Acta mater.

48 (2000) 151±178
www.elsevier.com/locate/actamat

ELECTROCERAMIC MATERIALS p

N. SETTER 1{ and R. WASER 2

1
Ceramics Laboratory, EPFL Swiss Federal Institute of Technology, 1015 Lausanne, Switzerland and
2
Forschungszentrum, 52425 JuÈlich & RWTH Aachen, 52056 Aachen, Germany

(Received 1 June 1999; accepted 15 July 1999)

AbstractÐElectroceramics research is driven by technology and device applications. This growing ®eld
includes a vast number of magnetic, dielectric, ionically conducting, semiconducting, and superconducting
ceramics used in domains as diverse as transportation, industrial production, power engineering, medicine
and health care, consumer electronics, and communication. At the turn of the decade, three major trends
are gaining importance:
. Materials integration issues play an increasingly important role driven by the interest in integrating elec-
troceramic functions into conventional semiconductor chips as well as by the evolution of multifunc-
tional components and systems.
. The industrial production process currently is in a transition from empirical studies and physical demon-
strators into virtual design and testing. To ®t into this evolution, for integrated as well as for discrete
electroceramic components, a rise in modeling and numerical simulation of material- and device-related
properties presently occurs.
. Electroceramic materials are following in the footsteps of conventional semiconductors with respect to
further miniaturization, and are experiencing the same evolution from microtechnology towards nano-
technology. Nanosize e€ects and nanotechnology issues are therefore gaining importance.
In the context of these three issues, we discuss the research in electroceramics during the last decade and
basic trends for the future. # 2000 Published by Elsevier Science Ltd on behalf of Acta Metallurgica Inc.
All rights reserved.

Keywords: Ceramics, functional; Electrical properties; Electroceramics

1. INTRODUCTION as high dielectric permittivity, high piezoelectric

Ceramics, by de®nition, comprise inorganic, non-
metallic, non-water-soluble compounds that show
ionic contributions in their chemical bonds. Along
with the revolutionary development of electronics in
the second half of the twentieth century, the huge
potential of ceramic materials has been unfolded
and introduced into a fascinatingly wide spectrum
of electrical and microelectronic devices and appli-
cations.
Starting in the mid-1920s, Ni±Zn and Mn±Zn
ferrites found increasingly widespread use as trans-
former and coil core materials in telephones and in
radio receivers. After the Second World War, the
technical exploitation of ferroelectric ceramics
began, because of their unique properties such
{ To whom all correspondence should be addressed.
p
The Millennium Special Issue Ð A Selection of Major
Topics in Materials Science and Engineering: Current
status and future directions, edited by S. Suresh.
constants and electromechanical coupling, high
pyroelectric coecients, and, under certain circum-
stances, high optical transparency and electro-optic
coecients. High-permittivity BaTiO3-based dielec-
trics were employed ®rst for small plate and tube
capacitors, and since the 1970s for monolithic mul-
tilayer capacitors (MLCs). Today, the annual pro-
duction level exceeds 100 billion MLCs. In
addition, microwave ceramics are increasingly used
for ®lters, resonator and mixers in systems for wire-
less communication.
Piezoelectric ceramics, usually based on
Pb(Ti, Zr)O3 (short: PZT) compositions, certainly
show the broadest range of individual applications
including, for instance, sonars, ultrasonic cleaners,
buzzers, accelerometers, hydrophones, surface
acoustic wave ®lters, delay lines, piezo transformers,
ultra-precision positioners for scanning probe analy-
sis (XPM) systems, ink jet print heads, touch con-
trols, and ultrasonic motors, e.g. for cameras. Ionic
conducting ceramics, such as heavily acceptor-

