Abs Part2 PDF

10
th
European Meeting on Ferroelectricity 2003
127
The Specific Heat of the
Urea/Alkane Inclusion Compounds
Around the Structural Phase
Transition
A. FRAILE-RODRGUEZ
1,A
, L. RUBIO-PEA
2
AND
A. LPEZ-ECHARRI
3
.
1
Dpt. of Physics. Uppsala University. Box 530, S-751 21
Uppsala, Sweden anmprupel@lg.ehu.es
2
Dpto. de Fsica Aplicada II.
3
Dpto. de Fsica de la Materia Condensada.Facultad de
Ciencias, UPV/EHU, Apdo. 644, 48080, Bilbao, Spain.
Urea inclusion compounds are composite materials of
particular interest because of their structural and dynamical
properties. In the case of the alkane derivatives, the helical
ribbons of the urea host substructure are only stable for
relatively long guest hydrocarbon chains (above n-hexane)
[1]. Most of these compounds exhibit several phase
transitions [2]. In particular we are concerned with the
phase transition from the high temperature orientationally
disordered phase to a phase in which the orientation of the
guest molecules shows a herringbone-like pattern and the
host substructure is slightly distorted from hexagonal to
orthorhombic symmetry. These transformations are also
associated with an abrupt change in the conformational and
vibrational properties of the guest molecules.
Here we present a calorimetric study of the structural
phase transitions undergone by the nonadecane and
heptadecane urea inclusion derivatives, including both
normal hydrogen and full deuterated compounds. Various
calorimetric techniques such as conventional DSC
measurements, together with adiabatic and AC calorimetry
were used in order to determine the phase transition
temperatures, the specific heat behaviour around the phase
transition temperatures and the associated thermodynamic
functions. In all the cases, DSC and AC calorimetric results
have revealed some unexpected anomalies around the phase
transition temperatures [3]. Some of these features were just
on the limits of the experimental resolution and only
accurate adiabatic measurements were found to be able for
an adequate physical characterization. The phase transition
temperatures usually depend on the hydrocarbon chain
length but are quite similar in nonadecane and heptadecane
crystals (about 159 K). However, the isotopic effect lowers
the transition temperature from that of the normal hydrogen
compounds (about 8 C in the case of the nonadecane).
Finally, it should be pointed out the strong dependence of
the specific heat on the heating or cooling rates and on the
thermal history of the various samples.
[1] A. E. Smith, Acta Cryst., 1952, 5, 224
[2] R. Forst, H. Boysen, F. Frey, H. Jagodzinski, C. Zeyen,
J. Phys. Chem. Solids, 1986, 47, 1089
[3] A. Fraile-Rodrguez, I. Ruiz-Larrea and A. Lpez-
Echarri, Eur. Phys. J. B, 2001, 24
Complex Elastic Properties and
Piezoelectric Activity in
Stoichiometric and Congruent
LiNbO
3
Single Crystals
I. FRANKE, J.P. SALVESTRINI*, M.D. FONTANA* AND
K. ROLEDER,
Institute of Physics, University of Silesia, ul.
Uniwersytecka 4, 40007 Katowice, Poland
* Laboratory MOPS, FRE CNRS 2304, University of Metz
and Suplec, 2 rue E. Belin, 57070 Metz, France
ifranke5@us.edu.pl
Lithium niobate based single crystals possess large
electrooptic effect and non-linear optical properties. These
are attractive materials to be used as electrooptic
modulators, switches, optical parametric oscillators, volume
holographic memory etc..
In the electrooptical effect the piezoelectric
phenomenon plays an essential role. The electrooptical
effect is considered as a sum of three components,
contribution of which depends on the frequency of the
modulating electric field in relation to frequency of the
acoustic resonance, lattice phonons and electrons [1]. In
practical application, modulating field is of frequency lower
than acoustic resonance and the piezoelectric effect decides
of the magnitude of secondary electrooptical effect. This
secondary effect, described as a sum of products of
photoelastic and piezoelectric tensors coefficients,
frequently preponderates over the electronic and lattice
contributions. That is why the knowledge of piezoelectric
activity is indispensable to observe and evaluate
electrooptic effect for low-frequency field.
It is also known that the electrooptical properties of
LiNbO3 strongly depend on crystal composition [2].
Progress made in crystal-growth techniques enable a better
control of chemical composition. Experiments have been
performed on two types of samples cut from the
stoichiometric (Li/Li+Nb=50 mole %) and congruent
(Li/Li+Nb=48.6 mole %) crystals in order to investigate the
influence of defects existing in these crystals on the
piezoelectric and elastic properties. The piezoelectric effect
allowed determining the elastic properties in the complex
form. Especially the imaginary part of elastic coefficient
can bring direct information about acoustic attenuation.
Observations of the piezoelectric activity enabled
determination of temperature dependence of the complex
elastic coefficient s*
11
.
Measurements of piezoelectric resonance by means of
dynamic method have been performed for both types of
LiNbO3 single domain single crystals in the temperature
range 20-180
o
C. It was found that the imaginary part s''
11
undergoes more anomalous behaviour with temperature
than the real part s '
11
. Differences in the s''
11
(T) runs
obtained are discussed from the point of view of nature of
defects existing in stoichiometric and congruent samples.
[1]: P. Gnter, ed., Electrooptic and Photorefractive
Materials (Springer-Verlag, Berlin, 1987)
[2]: T. Fujiwara et al. Comparison of electrooptic effect
between stoichiometric and congruent LiNbO3 .
Electronic Letters, 35, no.6, 499-500, (1999)
10
th
128
Photorefractive Self-focusing and
Spatial Solitons: From Theory to
Applications
N. FRESSENGEAS, D. WOLFERSBEGER, C. HESSE,
N. KHELFAOUI AND G. KUGEL
Laboratoire Matriaux Optiques, Photonique et Systmes,
CNRS-FRE 2304, 2 rue E.Belin, 57070 METZ, France,
Nicolas.Fressengeas@Supelec.fr
Photorefractive self-focusing and spatial solitons have
been evidenced in photorefractive media more than a
decade ago. Since then, intense theoretical and
experimental work has been undertook by the international
community to understand and master the complex
mechanisms which sustain these phenomena, in order to
carry out applications among which waveguide encryption
and all-optical routing are the most reported.
