form...................................................... 27
2.1.4 Reduction of the Tensor (Matrix Notation)............................................ 33
2.1.5 Matrix Notation of Electrostrictive Coefficients ...................................34
2.2 Phenomenology of Ferroelectricity ................................................................... 42
2.2.1 Fundamentals of Phenomenology.......................................................... 42
2.2.2 Landau Theory of the Phase Transition ................................................ 43
2.2.3 Phenomenology of Electrostriction ....................................................... 47
2.2.4 Converse Effects of Electrostriction ...................................................... 50
2.2.5 Temperature Dependence of Electrostriction ........................................ 50
2.3 Phenomenology of Antiferroelectricity............................................................. 51
2.3.1 Antiferroelectrics ................................................................................... 51
2.3.2 Phenomenology of Antiferroelectrics .................................................... 52
2.4 Ferroelectric Domain Contributions ................................................................. 54
2.4.1 Ferroelectric Domain Reorientation ...................................................... 54
2.4.2 Uchida–Ikeda Model ............................................................................. 57
2.4.3 Crystal Structure and Coercive Field .................................................... 61
2.4.4 Hysteresis Estimation Program ............................................................. 61
2.4.5 Domain Engineering .............................................................................64
References .................................................................................................................. 73

v
vi Contents

Chapter 3 Designing with Materials and Devices and Fabrication Processes............................ 75

3.1 Material Designing ............................................................................................ 75
3.1.1 Composition Selection............................................................................ 75
3.1.2 Dopant Effects on Ferroelectricity......................................................... 77
3.1.2.1 Domain Wall Stability ............................................................. 78
3.1.2.2 Crystallographic Deficiencies..................................................80
3.1.3 High-Power Characteristics ................................................................... 82
3.2 Fabrication Processes of Ceramics.................................................................... 85
3.2.1 Preparation of Ceramic Powders ........................................................... 85
3.2.1.1 Solid-State Reaction ................................................................ 85
3.2.1.2 Coprecipitation ........................................................................ 86
3.2.1.3 Alkoxide Hydrolysis ................................................................ 86
3.2.2 Sintering Process ................................................................................... 87
3.2.3 Single Crystal Growth ...........................................................................90
3.2.3.1 Quartz, LN, and LT .................................................................90
3.2.3.2 PZN–PT, PMN–PT, and PZT .................................................90
3.2.4 Templated Grain Growth .......................................................................90
3.3 Device Designing .............................................................................................. 91
3.3.1 Single Disks ........................................................................................... 91
3.3.2 Multilayers .............................................................................................92
3.3.3 Unimorphs/Bimorphs ............................................................................94
3.3.4 Flextension/Hinge-Lever Amplification Mechanisms .......................... 98
3.3.5 Flexible Composites...............................................................................99
3.3.6 Thin/Thick Films...................................................................................99
3.3.6.1 Film Manufacturing Techniques .............................................99
3.3.6.2 MEMS Applications.............................................................. 101
3.3.6.3 Constraints in Thin/Thick Films .......................................... 102
3.4 Size Effect on Ferroelectricity......................................................................... 102
3.4.1 Grain Size Effect on Ferroelectricity ................................................... 103
3.4.2 3-D Particle Size Effect on Ferroelectricity ........................................ 105
References ................................................................................................................ 112

Chapter 4 High-Permittivity Dielectrics ................................................................................... 115

4.1 Ceramic Capacitors ......................................................................................... 115
4.2 Chip Capacitors ............................................................................................... 116
4.2.1 Thin Multilayer Capacitor ................................................................... 116
4.2.2 Base-Metal Internal Electrode ............................................................ 117
4.2.2.1 Barium Titanate–Based Chip................................................ 117
4.2.2.2 PbTiO3-Based Chip ............................................................... 117
4.3 Hybrid Substrates ............................................................................................ 119
4.4 Relaxor Ferroelectrics ..................................................................................... 121
4.4.1 High Permittivity ................................................................................. 121
4.4.2 Diffuse Phase Transition ..................................................................... 122
4.4.3 Dielectric Relaxation ........................................................................... 124
References ................................................................................................................ 130

Chapter 5 Ferroelectric Memory Devices................................................................................. 131

5.1 DRAM ............................................................................................................. 131
5.1.1 Principle of DRAM .............................................................................. 131
5.1.2 Ferroelectric DRAM ............................................................................ 135
Contents vii

5.2 Nonvolatile Ferroelectric Memory .................................................................. 136

5.2.1 FeRAM (Inversion Current Type) ....................................................... 136
5.2.2 MFSFET .............................................................................................. 139
References ................................................................................................................ 142

Chapter 6 Pyroelectric Devices ................................................................................................ 145

6.1 Pyroelectric Materials ..................................................................................... 145
6.1.1 Pyroelectric Effect ............................................................................... 145
6.1.2 Responsivity ......................................................................................... 148
6.1.3 Figures of Merit ................................................................................... 150
6.2 Temperature/Infrared Sensors......................................................................... 152
6.3 Infrared Image Sensors ................................................................................... 152
6.4 Electrocaloric Devices..................................................................................... 154
6.4.1 Electrocaloric Effect ............................................................................ 154
6.4.1.1 Phenomenological Formula ................................................... 154
6.4.1.2 Electrocaloric Materials ........................................................ 157
References ................................................................................................................ 160

Chapter 7 Piezoelectric Devices ............................................................................................... 161

7.1 Piezoelectric Materials and Properties ............................................................ 161
7.1.1 Piezoelectric Figures of Merit .............................................................. 161
7.1.2 Piezoelectric Materials ......................................................................... 167
7.1.2.1 Single Crystals ....................................................................... 168
7.1.2.2 Polycrystalline Materials ....................................................... 168
7.1.2.3 Relaxor Ferroelectrics............................................................ 172
7.1.2.4 Polymers ................................................................................ 172
7.1.2.5 Composites ............................................................................ 173
7.1.2.6 Thin Films ............................................................................. 173
7.2 Pressure Sensors/Accelerometers/Gyroscopes ................................................ 174
7.3 Piezoelectric Vibrators/Ultrasonic Transducers .............................................. 177
7.3.1 Piezoelectric Resonance ....................................................................... 177
7.3.1.1 Piezoelectric Equations .......................................................... 177
7.3.1.2 Electromechanical Coupling Factor ...................................... 177
7.3.1.3 Longitudinal Vibration Mode ................................................ 180
7.3.2 Equivalent Circuits of Piezoelectric Vibrators..................................... 184
7.3.3 Piezoelectric Vibrators ......................................................................... 186
7.3.4 Ultrasonic Transducers ........................................................................ 187
7.3.4.1 Ultrasonic Imaging ................................................................ 187
7.3.4.2 Sonochemistry ....................................................................... 188
7.3.5 Resonators/Filters ................................................................................ 189
7.4 Surface Acoustic Wave Devices ...................................................................... 191
7.5 Micromass Sensors .......................................................................................... 193
7.5.1 Biosensor .............................................................................................. 193
7.5.2 Viscosity Sensor ................................................................................... 194
7.6 Piezoelectric Transformers .............................................................................. 194
7.7 Piezoelectric Actuators .................................................................................... 198
7.7.1 Ceramic Actuator Materials ................................................................. 198
7.7.2 Actuator Designs ..................................................................................200
7.7.3 Drive/Control Techniques .................................................................... 201
viii Contents

7.7.4
Device Applications .............................................................................207
7.7.4.1 Servo Displacement Transducers ...........................................207
7.7.4.2 Pulse-Drive Motors ................................................................208
7.8 Ultrasonic Motors ............................................................................................ 212
7.8.1 Ultrasonic Motors (USM) .................................................................... 212
7.8.2 Classification and Principles of Ultrasonic Motors ............................. 214
7.8.2.1 Standing-Wave Type .............................................................. 214
7.8.2.2 Propagating-Wave Type ......................................................... 215
7.8.3 Standing Wave–Type Motors ............................................................... 216
7.8.3.1 Rotary Motors........................................................................ 216
7.8.3.2 Linear Motors ........................................................................ 218
7.8.4 Propagating Wave–Type Motors .......................................................... 219
7.8.4.1 Linear Motors ........................................................................ 219
7.8.4.2 Rotary Motors ....................................................................... 220
7.8.4.3 Comparison of the Various Ultrasonic Motors ..................... 223
7.8.5 Smooth Impact Drive Mechanism (SIDM) .........................................224
7.9 Piezoelectric Energy Harvesting .....................................................................224
7.9.1 Piezoelectric Passive Damping to Energy Harvesting .........................224
7.9.2 High-Energy Harvesting (~W) ............................................................. 225
7.9.3 Low-Energy Harvesting (~mW) ........................................................... 227
References ................................................................................................................ 232

Chapter 8 Electro-Optic Devices .............................................................................................. 235

8.1 Electro-Optic Effect—Review ........................................................................ 235
8.2 Transparent Electro-Optic Ceramics .............................................................. 235
8.2.1 (Pb,La)(Zr,Ti)O3 ................................................................................... 236
8.2.2 PMN–PT.............................................................................................. 239
8.2.3 Pb(Zn1/3Nb2/3)O3 .................................................................................. 241
8.3 Bulk Electro-Optic Devices ............................................................................ 242
8.3.1 Ferpic ................................................................................................... 242
8.3.2 Eye Protection Application .................................................................. 243
8.3.3 Stereo TV Application ......................................................................... 243
8.3.4 Two-Dimensional Displays ..................................................................244
8.3.4.1 Fabrication Process of the 2-D Display .................................244
8.3.4.2 Characteristics of the Light Valve Array ..............................246
8.3.4.3 Construction of the Image Projector ..................................... 247
8.3.5 KTN Single Crystal Optical Switch .................................................... 251
8.3.6 Laser Beam Scanner ............................................................................ 252
8.4 Waveguide Modulators .................................................................................... 252
8.4.1 LiNbO3 Waveguide .............................................................................. 252
8.4.2 PZT Thin Film Waveguide .................................................................. 254
References ................................................................................................................ 259