1359-6454/00/$20.00 # 2000 Published by Elsevier Science Ltd on behalf of Acta Metallurgica Inc. All rights reserved.
PII: S 1 3 5 9 - 6 4 5 4 ( 9 9 ) 0 0 2 9 3 - 1
152 SETTER and WASER: ELECTROCERAMIC MATERIALS
doped, cubic ZrO2, are used for electrochemical
oxygen sensors in cars and for high-temperature
solid oxide fuel cells (SOFCs). Mixed ionic electro-
nically conducting ceramics are employed for the
cathode in SOFCs. In another class of electrocera-
mic material, the electronic charge transport across
grain boundaries is controlled by a potential barrier
at the boundary. The temperature dependence of
the barrier in n-doped semiconducting BaTiO3 cer-
amics leads to a positive temperature coecient
(PTC) of the resistivity, and ZnO ceramics exhibit a
strongly non-linear current±voltage behavior due to
the voltage dependence of the barrier. PTC ceramics
are used for a variety of self-controlled electrical
heating systems and for overload protection, while
ZnO ceramics are used for overvoltage protection
varistors. The mid-1980s brought the discovery of
the high-temperature superconducting ceramics
(HTSC) with transition temperatures beyond 100 K.
Despite the fact that grain boundaries limit the
critical current density, there are several HTSC-
based systems, e.g. for power applications, currently
in the development stage such as high-voltage
energy transmission cables (e.g. 1 GVA) and mag-
netic energy storage units (1±100 MWh).
The electroceramic materials and components
mentioned so far are typically produced by conven-
tional powder compacting, tape casting or screen
printing techniques followed by sintering processes.
In the late 1980s, these techniques were increasingly
supplemented by thin ®lm deposition techniques
such as sputtering, pulsed laser deposition (PLD),
chemical solution deposition (CSD), and chemical
vapor deposition (CVD). During these deposition
processes the electroceramic materials are syn-
thesized on a microscopic scale without powder
processing as an intermediate step, usually at tem-
peratures much below the typical sintering tempera-
tures for bulk ceramics. The rise of interest in
electroceramic thin ®lms was triggered by two
events. Firstly, the newly discovered HTSC prom-
ised to show considerably larger critical current
densities if deposited as thin ®lms. Secondly, an
idea originating in the late 1960s of ferroelectric-
semiconductor memories was taken up again by uti-
lizing the experience gained with the highly
advanced Si semiconductor technology. These pio-
neering lines led to a broad research and develop-
ment e€ort worldwide in order to combine the large
variety of functions o€ered by electroceramic thin
®lms with the standard integrated circuit chips. The
range comprises commercial high-k dielectric cer-
amic ®lms for decoupling capacitors in monolithic
microwave integrated circuits (MMICs) for mobile
telephones [1±3], three-dimensional integration of
high-k multilayer thin ®lm capacitors [4] and cell
dielectrics for gigabit dynamic random access mem-
ory (DRAM) devices [5±11]. True ferroelectric ma-
terials are employed in non-volatile ferroelectric
random access memories (FRAMs) [12±14], piezo-
electric actuators, pumps, and micromotors [15],
pyroelectric image arrays [16±21], and ferroelectric-
based electro-optic devices [22, 23]. Active electronic
devices such as ®eld-e€ect transistors with dielectric
or ferroelectric gate oxide have been produced on
an all-oxide base [24]. Electronically conductive
®lms based on (La, Sr)MnO3 and related compo-
sitions were found to show a colossal magnetoresis-
tive behavior [25]. HTSC thin ®lms are employed in
SQUID magnetic ®eld sensors [26, 55] and are
investigated for coatings of microwave resonators
to increase the Q-factor of the system.
Obviously, oxide ceramics cover a huge area of
functionalities. Hardly any other class of materials
(semiconductors, metals, polymers) o€ers such a
broad variety of properties which can be exploited
for electronic applications. Still, new materials are
likely to appear on the horizon just as HTSC did
and some of them will make it into industrializ-
ation. However, based on trends in current R&D
activities worldwide in the area of electroceramic
materials and in adjacent areas, we believe that the
main R&D e€orts in the next decade will be driven
by technology and devices. We group these trends
into three categories and will organize the sections
of our paper accordingly. Firstly, the materials inte-
gration issues (Section 2) will play an increasingly
important role driven by the integration of electro-
ceramic functions into conventional semiconductor
chips as well as by the evolution of multifunctional
components and systems. Secondly, the industrial
production process is currently in a transition from
empirical studies and physical demonstrators to vir-
tual design and testing. To ®t into this evolution,
for integrated as well as for discrete electroceramic
components, a rise in modeling (Section 3) and nu-
merical simulation of all material- and device-re-
lated properties is needed. Thirdly, as
electroceramic materials step into the footprints of
the conventional semiconductors with respect to
further miniaturization, we will experience the
expansion from microtechnology into nanotechnol-
ogy. Hence, nanosize e€ects and nanotechnology
issues (Section 4) will gain importance.
For every section, we will present examples that
we selected in view of their potential but also from
the aspect of being potentially the most interesting
examples for the readers. Certainly, the selection is
conducted by our individual tastes but also by the
limitation of the space provided. Given these
boundary conditions, the main idea is to provide an
impression of the dynamic evolution and the future
opportunities of our ®eld.
2. MATERIALS INTEGRATION
Advanced functional components are made of
materials systems rather than of discrete materials.
Integration issues increase therefore in importance.
This is particularly true in miniaturized systems
 SETTER and WASER: ELECTROCERAMIC MATERIALS
where interfaces play a very important role.
Integration issues comprise both the integration of
electroceramic thin ®lms with the substrates and the
semiconductor chips as well as the combination of
bulk ceramics of di€erent kinds and/or other ma-
terials such as metals, glass, or polymers to form
compound devices. In this overview, we will focus
on the ®rst issue since it currently shows the largest
impact in technology development. The integration
of functional ceramics into microelectronic com-
ponents will be discussed ®rst, and then issues
related to their integration into MEMS (micro-
electromechanical systems) will be addressed.
2.1. The integration of electroceramics into
microelectronic components
Due to its simple one-transistor/one-capacitor
(1T/1C) architecture and the ever increasing need
for faster random access memories, the DRAM has
remained the ``technology driver'' in microelec-
tronics since it was patented in 1967 [27]. Moore's
law of exponential growth of memory per chip at a
rate of quadrupling the memory every 3 years is
unbroken and is expected to continue at least for
another decade. To cope with the problem of
decreasing ¯oor area available for the capacitor of
every memory cell, the idea of replacing the current
Si-oxide/Si-nitride dielectrics exhibiting a permittiv-
ity of approximately 7 by a high-permittivity para-
electric or superparaelectric material o€ering
permittivities of well above 100, such as SrTiO3 and
(Ba, Sr)TiO3 (short: BST), was raised at the end of
the 1980s [8]. During the 1990s, numerous R&D
groups in the semiconductor industry and research
institutions ®rst investigated suitable ®lm deposition
methods as well as the ®lm properties and, sub-
sequently, the subtle integration issues which are to
be solved for every new material integrated into the
conventional Si technology (for reviews, see Refs [5,
6, 9, 28±34]). It turned out that MOCVD tech-
niques are most suitable for conformal deposition
on three-dimensional structured bottom electrodes
and for the highest ®lm qualities [32, 35]. The chal-
lenging material issues are the leakage current [43],
the dielectric relaxation [44], the long-term re-
liability under combined d.c. voltage and tempera-
ture stress [45], the high-frequency performance,
and the d.c. ®eld dependence of the permittivity
[46]. It is found that ®lms prepared with optimized
process parameters are able to ful®ll the require-
ments for DRAM operation with a sucient mar-
gin. In addition, material modi®cations such as Mn
doping [41] and alternative high-permittivity perovs-
kites such as Ba(Ti, Zr)O3 [42] are proposed to sig-
ni®cantly extend the margins.
Ferroelectric (FE) ®lms instead of high-k ®lms
are employed for FeRAMs with chip architecture
very similar to DRAMs. FeRAMs o€er non-vola-
153
tility and, compared with competitive ¯ash mem-
ories, a lower voltage operation as well as orders of
magnitude shorter write times and larger write cycle
numbers. FeRAM applications are embedded mem-
ories, for example, in smart cards, as well as poten-
tially large stand-alone non-volatile memories. The
materials proposed for FeRAM applications are
based on PZT compositions as well as on
SrBi2Ta2O9 (SBT) layered perovskite Aurivillius
phase systems. During the last decade, a number of
speci®c properties of FE thin ®lm capacitors poten-
tially limiting the FeRAM application were investi-
gated in detail. The fatigue e€ect represents a loss
of switchable polarization with an increasing num-
ber of switching cycles, so that read failures may
occur. While SBT ®lms are inherently more stable
to fatigue, the e€ect can be controlled in PZT sys-
tems by the ®lm orientation and the use of oxide
electrodes. Fatigue appears when a substantial part
of the volume of the material loses its ability to
generate new domains. There are two principal
types of fatigued state of the material: (i) The ma-
terial is ®lled up with domain walls immobilized by
ionic and electronic bulk defects [37] while ad-
ditional domains cannot be produced. (ii) The ma-
terial contains large monodomain areas each of
which contains numerous inactive (blocked by the
nearby-electrode injection) centers of the opposite
domain nucleation [38, 39]. The imprint e€ect
describes the shift of the hysteresis loop along the
voltage axis if the FE cell is resting in one remanent
position for a long time, up to the point where sub-
sequent write operations are not successful any
more. Again, SBT ®lms seem to be inherently more
stable to imprint, PZT ®lms are optimized by donor
doping and high Zr/Ti ratios. According to a recent
model, imprint is related to a charge injection
through a surface ``dead layer'' [40]. The same
phenomenon was shown [53] to be responsible for
the size e€ect on switching (thickness dependence of
the coercive ®eld) commonly observed in PZT ®lms
with metallic electrodes. The FE relaxation e€ect
denotes the fact that part of the charge during
switching is released with a delay, rendering the
di€erence between switching and non-switching
read-out operations smaller for shorter read access
times. This e€ect originates in the fact that the
Curie von Schweidler relaxation currents depend on
the direction of the polarization [47, 54]. The fre-
quency dependence of the coercitive voltage leads to
an increase of the required operation voltage for
short access times and may limit the operation fre-
quencies in the case of low voltage applications.
For all these e€ects, the physical understanding is
not yet ®rmly settled. The development of quanti-
tative physical models remains a challenge for the
future.
For the integration of high-k oxides as well as
FE oxides into high-density memories, numerous
technology problems have to be solved. One major
154 SETTER and WASER: ELECTROCERAMIC MATERIALS
Fig. 1. FeRAM memory cell with a capacitor on metal/via
stacked plug structure [51]. The layer between the Pt elec-
trode and the W plug is made of TiN.
problem arises as many of the elements constituting
the perovskite oxides and the appropriate electrodes
may chemically poison the Si-based CMOS transis-
tor structures. To avoid contamination during
handling, the process ¯ow is separated. In a ®rst
sequence of steps, the CMOS circuits are realized in
a conventional clean room area (``front-end pro-
cess''). In a separate back-end clean room area, the
electrode and capacitor structures and the ®nal
metallization interconnect layers are realized. At no
stage does the wafer return to the front-end area.
Another problem occurs due to the relatively high
annealing temperatures in combination with an oxi-
dizing atmosphere required to crystallize the perovs-
kite-type oxides. While the MOCVD process of
BST ®lms is conducted at approximately 6008C,
SBT ®lms have to be annealed at temperatures well
exceeding 7008C. In selected cases, e.g.
Pb(Sc, Ta)O3 for pyroelectric detectors, the anneal-
ing temperature could be signi®cantly reduced by
rapid thermal annealing procedures [50]. In the
high-density structures, there is a conductive poly-Si
or W connection between the bottom electrode of
the capacitor and the underlying transistor struc-
ture. This poly-Si or W plug must be protected
from being oxidized through oxygen di€usion at the
high process temperatures. Oxygen di€usion bar-
riers such as (Ti, Al) nitride and (Ta, Si) nitride as
well as complex silicides have been investigated
(Fig. 1) [51]. Major requirements concern the bot-
tom electrode onto which the perovskite-type oxide
is deposited. It should be depositable with pro-
duction type tools, should adhere to Si dioxide and
the barrier material should not react with the oxide
deposited subsequently, and must be etchable with
high etching angles. In the case of DRAMs, the
bottom electrode should guarantee the lowest poss-
ible leakage currents, focussing the e€orts on Pt,
Ru, Ir, and IrO2. In FeRAM devices, the electrode
e€ect on the fatigue behavior has to be taken into
account. For this reason, Pt is favored for SBT
®lms while RuO2 or hybrid Pt/RuO2 or Ir/IrO2 [36]
is considered for PZT-based FeRAM systems. High
integration densities also require three-dimensional
stack structures of the cell capacitors, e.g. by a con-
formal oxide deposition onto bottom electrode
nodes. Although MOCVD is found to be most suit-
able for conformal coverage, the top area and the
side walls frequently still show di€erent ®lm thick-
nesses. In addition, the stoichiometry control of
both side walls and top area becomes increasingly
dicult at decreasing deposition temperatures.
Depending on the cell design, a dry etch step
usually follows after the top electrode deposition.
Dry etching of the novel electrode materials as well
as of the perovskite-type oxides represents ad-
ditional challenges as the etch products often show
a very low volatility and a non-stoichiometric etch-
ing process must be avoided during the perovskite
oxide thin ®lm etch. Finally, the capacitor cell has
to retain its required properties through all sub-
sequent back-end process steps such as the intercon-
nect metallization and the forming gas anneal at
approximately 4508C. Obviously, the stress induced
by large Al metallization lines in the interconnect
region above the FE caps may cause a more severe
deterioration of the hysteresis properties than the
e€ect of the reducing atmosphere during the anneal
[49].
2.2. Electroceramics in microsensors and MEMS
The integration of sensors into microprocessors
originated some 15 years ago. The excellent micro-
machinability of silicon added new perspectives in
sensor design: micromachined silicon structures
such as cantilever beams, free-standing bridges,
membranes, and channels led to novel structures of
miniature transducers resulting in the emergence of
the new ®eld of microelectromechanical systems
(MEMS). MEMS are miniature devices or arrays of
devices that combine electronics with other com-
ponents such as sensors, transducers and actuators,
and are fabricated by IC processing techniques. For
a number of applications the MEMS concept facili-
 SETTER and WASER: ELECTROCERAMIC MATERIALS
Fig. 2. Micrograph of a single microhotplate (left) and representation of the functional components
within the microhotplate structure (right) [59]. Electrically insulating SiO2 layers, present above and
below the thermometer plate, have been deleted.
tates better device quality (e.g. higher sensitivity,
better reproducibility, and faster response), and
involve low costs with, very often, lower power con-
sumption in comparison with discrete devices.
Examples of MEMS products are the air-bag accel-
erometer, which reached the market at the begin-
ning of the 1990s, and the more recent digital
micromirror display (TV screen) in which a large
array of electronically controlled mirrors etched
onto a MEMS converts video data into high-resol-
ution TV images. The integration of functional cer-
amics, in the form of thin or thick ®lms, with
silicon promises to add versatility to the MEMS
leading to new functionalities. Research in this
direction increased in importance in very recent
years, and is very likely to continue to grow in the
future.
Various types of electroceramics such as super-
conductors, ionic conductors, oxide semiconductors
and piezoelectrics are of interest for microsensors.
Important examples of MEMS having functional
ceramics at the ``heart'' of the device include chemi-
cal microsensors, pyroelectric i.r. microsensors, and
piezoelectric micro-motors. They are described
below with equal emphasis on devices and on inte-
gration-related materials issues. In addition, HTSC
integrated thin ®lm devices and MFM (magnetic
®eld microscopy) tips are brie¯y mentioned.
2.2.1. Chemical microsensors. MEMS may pro-
vide substantial improvements in the ®eld of cer-
amic chemical sensors [52]. Ceramic sensors, based
on semiconductors such as SnO2, will be used to il-
lustrate this potential. These sensors function by
conductometric sensing (absorption induced con-
ductance change). They operate at elevated tem-
peratures and su€er from relatively poor selectivity
and to a lesser extent, poor stability. In addition,
high power consumption is a limitation in portable
devices. The use of MEMS technology is therefore
advantageous: arrays that contain elements sensitive
155
to di€erent chemicals can be made easilyÐimprov-
ing selectivity. Sensitivity is further increased
because of the faster thermal response of the micro-
element sensors. The power consumption of the
devices is reduced due to their reduced size.
Semanik and Cavicchi [59] showed a remarkable
chemical sensor using SnO2 thin ®lms integrated
into micromachined structures. This highly sensi-
tive, low-power, portable sensor is made of array
devices based on replicated low-mass suspended el-
ements (called ``microhotplates''). The elements are
covered with sensing ®lms deposited in a self-litho-
graphic CVD procedure which allows the covering
of the di€erent sensing elements with ®lms of di€er-
ent compositions, resulting in a high-selectivity sen-
sor (Fig. 2). The low mass devices allow a further
enhancement of the sensitivity through the use of
kinetic sensitivity: individually addressable, fast
temperature control adds temperature±time re-
sponse signatures of the sensed gasses to their static
signatures. While gas sensitivity is a surface
phenomenon, and ®lm thickness and microstructure
have a signi®cant in¯uence on it, no comprehensive
studies have been reported to date on the e€ect of
these parameters on the chemo-electronic response
of these sensors in the form of thin ®lms on micro-
hotplates. In the ®eld of chemical microsensors as
well as in other MEMS devices with ceramic thin
®lms, the fabrication processes introduce new
requirements, such as a need to process at low tem-
peratures for integration into CMOS.
2.2.2. Pyroelectric IR microsensors. An area in
which ceramic thin ®lms on silicon have a clear
commercialization potential is that of pyroelectric
sensors. Therefore, pyroelectric microsensors will be
used here to discuss ceramic materials and material
systems issues in MEMS in some detail.
Pyroelectrics respond to changing temperature (or
i.r. radiation) by generating electric current and are
widely used as ®re alarms, intruder alarms and
156 SETTER and WASER: ELECTROCERAMIC MATERIALS
Fig. 3. Partial array of a pyroelectric i.r. detector …320  240 pixel array fabricated with straight thermal
isolation arms) demonstrated by Raytheon [61].
uncooled i.r. cameras (thermal imaging). To obtain
high sensitivity, a high pyroelectric coecient is
needed, and a low thermal capacity. In addition, a
low heat loss to the surrounding is required.
Improved response therefore favors the use of thin
pyroelectric layers on thin membranes (bulk micro-
machining of silicon), or suspended pyroelectric
layers on bridges (surface micromachining with sili-
con). Using silicon as the substrate of the pyroelec-
tric array, a full integration of the sensor with the
preampli®ers and the read-out electronics can be
achieved [60] (Fig. 3). Reported applications of
pyroelectric thin ®lm-based sensor arrays include
the i.r. focal plan array for uncooled i.r. imaging
fabricated by Raytheon [61], Siemens [62], GEC-
Marconi [63] and a 64-element linear array i.r. for
gas spectrometer fabricated by Muralt's group [64]
at the ceramics laboratory of EPFL.
Materials issues in the integration of the pyro-
electric ®lm array on silicon are connected with the
processing of the materials system, that constitutes
the device, and with the processing of the pyroelec-
tric layer itself.
In a typical pyroelectric array fabricated by bulk
micromachining, the pyroelectric ceramic layer is
only one of some ®ve to eight layers, superimposed
on each other and onto the silicon, that form the
device. The layers include a di€usion barrier, an ad-
hesion layer, a bottom electrode, a template layer,
the pyroelectric ®lm, a top electrode and an i.r.
absorption layer, and may include additional layers
as well. The description of the layers and relevant
materials issues are given in Table 1.
The pyroelectric ceramic layer can clearly illus-
trate important materials problems in the im-
plementation of functional ceramics in micro-
devices: (i) The best composition for a thin ®lm
device is not always the same as that of a bulk
device. Lead titanate is one of the best pyroelectrics;
however, in the bulk form the material cracks
during the post-sintering cooling process due to the
large volume change during the paraelectric/ferro-
electric transition. In addition, the very high coer-
cive ®eld of the material prevents its poling. In
contrast, in the thin ®lm form, the material can be
processed and poled. (ii) Unlike bulk ceramics, thin
®lms can be grown in an oriented fashion, or epi-
taxially. Therefore, the anisotropy of properties can
be readily exploited in thin ®lms. Pyroelectric re-
sponse can be maximized by suitable orientation of
the ®lms. Excellent control of orientation has been
achieved through the use of template layers: for
(111) orientation, a (111) Pt electrode is used, fol-
lowed by a template layer of TiO2, resulting in a
tight (111) orientation of the pyroelectric layer [65].
Moreover, the titania (non-polar) layer is resorbed
through reaction with the lead-containing pyroelec-
tric layer. For other applications, e.g. for piezoelec-
tric microactuators, a (100) PZT layer can be
grown on Si±SiO2±Pt substrate using PbTiO3 tem-
plates. (iii) Due to size reduction e€ects, a large
number of microstructural features have an
 SETTER and WASER: ELECTROCERAMIC MATERIALS 157