However, photorefractive materials exhibit a
nonlinearity of their own, both in space and time, which
leads to the existence of different self-focusing regimes
which in turn yields three distinct types of spatial solitons:
screening steady-state solitons, quasi-steady-state and
photovoltaic solitons. Mastering the transition from one to
the other is the key to the applications of photorefractive
self-focusing because it allows the fast re-configuration
properties one might expect from telecommunication
devices.
This talk will thus provide a detailed overview of the
theoretical background that allows the description of the
time and space behaviour of self-trapped beams in
photorefractive media, showing the origins of the process,
from the nanosecond regime up to steady-state. The
existence curves of steady-state and quasi-steady state
solitons will be retrieved from a unique time resolved
theory, whereas photovoltaic solitons will be shown to be
mathematically equivalent to steady-state ones. A specific
model devoted to very short excitation times will be
detailed and its connexions to the previous one investigated.
Experimental evidence will then be produced in order
to validate the theoretical considerations presented
above. Particular focus will be given to evidencing the
ability of photorefractive materials such as Bi12TiO20 and
SrxBa1-xNb2O6 to respond to nanosecond stimulation.
Emphasis will be brought on an unexpected application
to which our laboratory has given much interest: optical
limiting. Photorefractive materials will be shown to be able
to protect the detectors in optical systems with an
intermediate focal plane from intense radiation with a very
low threshold as compared to existing system. The system
has been tested with a Bi12Ti O20 crystal and optimized
using a SrxBa1-xNb2O6. Though self-focusing was thought
to be at the origin of optical-limiting, the optical branching
phenomenon due to modulation instability in SrxBa1-xNb2O6
has been shown to arise and to favour the optical limiting
application.
Finally, this talk will be concluded by an emerging
research fi el d: phot orefract i ve sol i t ons at
telecommunication wavelength, using, in particular, semi-
conductors such as InP:Fe and the resonance intensity they
exhibit.
Growth of RuO
2
and SrRuO
3
Conductive Oxides by Metal
Organic Chemical Vapour
Deposition
K. FROHLICH
1
, K. HUSEKOVA
1
, D. MACHAJDIK
1
,
V. CAMBEL
1
, P.K. BAUMANN
2
, J. LINDNER
2
,
M. SCHUMACHER
2
1
Institute of Electrical Engineering, SAS, Dbravsk cesta
9, 842 39 Bratislava, Slovak Republic
2
AIXTRON AG, Kackertstr. 15-17, D-52072 Aachen,
Germany
We have prepared RuO2 and SrRuO3 conductive oxides
by metal organic chemical vapour deposition using TriJet
TM
liquid precursor delivery technology of AIXTRON AG and
thermal evaporation technique. X-ray diffraction analysis
of the RuO2 films grown at high deposition temperature
(TD = 500 C) showed epitaxial growth on SrTiO3, LaAlO3,
MgO and r-plane cut Al2O3 single crystal substrates. Room
temperature resistivity of the films on various substrates
varied between 30 and 40 cm. The best parameters were
obtained for epitaxialy grown RuO2 film on the r-plane cut
Al2O3 substrate with a room temperature resistivity
300 = 30 cm and residual resistivity ratio (resistivity
ratio between room temperature and 4.2 K) above 30. The
RuO2 films grown at low deposition temperature (TD =
250 C) on patterned Si/SiO2 substrates exhibited highly
conformal growth.
The SrRuO3 films grew epitaxialy on SrTiO3 and
LaAlO3 substrates at temperatures above 700 C.
Polycrystalline SrRuO3 films were prepared at deposition
temperatures below 500 C on Si/SiO2 substrates. RuO2 and
SrRuO3 conductive oxides films are promising candidates
for electrodes in ferroelectric random access memories.
10
th
129
Ferroelectric and Non-ferroelectric
Contributions to Piezo- and
Pyroelectricity in Polyamide 11
PETER FRBING
1
, ALEXANDER KREMMER
1
,
WERNER NEUMANN
1
, IAN L. GUY
2
, AND
REIMUND GERHARD-MULTHAUPT
1
1
Department of Physics, University of Potsdam, 14469
Potsdam, Germany,
E-mail: fruebing@rz.uni-potsdam.de
2
Department of Physics, Macquarie University Sydney,
NSW 2109, Australia
It is known that the odd-numbered polyamides may
form ferroelectric domains, where the polymer chains are
aligned in parallel in the plane of the film and the amide-
group dipoles are oriented perpendicular to them, also in the
film plane. The amide groups are linked by hydrogen
bonds. This structure is called doubly oriented hydrogen-
bonded sheet structure [1].
Ferroelectric polyamide-11 films were prepared by
melting powder (RILSAN
B) in a hot press at 200 C,

quenching in ice-water, uniaxial drawing with a ratio of 3:1
and subsequent electrical poling up to 200 MV/m at room
temperature. The films show ferroelectric hysteresis with a
remanent polarisation of up to 35 mC/m
2
and a coercive
field of 75 MV/m at room temperature. Piezoelectric d33
coefficients were determined from thickness-extension
resonances in the dielectric spectrum as well as by
interferometrical measurements. Pyroelectric coefficients
were determined by quasistatic pyroelectrical
measurements. The piezoelectric d33 coefficient and the
pyroelectric coefficient are reduced by heating the film just
below the melting region (170 C), but remain at about 3
pc/N and 8 C/(m
2
K), respectively, during further heat
treatment.
Differential scanning calorimetry (DSC), dielectric-
relaxation spectroscopy (DRS) and thermally stimulated
depolarisation (TSD) are applied for investigating the
conformational changes induced by melt-quenching, cold-
drawing and annealing. The results indicate that the cold-
drawn film mainly consists of a rigid amorphous phase
which exhibits considerably lower conductivity, no glass
transition and consequently no associated dielectric
relaxation ( relaxation). Instead, a relaxation at higher
temperature (r relaxation) is found, which is supposed to
be related to chain movements in regions of the rigid
amorphous phase where the amide-group dipoles are not
perfectly ordered. Annealing removes the r relaxation and
restores the relaxation, but does not affect the
ferroelectric polarisation. Therefore, it may be concluded
that it is essentially the r relaxation that causes the
thermally non-stable part of the piezo- and pyroelectricity
in polyamide 11.