Chapter 9 PTC Materials .......................................................................................................... 261

9.1 Mechanism of PTC Phenomenon .................................................................... 261
9.1.1 PTC Phenomenon ................................................................................. 261
Contents ix

9.1.2 Mechanism of the PTC Phenomenon................................................... 261

9.1.2.1 Semiconducting Properties .................................................... 261
9.1.2.2 Schottky Barrier Effect ......................................................... 263
9.1.2.3 Experimental Verification ..................................................... 265
9.2 PTC Thermistors .............................................................................................266
9.3 Grain Boundary Layer Capacitors................................................................... 269
References ................................................................................................................ 272

Chapter 10 Composite Materials ................................................................................................ 273

10.1 Connectivity................................................................................................... 273
10.2 Composite Effects.......................................................................................... 274
10.2.1 Sum Effects ...................................................................................... 274
12.2.2 Combination Effects ........................................................................ 275
10.2.3 Product Effects ................................................................................. 276
10.3 PZT:Polymer Composites .............................................................................. 277
10.3.1 Piezoelectric Composite Materials ................................................... 277
10.3.2 Principle of PZT:Polymer Composites ............................................. 278
10.3.3 Theoretical Models for 0-3 Composites ........................................... 281
10.3.4 Advanced PZT:Polymer Composites................................................ 283
10.4 Composite Dampers and Energy Harvesters .................................................284
10.4.1 Piezoelectric Composite Dampers....................................................284
10.4.2 Piezoelectric Composite Energy Harvesting.................................... 288
10.5 Magnetoelectric Sensors................................................................................ 290
References ................................................................................................................ 296

Chapter 11 Future of Ferroelectric Devices................................................................................ 297

11.1 Market Share .................................................................................................. 297
11.1.1 Market Share of Ferroelectric Devices ............................................. 297
11.1.2 Market Share of Piezoelectric Actuators .......................................... 298
11.2 Reliability Issues ............................................................................................300
11.2.1 Materials Improvements ...................................................................300
11.2.2 Reliability of Devices ....................................................................... 301
11.2.3 Drive/Control Techniques ................................................................ 303
11.2.4 Safety Systems.................................................................................. 303
11.3 Development of Bestselling Devices .............................................................304
11.3.1 Three Creativities .............................................................................304
11.3.2 Technological Creativity...................................................................304
11.3.2.1 Discovery of a New Function or Material ........................304
11.3.2.2 Performance Improvement ...............................................308
11.3.3 Product Planning Creativity ............................................................. 314
11.3.3.1 Seeds and Needs ............................................................... 314
11.3.3.2 Innovation Obstacle in Technology Management ............ 316
11.3.3.3 Development Pace ............................................................. 316
11.3.3.4 Specifications .................................................................... 316
11.3.3.5 Product Design Philosophy............................................... 318
11.3.3.6 Smart Systems................................................................... 318
x Contents

11.3.4 Marketing Creativity ........................................................................ 319

11.3.4.1 Choose Your Customers.................................................... 320
11.3.4.2 Narrow Your Focus ........................................................... 322
11.3.4.3 Dominate Your Market ..................................................... 326
11.3.5 Business Strategy.............................................................................. 327
11.3.5.1 Analysis Tools ................................................................... 328
11.3.5.2 Internal Environmental Analysis ...................................... 329
11.3.5.3 External Environmental Analysis ..................................... 331
References ................................................................................................................ 337
Index .............................................................................................................................................. 339
Preface
Ferroelectrics can be used in various devices such as high-permittivity dielectrics, pyroelectric sen-
sors, piezoelectric devices, electro-optic devices, and positive temperature coefficient (PTC) com-
ponents. The concerned industries are constantly producing large amounts of simple devices such
as ceramic capacitors, piezoelectric igniters, buzzers, and PTC thermistors. However, ferroelectric
devices have, until now, failed to reach commercialization in more functional cases. In light sen-
sors, for example, semiconductive materials are superior to ferroelectrics in terms of response speed
and sensitivity. Magnetic devices and semiconductive “Flash” memories are much more popular in
the memory field, and liquid crystals are typically used for optical displays. Ferroelectric devices
often fail to be developed when other competitive materials exist. However, taking into consider-
ation recent strides that have been made at commercialization, I have not given up on ferroelectric
devices. I believe that these earlier failures were mainly due to a lack of systematic accumulation of
fundamental knowledge of the materials and developmental experiences of the devices.
During my 35-year teaching period on ferroelectric devices, I was unable to find any book dedi-
cated exclusively to this field, other than some professional publications such as multiauthored paper
collections. Hence, I decided to collect my lecture notes, including my device-development phi-
losophy, and write this comprehensive book. This book provides an introduction to the theoretical
background of ferroelectric devices, practical materials, device designs, drive/control techniques,
and typical applications, and looks forward to future progress in this field. Although ferroelectricity
was discovered a long time ago, device development is relatively new and interdisciplinary, and it
is therefore almost impossible to cover all the recent studies in one single book. Therefore, in this
second edition, I have focused on the important ideas to understand how to design and develop
ferroelectric devices by adding some up-to-date device developments to the original devices.
This book is organized as follows. Chapter 1 provides a general introduction while Chapter 2
provides more of a theoretical background. Chapter 3 deals with the practical designing and manu-
facturing of the devices, including recent single-crystal and thin-film processes. Chapter 4 elaborates
on capacitor applications while Chapters 5 and 6 deal with thin- and thick-film applications, i.e.,
ferroelectric memory devices and pyroelectric devices, respectively. A new section on electrocaloric
devices has been inserted in the last part of Chapter 6. Chapter 7 deals with piezoelectric actua-
tors and ultrasonic motors as well as acoustic transducers and piezoelectric sensors. Piezoelectric
energy harvesting is a new piezoelectric topic. Chapter 8 provides a description of optical devices
such as light valves, displays, wave guides, and bulk photovoltaic devices. In Chapters 9 and 10, the
basic concepts of PTC materials and composite materials are explained and their device applica-
tions are demonstrated. Finally, Chapter 11 discusses the future of ferroelectric devices, that is, the
market size and the remaining reliability/lifetime issues, and the author’s strategy for developing
best-selling devices.
One decade has passed since the first edition appeared. During this period, the book was for-
tunately a commercial success and has been well received as a standard in this field. Although the
fundamental principles, including Maxwell equations, phenomenology, and piezoelectric relations,
have not been altered, the applications have been updated in keeping with the times.
The second edition aims primarily at including up-to-date research and developmental trends,
reflecting nano- and optical technologies, environmental regulation, and alternative energy
sources. The new sections in this edition include (1) Pb-free piezoelectrics, (2) size effects on fer-
roelectricity, (3) electrocaloric devices, (4) micro-mass sensors, (5) piezoelectric energy harvesting,
(6) light valves and scanners, and (7) multiferroic devices, which, in turn, include magnetoelectric
sensors.

xi
xii Preface

Even for traditional devices, such as capacitors, piezoelectric speakers, clocks, and transformers,
old data have been updated with an eye to the future.
This edition is a more complete book; in addition to the chapter summaries, example problems,
and chapter problems,

• FAQs (frequently asked questions)—to answer common in-class questions,

• Lab Demonstrations—to provide effective in-class demos for practical understanding
• Check Points—to have a fundamental understanding check for students

have been newly inserted in every chapter. Over the years, all of these had accumulated in my
notebook, courtesy of students’ feedback and comments. These three additions will help the
reader correctly understand the essence of this book. Furthermore, due to strong requests by junior
instructors, model solutions have been added for the check point and chapter problems in a separate
solutions manual. I usually use check points for quizzes, example problems for homework, and
chapter problems for mid-term and final exams. I hope this will make it easier for the instructor to
prepare exam and homework problems.
Most errors in mathematical formulas, English expressions, and typos have been completely
revised and fixed in this edition.
This book was written for graduate students, undergraduate junior and senior levels, and industry
engineers studying or working in the fields of electronic materials, optical materials and communi-
cations, precision machinery, and robotics. Although this book is designed as a course with thirty
75-min lectures, readers can learn by themselves aided by the examples and problems.
For those who seek more detailed information on smart piezoelectric actuators and sensors,
Micromechatronics by K. Uchino and the late Jayne R. Giniewicz, published by CRC/Dekker in
2003, is recommended. Further, FEM and Micromechatronics with ATILA Software, published by
CRC Press in 2008, is a perfect manual for practical device designing.
Even though I am the sole author of this book, it includes the contributions of many others.
I express my gratitude to my ICAT center faculty members who have generously given me their
advice and help during the writing, particularly Professor Uma Belegundu at Lock Haven University,
who worked out all the problems. Specific acknowledgment and condolences are also dedicated to
my former student at Indiana University of Pennsylvania, Professor Jayne Giniewicz, who reviewed
and criticized the entire manuscript and made linguistic corrections, but passed away unexpectedly
at a very young age. Finally, my wife Michiko’s constant assistance is greatly appreciated with my
deepest love.
Critical review and corrections to this book will be highly appreciated. Send your feedback
directly to Kenji Uchino at 134 Materials Research Laboratory, The Pennsylvania State University,
University Park, PA 16802-4800; fax: 814-863-6734; e-mail: [email protected].