Oxidation control: avoids migration through grain boundaries of the electrodes

Fabrication issues

Orientation, stresses, poling, patterning

Contact holes to pyroelectric layers

Orientation, patterning

Deposition, patterning

Fig. 4. Pyroelectric ®gure of merit of nanoporous Ca-

Crystallinity control

doped PbTiO3 [66] compared with dense ®lms of similar

compositions.
Stress control
Table 1. Materials issues in the fabrication of a materials system for i.r. arrays

increased importance in functional ceramic thin ®lm

devices in comparison with the bulk. This includes
±

interface e€ects at the boundary between the elec-

Controls the nucleation and the desired orientation of the pyroelectric layer

trodes and the ceramic, grain size and grain bound-

Mechanical support, di€usion barrier and thermally insulating membrane

ary e€ects, sub-granular features such as pinning of

domain walls. Nanostructural features that are
introduced during the processing steps have been
shown to signi®cantly in¯uence the properties of
functional ceramic thin ®lms. For example, the
introduction of nanoporosity in (Pb, Ca)TiO3 has
increased the voltage response of the pyroelectric
Purpose of the layer

®lm by four- to eight-fold [66] (Fig. 4). This is a

result of the reduction in the permittivity of the
Prevents delamination of the electrode

®lms due to the porosity, which is not accompanied

by a corresponding reduction in the pyroelectric
Reduction of parasitic capacity

coecient.

2.2.3. Piezoelectric microdevices. Piezoelectric

Temperature sensing

Infrared absorption

microdevices have been the subject of interest since

Electrical contact

Electrical contact

the beginning of the 1990s, although they have not

reached broad commercialization to date. A large
number of devices have been demonstrated: micro-
actuators, such as ultrasonic micromotors [67±69],
micropumps [70], micro®lters [71], PFOMs [72]
(piezoelectric coating on optical ®bers for use as
phase modulators, and coating on optical ®bers
Typical composition

with Bragg grating for tunable wave ®lters), and a

number of devices based on actuating cantilevers
Pb(Zr0.15Ti0.85)O3

(e.g. mirror tilters), sensors, such as pressure sensors

[73], accelerometers [74], and AFM cantilevers [75],
SiO2±Si3N4

high-frequency devices: ®lters of surface [76] or

Black Pt
Au±Cr
Ta, Ti

bulk [77] acoustic waves. As with other functional

TiO2

SiO2
Pt

ceramic-based microdevices, a major advantage of

integrated piezoelectric technology is the relative
ease and low cost of fabrication of one- or two-
Membrane material

Infrared absorber

dimensional arrays. In piezoelectric-based devices

Pyroelectric layer
Bottom electrode

Upper electrode
Adhesion layer

Template layer

Isolation layer

arrays are useful for ultrasonic transducers, and

Layer type

research in this ®eld is being pursued for ultrasonic

high-frequency imaging: medical imaging [78] and
sonar applications [79].
158 SETTER and WASER: ELECTROCERAMIC MATERIALS
For ultrasonic imaging applications, and for
high-force actuator applications, thicker ®lms are
necessary. The required thickness range is 5±
100 mm. To date, the ®lms have been prepared prin-
cipally by the following four methods: thick layers
of thin ®lms (e.g. diol-based sol±gel method [80]),
thin layers of thick ®lms (e.g. screen printing) [81],
a mixed method of thin ®lms prepared by chemical
routes and loaded with powder of similar compo-
sition [78], and a hydrothermal method [82]. Screen
printing is presently the only practical method for
thicknesses exceeding 10 mm. It demands the highest
thermal budget for sintering. In order to reduce the
processing temperature, while maintaining high den-
sity, excessive lead [81] or glass additives have been
used, with the penalty of lower piezoelectric per-
formance. Fully designed devices based on piezo-
electric thick ®lms on silicon or on other substrates
such as alumina, or metal, are still awaiting demon-
stration.
Thin ®lms on substrates are planarly clamped.
This reduces the piezoelectric response perpendicu-
lar to the substrate (e€ective d33). The calculated
d33 of planarly clamped PZT on silicon is about
half its bulk value. On the other hand, the e€ective
transverse coecient e31 (connecting the in-plane
stress with the applied electric ®eld through the
thickness of the ®lm) is enhanced [83]. Ample evi-
dence indicates that domain walls are much less
active in thin ®lms in comparison to bulk ceramics
[84], and it is believed that this results from stresses
in the ®lms due to the ®lm/substrate thermal expan-
sion mismatch. In highly sensitive bulk piezocera-
mics, such as Pb(Zr0.48Ti0.52)O3, the domain walls
contribution to the piezoelectric response (so-called
``extrinsic e€ect'') is substantial, being responsible
for about 50% of the signal. Therefore, the e€ective
piezoelectric coecient of thin ®lms is less than half
that of the bulk value. The induced piezoelectric re-
sponse of relaxor thin ®lms [e.g. Pb(Mg1/3Nb2/3O3)],
is also reduced [85]; however, the relaxor±ferroelec-
tric compositions showing superior piezoelectric
conversion eciency in (100)-oriented crystals also
show superior properties in the (100) epitaxial thin
®lm form [86].
One of the useful aspects of the deposition pro-
cess of ceramic thin ®lms onto substrates is the
possibility of orienting them and of bene®ting, with
appropriate design, from the anisotropy of their
properties. Bulk ceramics consist of randomly
oriented grains, and oriented ceramics can only be
achieved with special methods, mainly with cer-
amics of highly anisotropic crystalline structures
(and grain morphology), such as Aurivillius phase
ceramics (superconductors and piezoelectric cer-
amics) and hexagonal ferrites. The advantage of
orientation has been discussed above, but an im-
portant additional feature of the growth process, of
relevance in piezoelectric applications, is the possi-
bility of growing self-poled ®lms. Ferroelectric thin
Fig. 5. Cross-section dark ®eld image showing the colum-
nar dense structure of AlN ®lms [94].
®lms have been grown in a highly oriented and self-
polarized form [87]. Moreover, polar non-ferroelec-
tric ceramic thin ®lms such as AlN were grown in
an oriented manner and with a net polarizationÐ
thus becoming piezoelectrically active, in contrast to
the bulk ceramic AlN which cannot be piezoelectri-
cally active. The dense c-oriented columnar grains
are of about 50 nm diameter (Fig. 5). The piezoelec-
tric properties of these AlN ®lms are comparable to
the single crystal values [88] and the material is of
interest for a large number of sensor and transducer
applications, and for microwave ®lter applications.
The reasons for the self-poling of both polar non-
ferroelectric materials and ferroelectric materials are
not yet clear.
2.2.4. Further areas. Additional classes of electro-
ceramic materials that are developed into integrated
devices are superconductive and magnetic oxides.
Superconducting quantum interference devices
(SQUIDs), based on HTSC (high Tc ceramic super-
conductor) thin ®lms, and related devices, are being
developed with applications foreseen in magnetocar-
diology, and magnetoencephalography, in non-
destructive evaluation of materials, microscopy, and
geophysics. HTSC ceramics are sensitive to proces-
sing conditions and are not chemically and structu-
rally stable. On the other hand, the microstructure
and the defect structure of the material has a crucial
in¯uence on the transport and noise characteristic
of the devices. The magnitude of the noise, and
with it the limit of detection, depends strongly on
the crystallinity of the superconducting thin ®lms
and on the interface with the insulating layer.
Therefore, epitaxial YBa2Cu3O7ÿx (YBCO) ®lms on
lattice-matched single-crystal substrates show the
highest sensitivity [55]. By using the short coherence
length in the order of aÊngstroÈms of HTSC super-
conductors and their large anisotropy, a variety of
grain-boundary junction devices was developed [56].
All are based on the fact that due to the small
coherence length there is only a weak coupling
between two superconducting grains, which acts as
a Josephson junction. For some applications, multi-
layers (superconducting and insulating), with vias
and crossovers are required [57]. The patterning of
the layers poses additional challenges, since the
YBCO layers deteriorate easily. Silicon-based
SQUIDs do not achieve the high performance
 SETTER and WASER: ELECTROCERAMIC MATERIALS
obtained by epitaxial growth on matching sub-
strates, but they are sensitive enough for some ap-
plications (e.g. Tian et al. [58], demonstrating a
sensitive magnetocardiometer).
Beside SQUIDs, there exists another important
development avenue of HTc Josephson junctions
using the a.c.-Josephson e€ect for high frequency
active devices and circuits. HTc Josephson junctions
are d.c.-voltage controlled millimeter and sub-milli-
meter wave (100 GHz±7 THz) oscillators [89, 90].
Considerable work has been performed on one- and
two-dimensional arrays of coupled HTc Josephson
junctions. Coupled junctions show superior proper-
ties with respect to out power and line width in
comparison to an individual junction [91]. Recently,
Klushin et al. used shunted bicrystal HTc
Josephson junction arrays for voltage standard ap-
plications at liquid nitrogen temperatures [92, 93].
On the basis of a sophisticated fabrication technol-
ogy and a carefully designed microwave layout, 256
HTc junctions were synchronized to an external
microwave irradiation of approximately 27 GHz.
This is a milestone towards complex HTc junction
circuits.
Magnetic ceramics provide additional opportu-
nities for integrated sensors: for example, a highly
sensitive magnetometer for potential use in mag-
netic ®eld microscopy (MFM) has been demon-
strated of g-Fe2O3 ferrimagnetic acicular particles
mounted at the end of a micro-cantilever beam [21].
By an optical detection of the torque of the cantile-
ver, changes in the applied magnetic ®eld as small
as 10ÿ4 G were resolved.
Certainly, the last decade has seen only the begin-
ning of a development which aims at the integration
of a wide spectrum of electroceramic materials into
new, miniaturized devices. Certainly, in the future,
the materials base as well as the integration com-
plexity will be growing considerably.
3. MODELING
For centuries, scientists and engineers have tried
to model natural and technical systems by theories
in order to generalize the understanding of systems
and to make predictions. Theories are typically
based on the fundamental principles such as the
Newton laws of mechanics, the Maxwell equations
of electrodynamics, the laws of thermodynamics, or
the concept of quantum mechanics. For simple or
simpli®ed systems, a description can be achieved by
applying the boundary conditions of the system to
the appropriate fundamental principles and search-
ing for analytical solutions of the problem. For
highly complex systems such as biochemical mol-
ecules, VLSI semiconductor chips, or aircraft
engines, realistic descriptions can only be achieved,
however, by employing numerical methods based
on computer-aided simulation methods. In the con-
text of this paper, we will consider modeling as a
159
method which is based on empirical observations
and/or the fundamental principles of physics and,
by applying computer simulation, describes complex
materials or systems allowing interpolations or
extrapolations of their properties and behavior
within areas not (yet) covered by experimental data.
This computer-aided modeling is spreading into
all areas of industrial production technologies
today. Let us consider the fabrication process in the
semiconductor industry as a leading area with
respect to modeling. Before any production step of
a new CMOS chip is started, the complete chip
with all its internal and external electrical functions,
the architecture on the semiconductor wafer, and
all fabrication steps are simulated using computer
models. Only after the chip is completely oper-
ational and has been tested in this virtual world is
the real production started. In electroceramics, the
situation is much less mature. This is due to the
fact that electroceramic materials are much more
complex (due to their polycrystalline nature, the
typical multicomponent compositions, secondary
phases, a wide spectrum of point defects and
extended defects, mobile ionic species, ferroic
domain formation and domain kinetics, etc.) than
highly pure, single-crystalline Si, on the one hand,
and electroceramic devices are much less complex
than integrated semiconductor chips, on the other
hand. As a consequence, empirical and experimental
methods prevail in the design of new components.
As an introduction, Section 3.1 will give a few
examples, in which the fundamental principles are
extended into new areas of electroceramic materials.
Theoretical work of this kind is not modeling in
our de®nition, it is rather a valuable contribution to
broadening the foundations on which computer-
aided modeling can be based. Modeling will be
described on a macroscopic scale in Section 3.2
focussing on ®nite-element methods in which the
matter is considered continuously, and on a micro-
scopic scale in Section 3.3 outlining molecular
approaches.
3.1. Theoretical background
Classical approaches given by mechanics, thermo-
dynamics, chemical kinetics, electrodynamics,
optics, or quantum mechanics form the theoretical
base for any computer simulation. The power of
the computer is to apply these theories simul-
taneously to many constituents of a complex system
and the interactions between them. To illustrate
that the classical theories are still relevant for the
ongoing research, three examples will be given to
show recent achievements in explaining experimen-
tal ®ndings.
1. The classical thermodynamic theory has been fre-
quently applied in the last decades to empirically
describe the behavior of ferroelectric and dielec-
160 SETTER and WASER: ELECTROCERAMIC MATERIALS