[1] J. I. Scheinbeim, and B. A. Newman, Electric Field
Induced Changes in Odd-numbered Nylons, Trends in
Polymer Science, vol. 1, pp. 394-400 (1993)
Frequency Dependence of
Polarization Hysteresis Loop in
CaBi
4
Ti
4
O
14
Ferroelectric Thin
Films
DESHENG FU, HAZUYUKI SUZUKI, AND KAZUMI KATO
Ceramics Research Institute, AIST, 2266-98 Anagahora,
Shimoshidami, Moriyama-ku, Nagoya 463-8560, Japan.
Email: desheng-fu@aist.go.jp
Ferroelectric thin films are currently attracting
worldwide attention due to their applications to the new
generation of novel devices, in particular to the nonvolatile
ferroelectric memories. Bi-based ferroelectric materials are
regarded as potential materials for memory applications due
to their good fatigue property and high leakage resistance.
The ferroelectric properties of the thin film are generally
evaluated from the hysteresis by electric measurements.
Usually, the measurements are performed at constant
frequency using a commercially available instrument, and
the frequncy dependence of polarization hysteresis is lack
of understanding. In this study, we used a modified Sawyer-
Tower circuit to measure the hysteresis and study its
frequency dependence. The samples used in the study was
CaBi4Ti4O15(CBT) thin film with a thickness of about
100 nm. We revealed that the hysteresises of CBT film
were frequency dependent. As shown in the following
figure, in the frequency range from 10 Hz to 100 kHz, both
the maximum and remanant polarizations decreased as
increasing the frequency. On contrast, the coercive field
increased with the increase of frequency. These results
indicate that the frequency dependence of ferroelectric
properties must be considered for the practical device
applications.
Fig. 1 Frequency dependence of hysteresis in
CaBi4Ti4O15 film.
10
th
130
Fig. Retention properties
of Pt/YMnO3/Y2O3/Si
capacitor. (a) as-depo., (b)
N2 annealed, (c) O2
annealed for 3 min, (d) O2
annealed for 6min.
Light Deflection Study of the
Formation Process of the
Ferroelastic Domain
YASUHIRO FUJII
1
, SHINYA YOSHIOKA
2
AND
SHUICHI KINOSHITA
2
1
Dep. of Physics, Graduate School of Science, Osaka
University
2
Graduate School of Frontier Biosciences, Osaka
University, 1-1 Machikaneyama, Toyonaka, Osaka 560-
0043, Japan, fujii@fbs.osaka-u.ac.jp
When a crystal undergoes ferroelastic phase transition,
an acoustic phonon mode softens to cause the elastic
instability. While the elastic fluctuation diverges towards
the transition point, the static ferroelastic domain structure
having the width of several 10 microns appears just below
the transition temperature. Thus it seems mysterious how
such dynamical properties change into static domain
structure at the phase transition point.
In the present paper, we have studied the domain
formation process of Rochelle salt by means of the
deflection of light. Rochelle salt undergoes
ferroelectric/ferroelastic phase transition at Tc=24
o
C. In the
low temperature phase, light is deflected at each domain
boundary and creates complex patterns in the far field,
because the optical indicatrices differs between adjacent
domains. [1] The intensity of the deflected light is
proportional to u
2
, where u denotes the spontaneous strain.
Since the deflected light is quite sensitive to the inclination
of the principal axis, extremely small strain could be
detected by this method. Further, the optical interference
among many boundaries produces the complex spatial
pattern which includes the information of various properties
of domains, such as positions, number or tilt of domain
walls.
We have found that the temperature dependence of the
intensity of the deflected light deviates considerably from
that expected from the phenomenological theory above Tc-
0.1
o
C, while it obeys Tc-T below Tc-0.1. Furthermore,
small amount of deflected light has been observed even in
the high temperature phase up to Tc+0.1
o
C, where the
domain structure should not exist. It is also found that 24
hrs. annealing at 3
o
C above Tc does not change the
interference pattern. These peculiar features suggest that
some reproducible embryotic domain exists even in the
high temperature phase.
To explain these results, we consider the model which
takes into account small amount of static stress distribution
inside a crystal. We then simulate the domain formation
process introducing the strain-stress coupling term in
Landaus phenomenological free energy. It is found the
presence of small static stress considerably affects the
generation of spontaneous strain in the vicinity of Tc,
because the elastic fluctuation diverges toward Tc, while it
does not work eventually at the temperature far from Tc.
The simulated temperature dependence of u
2
is in good
agreement with the peculiar behavior of the deflected light
intensity near Tc.
[1] Tsukamoto et. al, J. Phys. Soc. Jpn. 51, 3948 (1982)
Origin of the Retention Property of
YMnO
3
based MFIS Capacitors
NORIFUMI FUJIMURA, DAISUKE ITO AND
TAKESHI YOSHIMURA
Dept. of Applied Materials Science, Graduate School of
Eng., Osaka Prefecture Univ., Osaka, JAPAN
fujim@ams.osakafu-u.ac.jp
We have investigated (0001)YMnO3/(111)Y2O3/(111)Si
structure as MFIS type ferroelectric gate FET and
succeeded in fabricating YMnO3 epitaxial films with 2Pr of
3.4 C/cm
2
on (111)Pt/sapphire substrates and epitaxially
grown (0001)YMnO3/Y2O3/Si capacitors with ferroelectric
type C-V hysteresis loops. By optimizing the sample
structure, the saturation of the memory window was
observed at the same value of twice coercive voltage of the
YMnO3 epitaxial films. This indicates that sufficient
voltage was applied to the YMnO3 layer in the
YMnO3/Y2O3/Si capacitors. We have also demonstrate that
the YMnO3 films could be fully polarized above 13 V even
in the MFIS structure. This sample seems to be suitable to
study the relationships between retention property and state
of polarization or leakage current density. This paper
describes the influence of the polarization and leakage
current behaviors on the retention property of the epitaxial
YMnO3/Y2O3/Si capacitors
The Y2O3 epitaxial films with a thickness of 20 nm
were deposited by a pulsed laser deposition (PLD) method.