Kenji Uchino
Suggested Teaching Schedule
(75 min × 30 times per semester)

0. Course Explanation and Prerequisite Knowledge Check 1 Time

1. General View of Ferroelectrics 4 Times
2. Mathematical Treatment of Ferroelectrics 4 Times
3. Designing with Materials and Devices and
Fabrication Processes 2 Times
4. High-Permittivity Dielectrics 2 Times
5. Ferroelectric Memory Devices 1 Time
6. Pyroelectric Devices 2 Times
7. Piezoelectric Devices 5 Times
8. Electro-Optic Devices 2 Times
9. PTC Materials 1 Time
10. Composite Materials 2 Times
11. Future of Ferroelectric Devices 1 Time

Lab Demonstration 2 Times

Review/Q&A 1 Time

xiii
Prerequisite Knowledge
In order to understand ferroelectric devices, some prerequisite knowledge is expected. Try to solve
the following questions without seeing the answers on the next page.
Q1 Describe the definitions of elastic stiffness c and compliance s, using a stress X–strain
x relation.
Q2 Indicate a shear stress X4 on the following square.

Q3 Describe the sound velocity v in a material with mass density ρ and elastic compliance sE.
Q4 Calculate the capacitance C of a capacitor with area S and electrode gap t filled with a material
of relative permittivity ε.
Q5 Calculate the polarization P of a material with dipole density N (m−3) of dipole moment
qu (C m).
Q6 Describe the Curie–Weiss law of relative permittivity ε, using a Curie–Weiss temperature T0
and a Curie–Weiss constant C.
Q7 Describe the light velocity in a material with a refractive index n (c: light velocity in
vacuum).
Q8 Indicate the work function in the following energy band of a metal:

Vacuum level
Energy

Fermi level

Inside
of metal Outside

Q9 There is a voltage supply with an internal impedance Z 0. Indicate the external impedance Z1
to obtain the maximum output power.
Q10 Calculate the induced polarization P under an external stress X in a piezoelectric with a piezo-
electric constant d.

xv
xvi Prerequisite Knowledge

ANSWERS
(Correct rate more than 60% of the full score is expected)
Q1 X = cx, x = sX
Q2 X4 = 2X23 = 2φ (rad)

X4
φ

Q3 v = 1 / ρS E [0.5 point for v = 1/ρsE]

Q4 C = ε0ε(S/t) [0.5 point for C = ε(S/t)]
Q5 P = Nqu
Q6 ε = C/(T – T0) [0.5 point for ε = C/T]
Q7 c′ = c/n
Q8 (Work function)

Vacuum level
Work
function
Energy

Fermi level

Inside
Outside
of metal

Q9 Z1 = Z 0
On Z1, the current and voltage are given as V/(Z 0 + Z1) and [Z1/(Z 0 + Z1)]V, leading to the
power:
Power = V 2 Z1/(Z 0 + Z1)2 = V 2/(Z 0 / Z1 + Z1 )2 ≤ (1/4)V 2/Z 0
The maximum is obtained when Z0 / Z1 = Z1 . Hence, Z1 = Z 0.

Z0

V Z1

Q10 P = dX (refer to x = dE)

Author
Kenji Uchino, one of the pioneers in piezoelectric actuators and electro-optic displays, is the director
of the International Center for Actuators and Transducers (ICAT) and professor of electrical engineer-
ing at The Pennsylvania State University. He is currently teaching “ferroelectric devices,” making
use of this book, as well as two other books, Micromechatronics and FEM and Micromechatronics
with ATILA Software, that have been published by CRC Press. He is also the senior vice president
and CTO of Micromechatronics Inc., a spin-off company of ICAT, where he is trying to commer-
cialize ICAT-invented piezoactuators and transducers. He has also started teaching “how to start-up
a high-tech company” for young engineers using a textbook Entrepreneurship for Engineers pub-
lished by CRC Press.
After receiving his PhD from the Tokyo Institute of Technology, Japan, Uchino became a
research associate in the physical electronics department at the same university. He then joined
Sophia University, Japan, as an associate professor of physics in 1985. Subsequently, in 1991, he
moved to Pennsylvania. He was also involved with the Space Shuttle Utilizing Committee at the
National Space Development Agency (NASDA), Japan, during 1986–1988, and was the vice presi-
dent of NF Electronic Instruments, United States, during 1992–1994. Uchino has an additional mas-
ter’s degree in business administration from St. Francis University, Loretto, Pennsylvania. He has
served as a consultant for more than 100 Japanese, U.S., and European industries to commercialize
piezoelectric actuators and electro-optic devices. He is the chairman of the Smart Actuator/Sensor
Study Committee that is partly sponsored by the Japanese government, Ministry of International
Trade and Industry (MITI). He is also the associate editor of the Journal of Materials Technology
(Matrice Technology) and an editorial board member of the Journal of Ferroelectrics (Gordon &
Breach) and the Journal of Electroceramics (Kluwer Academic). He also served as an administra-
tive committee member for the IEEE Ultrasonics, Ferroelectrics, and Frequency Control Society
during 1998–2000.
Uchino’s research interests are in solid-state physics—especially dielectrics, ferroelectrics, and
piezoelectrics, including basic research on materials, device designing, and fabrication processes;
he is also interested in the development and commercialization of solid-state actuators and dis-
plays for precision positioners, ultrasonic motors, projection-type TVs, etc. He has authored 550
papers, 54 books, and 26 patents on the subject of piezoelectric actuators and optical devices. He
has been a fellow of the American Ceramic Society since 1997, and is also a recipient of the SPIE
Smart Product Implementation Award (2007), the R&D 100 Award (2007), the ASME Adaptive
Structures Prize (2005), the Outstanding Research Award from the Penn State Engineering Society
(1996), the Academic Scholarship from Nissan Motors Scientific Foundation (1990), the Best Movie
Memorial Award at the Japan Scientific Movie Festival (1989), and the Best Paper Award from the
Japanese Society of Oil/Air Pressure Control (1987).
Apart from his academic pursuits, Uchino is an honorary member of KERAMOS (National
Professional Ceramic Engineering Fraternity) and has received the Best Movie Memorial Award as
the director/producer of several educational videos on “dynamical optical observation of ferroelectric
domains” and “ceramic actuators” at the Japan Scientific Movie Festival (1989).

xvii
List of Symbols
c Elastic stiffness
C Curie–Weiss constant
D Electric displacement
d, g Piezoelectric coefficients
E Electric field
g Secondary electro-optic coefficient
G1 Gibbs elastic energy
k Electromechanical coupling factor
M, Q Electrostrictive coefficients
n Refractive index
p Pyroelectric coefficient
P Dielectric polarization
Ps Spontaneous polarization
r Primary electro-optic coefficient
s Elastic compliance
T0 Curie–Weiss temperature
TC Curie temperature (phase transition temperature)
v Sound velocity
x Strain
X Stress
xs Spontaneous strain
α Ionic polarizability
γ Lorentz factor
Γ Phase retardation
ε Relative permittivity
ε0 Vacuum permittivity
η Energy transmission coefficient
μ Dipole moment

xix
 1 General View of Ferroelectrics
Let us start with the “smartness” of a material. Table 1.1 lists the various effects relating the input
(electric field, magnetic field, stress, heat, and light) with the output (charge/current, magnetiza-
tion, strain, temperature, and light). Conducting and elastic materials, which generate current and
strain outputs, respectively, for the input voltage or stress (well-known phenomena), are sometimes
called “trivial” materials. On the other hand, pyroelectric and piezoelectric materials, which gen-
erate an electric field with the input of heat and stress (unexpected phenomena), respectively, are
called “smart” materials. These off-diagonal couplings have corresponding converse effects, the
electrocaloric and converse piezoelectric effects, and both “sensing” and “actuating” functions can
be realized in the same materials. “Intelligent” materials must possess a “drive/control” or “pro-
cessing” function which is adaptive to changes in environmental conditions, in addition to actuator
and sensing functions. Ferroelectric materials exhibit most of these effects with the exception of the
magnetic phenomena. Thus, ferroelectrics are said to be very “smart” materials.
Ferroelectrics are utilized in various devices such as high-permittivity dielectrics, pyroelectric sen-
sors, piezoelectric devices, electro-optic devices, and positive temperature coefficient (PTC) of resistiv-
ity components. However, ferroelectric devices often fail to be commercialized in areas of application
where competitive materials exist. Light sensors, for example, typically are manufactured from semi-
conductive materials which are superior to ferroelectrics in response speed and sensitivity. Magnetic
devices are much more popular for memory applications, and liquid crystals are typically used for opti-
cal displays. One reason for this is due to the lack of systematic and comprehensive compilation of
knowledge on ferroelectric materials. In this chapter, we will learn the fundamentals of ferroelectricity.

1.1 CRYSTAL STRUCTURE AND FERROELECTRICITY

In the so-called dielectric materials, the constituent atoms are considered to be ionized to a certain
degree and are either positively or negatively charged. In such ionic crystals, when an electric field
is applied, cations are attracted to the cathode and anions to the anode due to electrostatic inter-
action. The electron clouds also deform, causing electric dipoles. This phenomenon is known as
electric polarization of the dielectric, and the polarization is expressed quantitatively as the sum of
the electric dipoles per unit volume (C/m2). Figure 1.1 shows schematically the origin of the electric
polarization. There are three primary contributions: electronic, ionic, and dipole reorientation-
related. The degree to which each mechanism contributes to the overall polarization of the material
depends on the frequency of the applied field. Electronic polarization can follow alternating fields
with frequencies from terahertz (THz) to petahertz (PHz) [(1012−1015 cycle/s), higher than visible
light wave] and ionic polarization responds to frequencies from gigahertz (GHz) to THz [(109–1012
cycle/s), microwave region]. Thus, you should understand that a famous relation between the relative
permittivity ε and the refractive index n:

ε = n2 (1.1)
is valid only when the applied electric field has a frequency on the order of THz or higher. Permanent
dipole reorientation can follow only frequencies from megahertz (MHz) to GHz (106 –109 cycle/s).
This is why ferroelectric materials with permanent dipoles cannot be used for microwave dielectric
materials; their permittivity is typically high at low frequencies (kHz), but decreases significantly
with increasing applied electric field frequency. Frequency dependence of the total polarizability (or
permittivity) is depicted in Figure 1.2.