Fig. 6. Phase diagram of BaTiO3: (a) bulk single crystal and (b) epitaxial (001) single domain thin ®lms
grown on cubic substrates of high temperatures as a function of the mis®t strain (redrawn from Ref.
[96] and illustrated). The second- and ®rst-order phase transitions are shown by thin and thick lines, re-
spectively.

tric materials and their phase transitions based ®lms. Not only in FE phases, but also in para-
on the calculation of the minimum of the Gibbs electric phases of high-k oxides, is the dielectric
energy as a function of external parameters such permittivity known to show a signi®cant decrease
as stresses, temperature, and electric ®eld as with increasing bias ®elds. This is illustrated in
introduced by Landau, Ginsberg, and Fig. 7 that displays the permittivity±®eld depen-
Devonshire (LGD) [95]. For thin ®lms, modeling dence for BST thin ®lms in their paraelectric
has to take into account the fact that the phase phase as a function of the ®lm thickness. This
diagram is in¯uenced by constraints such as two- non-linear dielectric behavior can be described
dimensional clamping. For epitaxial BaTiO3 by the LGD theory as shown by Basceri et al.
®lms on cubic substrates, an appropriate phase [98], perfectly ®tting the experimental data. From
diagram has been calculated recently by Pertsev the interpretation of the coecients, the proper-
et al. as a function of the mis®t strain [96]. The ties of a postulated dielectric interface layer can
authors introduced a new form of the thermo-
dynamic potential in which the stress is replaced
by the mis®t strain as an independent variable
using a Legendre transformation of the Gibbs
energy. The formalism has been applied to
single-domain PbTiO3 and BaTiO3 to calculate
the spatial direction of the FE polarization as
well as the phase transitions and their order as a
function of the mis®t strain and the temperature.
The result for BaTiO3 thin ®lms is shown in Fig.
6. Obviously, the phases and transition tempera-
tures are completely di€erent from those of the
classical three-dimensional single crystal. This
model has been successfully modi®ed to describe
the permittivity±temperature behavior of colum-
nar-structured BaTiO3 and SrTiO3 ®lms [97] pre-
pared by chemical solution deposition methods.
Fig. 7. Thickness dependence of the capacity density vs
2. An LGD approach has also been used to eluci- applied d.c. bias at room temperature of a set of Pt/BST/
date the reason for the thickness dependence of Pt/SiO2/Si samples with MOCVD-processed BST samples
the dielectric properties of paraelectric BST thin in a thickness range from 24 to 160 nm [98].
 SETTER and WASER: ELECTROCERAMIC MATERIALS 161

Fig. 8. Inverse permittivity vs temperature showing the summary of contributions to the dielectric beha-
vior of BST thin ®lms of composition (Ba0.7Sr0.3)Ti1+yO3, with estimates of the magnitudes of the var-
ious mechanisms discussed here, schematizing the pathway from bulk material to a prototypical ®lm of
y ˆ 0:015 and t ˆ 40 nm [101]; bulk ceramic data from Ref. [264].

be derived which are obviously responsible for
the reduction of the average permittivity with
decreasing ®lm thicknesses. In addition to the
interfacial layer e€ect, the permittivity of BST
thin ®lms is determined by the biaxial stress as
determined experimentally by Shaw et al. [99,
100]. They found that BST ®lms on platinized Si
substrates experience a tensile stress of 610 MPa
and show an electrostrictive constant of Q12 ˆ
0:029 m4 =C2 at T ˆ 298 K, and they calculated
the deviation from the Curie±Weiss law for con-
ventional bulk BST ceramics due to stress e€ects.
Recently, Strei€er et al. [101] studied the e€ect of
non-stoichiometry on the Curie±Weiss constant
and supplemented the thermodynamic descrip-
tion to explain semiquantitatively the suppression
of the permittivity of BST thin ®lms compared to
bulk ceramics of the same composition by the
e€ect of the non-stoichiometry, the stress, and
the interfacial e€ect (Fig. 8).
3. The bulk conductivity of BaTiO3 and SrTiO3
and their solid solutions in the high- and mid-
temperature regime depends on the temperature,
the oxygen partial pressure, the type of dopant,
and the dopant concentration. The dependencies
can be described by another thermodynamics-
based theory that employs the chemical reactions
of point defects and solves the corresponding sys-
tem of mass action equations. Appropriate
boundary conditions have to be taken into
account. The material constants such as the band
gap, the activation energy of the dopant ions, the
concentration of native defects (oxygen and cat-
ion vacancies) as well as the oxidation/reduction
enthalpies are obtained from ®tting the calcu-
lated data to the experimental results. In many
cases, these material constants have been veri®ed
by independent physical experiments (e.g. spec-
troscopy, thermogravimetry). While acceptor-
doped titanates have been described in this way
since the 1970s [102±114], recently the donor-
doped titanates only gained entry into a similarly
consistent picture more recently [115±118]. In the
last few years, strong experimental evidence has
been built up indicating that the surface and the
surface-near region of the ideal perovskite phase
is not stable at high temperatures. Szot et al.
have shown for several perovskite systems that
segregation processes take place which lead to a
change of the stoichiometry and the formation of
layered phases [119, 120]. It will be the task of
the coming years to build up a description which
comprises the interaction between point defects
and extended defects.
3.2. Finite-element models
The most common version of computational
techniques in engineering and science is the ®nite-
element method (FEM). It had ®rst been applied to
162 SETTER and WASER: ELECTROCERAMIC MATERIALS

Fig. 9. FEM results of a half-model of a moonie-type transducer (inset upper right) consisting of a
PZT core and brass end cap. The results show the e€ect of grooves introduced to the end cap on the
displacement characteristics of the actuator. Displacements are shown in parentheses [128].

calculate the mechanical behavior of complex tech-
nical structures (such as buildings, bridges, ma-
chines, planes and spacecrafts), investigating the
stress±strain behavior, the elastic and plastic prop-
erties, and the mechanical breakdown limits. Soon
FEM was extended to all kinds of, for example,
thermal, electrodynamical, and chemical problems.
The system to be analyzed is geometrically divided
into cells and the material properties at a few points
(nodes) around the cell boundary are allocated. By
means of the physical laws relevant to the problem
to be solved, a system of di€erential equations is
generated which is solved by numerical methods. In
contrast to the models on the molecular scale
(Section 3.3), the FEM analysis treats the solids
involved by continuum theories. The same applies
to the related ®nite-di€erence method (FDM) which
is based on dividing systems into cells in the same
way as the FEM technique, however, transforming
the di€erential equations into appropriate di€erence
equations.
In the modeling of electroceramic systems, FEM
techniques are most frequently applied to piezoelec-
tric and related ceramics and transducer appli-
cations (for a review see Ref. [121]). For example,
the development of miniature PZT piezoelectric hol-
low sphere transducers has been assisted by FEM
analysis. These transducers show up to three orders
of magnitude higher ®gures of merit for the hydro-
phone boundary conditions compared with bulk
PZT and have been analyzed in their ellipsoidal, cir-
cumferential, breathing, and coupled modes by
FEM [122]. In another application, the FEM tech-
nique has been used for the design and modeling of
integrated acousto-optic tunable ®lters with
weighted coupling on a piezoelectric substrate.
Two-dimensional pro®les were calculated in di€er-
ent parts of the devices and used for constructing
three-dimensional strain and electric ®eld pro®les.
Subsequently, the refractive index changes due to
acousto-optic (AO) and electro-optic (EO) e€ects
are derived which are employed to simulate the
overall optical ®lter characteristics [126]. A micro-
piezoelectric actuator with large force, long stroke,
and precise positioning capabilities has been rea-
lized by including spring plates which are ®xed to
both sides of a slider in order to press the actuator
grip points and, by pressing, generate a friction
 SETTER and WASER: ELECTROCERAMIC MATERIALS 163

bias conditions [129]. A bias leads to electrostrictive

Fig. 10. Spatial pro®les along an axis perpendicular to the
GB of the logarithm of the defect concentrations. All plots
are simulation results for 0.2 at.% Ni-doped SrTiO3 at a
temperature of T ˆ 500 K with an interface density DGB
of donor-type GB states of 2.5  1014/cm2 [139].
drive force. The design has been assisted by FEM
analysis [127]. An impressive example is given in
Dogan et al. [128] in which the optimization of the
displacement for moonie- and cymbal-type trans-
ducers is calculated by FEM techniques (Fig. 9).
Beyond the transducer applications, the FEM tech-
nique has been employed to analyze the coupling
between the mechanical, thermal, and electrical
properties of multilayer ceramic capacitors made
from high-permittivity dielectrics, including a simu-
lation of the impedance spectrum under d.c. voltage
resonances that should be avoided during oper-
ation. Comprehensive reviews of the state of the
development in the industrially important multi-
layer ceramic capacitor area have recently been pre-
sented by Sakabe [130, 131]. Of similar importance
today are low-temperature co®red ceramics (LTCC)
technology which is a multilayer electronic packa-
ging and substrate technology for high density
interconnects for integrated microcircuits and for
microwave devices. Often it is used as substrate for
multichip modules. If di€erent materials are used as
a base, it has the potential to integrate passive com-
ponents such as resistors, capacitors, and inductors
in a monolithic package including complex shape
buried components [123, 124]. The integration pro-
ceeds today by combining thick ®lm and LTCC ma-
terials, and processes with advanced patterning
technology in order to extend the capabilities of cer-
amic interconnect technology and to meet current
MCM demands for high density interconnect and
microwave applications [125].
FEM analysis is not restricted to device modeling
but can be employed for material modeling as well.
For example, the fracture process in piezoelectric
ceramics under combined electrical and mechanical
loads has been described in detail by applying a
FEM model to the process zone and determining
the mechanical stress intensity factor [132].
On the mesoscopic scale, electrostatics, band
models similar to (but more complex than) those of
the well-known standard semiconductors, and ther-