The deposition of YMnO3 films was also carried out by the
same system. The thickness of films was fixed at 300 nm.
The I-V, I-t, C-f, C-V, C-t and ICTS measurements were
conducted using MFIS configuration in the temperature
range from 20 to 100 C.
The ferroelectric type C-V hysteresis with the memory
window saturated at 13 V was obtained. The memory
retention time of the sample was significantly affected by
the polarization state of the YMnO3 film. The retention time
of the MFIS with fully polarized YMnO3 was more than
10
4
sec. Detailed analyses of temperature dependence of
I-V, I-t, C-f, C-V, C-t and ICTS measurements reveal that
the origin of the leakage current density at high electric
field (>4 V) is Poole-Frenkel emission caused by existence
of Mn
4+
, which is due
to the excess oxygen.
At the lower applied
electric field, however,
Schot t ky emi ssi on
became dominat. As the
leakage current density
of the as-deposited
capaci t or can be
controled from 10
-10
to
10
-8
A/cm
2
at 3 V, the
relationship between
the retention time and the
l eakage cur ent wer e
performed. As shown in
Fi gur e, t he di s t i nct
relationship between these
properties is recognized. The
origin of the vanishment of
memory retention will be presented.
10
th
131
PFM Observations of Switching
Behavior in Ferroelectric
Capacitors with Epitaxial
Pb(Zr,Ti)O
3
Thin Films
HIRONORI FUJISAWA, TATSUYA YAGI,
MASARU SHIMIZU AND HIROHIKO NIU
Department of Electrical Engineering and Computer
Sciences, Himeji Institute of Technology, 2167 Shosha,
Himeji, Hyogo 671-2201, Japan
fujisawa@elnics.eng.himeji-tech.ac.jp
Understandings of switching behavior in ferroelectric
thin films are important especially for non-volatile memory
applications because polarization switching is used as read
and write operations. In-situ observation of domain motions
is one of the most comprehensible method to understand
switching behavior experimentally. However, for thin films,
the in-situ observation of ferroelectric domains during
switching period is very difficult. Therefore, ex-situ
observation after a removal of external fields will be the
best way to observe polarization switching. In this study,
switching behavior in ferroelectric capacitors with epitaxial
Pb(Zr,Ti)O3 (PZT) thin films was evaluated by applying the
Ishibashi theory to ex-situ PFM (piezoresponse scanning
force microscopy) observations of domain structure of
partially switched capacitors after applying switching
pulses shorter than the switching time. Switching transient
currents were also evaluated during the partial switching.
100-500nm thick PZT thin films were epitaxially grown
on SrRuO3/SrTiO3(100), (110) and (111) by metalorganic
chemical vapor deposition (MOCVD). Pt or Ir top
electrodes (=50m, t=100nm) were fabricated by
sputtering. Switching pulses (2-8V and 10ns-1ms) were
applied between top and bottom electrodes and domain
structure was observed by PFM through top electrodes. The
RC time constant of the PFM system was less than 20ns.
From PFM images after applying switching pulses of
200kV/cm and 30-100ns to Pt/tetragonal PZT
(250nm)/SRO/ STO(100) capacitors, the switching time
and domain wall velocity were obtained as 70ns and 8m/s,
respectively. A fraction of switched domains to the scanned
area increased from 9 to 83% as the pulse width increased
from 30 to 80ns and can be described with a good
agreement by the Ishibashi theory. By applying the
Ishibashi theory to experimental results, it was found that
new nucleation occurred during the switching period and
that a nucleation rate was 43s
- 1
m
-2
. In addition, the
switching time and shape index obtained from PFM
observations agreed well with those from switching
transient currents.
Comparing characteristic values of polarization
switching of PZT capacitors with those reported in BaTiO3
single crystals, it was found that new nucleation was
dominant rather than the lateral domain growth in
polarization switching of PZT thin films.
Details of switching behaviors in ferroelectric
capacitors with (110) and (111)-orientated PZT thin films
will also be presented at the conference.
Temperature Dependence of
Structures and Order Parameters
in Antiferroelectric PbHfO
3
HIDESHI FUJISHITA
1
, YUYA ISHIKAWA
1
, AKIRA
OGAWAGUCHI
1
, KENICHI KATO
2
, EIJI NISHIBORI
3
,
MASAKI TAKATA
3
, MAKOTO SAKATA
3
1
Dept. of Physics, Kanazawa University, Kanazawa,
Japan; fujishit@kenroku.kanazawa-u.ac.jp
2
SPring-8/JASRI, Koto, Mikazuki-cho, Sayo-gun, Hyogo,
Japan
3
Dept. of Applied Physics, Nagoya University, Nagoya,
Japan
An order parameter is an atomic shift in structural phase
transitions. Its temperature dependence near Tc is described
by a phenomenological theory with Landau potential. Salje
et al. derived a quantum expansion of the potential.[1]
Recently we made X-ray and neutron diffraction of
antiferro-electric PbZrO3:[2] The antiferroelectric
3
(TO)
and the R25 superlattice-reflection intensities and the lattice
distortion showed the same temperature dependence below
room temperature, showing a remarkable saturation below
60K. Above room temperature, however, they indicated
rather different temperature dependences each other. These
dependences can be described well by the free energy based
on a group theoretical method, which includes the quantum
effect. The atomic shifts do not necessarily conform to a
simple concept of order parameter in soft mode
condensation. However the antiferroelectric phase transition
can be understood by the phenomenological theory if
applied over the whole temperature region. PbHfO3 is
isostructural with PbZrO3.[3] It undergoes two
antiferroelectric phase transitions. Recently we have
reported powder X-ray diffraction experiments of
PbHfO3:[4] Super-lattice-reflection intensities and lattice
distortions showed saturation below 60K. The temperature
dependence of the lattice distortions could be fitted well by
the dependencies obtained from a conventional and a
quantum expansion of phenomenological theory.