1
2 Ferroelectric Devices

TABLE 1.1
Various Effects in Materials

Input Material Output

device

Output Charge Magnet-

Input current ization Strain Temperature Light

Permittivity Elect.-mag. Converse Elec. caloric Elec.-optic

Elec. field
Conductivity effect piezoeffect effect effect

Mag.-elect. Magneto- Mag. caloric Mag. optic

Mag. field Permeability
effect striction effect effect

Piezoelectric Piezomag. Elastic Photoelastic

Stress ___
effect effect constant effect

Pyroelectric Thermal Specific

Heat ___
effect expansion heat

Photovoltaic Refractive
Light Photostriction ___
effect index

Diagonal coupling Sensor

Off-diagonal coupling = Smart material Actuator

Compared with air-filled capacitors, dielectric capacitors can store more electric charge due to
the dielectric polarization P as shown in Figure 1.3. The physical quantity corresponding to the
stored electric charge per unit area is called the electric displacement D, and is related to the electric
field E by the following expression:

D = ε0 E + P = εε 0 E. (1.2)

Here,
ε0 is the vacuum permittivity (=8.854 × 10 −12 F/m)
ε is the material’s relative permittivity (also simply called permittivity or dielectric constant, and
in general is a tensor property)

E=0 E

Electronic
+ – +
polarization –

Ionic
polarization + – + + – +

– +
– + – + – + – + –+ – +
Dipole + –
reorientation – +
+ – – + – + – + – + – +
+ –

FIGURE 1.1 Microscopic origins of the electric polarization.

General View of Ferroelectrics 3

Microwave Infrared Ultraviolet

Total polarizability (real part)

αdipolar

αionic

αelectronic

108 1012 1016

Frequency (Hz)

FIGURE 1.2 Frequency dependence of the polarizability (or permittivity).

–
–σf – – – – – –

+ + + + +σb
+
– – – – –
Dielectric
E + + + + +
– – – – –
–σb

+σf + + + + + +
σt = σb + σf
+

σf : Free charge σb: Bound charge σt: True charge

FIGURE 1.3 Charge accumulation in a dielectric capacitor.

Depending on the crystal structure, the centers of the positive and negative charges may not
coincide even without the application of an external electric field. Such crystals are said to possess
a spontaneous polarization. When the spontaneous polarization of the dielectric is reversed by an
electric field, it is called ferroelectric.
Not every dielectric is a ferroelectric. Crystals can be classified into 32 point groups according to
their crystallographic symmetry, and these point groups can be divided into two classes, one with a
center of symmetry and the other without as indicated in Table 1.2. There are 21 point groups which
do not have a center of symmetry. In crystals belonging to 20 of these point groups [point group
(432) being the sole exception], positive and negative charges are generated on the crystal surfaces
when appropriate stresses are applied. These materials are known as piezoelectrics.
Pyroelectricity is the phenomenon in which, due to the temperature dependence of the sponta-
neous polarization, a change in temperature of the crystal produces electric charges on the surface
of the crystal corresponding to the change of spontaneous polarization. Among the pyroelectric
crystals, those whose spontaneous polarization can be reversed by an electric field (not exceeding
the breakdown limit of the crystal) are called ferroelectrics. There is some experimental ambigu-
ity in this definition. In establishing ferroelectricity, it is necessary to apply an electric field to a
pyroelectric material and experimentally ascertain the polarization reversal.
4 Ferroelectric Devices

TABLE 1.2
Crystallographic Classification according to Crystal Centrosymmetry
and Polarity

Crystal System

Rhombo- Ortho- Mono-

Polarity Symmetry Cubic Hexagonal Tetragonal hedral rhombic clinic Triclinic

Centro
(11) m3m m3 6/mmm 6/m 4/mmm 4/m 3m 3 mmm 2/m 1

Nonpolar
(22) 432 622 422
23 6 4 32 222
Noncentro 43m 6m2 42m
(21)
Polar 2
(pyroelectric) 6mm 6 4mm 4 3m 3 mm2 1
(10) m

Note: Inside the bold line are piezoelectrics.

1.2 ORIGIN OF SPONTANEOUS POLARIZATION

Why is it that crystals which, from a consideration of elastic energy, should be stable by being non-
polar, still experience the shifting of cations and anions and become spontaneously polarized? The
reason is briefly explained below. For simplicity, let us assume that dipole moments result from the
displacement of one type of ion A (electric charge q) relative to the crystal lattice. Consider the case
in which the polarization is caused by all the A ions being displaced equally in a lattice.
This kind of ionic displacement can be expected through lattice vibrations at a finite tempera-
ture. Figure 1.4 shows some of the possible eigen lattice vibrations in a perovskite-like crystal.
Figure 1.4a shows an initial cubic (symmetrical) structure, Figure 1.4b is a symmetrically elon-
gated one, Figure 1.4c has coherently shifted center cations, and Figure 1.4d exhibits an anti-
polarized shift of the center cations. If one particular lattice vibration lowers the crystal energy,
the ions will shift and stabilize the crystal structure so as to minimize the energy. Starting from
the original cubic structure (Figure 1.4a), if Figure 1.4b is stabilized, only oxygen octahedra

(a) (b) (c) (d)

FIGURE 1.4 Some possible eigen lattice vibration modes in a perovskite crystal. (a) Initial symmetric cubic,
(b) symmetrically elongated, (c) coherently shifted centre cations, and (d) antipolarized shift of the centre
cations.
General View of Ferroelectrics 5

+ + + Equipotential
– – –
E-line

r1
+ pi
ri –

E0

+ + +
– – – Dielectric material

FIGURE 1.5 Concept of the local field. Eloc is given by E loc = E0 + ∑ i [3(pi ⋅ ri )ri − ri2 pi ]/4πε 0 ri5 .

are distorted without generating dipole moments (acoustic mode). On the other hand, when
Figure 1.4c or d is stabilized, dipole moments are generated (optical mode). The final stabilized
states Figure 1.4c and d correspond to ferroelectric and antiferroelectric states, respectively. If
this particular mode becomes stabilized, with decreasing temperature, the vibration mode fre-
quency decreases (soft phonon mode), and finally at a certain phase transition temperature this
frequency becomes zero.
It follows that, at any individual A ion site, there exists a local field from the surrounding polar-
ization P, even if there is no external field. The concept of the local field is shown schematically in
Figure 1.5. It can be shown that

E loc = E0 + ∑ [3(p ⋅ r )r − r p ]/4πε r .

i
i i i i
2
i 0 i
5

= (γ /3ε 0 )P. (1.3)

This local field is the driving force for the ion shift. Here γ is called the Lorentz factor. For an
isotropic cubic system, it is known that γ = 1.1 ε0 is the permittivity of vacuum and is equal to 8.854 ×
10 −12 F/m. If the ionic polarizability of ion A is α, then the dipole moment of the unit cell of this
crystal is

μ = (αγ /3ε 0 )P. (1.4)

The energy of this dipole moment (dipole–dipole coupling) is

wdip = −μ ⋅ E loc = −(αγ 2/9ε 20 )P 2. (1.5)

Defining N to be the number of atoms per unit volume:

Wdip = Nwdip = −( N αγ 2/9ε 02 )P 2. (1.6)

Furthermore, when the A ions are displaced from their nonpolar equilibrium positions, the elastic
energy also increases. If the displacement is u, and the force constants are k and k¢, then the increase
of the elastic energy per unit volume can be expressed as

Welas = N [(k /2)u2 + (k ′ /4)u 4 ]. (1.7)

6 Ferroelectric Devices

Wdip Welas

P
(a) (b)

Wtot

P
(c)

FIGURE 1.6 Energy explanation of the origin of spontaneous polarization. (a) Dipole interaction:
Wdip = – (Nag2/9e 02 )P2. (b) Elastic energy: Welas = (k ¢/2Nq2 )P2 + (k/4N3 q4 )P4. (c) Total energy: Wtot = Wdip + Welas.

Here, k¢ (>0) is the higher order force constant. It should be noted that in pyroelectrics, k¢ plays
an important role in determining the magnitude of the dipole moment. By rewriting Equation 1.7
using

P = Nqu, (1.8)

where q is the electric charge, and combining with Equation 1.6, the total energy can be expressed
as follows (see Figure 1.6):
Wtot = Wdip + Welas

= [(k /2Nq 2 ) − (N αγ 2 / 9ε 20 )] P 2 + [k ′ /4N 3q 4 ]P 4 . (1.9)

From this, one can see that if the coefficient of the harmonic term of the elastic energy is equal to or
greater than the coefficient of the dipole–dipole coupling, then P = 0; the A ions are stable and remain at
the nonpolar equilibrium positions. Otherwise, a shift from the equilibrium position (P2 = [(2Nαγ 2/9ε02)
− (k/Nq2)]/[k¢/N 3q4]) is stable. Spontaneous polarization can occur more easily in perovskite type crys-
tal structure (e.g., barium titanate, BT) due to a higher value of Lorenz factor γ (=10)2 than that of other
crystal structures. Note also that the polarizability is sensitive to temperature, leading to the phase tran-
sition. Suppose that the ionic polarizability of ion A, α, increases with decreasing temperature, even if
[(k/2Nq2) − (Nαγ 2/9ε02)] > 0 (paraelectric) at a high temperature, this value may become negative with
decreasing temperature, leading to a ferroelectric phase transition. Considering a first approximation,
a linear relation of the α with temperature, that is, the well-known Curie–Weiss law:

[(k /2Nq 2 ) − (N αγ 2 /9ε 20 )] ∝ (T − T0 )/C (1.10)

can be derived. This equation will be discussed again in detail in Section 2.2.2.