Fig. 11. Band diagram according to the Schottky model for Ni-doped SrTiO3. Notation: WC: conduc-
tion band edge; WV: valence band edge; WxNi4 1 : ®rst energy level of the Ni acceptors; W1Ni4 2 : second
energy level of the Ni acceptors; WxD4 1 : energy level of the GB donor states; WF: Fermi level.
164 SETTER and WASER: ELECTROCERAMIC MATERIALS
modynamical models such as the point defect chem-
istry mentioned in Section 3.1 can be combined
with FDM techniques to arrive at a powerful mod-
eling of the in¯uence of grain boundaries and grain
size e€ects on the electrical properties of ceramics.
Based on the well-known bulk defect chemistry of
alkaline earth titanates (see Section 3.1) a simu-
lation model of the grain boundary region was
developed which allows a computation of the
spatial pro®les of point defect concentrations, space
charge density, partial and total conductivities, elec-
tric potential and ®eld, and the band scheme along
a one-dimensional axis perpendicular to the grain
boundary plane (Figs 10 and 11). The fundamental
of this simulation model is the combination of
Poisson's equation, Fermi±Dirac statistics and the
defect chemical laws of mass action. The use of
Poisson's equation is necessary because the exist-
ence of electrically active interface states causes
space charge regions on both sides of the grain
boundaries. To guarantee a computationally e-
cient and physically precise simulation of the physi-
cal quantities, especially in the regions of their
largest gradients, the positions of the discrete
spatial nodes along the simulation axis are arranged
non-equidistantly by a special routine [133, 134].
The in¯uence of a large number of relevant input
quantities on the grain boundary properties can be
studied: temperatures and oxygen partial pressures
during various steps of the production process, con-
centrations of various dopants, concentrations and
energetic distributions of grain boundary-speci®c-
interface states, etc. For the ®rst time, such compu-
tational investigations allow a detailed picture of
the grain boundary point defect chemistry to be
developed [134, 135]. Analogous models exist for
the in¯uence of surface- and interface-induced
defects on the ionic conductivity of heterogeneous
solid electrolytes [136±138]. The electrostatically cal-
culated grain boundary pro®les are the platform for
further simulation steps. Using the grain boundary
pro®les of the total conductivity and the permittiv-
ity, a network consisting of a chain of parallel RC
branches is built along the above-mentioned one-
dimensional simulation axis. This network allows
the impedance spectrum of the ceramic to be calcu-
lated and model parameters of the electrical grain
boundary properties to be extracted by comparing
the simulation results with experimental data.
Furthermore, the temperature behavior of the grain
boundary impedance can be simulated and
explained. Here, the basic approach is to relate the
simulated temperature properties of the total grain
boundary impedance to those of the conductivity
and charge carrier pro®les. Their local minima con-
trol the temperature-dependent charge transfer
properties of the grain boundary in the small signal
regime [139]. The thermal activation energy of the
e€ective grain boundary conductivity is strongly re-
lated to the shape of the spatial conductivity pro®le
and the above-mentioned local minima of the con-
ductivity pro®le. The simulation results clearly
show that the potential barrier height itself is not
equal to this activation energy as one may assume
without the sophisticated insight given by the com-
puter simulations. The in¯uence of the barrier
height is only of an indirect nature. In the case of
very high potential barriers at the grain boundaries,
an inversion of the electronic charge carriers may
happen leading to the possibility of a non-negligible
charge transport along the grain boundaries. The
simulation models permit such e€ects to be investi-
gated by the construction of a quasi three-dimen-
sional RC network that includes the electrical
properties of the bulk of the grains and the charge
transfer characteristics across and along the grain
boundaries [140]. The simulation link between point
defect chemistry on the one hand and electrical
bulk and grain boundary properties on the other
hand is the ®rst step towards a complete process
and device simulation of electroceramic devices as
has been state of the art for silicon semiconductor
devices for many years.
3.3. Models on the molecular scale
Within the last two decades, enormous progress
has been achieved in the ability to calculate the
structures, the properties (e.g. thermodynamical,
mechanical, lattice-dynamical, transportational
properties), and the reactivity of solids starting
from atomistic approaches. This progress is due to
both the rapid expansion in the power of computer
hardware and in the development of algorithmic
methodology. The approaches can be classi®ed into
three categories [141]: (a) quantum-mechanical elec-
tronic structure calculations are based, at some
level of simpli®cation, on the solution of the
SchroÈdinger equation for a cluster of a few (up to
approximately 50) atoms and a set of (usually peri-
odic) boundary conditions [142]. Hartree±Fock type
methods calculate molecular wave functions from a
linear combination of atomic orbitals. The elec-
tron±electron interaction is taken into account by
Coulomb and exchange contributions and the calcu-
lation iteratively proceeds until a self-consistent
wave function is reached. A popular approach to
include the e€ects of electron correlation is the use
of local-density functional (LDF) methods. It is
based on the ®nding that the ground state energy of
a microscopic system is a unique function of its
electron density [143]. The eciency of the method
was signi®cantly improved by Car and Parinello
[144]. (b) Interatomic potential simulations start
from a given e€ective potential that describes the
interatomic forces in a system of atoms using essen-
tially classical techniques. The e€ective potential
used in the simulation of ionic crystals is modeled
by adding the short-range pair potentials to the
 SETTER and WASER: ELECTROCERAMIC MATERIALS
Fig. 12. Di€erence electron density map (solid minus iso-
lated Mo6+ and O2ÿ ions), in the plane through the outer-
most molybdenyl groups [Mo±O(1)] in adjacent layers of
a-MoO3, highlighting the zip-like connection of layers and
the short O(1)±O(1) equilibrium distance. The zigzag
dashed line in the center of the plot serves as a guideline
to separate the molybdenyl groups belonging to each
of the two facing layers. The lines correspond to positive
(Ð), negative (Ð) and zero (-
-
) di€erence. The interval
between the isodensity lines is 0:005eaÿ3
0 [147].
Coulombic potentials between the ions and by
including the ionic polarization using the shell-
model formalism developed by Dick and
Overhauser [145]. For crystals with a larger degree
of covalent bonding many-body terms have to be
taken into account, e.g. by incorporating speci®c
bond-angle dependent forces. The simulation algor-
ithms are based on static energy minimization
methods to calculate the structural con®guration of
the lowest potential energy, on molecular dynamics
methods including the kinetic energy widely used to
simulate fast di€usion and high-temperature proper-
ties, and on Monte Carlo methods which compute
random changes in the structure with results being
accepted or rejected on the energy criterion. Monte
Carlo methods are suitable to treat disordered sys-
tems and, for example, the vacancy distribution and
ion motions in heavily doped, fast ionically con-
ducting ¯uorite oxides [146] such as CeO2 that are
applied in solid oxide fuel cells. (c) Hybrid tech-
niques use, for example, quantum-mechanical tech-
niques to provide the e€ective potentials needed for
the simulation of interatomic forces.
With the improvement in hardware and software
tools, the ab initio electronic structure calculations
gain importance since they can deal with increas-
ingly complex systems and yield higher precisions in
the result. Along with this trend the hybrid tech-
niques grow in relevance. For reviews see Refs
[146±151].
As an example, calculations of the structure and
electron density of BO3 binary oxides …B ˆ Mo, W,
Re) will be brie¯y discussed. The base structure is
given by the cubic ReO3 phase exhibiting a network
165
Fig. 13. Schematic representation of the h001i surface of
b-MoO3 and WO3 (a), and of the h102i surface of WO3
(b). The numbers in parentheses indicate the coordination
number; an index s is added to the ions directly exposed
to the surface [147].
of corner-sharing BO6 octahedra, with all the oxy-
gen ions in a two-coordinate, bridging position
between adjacent metal sites. In this manner, BO3
represents the core of the ABO3 perovskite structure
with a missing A cation sub-lattice. Hartree±Fock
and density-functional calculations have been per-
formed by the group of Catlow [152±155]. For the
electronic band structure, the results show that the
valence band (VB) is mainly formed by O 2p states.
The conduction band (CB) is made from the Re 5d
t2g orbitals, while the Re 5d eg states lie higher in
energy. The density-functional calculation reveals
the details of the ionic and covalent interaction of
the participating orbitals. In agreement with the ex-
periment, the Hartree±Fock calculations reproduce
the lower-symmetry b-MoO3, and WO3 tetragonal,
and the a-MoO3 orthorhombic phases. The tetra-
gonal phases show a displacement of the transition
metal ion along the [001] direction towards one of
its six nearest neighboring oxygen ligands. This dis-
placement gives rise to a polar (in fact, an FE)
phase. The shifted cation and the nearest oxygen
show an increase in covalence and allow the short
B±O pairs in MoO3 and WO3 to be labeled as
molybdenyl and tungstyl groups, respectively. The
elongated B±O bond gives rise to a layered-type
structure, as shown in Fig. 12 as an example, and
preferred cleavage directions. Based on these calcu-
lations, the mechanical properties, e.g. the bulk
moduli, have been determined and explained.
The FE shift of the cations leads to modi®cations
of the valence and conduction bands by, for
example, additional p bonding contributions that
are symmetry forbidden in the cubic phase. The cal-
culations show that the relative stability of the
cubic and tetragonal phases depends on the number
of VB electrons and, hence, can explain the fact
that lower-symmetry phases may occur for MoO3
and WO3 but not for ReO3, due to its additional
valence electron (Fig. 13). In addition, the net
charges at the ions, the equilibrium bond distances
166 SETTER and WASER: ELECTROCERAMIC MATERIALS
and the bond population (i.e. the degree of cova-
lence) can be calculated for all BO3 phases.
Through the evolution of the hardware and the
software concepts within the last decade, it has
become increasingly possible to calculate the lattice
dynamics and dielectric properties, the sequence of
structured phase transitions as well as the transition
temperatures for FE oxides from ®rst principles.
For example, frozen-phonon studies [156] were used
to identify the eigenvectors and frequencies of zone-
center transverse optical (TO) modes, and to give
detailed insight into the FE soft modes. For the
understanding of FE materials, it is of great import-
ance to calculate the spontaneous polarization Ps.
King-Smith [157] used an e€ective charge approach
to determine Ps with a remarkable precision. Based
on this approach, it was found that FE oxides typi-
cally exhibit a unique mixture of ionic±covalent
bond characters and a speci®c hybridization
between O 2p and B-atom 3d or 4d orbitals in the
ABO3 systems [158±162]. These calculations pro-
vided a more detailed understanding of the origin
of the FE instability and its relation to the long-
range Coulomb interaction [162]. For calculating
the phase transition temperatures, an e€ective
Hamiltonian may be employed. The resulting model
can be subjected to Monte Carlo or molecular
dynamics simulations in order to arrive at a reason-
able reproduction of the phase transition tempera-
tures of, for example, PbTiO3 [163], KNbO3 [163],