Superlattice-reflection intensities showed the similar
dependence on temperature as that of the lattice distortions.
Reflections associat-ed with a large cell volume appeared
between 435K and 480K instead of the antiferroelectric
reflection. Reflections at R-point remained in the
intermediate phase. To study the relation between atomic
shifts and the phenomenological theory, structure analyses
of PbHfO3 between 100K and 525K were performed using
synchrotron radiation. Squares of Pb shifts were found to
show the same dependence on temperature as that of the
lattice distortion. Phenomenological relations between order
parameters will be discussed. Back-ground level of X-ray
diffraction became very high in cubic phase,[4] which
means an existence of some kind of disorder. Disordered
arrangement of Pb atoms in the cubic phase, which was
recently reported in PbZrO3 [5], was also analyzed.
[1] E. K. H. Salje, Acta Cryst. A47, 453 (1991). [2] H.
Fujishita et al., J. Phy. Soc. Jpn., in print. Ferroelectrics
266, 27 (2002). ibid 258, 37 (2001). [3] D. L. Corker et al.,
Acta Cryst. B54, 18 (1998). [4] H. Fujishita and Y.
Ishikawa, Ferroelectrics 269, 135 (2002). [5] S. Aoyagi et
al., J. Phys. Soc. Jpn. 71, 2353 (2002).
10
th
132
Crystal Structure and Electrical
Properties of Epitaxial and
One-axis Oriented PZT Films
Having MPB Composition
HIROSHI FUNAKUBO
1
, SHINTARO YOKOYAMA
1
,
TAKAHIRO OIKAWA, YOSHIHISA HONDA
1
,
TAKASHI IIJIMAMA
2
, HIROFUMI MATSUDA
2
AND
KEISUKE SAITO
3
1 Dep.Innov.Eng.Mater., Tokyo Inst.Tech., G1-405, 4259,
Nagatsuta-cho, Midori-ku, Yokohama, 226-8502,
Japan. E-mail:funakubo@iem.titech.ac.jp
2 Smart Structure Center, AIST, 1-1-1 Umezono, Tsukuba
305-8568, Japan
3 XRD Section, Analytical Dep., PANalytical Division,
7-3 Hamamatsucho 1, Minato-ku, Tokyo, 105-0013,
Japan
MPB composition of PZT is well known to have superior
properties and was widely investigated for various
applications. Because of the existence of the polar axis,
crystal orientation dependence of the electrical properties at
MPB composition is expected, but the experimental
approach has been hardly reported. In the present study, I
will introduce the compositional dependence of the crystal
structure and the electrical properties for the MOCVD-PZT
films with the film thickness ranging from 50 nm-2000 nm.
200 nm-thick epitaxial PZT films were grown on (100),
(110) and (111) SrRuO
3
//SrTiO
3
substrates. {100}-, {110}-
and {111}- oriented epitaxially grown PZT films were
ascertained to be deposited on each substrates. Relative
dielectric constant,
r
, took maximum value near the MPB
composition regardless of the film orientation, which was in
good agreement with the data for the randomly oriented
sintered body. Crystal orientation dependence of
r
was
detected and (111) -oriented films took maximum values
for all composition. On the other hand, remnant
polarization took maximum values near MPB composition
for {111}-oriented films, but contrary minimum for {100}-
and (110)-oriented films.[1] Electric-field-induced strain
measurement of the 2000 nm-thick films also followed this
200 nm thick films data.[2]
These films were found to be consist of the mixed phase
of the tetragonal and rhombohedral PZT near MPB
composition by x-ray reciprocal space mapping.[3]
These are helpful to understanding the amorous
properties at MPB composition.
[1] T.Oikawa, M.Aratani, H.Funakubo, K.Saito and
M.Mizuhira, J.Appl.Phys., submitted
[2] K.Saito, S.Yokoyama, H.Morioka, T.Oikawa,
H.Funakubo (2003). Mat.Res.Soc.Proc., 748U13.4.1
[3] S.Yokoyama. Y.Honda, H.Morioka, T.Oikawa,
H.Funakubo, T.Iijima, H.Matsuda and K.Saito,
Appl.Phys.Lett., submitted.
Leakage Current Suppression of
Pt/Bi
4-x
La
x
Ti
3
O
12
/Ru Capacitors by
Post-annealing of Ru Films
T. FURUKAWA
1
, T. KUROIWA
1
, Y. FUJISAKI
1,2
,
T. SATO
1
, AND H. ISHIWARA
2
1 R&D Association for Future Electron Devices, 4259
Nagatsuta-cho Midori-ku, Yokohama 226-8503,
JAPAN
2 Frontier Collaborative Research Center, Tokyo Institute
of Technology, 4259 Nagatsuta-cho Midori-ku,
Yokohama 226-8503, JAPAN.
furukawa@neuro.pi.titech.ac.jp
Because fine ruthenium structures can easily be
fabricated by reactive ion etching, Ru is a promising
material for use in future ferroelectric random access
memory (FeRAM). Ruthenium deposited by the
metalorganic chemical vapor deposition (MOCVD) method
is attractive, particularly for the fabrication of MFMIS
structures, because we can expect a reduction of damage
induced in the insulating buffer layer. Moreover, good step
coverage of the MOCVD film might be necessary for the
fabrication of 3D-type FeRAM. We have already shown
that Pt/BLT/Ru capacitors using MOCVD-deposited Ru
exhibit good ferroelectric properties[1-2]. In this study, we
investigated the effects of Ru post-deposition annealing on
leakage current characteristics for the Pt/BLT/Ru
capacitors.
A ruthenium film was deposited on a SiO2/Si substrate
by MOCVD using Ru[EtCp]2 as a source material. We
were able to produce a smooth, flat Ru film with a
deposition temperature of 350C. Post annealing was
performed for the Ru film at 400C. Then, a BLT film was
formed by spin-coating using the sol-gel solution, which
was annealed for crystallization in a vacuum to suppress Ru
oxidation. Platinum electrodes were then formed by
electron beam evaporation through a metal mask.