EXAMPLE PROBLEM 1.1

BaTiO3 exhibits ionic displacements as illustrated in Figure 1.7 at room temperature (RT).
Calculate the magnitude of the spontaneous polarization. The lattice constants are c = 4.036 Å
and a = 3.992 Å.
Hint
P = Nμ (N: number of the dipole moments included in a unit volume)
General View of Ferroelectrics 7

0.061 å

Ti4+ O2–
Ba2+
Ba2+ 0.036 å

Ti4+ 0.12 å
O2–

FIGURE 1.7 Ionic displacements in BaTiO3.

Solution
The dipole moment is calculated by taking the product of the charge magnitude and its
displacement. The total dipole moment in a unit cell is calculated by summing the Ba2+, Ti4+,
O2− related dipoles (notice the fractional contribution of each atom, i.e., 1/8 for corner atoms and
1/2 for face-centered atoms)

p = 8(2e /8)(0.061 × 10 −10 m) + 4e(0.12 × 10 −10 m) + 2(− 2e /2) (− 0.036 × 10 −10 m)

= 0.674 × 10 −10 e m
_ 29
= 1.08 × 10 C m, (P1.1.1)

where e = 1.602 × 10 −19 C. The unit cell volume is given by

v = a 2 c = (3.992)2 (4.036) × 10 −30 m 3

= 64.3 × 10 −30 m 3 . (P1.1.2)

The spontaneous polarization is defined as the polarization (total dipole moment) per unit
volume:

PS = p /v = 1.08 × 10 −29 C m / 64.3 × 10 −30 m 3

= 0.17C/m 2. (P1.1.3)

The experimental value of PS is about 0.25 C/m2.

1.3 ORIGIN OF FIELD-INDUCED STRAIN

Solids, especially ceramics (inorganic materials), are relatively hard mechanically, but still expand
or contract depending on the change of the state parameters. The strain (defined as the displacement
ΔL/initial length L) caused by temperature change and stress are known as thermal expansion and
elastic deformation, respectively. In insulating materials, the application of an electric field can also
cause deformation. This is called electric-field-induced strain.
8 Ferroelectric Devices

Lattice constant Lattice constant

E E

– + – + – + – +

Ion pair potential energy Ion pair potential energy

δ1 δ2 δ1 δ2
(a) (b)

FIGURE 1.8 Microscopic explanation of the (a) piezoelectric strain and (b) electrostriction.

Generally speaking, the word electrostriction is used in a general sense to describe elec-
tric-field-induced strain, and hence frequently also implies the “converse piezoelectric effect.”
However, in solid-state theory, the converse piezoelectric effect is defined as a primary elec-
tromechanical coupling effect, that is, the strain is proportional to the electric field, while elec-
trostriction is a secondary coupling in which the strain is proportional to the square of the electric
field. Thus, strictly speaking, they should be distinguished. However, the piezoelectricity of a
ferroelectric, which has a centrosymmetric prototype (high temperature) phase, is considered to
originate from the electrostrictive interaction, and hence the two effects are related. The above
phenomena hold strictly under the assumptions that the object material is a monodomain single
crystal and that its state does not change under the application of an electric field. In a practi-
cal piezoelectric ceramic, additional strains accompanied by the reorientation of ferroelectric
domains are also important.
Why a strain is induced by an electric field is explained herewith.3 For simplicity, let us consider
an ionic crystal such as NaCl. Figure 1.8a and b shows a one-dimensional (1-D) rigid-ion spring
model of the crystal lattice. The springs represent equivalently the cohesive force resulting from
the electrostatic Coulomb energy and the quantum mechanical repulsive energy. Figure 1.8b shows
the centrosymmetric case, whereas Figure 1.8a shows the more general noncentrosymmetric case.
In Figure 1.8b, the springs joining the ions are all the same, whereas in Figure 1.8a, the springs
joining the ions are different for the longer and shorter ionic distances; in other words, hard
and soft springs existing alternately are important. Next, consider the state of the crystal lattice
Figure 1.8a under an applied electric field. The cations are drawn in the direction of the electric
field and the anions in the opposite direction, leading to the relative change in the interionic
distance. Depending on the direction of the electric field, the soft spring expands or contracts
more than the contraction or expansion of the hard spring, causing a strain x (a unit cell length
change) in proportion to the electric field E. This is the converse piezoelectric effect. When
expressed as

x = dE, (1.11)
the proportionality constant d is called the piezoelectric constant.
On the other hand, in Figure 1.8b, the amounts of extension and contraction of the spring
are nearly the same, and the distance between the two cations (lattice parameter) remains
almost the same, hence, there is no strain. However, more precisely, ions are not connected by
such idealized springs (those are called harmonic springs, in which force (F) = spring constant
General View of Ferroelectrics 9

(k) × displacement (Δ) holds). In most cases, the springs possess anharmonicity (F = k1Δ − k2Δ2),
that is, they are somewhat easy to extend but hard to contract. Such subtle differences in the dis-
placement causes a change in the lattice parameter, producing a strain which is independent of the
direction of the applied electric field (+E or −E), and hence is an even function of the electric field.
This is called the electrostrictive effect and can be expressed as

x = ME 2 , (1.12)

where M is the electrostrictive constant.

The 1-D crystal pictured in Figure 1.8a also possesses a spontaneous bias of electrical charge, or
a spontaneous dipole moment. The total dipole moment per unit volume is called the spontaneous
polarization. When a large reverse bias electric field is applied to a crystal that has a spontaneous
polarization in a particular polar direction, a transition “phase” is formed which is another stable
crystal state in which the relative positions of the ions are reversed. (In terms of an untwinned
single crystal, this is equivalent to rotating the crystal 180° about an axis perpendicular to its polar
axis. This is also understood from the potential double minima in Figure 1.6.) This transition,
referred to as polarization reversal, also causes a remarkable change in strain. This particular class
of substances is referred to as ferroelectrics, as mentioned in Section 1.1. Generally, what is actu-
ally observed as a field-induced strain is a complicated combination of the three basic effects just
described.
Figure 1.9 shows typical strain curves for a piezoelectric lead zirconate titanate (PZT)-based
ceramic and an electrostrictive lead magnesium niobate (PMN)-based ceramic.4 An almost linear
strain curve in PZT becomes distorted and shows large hysteresis on increasing applied electric
field level, which is due to the polarization reorientation. On the other hand, PMN does not exhibit
hysteresis under an electric field cycle. However, the strain curve deviates from the quadratic rela-
tion (E2) at a high electric field level.
We described the converse piezoelectric effect above. Then, what is the normal or direct piezo-
electric effect? This is the phenomenon whereby charge (Coulomb per unit area) is generated by
applying an external stress (force per unit area). Note that the same piezoelectric coefficient d in
Equation 1.11 is used in the relation

P = dX . (1.13)
Strain ΔI/I

×10–3 ×10–3
4 1
Strain ΔI/I

3 0.75

2 0.5

1 0.25

–15 –10 –5 0 5 10 15 –15 –10 –5 0 5 10 15

(a) Electric field (kV/cm) (b) Electric field (kV/cm)

FIGURE 1.9 Typical strain curves for a piezoelectric PZT-based ceramic (a) and an electrostrictive
PMN-based ceramic (b).
10 Ferroelectric Devices

EXAMPLE PROBLEM 1.2

One of the PZT ceramics has a piezoelectric constant of d33 = 590 × 10 −12 C/N with a dielectric
constant ε3 = 3400 and an elastic compliance s33 = 20 × 10 −12 m2/N.

(a) Calculate the induced strain under an applied electric field of E3 = 10 × 105 V/m. Then,
calculate the generative stress under a completely clamped condition.
(b) Calculate the induced electric field under an applied stress of X3 = 3 × 107 N/m2. The
induced field does not coincide with the above-mentioned 10 × 105 V/m. Explain the rea-
son, taking account of electromechanical coupling factor k.

Hint
We will introduce the tensor quantities in Chapter 2. However, try to solve the problems by
neglecting the subscripts at the moment, in order to make the reader understand the concept of
electromechanical coupling factor k.

x = dE, (P1.2.1)

P = dX , (P1.2.2)

and

k 2 = d 2/(sε 0 ε). (P1.2.3)

Solution
_
(a) x3 = d3 E3 = (590 × 10 12
C/N)(10 × 10 5 V/m)
_
= 5.9 × 10 4. (P1.2.4)

Under a completely clamped condition

_ _12
X3 = x3 /s33 = 5.9 × 10 4/ 20 × 10 m 2 /N

= 3.0 × 10 7 N/m 2. (P1.2.5)

(b) P3 = d33 X3 = (590 × 10 −12 C /N) (3 × 10 7 N/m 2 )

= 1.77 × 10 −2 C/m 2. (P1.2.6)

_
E3 = P3 /ε 0 ε 3 = (1.77 × 10 −2 C/m 2 )/(3400 × 8.854 × 10 12
F/m)

= 5.9 × 10 5 V/m. (P1.2.7)

The induced field is only 59% of the field in the case of (a); this is explainable by the electrome-
chanical coupling factor k. When electric energy is supplied to a piezoelectric sample and some
part is transduced into mechanical energy, the electromechanical coupling factor k is defined by

k 2 = (Stored mechanical energy)/(Input electrical energy).

= (1/2)(x 2/s)/(1/2)(ε 0 εE 2 ) = (1/2)((dE )2/s)/(1/2)(ε 0 εE 2 )

= d 2/sε 0 ε. (P1.2.8)
General View of Ferroelectrics 11

On the other hand, when mechanical energy is supplied to the sample and some part is trans-
duced into electrical energy, k is also defined (notice the same result) by

k 2 = (Stored electrical energy)/(Input mechanical energy).