and BaTiO3 [164, 165]. During the last years, ®rst
steps have been taken to extend the ®rst-principle
calculations to solid solutions such as PZT,
Pb(Zn, Nb)O3, and Ba(Zn, Nb)O3 [166, 167], to
domain walls [168], to the electromechanical beha-
vior [169], and to surfaces [170, 171].
Grain boundaries and twin boundaries in ionic
crystals have been simulated by separating the mod-
eling task into two steps: ®rstly, the unperturbed
bulk crystal is calculated from ®rst principles or
semi-empirically, and then a boundary is inserted
and in the vicinity of the boundary the ions are
allowed to relax from their bulk position [172, 173].
Point defects are successfully treated in simu-
lation procedures by means of the Mott±Littleton
approach [174] which partitions the crystal into two
regions around a point defect. In an inner region,
the neighboring ions and their relaxations are con-
sidered by an atomistic model, while the rest of the
crystal is treated by more approximate quasi-conti-
nuum methods. On the precondition of reliable
interatomic potentials and a suciently large inner
region, these methods can provide values of the
energies of the defect formation, the defect mi-
gration, the formation of defect clusters [175±180].
For example, the perovskite-type oxides LaBO3
…B ˆ Cr, Mn, Fe, Co), which are widely employed
as base compounds for SOFC electrodes and con-
ductive oxide electrodes in integrated ferroelectric
thin ®lm devices (see Section 2), have been compre-
hensively modeled by Cherry et al. [180]. In a ®rst
step, the experimentally indicated and generally
accepted formation of oxygen vacancies and the
oxygen transport by vacancy hopping has been con-
®rmed. It has been found that the oxygen vacancy
hopping takes place along the anion octahedra edge
along a curved path, revealing migration energies in
excellent agreement with experimental data.
Furthermore, the calculations demonstrate the im-
portance of lattice relaxation e€ects at the mi-
gration saddle point. Useful predictions have been
made on variations of the A-site and B-site cation
to lower the migration energies and, hence, improve
the oxygen transport. Finally, the formation of
defect clusters and their impact on the transport
properties were simulated. For the simulation of the
proton mobility in perovskite-type proton conduc-
tors such as BaZrO3 and BaCeO3, molecular
dynamics simulations have been successfully
employed [181]. The results are employed to sup-
port the development of optimized proton conduct-
ing oxides for possible use in SOFC applications.
Although accurate predictions for a limited range
of compositions are possible today, it is still not yet
possible to predict completely new materials with
optimized ionic conductivity solely from computer
simulations in a generalized approach. This will
remain a task for theoretical solid state research in
the next few years.
4. NANOSIZE EFFECTS AND NANOTECHNOLOGY
Although size e€ects on the nanometer scale have
long been investigated, there has been a trend in
recent years to strengthen the utilization of these
e€ects and to synthesize ceramics in which the
properties are dominated by size e€ects. This is true
of bulk ceramics and thick ®lms as well as of thin
®lms. We will review a few examples of size e€ects
on the nanoscale in oxide ceramics in Section 4.1,
we will discuss preparation routes and applications
of nanocrystalline ceramics in Section 4.2, and
®nally, describe trends to develop the microtechnol-
ogy of integrated electroceramic ®lms in a nano-
technology (Section 4.3), parallel to the evolution in
the semiconductor area.
4.1. Nanosize e€ects
Size e€ects on the nanometer scale occur in all
material classes within the area of electroceramics.
Most widely reported are size e€ects in ionically
conducting ceramics and, to a wide variety, in fer-
roic (i.e. ferromagnetic, ferroelectric, and ferroelas-
tic) ceramics. The direct observation of nanosize
e€ect is made available through nanoanalysis.
4.1.1. Nanosize e€ects in ionically conducting cer-
amics. Grain boundary e€ects in relation to conduc-
tivity, especially in solid state ionics, have been
 SETTER and WASER: ELECTROCERAMIC MATERIALS
Fig. 14. Grain size dependence of the permittivity of BaTiO3 bulk ceramics (squares, circles) and thin
®lms (triangles) at T ˆ 289 K:
studied for some time. However, with the present
interest in nanosize phenomena, grain boundary
and sample thickness e€ects increase in importance.
Conductivity at interfaces is a complex phenom-
enon: conduction enhancement may occur parallel
to the interface although grain boundaries may sim-
ultaneously block the transport by a resistive core,
the ratio of ionic/electronic conductivity may di€er
in the grain boundary in comparison with the
grains themselves, etc. Theoretically, Maier has
shown long ago that if the sample thickness or
grain size is not large compared with the Debye
length, then space charge regions interfere and the
sample is charged throughout, so that an enhance-
ment of conductivity may occur [213]. A recent case
in which this situation may have been observed is
that of enhancement of conductivity in AgI:Al2O3
nanocomposites. It has been shown [214] that an
interfacial structure of stacking faults occurs at the
interfaces. These stacking faults may be conceived
as heterostructures in which b and g layers of AgI
alternate, the layer distance being of atomistic
dimensions. If interfacial e€ects at the b/g boundary
are supposed, the increase in conductivity can be
explained on the basis of space charge e€ects [215].
An important increase in conductivity has also been
observed in nanocrystalline CaF2 [216], in nanocrys-
talline ceria [217] and in nanocrystalline yttria-
stabilized zirconia [218].
4.1.2. Nanosize e€ects in ferroic ceramics. On the
route towards smaller particle sizes, ferroic ma-
terials with moveable domain walls show a distinct
change of their properties [182]. Macroscopic par-
ticles and grains in ceramic bodies show complex
167
domain patterns. As the particle size is reduced suf-
®ciently, the particles become single domain.
Ferrimagnetic g-Fe2O3 particles show this transition
at approximately 40 nm [183] in good agreement
with theoretical estimations [184]. Ferroelectric
PbTiO3 particles were investigated in 0±3 PbTiO3/
polymer composites [185] for which a critical tran-
sition to single domain particles at approximately
200 nm was found. Upon further decrease of the
particle size, the ferroic state with distinct direction
of the polarization undergoes a transition into a
``superparoic'' state, characterized by a zero spon-
taneous polarization and the disappearance of hys-
teresis, but still non-linear physical properties. This
transition is correlated with the size at which the
decrease in volume free energy accompanying the
polarization is in the order of the thermal energy.
For g-Fe2O3, a critical size of approximately 30 nm
[183] is reported, while for PbTiO3 a critical size of
approximately 8 nm [186] is found. Further decreas-
ing particle sizes leads to a disappearance of the
non-linear behavior and a ``paroic'' state strongly
dominated by surface e€ects.
The e€ect of the grain size on the permittivity
and on the phase transition temperatures has been
studied in particular detail for ferroelectric BaTiO3
ceramic. In Fig. 14, the grain-size dependence of
the permittivity at room temperature is compiled
from di€erent sources [187±191]. As found for
BaTiO3 bulk ceramics, the permittivity exhibits a
pronounced maximum at an average grain size of
approximately 800 nm. Obviously, this maximum
results from the superposition of two e€ects.
Firstly, below the grain size of a few micrometers
168 SETTER and WASER: ELECTROCERAMIC MATERIALS
the average permittivity of the grain interior
increases due to a stress e€ect as shown by Buessem
et al. [192]. Secondly, the drop of er below approxi-
mately 800 nm may be interpreted by an intrinsic
dead layer e€ect at the grain boundaries, recently
proposed by Frey et al. [188] using a dielectric
brick-wall model as mentioned in Section 3.1. From
their data, they calculated a low-permittivity layer
of 0.8 nm thickness and er,GB values of approxi-
mately 130. It has been checked by high resolution
TEM that the grain boundaries do not show any
secondary phase. The intrinsic dead layer can be
explained by means of a local ®eld theory using the
dipole interactions in the vicinity of the surface of
particles and of thin ®lms [193, 194]. In addition,
Frey et al. found that the phase transition tempera-
ture TC does not depend on the grain size, indicat-
ing the high purity of their BaTiO3 material.
Compared to the ®ne-grained bulk ceramics, thin
BaTiO3 ®lms of the same average grain size show a
signi®cantly lower permittivity (Fig. 14). This di€er-
ence can be explained by a combination of the
intrinsic dead layer e€ect, a stress e€ect, an e€ect of
the microstructure within the ®lm, and an e€ect of
the stoichiometry, as outlined in Section 3.1.
Another class of oxide materials in which the
unusual and interesting properties are explained by
nanosize e€ects are the ferroelectric relaxors.
Relaxors attracted scienti®c and industrial interest
at the beginning of the 1980s when their large and
non-hysteretic electrostrictive strain [195] became of
interest for actuator applications. Their large per-
mittivity over a wide temperature range together
with the relatively low sintering temperature …<
10008C for some) made them attractive for multi-
layer capacitors, too. Since under d.c. bias they
exhibit very high piezoelectric coecients, these
complex oxides are also of interest in thin or thick
®lm form for piezoelectric applications. Recently
(100)-oriented crystals at the ferroelectric±relaxor
boundary were shown [196] to possess piezoelectric
coupling coecients (electrical/mechanical energy
conversion eciency) exceeding 90%. This value is
much higher than that of conventional piezoelectric
ceramics and therefore intensive research is being
carried out in pursuit of ceramics that will exhibit
properties similar to those of relaxor±ferroelectric
single crystals.
The origin of relaxor behavior has been studied
for 40 years, but it is only in the last decade that
microscopic mechanisms, with solid experimental
evidence to support them, were proposed. The
relaxors do not undergo a macroscopic phase tran-
sition from the paraelectric phase into a ferroelec-
tric phase, but they become rather ``frustrated''
ferroelectrics. The relaxors are complex oxides, and
the origin of the ``frustration'' is compositional in-
homogeneity on a nanometer scale that results from
partial positional disorder in a speci®c lattice site.
This disorder prevents the macroscopic transform-
Fig. 15. Real part of the permittivity of Pb(Sc1/2Ta1/2)O3
(PST) as a function of temperature for (PST-DV) disor-
dered with Pb vacancies showing relaxor behavior, disor-
dered (PST-D) showing transition from relaxor to normal
ferroelectric, and ordered (PST-O) showing normal ferro-
electric behavior [201].
ation into the ferroelectric phase. A picture coher-
ent with experimental results is that of a
paraelectric matrix in which ferroelectric regions of
10±50 nm size are formed upon cooling, without
the evolution of a coherent macroscopic ferroelec-
tric phase. Evidence of the size of the ferroelectric
nanoregions was found by XRD [197] and neutron
di€raction studies [198] of the correlation length of
ionic shifts. The dielectric permittivity in a wide
range of temperatures, frequencies, a.c. ®elds and
d.c. bias [199] can be explained with a model of
``breathing'' boundaries between the polar nanore-
gions and the paraelectric matrix. Some relaxors,
such as the prototypical relaxor Pb(Mg1/3Nb2/3)O3,
become ferroelectric upon cooling under strong d.c.
bias [200]. In other cases, e.g. Pb(Sc1/2Ta1/2)O3, they
exhibit relaxor behavior in a certain temperature
range, and then transform spontaneously into nor-
mal ferrroelectrics upon further cooling [201] (Fig.
15).
The unusual dielectric properties of relaxors are a
consequence of the small dimensions of the ferro-
electric regions: due to their mesoscopic size, the
ferroelectric regions are electrically soft in that they