Remanent polarization of a Pt/BLT/Ru capacitor
fabricated on a post-annealed Ru film remained unchanged
(20 C/cm
2
). However, leakage current density decreased
significantly to 1/100 of its original value by post-annealing
for 10 min, as shown in the figure below.
This work was performed under the auspices of the
R&D Projects in Cooperation with Academic Institutions
(Next-Generation Ferroelectric Memories), supported by
NEDO (New Energy and Industrial Technology
Development Organization in Japan) and managed by FED
(R&D Association for Future Electron Devices).
[1] T.Sato et al. Jpn. J. Appl. Phys. 41 2105 (2002).[2] T.
Furukawa et al. Abstract of ISIF 2003, 8.2.2-C (2003).
10
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133
Features of Incommensurate Phases
in Layered Ferroelectrics
Semiconductors
B.R. GADJIEV
Institute of Physics, National Academy Science of
Azerbaijan, 37000, 33 pr.Narimanova, Baku,
Azerbaijan Republic, bahruz17@yahoo.com
The characteristics of soliton regime of
incommensurate phase of layered ferroelectrics
semiconductors crystals are investigated. The space
dependence of the dielectric permeability and temperature
dependence of the thermodynamical function in
incommensurate phase is derived. The temperature
dependences of the light transmission coefficient, of the
intensity of the second harmonic generation, of the exitons
spectra and of the photoconductivity in layered
ferroelectrics semiconductors in soliton regime of an
incommensurate phase are determined. The comparative
analysis of theoretical results with experimental data for
layered crystals TlGaSe2 and TlInS2 is carried out. The
features inherent in an incommensurate phase in layered
crystals are revealed.
Raman Study of Ba
0.7
Ca
0.23
TiO
3
Crystals
P. GALINETTO
1
, E. GIULOTTO
1
, G. SAMOGGIA
1
,
V. TREPAKOV
2
, S. KAPPHAN
3
, R. PANKRATH
3
AND
L. JASTRABIK
4
1
Dip artimento di Fisica A. Volta, Univ ersit di Pavia an d
Istituto Nazion ale per la F isica della Materia, 271 00 Pav ia,
Italy
2
A.F . Ioffe Physical-T echnical Institute, 1940 21, St.
Petersburg, Russia
3
FB Physik , Univ ersity of Osnabrck, D-4 9069 O snabr ck,
Germany
4
In stitute of P hysics AS CR , 1822 1 Prah a 8, C zech R epublic
Congruently grown barium calcium titanate,
Ba0.77Ca0.23TiO3 (BCT77/23) can be fabricated as high
optical quality [1] single crystals, possess large electro-o ptic
coefficients an d high holog raphic sensitivity mak ing it
excellent candidate for various p hotorefraction based
app lications [2 ,3]. A nother great advan tage o f BCT is that the
tetragonal-orto rhombic phase tran sition , which is d estructive in
BaT iO3, is depressed in BCT 77/23 .
In the present work we report on Raman study of BCT
77/33 crystals have been performed in the temperature
region between 420K-10K. To our knowledge, this is first
Raman light scattering study of BCT 77/23. We believed to
gain insight on the nature of the cubic-tetragonal
ferroelectric phase transition (PT) in BCT 77/23, on the role
of Ca admixture, and search manifestations of the possible
low temperature tetragonal-orthorhombic PT has been
reported in [4].
A special attention was paid to detailed studies of the
low energy region 5 200 cm-1 and to temperature
evolution of A and E components of the 15 modes. A
detailed polarization analysis was performed. The
integrated intensities and bandwidth are deduced from
fitting analysis. The data regarding the cubic-tetragonal PT
are in agreement with previous results about dielectric
permittivity confirming the complex nature of these phase
transitions [4].
The Raman data at low er tem peratu res give no clear
ind icatio ns abo ut the occurrence of the T-O P T, at least down
to 10 K. In ad dition weak features aro und 10 0 cm-1 were
fou nd, wh ich are not observ ed in BaTiO3 matrix and probab ly
arising from th e presence o f Ca ions.
10
th
134
Cubic-tetragonal Phase Transition
in Ca
0.04
Sr
0.96
TiO
3
: A Combined
Specific Heat and Neutron
Diffraction Study
M.C. GALLARDO
1
, A.I. BECERRO
1
, F.J. ROMERO
1
,
J. DEL CERRO
1
, F. SEIFERT
2
AND S.A.T. REDFERN
3
1
Departamento de Fsica de la Materia Condensada.
Instituto de Ciencia de Materiales de Sevilla.
Universidad de Sevilla-CSIC, P.O. Box 1065, 41080
Sevilla, Spain
2
Bayerisches Geoinstitut. Universitt Bayreuth, 95440-
Bayreuth, Germany
3
Departament of Earth Sciences, University of Cambridge,
Downing Street, Cambridge CB2 3EQ, UK
The specific heat corresponding to the tetragonal to
cubic transition in Ca0.04Sr0.96TiO3 perovskite has been
measured by conduction calorimetry. The order parameter
of the transition has been obtained by means of neutron
diffraction at low temperatures. Comparison of calorimetric
data with the evolution of the order parameter indicates that
this transition seems to follow a mean field Landau
potential as in SrTiO3. The linear behaviour of the excess of
entropy versus temperature suggests that 2-4 Landau
potential is sufficient to describe the transition.
Preparation and Characterization
of Ferroelectric Mn:SLN and
Mn:Tb:SLN Single Crystals
GANESAN RAVI*, KENJI KITAMURA,
SHUNJI TAKEKAWA, MASARU NAKAMURA,
SOMU KUMARAGURUBARAN, RAMASAMY JAYAVEL
Advanced Materials Laboratory, National Institute for
Materials Science (AML/NIMS), 1-1 Namiki, Tsukuba,
Ibaraki 305-0044, Japan.
* Corresponding author: Ganesan.Ravi@nims.go.jp
The emergence of photonics for communications, data
storage, display and defence applications resulted from the
invention of new photorefractive materials. The crystal
growth of lithium niobate is perfected to an extent that high
quality single domain single crystals can be prepared. A
widespread technological application of this material
preceded a complete understanding of many of the
fundamental physical processes occurring in these crystals.