= (1/2)(P 2/ε 0 ε)/(1/2)sX 2 = (1/2)((dX )2 /ε 0 ε)/(1/2)sX 2

= d 2 /sε 0 ε. (P1.2.9)

In the above case

2
k33 = d33
2
/s33ε 0 ε 3

= (590 × 10 −12 C/N)2 /(20 × 10 −12 m 2 /N)(3400 × 8.854 × 10 −12 F/m)

= 0.58. (P1.2.10)

The reason why the induced field in (b) is about k2 of the 10 × 105 V/m of (a) is this transduction
ratio; that is, each energy transduction ratio accompanying the E → M and M → E processes
is k2. Thus (last electrical energy)/(initial electrical energy) = k 4, leading to (last induced field)/
(initial applied field) = k2.

1.4 ELECTRO-OPTIC EFFECT

Since light is an alternating electromagnetic wave with electric and magnetic field vibration direc-
tions mutually perpendicular to one another, the electric field induces an electric polarization in a
dielectric crystal and the light itself is influenced by the crystal. The alternating frequency of the
light is so high (PHz = 1015 Hz) that only the electronic polarization can follow the electric field
change (see Figure 1.2), and the relative permittivity of an optically transparent crystal is small, not
exceeding 10. The relative permittivity ε at this high frequency is related to the refractive index n
by the following equation:

ε = n2 . (1.14)

When an external electric field is applied to the crystal, ion displacement is induced, deforming the
shape of the electron cloud, and consequently the refractive index is changed. This phenomenon is
called the electro-optic effect.
Generally, the refractive index is treated as a symmetrical second-rank tensor quantity and is
represented geometrically by the optical indicatrix which is described by

x 2 y2 z2
2
+ 2 + 2 = 1, (1.15)
n1 n2 n3

where n1, n2, and n3 are the principal refractive indices. With the application of an electric field, the
change in refractive index is given by a Taylor expansion expression in terms of E:

1/nij2 (E ) − 1/nij2 (0) = ∑r E + ∑ R

ijk k ijkl Ek El . (1.16)

Here n(E) and n(0) are the refractive indices at E and zero field, respectively, and rijk is the pri-
mary electro-optic coefficient (Pockels effect) and Rijkl is the secondary coefficient (Kerr effect).
Remember that the expansion is not based on nij, but on 1/n2ij.
12 Ferroelectric Devices

Considering the paraelectric phase of a perovskite crystal (m3 m) as an example, the Kerr coef-
ficients are represented in the following matrix:

⎛ R11 R12 R12 0 0 0 ⎞

⎜ ⎟
⎜ R12 R11 R12 0 0 0 ⎟
⎜ R12 R12 R11 0 0 0 ⎟
⎜ ⎟
⎜ 0 0 0 R44 0 0 ⎟
⎜ 0 0 0 0 R44 0 ⎟
⎜⎜ ⎟
⎝ 0 0 0 0 0 R44 ⎟⎠

so that the refractive indicatrix under an electric field applied along the z-direction is expressed as

x 2 + y2 z2
2
+ 2
= 1. (1.17)
⎡ ⎛ n2 ⎞ ⎤ ⎡ ⎛ n2 ⎞ ⎤
n ⎢1 − ⎜ 0 ⎟ R12 Ez2 ⎥
2
0 n ⎢1 − ⎜ 0 ⎟ R11Ez2 ⎥
2
0
⎣⎢ ⎝ 2 ⎠ ⎥⎦ ⎣⎢ ⎝ 2 ⎠ ⎥⎦

The refractive index change under an external electric field is explained intuitively as follows. When
an electric field Ez is applied to a cubic perovskite crystal, the crystal is elongated along the z-axis
and contracted along both the x- and y-axes. Consequently, the material’s density or compactness
will be decreased along the z-axis and densified along the x- and y-axes, leading to a decrease in
the refractive index nz and an increase of the indices nx and ny, as shown in Figure 1.10 (sphere
becomes a doughnut-shape). Note that the refractive index is proportional to the electron density
or ion compactness along the polarized light electric field direction which is perpendicular to the
light propagation direction. Taking into account the above description, R11 and R12 in Equation 1.16
should be positive and negative, respectively, in this perovskite structure.
When light is transmitted along the y-direction, the phase retardation Γy between the ordinary
(polarized along the x orientation) and extraordinary waves (polarized along the z orientation) is
given by (refer to Figure 1.11)

Γ y = (2π /λ)(n03 /2)(R11 − R12 )L (Vz /d )2 , (1.18)

z
nz
y

ny
nx
x

FIGURE 1.10 Refractive indicatrix change of a cubit crystal with electric field (Kerr effect) (left). An origi-
nal sphere becomes a doughnut shape. Perovskite unit cell change with electric field (right).
General View of Ferroelectrics 13

Unpolarized light
+ L

45° ne
n0 d

Polarizer
–45°

Electro-optic crystal

Polarizer

FIGURE 1.11 Optical phase retardation through an electro-optic crystal. Notice the crossed polarizer
configuration.

where
d is the electrode gap
L is the optical path length

Placing the crystal between crossed polarizers arranged at an angle of 45° (one +45° and the other
−45°) with respect to the z-axis, the output light intensity is modulated as a function of applied
voltage according to

I = I 0 sin 2 (Γ y /2) = (1/2)I 0 (1 − cos Γ y ). (1.19)

This is the principle behind the operation of a light shutter/valve, and the voltage required for the
first intensity maximum (i.e., Γy = π) is an important characteristic called the half-wave voltage. The
detailed derivation process is given in Example Problem 1.3.

EXAMPLE PROBLEM 1.3

A paraelectric La-doped PZT (PLZT) sample with a rectangular shape (optical pathlength: L)
is put between two crossed polarizers arranged at 45° with respect to the z-axis (Figure 1.11).
Assuming a voltage Vz is applied to the sample with an electrode gap d, and light with a wave-
length of λ (incident intensity: I0) is transmitted through it, derive the output light intensity I(Vz)
by neglecting light absorption in the PLZT. Other parameters are listed below:
Refractive index at E = 0: n 0
Electro-optic Kerr coefficients: R11, R12
Phase retardation: Γy
Reflectance at the crystal surface (normal incidence): Re = [(n − 1)/(n + 1)]2
Hint
The initial spherical indicatrix will be deformed into an ellipsoidal one under an applied electric
field Ez:

x 2 + y2 z2
2
+ 2
= 1. (P1.3.1)
⎡ ⎛ n2 ⎞ ⎤ ⎡ ⎛ n2 ⎞ ⎤
n ⎢1 − ⎜ 0 ⎟ R12 E2z ⎥
2
0 n ⎢1 − ⎜ 0 ⎟ R11E2z ⎥
2
0
⎣⎢ ⎝ 2 ⎠ ⎥⎦ ⎣⎢ ⎝ 2 ⎠ ⎥⎦

The output light intensity is reduced twice, once at the inlet and once again at the outlet crystal
surfaces by a factor of (1 − Re)2.
14 Ferroelectric Devices

Also you should notice that the incident light (after passing through the first polarizer) has
ordinary and extraordinary light components of equal magnitudes, because of 45° cant angle of
the polarizer.

Solution
In a cubic structure, the refractive index change under an external electric field along z-axis is
expressed by the following two equations:

1/nz2 (Ez ) − 1/n02 = R11Ez2 , (P1.3.2)

1/nx2 (Ez ) − 1/n02 = R11Ez2 . (P1.3.3)

Taking into account the relation, d(1/n2) = −(2/n3)dn

nz (Ez ) = n0 −(1/2)n03 R11Ez2 , (P1.3.4)

nz ( Ez ) = n0 −(1/2)n03 R12 Ez2 , (P1.3.5)

where R11 > 0 and R12 < 0 in most cases.

Since the wavelengths of the extraordinary (polarized along z-direction) and the ordinary
(polarized along x) waves are described as

λ z = λ 0 /nz , (P1.3.6)

λ x = λ 0 /nx , (P1.3.7)

where λ0 is the vacuum wavelength of the incident light, and the waves existing in the crystal
with an optical pathlength of L are L/λz and L/λx, respectively, the phase difference between
these waves (retardation Γy) is given by
Γ y = 2π(L /λ x − L /λ z ) = (2π /λ 0 )L Δn

= (2π /λ 0 )L (1/2)n03 (R11 − R12 )(Vz /d )2 . (P1.3.8)

The retardation is proportional to the birefringence Δn (=nx – nz).

First, in comparison with the unpolarized light intensity, the intensity from one polarizer is
just a half (by neglecting the light absorption by the polarizer). We will take this intensity from
one polarizer as the incident light intensity I0. Second, we describe the linearly polarized light
incident on the PLZT in terms of its electric field vector as

⎛ ⎡⎛ 2π ⎞ ⎤⎞
⎜ sin ⎢⎜ ⎟ y − ωt ⎥⎟
⎛ ex ⎞ ⎜ ⎣⎝ λ 0 ⎠ ⎦⎟
⎜⎝ e ⎟⎠ = l0 ⎜ . (P1.3.9)
⎡⎛ 2π ⎞ ⎤⎟
z
⎜ sin ⎢ ⎟
⎜⎝ ⎜ ⎟ y − ωt ⎥ ⎟
⎣⎝ λ 0 ⎠ ⎦⎠

Note here that the 45° arrangement generates the same electric field amplitude along x- and
z-directions, and that the relationship I = e2/2, i.e., the intensity is an average of e2 in terms of
time. Third, the output light from the PLZT can be described as

⎛ ⎡⎛ 2π ⎞ ⎤ ⎞
⎜ sin ⎢⎜ ⎟ y − ωt + φ⎥ ⎟
⎛ ex ⎞ ⎜ ⎣⎝ λ 0 ⎠ ⎦ ⎟
⎜⎝ e ⎟⎠ = (1 − Re ) l0 ⎜
2
. (P1.3.10)
⎡ ⎤⎟
z
⎜ sin ⎢⎛ 2π ⎞ y − ωt + φ − Γ y ⎥⎟
⎜⎝ ⎜ ⎟ ⎟
⎣⎝ λ 0 ⎠ ⎦⎠
General View of Ferroelectrics 15