can expand or contract (``breathe''). The consequen-
tial useful properties are numerous: (a) very high
permittivity over a wide temperature range, (b)
large electrostrictive e€ects which are believed to
originate from ®eld-activated coalescence of the
polar nanoregions to macrodomains, and (c) strong
piezoelectric, pyroelectric and electro-optic response
under a bias ®eld.
Thin and thick ®lm relaxors are currently being
studied. To date, the properties of the ®lms are in-
ferior to those of bulk ceramics (see Section 2.2). It
is likely, but not proven yet, that the nanoregions
are hardened due to clamping or lattice defects.
For ferroelectric thin ®lms, the question of the
disappearance of the spontaneous polarization
 SETTER and WASER: ELECTROCERAMIC MATERIALS
below a critical thickness is of fundamental import-
ance for future integrated devices. This e€ect as
well as the additional e€ect of constrained geome-
tries has been consistently determined by Scott and
Hartmann [202]. Obviously, the critical value
strongly depends on the nature of the ferroelectric
material as well as on the stress situation of the
®lm, linking the depolarization e€ect [203] and the
intrinsic dead layer e€ect. The thinnest ®lm for
which full ferroelectric switching has been reported
is a 0.9 nm PVF2 copolymer ®lm prepared by a
Langmuir±Blodgett technique [204]. For perovs-
kites, the situation can be tuned by adjusting the
biaxial stress using the lattice mis®t of heteroepitax-
ial ®lms such as (Ba1ÿxSrx)TiO3 on SrRuO3/SrTiO3.
The Curie temperature is shifted to signi®cantly
higher values as shown theoretically and experimen-
tally by Abe et al. [205].
The coercitive ®eld EC in an FE thin ®lm capaci-
tor stack is frequently found to increase with
decreasing PZT ®lm thicknesses (see Ref. [206] and
references cited therein). The e€ect is especially pro-
nounced for the common Pt/PZT/Pt stack. An insu-
lating, non-ferroelectric, low-k intrinsic dead layer
at the electrode interfaces described above is not
suitable to explain this e€ect [207]. Rather, the dead
layer leads to a shearing of the hysteresis curve, i.e.
a reduction of the remanent polarization Pr, yet
maintaining the EC values. However, because of the
low permittivity in the dead layer, the electric ®eld
within the intrinsic dead layer is much larger than
the average ®eld throughout the ®lm. Hence, above
a threshold ®eld Eth, charge injection from the elec-
trode will occur leading to screening charges for the
polarization in the core of the ®lm [208]. As quanti-
tatively shown by Tagantsev and Stolichnov, this
e€ect explains the thickness dependence of EC [209].
In addition, their model explains why the thickness
dependence is reduced for PZT ®lms with oxide
electrodes and for SBT thin ®lms as is the impact
on fatigue [210].
Another size e€ect of thin ®lms has been
observed for antiferroelectric materials such as
PbZrO3 and BiNbO4 deposited on doped Si(100)
substrates by PLD [211]. Below a critical thickness,
the ®lms start to exhibit ferroelectric behavior,
obviously related to a self-polarization during the
growth of the ®lm in the thickness regime of a
single domain situation. Increasing thicknesses lead
to multidomain ®lms which restore the bulk like
(antiferroelectric) properties. For FE ®lms on semi-
conductor substrates with and without additional
dielectric insulator layers, the stabilization of the
polarization due to the band bending at the inter-
face has been theoretically examined by Watanabe
[212].
4.1.3. Nanoanalysis. Functionality of electrocera-
mics is interpreted using structural characterization
techniques combined with electrical measurements.
169
As feature size decreases, local probe techniques
become essential. Clari®cation of the role of
domain and grain boundary phenomena in electro-
ceramic thin ®lms and nanograin bulk ceramics
are obtained using advanced transmission electron
microscopy (TEM), and scanning probe mi-
croscopy (SPM) techniques. AEM (analytical
TEM) is used to reveal low concentration of
dopants and impurities at grain boundaries and
HRTEM (high resolution TEM) serves to investi-
gate the atomistic structure of grain boundaries,
and domain walls [257]. Recently probe microsco-
pies have been used to determine simultaneously
the structures, some times at atomic dimensions,
and the local properties of electroceramics sur-
faces. Using SPM it was possible to examine local
properties of surfaces by evaluation of contact po-
tential between metals and ceramics, local electro-
static ®elds at grain boundaries and current ¯ow
across boundaries [258].
Spatial homogeneity of the switching properties
of ferroelectric ®lms at the nanoscale level became
recently an important issue due to the increasing
e€orts to scale down ferroelectric memory capaci-
tors, targeting sub-micrometer size. For capacitor
cells of size equivalent to a few grains, the re-
sponse of individual grains and the sub-grain re-
sponse are of great importance. Scanning force
microscopy (SFM) is combined with in situ
measurements of the inverse piezoelectric e€ect to
complete the observation of topographical features
with details about the polarization state, and give
the needed local information. The use of SFM in
the piezoresponse mode is based on the detection
of the piezoelectric vibration of the ferroelectric
®lm caused by an external a.c. voltage applied
through the conductive probing tip [259], or, for
study of fatigue behavior, the a.c. voltage is
applied between top and bottom electrodes and a
lock-in ampli®er determines phase and amplitude
of the piezoelectric vibration [260].
The evolution of the ferroelectric switching
upon fatiguing cycles, was used to obtain infor-
mation about the fatigue mechanisms. The direct
observation of the existence, size, shape, and
evolution of regions with frozen polarization
during fatigue onset has been reported. It was
shown that fatigue proceeds ``region by region''
(namely, ``on/o€'' process) and not by a gradual
reduction in switched polarization throughout the
®lm [261, 262]. This is important information for
the development of ferroelectric memories. The
conductive probing tip has been used also to
``write'' (polarize) domains locally, and to study
their retention properties. In this way dots hav-
ing diameter smaller than 100 nm could be writ-
ten and imaged on atomically smooth PZT ®lms
grown epitaxially on Nb:SrTiO3 single crystal sub-
strates [263].
170 SETTER and WASER: ELECTROCERAMIC MATERIALS
4.2. Nanopowders and nanostructured ceramics
The production of ultra®ne ceramic powders is of
interest for enhanced sintering rates, low sintering
temperature, and ultra®ne grain sizes of the dense
ceramic. Nanopowders with controlled and uniform
size have been produced with much success during
the last decade by a variety of chemical routes
[219]: sol±gel processing, hydrothermal synthesis,
synthesis by gas-phase reaction, etc. Enhanced den-
si®cation rates have indeed been shown for a large
number of compounds, however, very often the
densi®cation is accompanied by coarsening.
The reduction of the sintering temperature by
very small particle sizes can be utilized to co®re
di€erent ceramic materials. For example, for gas
sensors ZrO2 has been joined with Al2O3 ceramics
by co®ring a ®ne grained ZrO2 powder with an
ultra®ne grained Al2O3 powder. The average par-
ticle size was selected to adjust the conventionally
higher sintering temperature of Al2O3 to that of the
ZrO2 [220].
The use of external pressure was shown to be
e€ective for control of the ®ne ®nal microstructure.
In such a way, ultra®ne titania (grain size 50 nm)
with 98% density has been obtained at 4508C
…11=3Tm † under high pressure (1.5 GPa) [221].
Alternatively, dopants are used for the control of
the ®ne ®nal microstructure. Dopants will, however,
modify the properties. MeO-coated ceria (oxide
electrolyte) has been shown to densify [222] at
9008C (in comparison with 13508C sintering of
uncoated powder) retaining a grain size of 80±
100 nm. The mechanism that underlines the sinter-
ing of coated powders is not wholly explained yet.
Chiang and co-workers recently reported [223] a
strong enhancement of rate of sintering (``activated
sintering'') of nanosize ZnO powders doped with
small and uniformly distributed amounts of Bi2O3.
The enriched amorphous ®lms of 11 nm thick-
nesses formed at the grain boundaries below the
eutectic temperature are believed to cause the acti-
vated sintering. The amorphous ®lm has an
increased solubility of ZnO. In addition, the grain
boundary oxygen di€usion coecient in samples
containing the intergranular amorphous ®lms has
been found to be 105±106 higher than that in
undoped samples. Accelerated mass transport
through these subeutectic intergranular amorphous
®lms is thought therefore to be responsible for the
strong enhancement of the sintering rate.
The compaction and sintering of ceramics will
increasingly include more complex particles which
comprise individual functions. Trends in this respect
may be set by the discovery of carbon fullerenes
and carbon nanotubes [224] and that of nanotubes
stu€ed with metal or metal carbides [225].
Following this, it has also been shown that nano-
particles of two-dimensional layered metal dichalgo-
genide compounds such as WS2, and MoS2 can
collapse into fullerene-like cages and nanotubes
[226]. Inorganic fullerenes (IFs) are expected to be
found among various other layered compounds,
including layered oxides [227].
Inorganic layered compounds with a strong co-
valent character which is symmetrical about the c-
axis, and includes topological elements of lower
symmetry that induce bending into the network,
have the driving force to become IFs. These con-
ditions can be found in a number of oxides such as
MoO3 and V2O5. However, to the best of our
knowledge no oxide IFs have been synthesized to
date using spontaneous transformation.
On the other hand, using carbon nanotubes as
templates, a number of compounds have so far
been synthesized such as V2O5 [228] and MoO3
[229]. Very recently, the synthesis of TiO2 [230] has
been reported, however, in this case the materials
are only partially crystalline. It is too early to pre-
dict the potential of these materials, but the study
of their properties is certainly an exciting perspec-
tive.
Within the nanoparticle technology, a second
emerging issue is the introduction of nanoscale por-
osity in ceramics. The achievement of either open
or closed, size-controlled nanoporosity is a challen-
ging processing problem.
The best example of the important role open
nanoporosity may play in functional ceramics is the
Graetzel photoelectrochemical cell [232]. The heart
of the cell is a nanocrystalline ®lm of semiconduc-
tive TiO2 that is covered by a chemically adsorbed
monolayer of photo-sensitive dye. When excited by
photons, the dye transfers electrons to the conduc-
tive titania and positive charges to a redox electro-
lyte. In this way, a photoelectrochemical cell is
created. A solar cell with 110% eciency of visible
light to electrical current conversion can be made
by the already existing, low-cost technology.
Since the dye is adsorbed on the TiO2 layer, a
very large speci®c surface area of the latter, through
nanoporosity and rough surface structure, is im-
perative for ecient photon to current conversion.
The starting material for the preparation of the
controlled mesoporous thick ®lm is a colloidal pow-
der of titania. The colloidal titania powder is coar-
sened by hydrothermal growth to give particles of
10±25 nm size and pronounced anatase mor-
phology. These particles are transformed, processed
into screen-printable ink which is densi®ed at tem-
peratures in the range of 400±5008C yielding the
desired ``sponge'' structure with a pore diameter of
20 nm [233].
Nanoporous silica for low permittivity medium in
current ultra-large-scale-integration (ULSI) technol-
ogy represents an example of a material that needs
to be processed to a high volume fraction (70% and
more) of closed nanoporosity. In the interconnect
layers, low dielectric constant (low-k ) materials
reduce the signal transition times and reduce power
 SETTER and WASER: ELECTROCERAMIC MATERIALS 171