There are number of reports on lithium niobate crystals,
however lots of new and interesting results are still being
reported, in part because LiNbO3 has a nonstoichiometric
range and a variety of physical properties can be greatly
changed by controlling Li/Nb ratio. Since structures and
densities of intrinsic (non-stoichiometric) defects caused
due to Li/Nb ratio substantially influence the optical
properties, the relationship between the defects and
properties has been an important subject of investigation.
In the present study, growth aspects of optical quality Mn
doped and Mn&Tb co-doped near-stoichiometric lithium
niobate (SLN) crystals have been investigated for different
doping concentrations and good quality crystals have been
grown with optimized growth conditions. For doped SLN
crystals, the absorption edge is shifted to longer wavelength
side with the doping level. A change in Curie temperature
with respect to doping concentrations has been observed.
The effect of Mn doping on the dielectric and switching
properties has been analyzed. The results will be presented
in detail.
10
th
135
Temperature Dependence of Monte
Carlo Ising 4D Order Parameter vs.
Normalized Spontaneous
Polarization
J. GARCA, C. ARAG, J.A. GONZALO
Dpto. Fsica de Materiales. Universidad Autnoma de
Madrid. 28049 Madrid. Spain
Monte Carlo simulations on a 4D Ising model have
been performed providing information about the behaviour
of the temperature dependence of the susceptibility and
the order parameter S in the absence of external applied
field.
From S (T) we can also infer the character of the transition
at critical temperature TC given up by the strength of the
quadrupolar interaction term after the effective field
approach. The theoretical results are compared with
experimental data of the dielectric constant and the
normalized spontaneous polarization of ferroelectric
crystals like triglycine sulfate (TGS), and lithium tantalate
(LiTaO3).
Pulsed Laser Deposition and
Characterization of Nd-doped
Bi
4
Ti
3
O
12
Films
ASHISH GARG
1*
, ALAN SNEEDON
2
, PHIL LIGHTFOOT
2
,
XIAOBING HU
1
AND ZOE BARBER
1
1
Dept. of Materials Science and Metallurgy, Pembroke
Street, Cambridge CB2 3QZ, UK
2
School of Chemistry, University of St. Andrews, St.
Andrews, Fife, KY16 9ST, UK
* ashish_13@yahoo.com
Since the discovery of fatigue free La doped Bi4Ti3O12
(BLT) films, considerable interest has been shown in
studying the effects of various other rare earth dopants (e.g.
Nd, Sm) on the ferroelectric properties of this material for
applications in non-volatile ferroelectric random access
memories. We have grown Nd-doped films of composition
Bi3.15Nd0.85Ti3O12 by pulsed laser ablation. Films of
different crystallographic orientations (c-axis and non-c-
axis oriented) have been grown on various different
substrates to study the effect of the substrate orientation on
the film structure and ferroelectric properties. Films have
been characterized using X-ray diffraction and Atomic
Force Microscopy. Ferroelectric measurements have been
performed to invesitgate the dependence of film properties
on crystallographic orientation.
10
th
136
Dielectric Study on the Phase
Transitions in RbMgBr
3
and
Cs
2
MgBr
4
KAZUO GESI
Iwaki Meisei University, 5-5-1 Iino, Chuodai, Iwaki
Fukushima 970-8551, Japan
e-mail address: kazuo.gesi@nifty.ne.jp
Single crystals of RbMgBr3 and Cs2MgBr4 were grown
and the phase transitions have been studied by dielectric
measure-ments. The crystal RbMgBr3 is a member of the
hexagonal AX-Y3-type crystals which consist of infinite
chains of the [XY3
_
]n along the c-direction. Kirklin and
McPherson showed that Rb-MgBr3 undergoes a first order
transitions at 449 K and a diffuse transition around 228~235
K

[1]. The high-temperature phase (phase I) and the room-
temperature phase (phase II) have the hexagonal CsNiCl3
structure (space group: P63/mmc) and the KNiCl3 structure
(space group: P63cm), respectively. The lattice parameter a
= b in phase I is
3
times of that in phase I [1, 2]. On the
other hand, Kato et al. reported that phase transitions do not
exist between room temperature and 4.2 K [3]. So that,
there are contradicting data with respect to the phase
transitions of RbMgBr3. The crystal Cs2MgBr4 is one of the
orthorhombic A2XY4-type crystals of which normal phase
takes the K2SO4-II structure with the space group Pmcn [2].
Kato et al. found two phase transitions in Cs2MgBr4 at 125
K and 84 K from a birefringence measurement [4]. Whether
Cs2MgBr4 shows an incommensurate and a locked-in
ferroelectric structure as found in many A2XY4-type crystals
would be an interesting problem.
The temperature dependence of the dielectric constant
along the c-direction c of RbMgBr3 shows a step-like
anomaly at 500 K. As temperature decreases, c increases
and reaches a maxi-mum at 235 K, then it again decreases
at 225 K making a pla-teau between 235 K and 225 K. The
result indicates that there are three phase transitions in
RbMgBr3 at 500 K, 235 K, and 225 K. This is in agreement
with the result given by Kirklin and McPherson. However,
the anomaly around 225 K~235 K is not a single diffuse
transition but it corresponds to two phase transi-tions. The
temperature dependence of c is quite similar to that found
in the KNiCl3-group ferroelectrics [5]. This would imply
that RbMgBr3 is ferroelectric in the phase between 225 K
and 235 K alike KNiCl3. The effect of hydrostatic pressure
on the phase tran-sitions in RbMgBr3 will be also reported.
The temper-ature variation of the dielectric constant along
the b-direction of Cs2MgBr4 shows a kink at 125 K and a
discontinuous change at 84 K. This confirms the result by
Kato et al. In addition, how-ever, there is a small -type
peak in the dielectric constant along the c-direction at 50 K
indicating that there is an additional phase transition. At
present ferroelectric hysteresis loop has not been observed
along any of the three crystallographic axes in the phases
below room temperature.