Remember to consider two reflections on the front and backside of the PLZT sample. Also,
basically the extraordinary ray speed corresponding to output ez is faster than the ordinary ray
speed (ex), leading to the phase delay of Γy in ez when we consider the optical pathlength L.
Fourth, through the polarizer arranged at the −45° orientation, the electric field component in
this direction e−45cant is represented (taking into account the electric field vector projection on this
−45° orientation) by

l0
ex / 2 − ez / 2 = (1 − Re) {sin[(2π /λ 0 )y − ωt + φ] − sin[(2π /λ 0 )y − ωt + φ − Γ y ]}
2

l0
= (1 − Re) [(1 − cos Γ y ) sin[(2π /λ 0 )y − ωt + φ]
2
+ sin Γ y cos[(2π /λ 0 )y − ωt + φ]. (P1.3.11)

Thus, finally, the output intensity through the 2nd polarizer (−45° cant) is obtained from the
2
relation I = e−45cant /2:

I = (1/2)(1 − Re)2 (I 0 /2)[(1 − cos Γ y )2 + (sin Γ y )2 ]

⎛ 1 − cos Γ y ⎞
= (1 − Re)2 I 0 ⎜ ⎟⎠ .
(P1.3.12)
⎝ 2

Figure 1.12 shows the output intensity I as a function of applied voltage Vz, which exhibits maxi-
mum and minimum successively. The half-wave voltage, which is defined as the voltage required
to exhibit the first maximum in the transmitted light intensity, is given from the condition, cos Γy
= −1 or Γy = π. When we use a sample with Kerr (secondary) electro-optic effect, Γy is expressed
by Equation P1.3.8, and the half-wave voltage can be obtained as

λ0
Vz,λ /2 = d . (P1.3.13)
Ln03 ( R11 − R12 )

The intensity maxima can be sequentially obtained on increasing the applied voltage. Notice that
these half-wave, one-and-a-half-wave, two-and-a-half-wave voltages are not arranged linearly,
due to the nonlinear electro-optic effect.

Lab Demonstration 1.1—Polarizer

This is a demo with two polarizers by changing the angle between two. The reader is expected to
understand the polarized light characteristics (Figure 1.13).

Light
intensity
(1–Re)2 I0

0 Vz,λ/2 Applied voltage

FIGURE 1.12 Variation in the light intensity of a Kerr-effect electro-optic shutter with applied voltage.
16 Ferroelectric Devices

(a) (b)

(c) (d)

FIGURE 1.13 Demo with a pair of optical polarizers by changing the angle. (a) 0°, (b) 30°, (c) 60°, and
(d) 90° angles.

(a) (b)

(c)

FIGURE 1.14 Demo with a pair of optical polarizers by changing the angle, sandwiching a Scotch tape.
(a) 0°, (b) 90°, and (c) 45° angles.

Lab Demonstration 1.2—Scotch Tape Magic

Scotch tape is different from other manufacturers’ products. A Scotch tape is sandwiched by a
pair of polarizers. Dark and bright conditions are reversed in comparison with Lab Demo 1.1,
as demonstrated in Figure 1.14a and b. When the analyzer (second polarizer) is arranged along
the tape extended direction, no interference is observed. This is the basis for understanding the
birefringence and retardation of the inserted optical material between a pair of polarizers.

Comments
Scotch tape is manufactured by stretching the tape, so that the refractive index along the tape is
different from that of the width direction. This birefringence and the optical pathlength (tape thick-
ness) generate accidentally the retardation Γy of π (refer to Equation P1.3.8). This situation exhibits
the above-mentioned “Scotch tape” magic. By inserting an electro-optic PLZT (replacing Scotch
tape) and inducing the birefringence with electric field, a similar dark and bright conversion can
be introduced in a PLZT light valve.
General View of Ferroelectrics 17

1.5 EXAMPLE OF FERROELECTRICS

Quartz (SiO2) and zinc oxide (ZnO) are popular piezoelectrics, but non ferroelectric (paraelec-
tric) materials. The “direct” piezoelectric effect was discovered in quartz by Pierre and Jacques
Curie in 1880. The “converse” piezoelectric effect was discovered successively in 1881 by Gabriel
Lippmann. The shipwreck of Titanic and World War I were the motivation for the undersea
transducer, sonar. Paul Langevin developed the so-called Langevin-type transducer, which was
originally composed of natural tiny quartz single crystals sandwiched by two metal blocks, in
order to tune the transducer resonance frequency around 26 kHz which is a desired range for
underwater applications.
On the other hand, the first ferroelectric discovered is Rochelle salt (NaKC4H4O6 . 4 H2O) in 1921.
Though this material was studied from an academic viewpoint, it has not been widely utilized in
practice because it is water-soluble and its Curie temperature is just above RT. KH2PO4 (KDP) was
the second discovery in 1935, which is also water-soluble and the Curie temperature is −150°C. We
had to wait until World War II for the third and most famous ceramic ferroelectric, i.e., BT (BaTiO3),
which was actually commercialized first as a transducer material. In order to develop compact
capacitors for portable “radar” systems to be used in the battle fields, TiO2-based conventional “con-
denser materials” were widely researched by doping various ions such as CaO, SrO, BaO, MgO, and
Fe2O3. Three groups in the United States, Russia, and Japan discovered BaTiO3 almost the same
time as the World War II.

1.5.1 BARIUM TITANATE

We describe basic properties of ferroelectrics using BT as an example. As shown in Figure 1.15,
BaTiO3 has a perovskite crystal structure. In the high-temperature paraelectric phase (nonpolar
phase) there is no spontaneous polarization (the symmetry is Oh – m3 m). Below the transition tem-
perature TC called the Curie temperature (about 130°C), spontaneous polarization occurs, and the
crystal structure becomes slightly elongated, that is, tetragonal (C4 v – 4 mm). The detailed ionic
shift is illustrated in Figure 1.7. Figure 1.16 shows schematically the temperature dependence of the
spontaneous polarization PS and permittivity (dielectric constant) ε in a BT-like first-order transition
ferroelectric. PS decreases with increasing temperature and vanishes at the Curie temperature, while
ε tends to diverge near TC. Also, the reciprocal (relative) permittivity 1/ε is known to be linear with
respect to the temperature over a wide range in the paraelectric phase (so-called Curie–Weiss law)

ε = C /(T − T0 ), (1.20)

Ti4+

Ba2+

O2–

T > TC T < TC

TC: Curie temperature

FIGURE 1.15 Crystal structures of BaTiO3: Higher than TC (left) and lower than TC (right).
18 Ferroelectric Devices

Physical properties (a) Capacitor

Permittivity ε

Spontaneous PS

(b) Memory Inverse permittivity 1/ε

(c) Pyrosensor

T0 TC
Temperature
(Curie temp.)

(e) Piezoelectric transducer (d) Electro-optic device

(f) Electrostatrictor

FIGURE 1.16 Temperature dependence of the spontaneous polarization and permittivity in a ferroelectric
material. (a)–(f) indicate the temperature ranges for each application.

where
C is the Curie–Weiss constant
T0 is the Curie–Weiss temperature

T0 is slightly lower than the exact transition temperature TC.

It is also known that the spontaneous polarization PS and the spontaneous strain xS follow the
relationship:

xS = QPS2 , (1.21)

and xS decreases almost linearly with increasing temperature. In the case of BaTiO3, it exhibits the
piezoelectric effect in the ferroelectric phase, while in the paraelectric phase, it is nonpiezoelectric
and exhibits only the electrostrictive effect.
If the above consideration is rephrased from the application viewpoints, the Curie temperature
for capacitor materials is designed to set around RT; TC for memory materials around 100°C higher
than RT; TC for pyrosensors just above RT; TC for piezoelectric transducers typically much higher
than RT, higher than 200°C; TC for electro-optic and electrostrictive devices are lower than RT to
use their paraelectric state. In other words, we will design practical materials with their Curie points
suitable for each application.
With decreasing temperature from RT, however, BT undergoes a series of complicated phase
transitions. Figure 1.17 illustrates these successive phase transitions.

1.5.2 PZT
PZT solid solution systems were discovered in 1954 by Japanese researchers, Gen Shirane, Etsuro
Sawaguchi et al. However, the enormous piezoelectric properties were discovered by B. Jaffe, Clevite
Corporation, and Clevite took the most important PZT patent for transducer applications. Because
General View of Ferroelectrics 19

Rhombohedral Orthorhombic Tetragonal Cubic

Ps Ps Ps
Dielectric constant
10,000

5,000 εa

εc
0
–150 –100 –50 0 50 100 150
Temperature (°C)

FIGURE 1.17 Various phase transitions in BT.

of this strong basic patent, Japanese ceramic companies were encouraged actually to develop ter-
nary systems to overcome the performance, and more importantly, to escape from the Clevite’s
patent; that is, PZT + a complex perovskite such as Pb(Mg1/3Nb2/3)O3 (Matsushita Panasonic),
Pb(Ni1/3Nb2/3)O3 (NEC), and Pb(Zn1/3Nb2/3)O3 (Toshiba), which are the basic compositions in recent
years. The performance details are discussed in Chapter 7.

1.5.3 POLYVINYLIDENE DIFLUORIDE (PVDF)

Thanks to Kawai’s efforts, polyvinylidene difluoride (PVDF or PVF2) was discovered in 1969.
Though the piezoelectric d constant is not as high as piezoceramics, high piezoelectric g constant
due to small permittivity is attractive from the sensor application viewpoint.
PVDF is a polymer with monomers of CH2CF2. Since H and F have positive and negative ion-
ization tendency, the monomer itself has a dipole moment. Crystallization from the melt forms the
nonpolar α-phase, which can be converted into the polar β-phase by a uniaxial or biaxial drawing
operation; the resulting dipoles are then reoriented through electric poling (see Figure 1.18).
Large sheets can be manufactured and thermally formed into complex shapes. Piezoelectric
polymers have the following characteristics: (a) small piezoelectric d constants (for actuators) and
large g constants (for sensors), (b) light weight and soft elasticity, leading to good acoustic imped-
ance matching with water or the human body, (c) a low mechanical quality factor Qm, allowing for
a broad resonance band width.