Fig. 16. SEM images, at di€erent magni®cations, of hierarchically ordered materials with three distinct
order length scales. The overall pattern (left) repeats the motif …01000 nm† shown on the right, which
is made up of a macroporous …0100 nm† framework of cubic mesoporous …010 nm† silica, as con®rmed
by TEM and low-angle X-ray di€raction. The sample was calcined at 4508C in air to remove the latex
and block copolymer species (from Ref. [237]). Reprinted with permission from Yang et al., Science,
1998, 282, 2244. Copyright 1998 American Association for the Advancement of Science.

consumption and cross-talk. Polymers are low-k
materials but they have thermal stability and re-
liability problems. The permittivity of dense silica is
4, but appropriate introduction of porosity down to
a density of 10.4 g/cm3 (the density of fully dense
silica is 2.22 g/cm3) reduces it to k11:5 while main-
taining all other requirements (sucient thermal
conductivity, mechanical strength, and electrical
strength, low adsorption of humidity, and good gap
®ll capabilities). To satisfy these requirements, the
pore diameter has to be on the order of 20 nm. The
nanoporous silica is prepared by the sol±gel route,
and is suitable for the conventional spin-on tech-
niques used by the microelectronics industry. The
pore size is obtained by a strict control of the pre-
cursor chemistry, temperature, pH, reaction time,
¯uid and drying conditions [234]. A critical point is
the elimination of all shrinkage after gelation.
Whereas the control of nanoporosity size and dis-
tribution is achieved in silica, more complex oxides,
such as ferroelectric perovskites, await this develop-
ment. As mentioned in Section 2, Ca-modi®ed
PbTiO3 with nanopores shows signi®cantly
enhanced pyroelectric performance. The porosity,
scaling at 100 nm, has been prepared by a con-
trolled evaporation of lead oxide. It is of interest to
achieve pores of smaller size.
Based on the availability of nanoporous silica
technology, interest is emerging in composite nano-
porous materials: the low-density nanoporous
nanoscale composites are synthesized by adding a
colloidal or dispersed solid to the about-to-gel silica
sol. The silica sol has been shown to incorporate a
range of chemically and physically diverse particles
into the three-dimensional silica network formed
upon gelation. Composites containing metal par-
ticles, titania aerogels, zeolites, and carbon blacks
have been introduced in this way [235].
A di€erent approach for the introduction of
nanopores is taken by a number of researchers who
incorporate organic templates such as surfactant
arrays, emulsion droplets or latex spheres while pro-
cessing various oxides from organometallic precur-
sors. The pores thus obtained have sizes ranging
from 5 nm to 1 mm. For example, titania, zirconia,
and alumina samples with pores of 1300 nm size
were obtained, using latex spheres with periodic
close-packed ordered three-dimensional arrays [236]
(Fig. 16). These ceramics will clearly ®nd appli-
cations in various domains.
Finally, it is of interest to mention a recent dem-
onstration of porous composites which contain
di€erent scales of pores with discrete characteristic
lengths, the so-called ``hierarchically ordered solids''
[237]. In this spectacular work, porous silica, niobia,
and titania with three-dimensional structures pat-
terned over multiple-length scales were prepared by
combining micromolding, polystyrene sphere tem-
plating, and cooperative assembly of inorganic sol±
gel species with amphiphilic triblock copolymers.
The resulting materials show hierarchical ordering
over several discrete and tunable length scales ran-
ging from 10 nm to several micrometers. The re-
spective ordered structures can be independently
modi®ed by choosing di€erent mold patterns, latex
spheres, and block copolymers.
4.3. Nanostructuring technology
During the ®rst decade of the new millennium,
the feature size is expected to be decreased below
100 nm according to the SIA road map that antici-
pates the development of semiconductor-based
microelectronics. In order to further support the in-
tegration of electroceramic oxides into the semi-
conductor world (see Section 2) when the
172 SETTER and WASER: ELECTROCERAMIC MATERIALS
Fig. 17. Z-contrast image of SrTiO3 on (001) Si. The epi-
taxy that is apparent is (001) SrTiO3 k…001†Si and
TiO2 ‰100ŠkSi‰110Š: On the left-hand side there is an inset
model of the perovskite/Si projection [242].
nanotechnology age is entered, the oxides must
meet the challenges of nanostructuring. The re-
duction of the sizes applied (1) to the vertical
dimension on a wafer, i.e. the thickness of ®lms will
have to be further reduced while maintaining the
morphological and physical ®lm quality, and (2) to
the lateral dimension, i.e. the feature size of pattern-
ing processes.
4.3.1. Ultrathin ®lms. Due to the reduction of the
feature size, the capacity of the gate electrode of
MOSFETs will decrease. Since there is an inherent
limit to which this decrease can be accepted, sol-
utions have to be found to increase the capacity per
area density. As the SiO2 will reach its thickness
limit of approximately 1.5 nm in the year 2006 with
unacceptable high tunneling currents below this
limit, a search for gate oxides with higher permittiv-
ities started recently. The boundary conditions for
the material choice and the possible candidates
have been systematically shown by Kingon and
Strei€er [238]. Obviously, only a few oxides are
thermodynamically stable in direct contact with Si
as shown in a theoretical study covering all binary
oxides [239]. Given the additional constraints, a
(thin) SiO2 intermediate layer has to be accommo-
dated in most cases. The novel gate oxides must be
either epitaxially grown or amorphous to avoid
unacceptable scatter of the properties due to granu-
larity e€ects. Within either solution, only a very
limited range of oxides are suitable due to the con-
straints of a suitable permittivity (values up to 100
are sucient) and low loss at the operating frequen-
cies, a large band gap for a high breakdown ®eld,
appropriate band alignment, stability to resistance
degradation, and low reactivity with SiO2 at process
temperatures. Possible candidates investigated to
date are Ta2O5 [240], Sr2Ta2O7, La2O3,
Zr(Sn, Ti)O4, BiTaO4, and LaTaO4.
FE gate oxides utilized in FETs open up the
opportunity of high-density single-transistor (1T)
non-volatile, non-destructive read-out (NDRO)
memories and adaptive-learning analog memories
in arti®cial neural networks [241]. For this
purpose, metal±ferroelectric±semiconductor (MFS)
or metal±ferroelectric±insulator±semiconductor
(MFIS) stacks have to be realized. In order to over-
come the stability problem of oxides on Si, McKee
et al. developed a two-step MBE process to deposit
SrTiO3 epitaxially on Si (001) exploiting a layer-by-
layer energy minimization at the interface [242]
(Fig. 17). This procedure follows a concept which
was developed recently in an atomistic modeling
study [243] underlining the growing importance of
computer-based modeling as emphasized in Section
3.3. The ®rst atomic layer is grown by MBE depo-
sition of the alkaline earth metal on the Si surface
at high temperature (8508C) leading to silicide for-
mation, followed by subsequent perovskite layers
grown at much lower temperature (2008C) with
oxygen being introduced at appropriate intervals.
Only by this procedure could the interfacial for-
mation of SiO2 be avoided. Recently, the technique
has been used to deposit ferroelectric BaTiO3 on Si
[244]. In MFIS devices, a thin insulator layer,
usually SiO2 complemented by another binary
oxide, is deliberately placed between the semicon-
ductor and the ferroelectrics. The theory behind
this approach has been described in Watanabe
[212]. Experimental results have been reported in
Refs [245±247].
Stacks of ultrathin epitaxial ®lms can be depos-
ited to generate arti®cial superlattices which, typi-
cally, are thermodynamically metastable, kinetically
stabilized materials. For example, SrTiO3/BaTiO3
of di€erent periodicity [248, 249] as well as SrTiO3/
PbTiO3 have been reported [250]. In a few cases, an
enhancement of the permittivity and a weak tem-
perature dependence was observed and it has been
speculated that this is due to freezing the soft mode
in these strained superlattices by the compressive
stress in the BaTiO3 layers [248]. The formation of
arti®cial superlattices has been used intensively in
the HTSC area [251]. Driving forces for these stu-
dies have been: (1) the idea to create new materials
with improved HTSC properties and (2) the ®nding
that the insulating Bi±Sr-oxide layers in the
Bi2Sr2CaCu2O8 show intrinsic Josephson e€ects
between the superconducting Cu-oxide layers [252].
Based on this concept, arti®cial superlattices helped
to develop the theoretical understanding of the
transport mechanism in HTSC [253].
 SETTER and WASER: ELECTROCERAMIC MATERIALS
4.3.2. Lateral nanostructuring. The reduction of
the future size to the sub-100 nm will outrange the
conventional photolithography that is limited by
the wavelength. However, an extension of photo-
lithography towards u.v. laser standing wave based
atom beam deposition in combination with holo-
graphic pattern generation or the opportunities of
optical near ®eld techniques may lead into large-
area nanostructuring techniques. Another option is
seen in the mechanical transfer of the structures
into thermoplast coatings of the wafer by imprint.
The mold used for this nanoimprint lithography
technique is made by electron-beam lithography.
This technique can be combined with self-assembled
monolayers (SAM) which are based on a chain
molecule with an anchor function on one side and a
hydrophilic or hydrophobic side [266].
This technique has been employed for an area-
selected deposition of high-k dielectric thin ®lms
onto Si wafers [265]. Although this work is still on
the micrometer scale, it has the potential to utilize
the nanoimprint technique for electroceramic thin
®lms.
Self-patterning e€ects can be used for selected
material combinations. PLD-grown Bi-excess ferro-
electric Bi4Ti3O12 ®lms on LSCO electrodes were
processed at high temperatures. This led to the self-
assembling of Bi-oxide-based nanoelectrodes on top
of the ferroelectric ®lm [267]. Recently, the polariz-
ation switching of a macroscopic collection of these
nanoscale FE cells has been demonstrated [268].
The measurement of individual cells without an on-
chip charge ampli®er remains a challenge due to the
extremely small total charge (approximately 2000
electrons).
For R&D purposes, the large-area, low-cost
structuring is not required, and, instead, focussed
structuring methods such as electron-beam lithogra-
phy or focussed ion beam etching (FIB) can be
used. Electron-beam lithography has been employed
recently to fabricate cells of 100  100 nm2 from
SBT and PZT thin ®lms [269]. FIB has been used
to fabricate cells of 100  100 nm2 to 1  1 mm2
from CSD prepared Nd-doped PZT ®lms of 120 nm
thickness, followed by a characterization of the fer-
roelectric properties by means of an AFM [270].
The authors show that there are no deteriorating
scaling e€ects down to the minimum cell size they
have studied and, hence, no intrinsic limitations for
the FeRAM device to be extended into the GBit
regime.
5. CONCLUSIONS
In this paper we o€ered a concise overview of the
status and the prospects of electroceramic materials.
We summarized the trends as seen from our indi-
vidual point of view and tried to elaborate routes
that may guide developments during the onset of
the new millennium.
173
Although new materials may well continue to
revolutionarize the ®eld as, for example, HTSC did
in the past, we conclude that the major electrocera-
mic material systems are known and quite well opti-
mized. In the last 50 years, this work unfolded the
enormous potential of oxide ceramics based on
unique dielectric, ferroelectric, piezoelectric, pyro-
electric, ferromagnetic, magnetoresistive, ionically
conducting, electronically and superconducting,
grain boundary barrier controlled, electro-optic and
gas-sensitive properties. Currently, we observe a
change in the paradigm. The materials-oriented
research is replaced by more interdisciplinary and
method-linking work. (1) The integration of di€er-
ent materials, (2) the detailed theoretical treatment
of materials and components as well as (3) the
exploitation of nanosize e€ects and nanotechnology
will gain further emphasis. These three ®elds are
closely interlinked. For example, utilizing electro-
ceramic thin ®lms in microelectronics includes tasks
of materials integration such as mechanical stress
matching, control of interface reaction, and appro-
priate annealing conditions. However, for the same
goal, a comprehensive model of the integrated ®lm
must be developed and incorporated into the device
and circuit simulators of the semiconductor indus-
try. For an in-depth physical understanding this
should, at one time in the future, be complemented
by an atomistic modeling of the major regions in
the device such as the electrode interface and grain
and domain boundaries, with respect to relevant
issues such as the crystallographic structure, the lat-
tice dynamics, the electronic band structure, and
the transport properties. Upon further reduction of
the feature size and an increase of the density,
nanosize e€ects such as the intrinsic dead layer at
boundaries of polar materials gain importance. In
addition, nanotechnological methods will take over
once and, again, bring new challenges for materials
integration and modeling.
We are convinced that linking of the three areas
will be essential as the fascinating ®eld of electro-
ceramic materials continues to grow into the future
and will unfold new application domains.
AcknowledgementsÐThe authors would like to thank their
colleagues for stimulating discussions, suggestions and, in
many cases, for the permission to use their papers prior to
publication. In particular, we would like to thank, in
alphabetical order, L. Gauckler, W. GruÈnwald, R. Jansen,
A. I. Kingon, J. Maier, J. Mannhart, G. L. Messing, R.
Tenne and H. L. Tuller. We are also grateful to P.
Muralt, A. K. Tagantsev, S. Ho€mann, U. BoÈttger, H.
Kohlstedt and S. Bluegel for reading and correcting var-
ious parts of the manuscript, and to M. Garcia for assist-
ance in preparing and assembling the manuscript.
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