(CH2CF2)n

Carbon

Fluoride
z Hydrogen

FIGURE 1.18 Structure of PVDF.

20 Ferroelectric Devices

1.5.4 PB-FREE PIEZOCERAMICS

In 2006, the European Community started restrictions on the use of certain hazardous substances
(RoHS), which explicitly limits the usage of lead (Pb) in electronic equipments. Basically, we may the
need to regulate the usage of PZT, the most widely used piezoelectric ceramics, in the future. Japanese
and European communities may experience governmental regulation on the PZT usage in these 10 years.
Pb-free piezoceramics have started to be developed after 1999. The Pb-free materials include (1) (K,Na)
(Ta,Nb)O3-based, (2) (Bi,Na)TiO3, and (3) BaTiO3, which reminds us that “history will repeat.”

1.6 APPLICATIONS OF FERROELECTRICS

Ferroelectric materials, especially polycrystalline ceramics, are very promising for a variety of
applications such as high-permittivity capacitors (Chapter 4), ferroelectric memories (Chapter 5),
pyroelectric sensors (Chapter 6), piezoelectric and electrostrictive transducers (Chapter 7), electro-
optic devices (Chapter 8), and PTC thermistors (Chapter 9).
For capacitor dielectrics, the peak dielectric constant around the transition temperature (Curie) is
utilized, while for memory applications, the material must be ferroelectric at RT (refer to Figure 1.16).
A large temperature dependence of the spontaneous polarization below TC is sought for pyroelectric
sensors. The converse pyroelectric effect is the electrocaloric effect (electric field generates the tem-
perature decrease), which is becoming a hot research topic in this energy-saving age.
Piezoelectric materials are used as sensors and actuators, where the TC should be much above
RT. Pressure and acceleration sensors are now commercially available in addition to conventional
piezovibrators. Precision positioners and pulse drive linear motors have already been installed in pre-
cision lathe machines, semiconductor manufacturing apparatuses, and office equipment. Recently,
enthusiastic development is found in ultrasonic motors, aiming at electromagnetic, noise-free, and
very compact motor applications. In parallel to the new energy source programs, piezoelectric
energy harvesting systems have become popular. Waste mechanical energy such as noise vibration,
wind, and human walking can be converted into electrical energy and can be used directly for signal
transmission or to charge up batteries for portable electronics.
Electro-optic materials will become key components in displays and optical communication
systems in the future. Optical beam scanners, light valves, and switches are urgent necessities. For
thermistor applications, semiconductive ferroelectric ceramics with a PTC of resistivity based on a
junction effect have been developed from BT-based materials. We will discuss the above applica-
tions in detail in the following chapters.

Lab Demonstration 1.3—Applications in Cellular Phones

Portable communication devices such as cordless, portable, and car telephones have become
popular worldwide. The reader is requested to identify what kind of ferroelectric and dielectric
components are used in a cellular phone. An old design phone is dismantled to see reasonably
large components (Figure 1.19).
Comments
Chip monolithic ceramic capacitors
Microwave oscillators
Microwave filters
Chip monolithic LC filters
Ceramic resonators
High-frequency surface acoustic wave (SAW) filters
Ceramic filters
Piezoelectric receivers
Piezoelectric speakers
Recent designs include ferroelectric memory, piezoactuators for camera autozoom/focus
mechanisms.
General View of Ferroelectrics 21

FIGURE 1.19 Dismantled cellular phone. Identify the ferroelectric components.

Chapter Essentials

1. Category:
Dielectrics > Piezoelectrics > Pyroelectrics > Ferroelectrics
2. Ferroelectric materials are very promising for a variety of applications:
High-permittivity capacitors
Ferroelectric memories
Pyroelectric sensors, electrocaloric fridges
Piezoelectric/electrostrictive transducers, piezoelectric energy harvesting
Electro-optic devices
PTC thermistors
3. Origin of spontaneous polarization:
Dipole coupling with the local field—driving force of ionic displacement
Elastic anharmonic term—impeding ionic displacement
4. Field-induced strains:
Piezoelectric strain—x = dE in an asymmetric crystal
Strain associated with polarization reorientations
Electrostriction—x = ME2 in a symmetric crystal
Piezostriction: the difference of the harmonic term of the two equivalent springs
Electrostriction: anharmonicity of the equivalent springs
5. Electro-optic effect: refractive index change with an external electric field. The secondary
Kerr effect is frequently used. Devices making use of this effect require a pair of crossed
polarizers arranged at a 45° angle with respect to the electric field direction.
Half-wave voltage: minimum voltage required for an electro-optic crystal to exhibit the first
maximum light intensity.

Check Point

1. There are three microscopic origins of polarization: electronic polarization, ionic polariza-
tion, and [— (a)]. Fill in the blank.
2. The local field is the driving force for the spontaneous polarization. How is γ called, which
enhances the applied electric field E.
22 Ferroelectric Devices

3. (T/F) Taking into account a famous relation between the relative permittivity ε and the
refractive index n: ε = n2, we can obtain n = 4 for the crystal with ε = 16 (at 1 kHz). Is this
argument true or false?
4. The randomly oriented light passed through a polarizer. When we neglect the light absorp-
tion by the polarizer, what percentage of the light intensity can we obtain from the polar-
izer in comparison with the input intensity?
5. (T/F) The definition of Pockels electro-optic coefficient r1jk is given by an expansion expres-
sion: 1/nij ( E ) − 1/nij (0) = Σrijk Ek . True or False ?
6. (T/F) The Curie temperature of a capacitor ferroelectric material should be around RT.
True or False?
7. (T/F) The Curie temperature of a piezoelectric transducer material should be 100°C lower
than RT. True or False?
8. (T/F) The Curie temperature of a pyroelectric sensor material should be 200°C higher than
RT. True or False?
9. Provide a name of a representative polymer piezoelectric.
10. Provide a full expression of PZT.

Chapter Problems

1.1 Consider a 1-D infinite chain of two kinds of ions +q and −q, arranged alternately over
a distance a. Calculate the Coulombic potential energy at one +q ion, and obtain the
Madelung energy (Figure 1.20).
Hint

Remember U = −(1/4πε 0 ε)(q 2/r ).

Use an expansion series of log(1 + x) = x – x2/2 + x3/3 – x4/4 + …

This is the basic concept of a crystal structure stability, which will be discussed again
in Chapter 3 for considering nanoparticle ferroelectrics.

1.2 Potassium tantalate niobate K(Ta0.65Nb0.35)O3 is cubic at RT. By applying an electric

field Ez along a perovskite [100] axis, it exhibits an induced polarization P3, electrostric-
tive strains x3 = Q11P 32 and x1 = Q12P 32, and refractive index changes Δn3 = −(1/2)n 03g11P 32
and Δn1 = −(1/2)n 03g12P 32. Experimental values of these are Q11 = 0.090 m4/C2, Q12 =
−0.035 m4/C2; g11 = 0.136 m4/C2, g12 = −0.038 m4/C2. Comparing the absolute values
between Q and g and the ratios Q11/Q12 and g11/g12, discuss similarities in terms of the
crystal lattice compactness along and perpendicular to the electric field.
1.3 The following data was cited from Intel Corporation’s famous “Gordon Moore’s Law.”5
The number of transistors per die will increase logarithmically with year. From this
expectation, the following technologies will be definitely required (Figure 1.21):
(1) 90 nm lithography technology
(2) Replacement of the present gate oxide dielectric with a high-k oxide

+q –q

–4a –3a –2a –a 0 +a +2a +3a +4a

FIGURE 1.20 1-D atomic model.

General View of Ferroelectrics 23

Integrate-circuit complexity
Transistors
per die
1010 1965 Actual data 4G
1G2G
109 MOS Arrays MOS Logic 1975 actual data 512M
256M
128M ItaniumTM
108 1975 Projection 64M Pentium4â
Memory 16M PentiumIIIâ
107 4M
Microprocessor 1M PentiumIIâ
106 256K Pentiumâ
1486TM
64K
105 1386TM
4K 80286
104 16K 8086
1K
8008
103 4004
102
101
100
1960 1965 1970 1975 1980 1985 1990 1995 2000 2005 2010

FIGURE 1.21 Gordon Moore’s Law. (Courtesy of Intel Corporation, Santa Clara, CA, http://www.intel.com/
technology/mooreslaw.)

Questions
(a) In order to realize the above requirements (1) and (2), what sort of ferroelectric
devices should be developed? Consider these “Needs-pull” development strategies.
(b) What other ferroelectric applications can be considered, relating to “integrated-
circuit complexity?”
1.4 Expanding Lab Demo 1.3, collect more detailed information on practical designs of
multilayer capacitors (how small size?), SAW filters (what frequency?), speakers and
microphones (operation frequency range difference among speakers and microphones),
memories (flush or ferroelectric memories?), and piezoactuators in the recent cel-
lular phones. Note that the development of phone camera modules is remarkable in
particular.

REFERENCES
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5. Intel Corporation, Santa Clara, CA, http://www.intel.com/technology/mooreslaw/
General View of Ferroelectrics
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Designing with Materials and Devices and Fabrication Processes

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High-Permittivity Dielectrics
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Ferroelectric Memory Devices

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Piezoelectric Devices
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Electro-Optic Devices
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PTC Materials
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Murata Mfg. Comp. Catalog: Mysterious Stones.

Composite Materials
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Future of Ferroelectric Devices

J. Ceram. Soc. Jpn., December issue (1984).
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