[1] K. H. Kirklin and G. L. McPherson, J. Phys. C: Solid
State Phys., 16, 6539 (1083). [2] H. -J. Seifert and J. Wasel-
Nielen, Rev. Chim. Miner., 14, 503 (1977). [3] T. Kato et
al., J. Phys. Soc. Jpn., 61, 275 (1992). [4] T. Kato, private
communication. [5] K. Machida et al., Solid State
Commun., 91, 17 (1994).
Critical Thickness for
Ferroelectricity in Barium Titanate
Ultrathin Films
PHILIPPE GHOSEZ & JAVIER JUNQUERA
Dpartement de Physique (B5), Universit de Lige,
B-4000 Sart Tilman, Belgium
Philippe.Ghosez@ulg.ac.be, Javier.Junquera@ulg.ac.be
ABO3 ferroelectric perovskites are promising candidate
materials for Non-volatile Ferroelectric Random Access
Memories (FeRAM). While industry's demand for ultrahigh
density information storage imposes the reduction of cell-
sizes and thicknesses of the ferroelectric films, the
fundamental question concerning the possible existence of a
critical thickness for ferroelectricity becomes crucial.
Previous first-principles based effective hamiltonian
[1]
and
full first-principles calculations
[2]
predicted ferroelectric
ground states for ABO3 ultrathin films under zero-field
boundary conditions and suggested the absence of a critical
size. However, in these previous approaches, the role
played by the metallic electrodes on the structure and the
polarization of the system was not explicitely treated but
only implicitely included through particular electric and
mechanical boundary conditions.
Here, we report density-functional first-principles
calculations
[ 3]
on a realistic SrRuO3 /BaTiO3/SrRuO3
ferroelectric capacitor structure under short-circuit
boundary conditions. A critical thickness for
ferroelectricity
[4]
is identified and valued at 24 (six unit
cells of BaTiO3). A depolarizing electrostatic field, caused
by the existence of finite dipoles at the metal/ferroelectric
interfaces is responsible for the disappearance of the
ferroelectricity. Above the critical thickness, we recover a
polarized ground-state (although with a reduced
spontaneous polarization, only slowly converging to the
bulk value for increasing thicknesses) in good agreement
with experimental results
[5]
. A simple model, based on the
electrostatic of the system, is proposed to explain the
evolution of the ferroelectric properties with the film
thickness. Our results suggest a lower limit for useful
thicknesses of ferroelectric materials in electronic devices.
We hope that this work will stimulate experimental
groups on growing ultrathin perovskite films and on
measuring the thickness dependence of the polarization.
This work was supported by the VolkswagenStiftung
and the FNRS-Belgium.
[1] Ph. Ghosez and K.M. Rabe, Appl. Phys. Lett. 76, 2767
(1999)
[2] B. Meyer and D. Vanderbilt, Phys. Rev. B 63, 205426
(2001)
[3] Results were obtained using Siesta, J. Soler et al., J.
Phys. : Condens. Mat t er 1 4 , 2745 (2002);
http://www.uam.es/siesta .
[4] J. Junquera and Ph. Ghosez, Nature 422, 506 (2003).
[5] Th. Tybell, C. H. Ahn and J.-M. Triscone, Appl. Phys.
Lett. 75, 856 (1999)
10
th
137
The Morphotropic Phase Boundary
My Part in its Downfall
A.M. GLAZER
Clarendon Laboratory, Parks Rd., Oxford OX1 3PU
The so-called Morphotropic Phase Boundary (MPB)
was discovered first of all in the lead zirconate-titanate
(PZT) system, and a similar feature has been found since in
other ceramic compositions. The MPB coincides closely to
compositions for which piezoelectric activity is maximum,
and hence it is of importance to understand it in order to
design new piezoelectrics. Precisely what happens
structurally at the MPB has remained a mystery. However,
recently a great deal of attention has been focussed on the
discovery of a monoclinic phase at the MPB, and at last we
are beginning to understand the structures of these materials
in this region. In this talk I shall review the structural
evidence for PZT and suggest my own interpretation of
what I think is going on at the MPB.
New Approach to Ferroelectric
Nanomaterials and Thin Films
Description
MAYA GLINCHUK
1
, EVGENIY ELISEEV
1
,
ANNA MOROZOVSKAYA
1
, VLADIMIR STEPHANOVICH
2
,
LUBOMIR JASTRABIK
3
1
Institute for Problems of Materials Science, National
Academy of Science of Ukraine, Krjijanovskogo 3,
03142 Kiev, Ukraine, glin@materials.kiev.ua
2
Institute of Mathematics and Informatics, University of
Opole, 45-052 Opole, Poland
3
Institute of Physics, AS of the Czech Republic, Na
Slovance 2,182 21 Prague 8, Czech Republic
We suggest an approach to calculate the physical
properties of ferroelectric thin films and nanomaterials. Our
approach takes into account the depolarisation field, surface
tension and spatial inhomogeneity of the order parameter
inherent to these materials. Surface tension coefficient was
shown to be dependent on temperature via its relation to
dielectric permittivity of the materials. The solution of
corresponding EulerLagrange equation by the direct
variational method shows that the initial free energy
functional of a thin film and nanomaterials can be reduced
to some effective functional which does not include spatial
derivatives of the order parameter. The coefficients of this
new functional, however, are renormalized as compared to
those of the initial free energy functional. In particular the
coefficient before squared polarisation is shown to be
dependent on the size of nanoparticle or a film thickness,
temperature, contribution of depolarisation field and surface
tension coefficient. We present the detailed calculation of
the spontaneous polarisation, pyrocoefficient and dielectric
susceptibility. We analyse in details the spatial profile of
depolarisation field with special attention to its properties
near size-driven phase transition in a film and
nanomaterials.
10
th
138
Random Field Distribution
Function in the Relaxor
Ferroelectric Thin Films
MAYA GLINCHUK
1
, VLADIMIR STEPHANOVICH
2
,
EVGENIY ELISEEV
1
, LUBOMIR JASTRABIK
3
1
Institute for Problems of Materials Science, National
Academy of Science of Ukraine, Krjijanovskogo 3,
03142 Kiev, Ukraine, glin@materials.kiev.ua
2
Institute of Mathematics and Informatics, University of
Opole, 45-052 Opole, Poland
3
Institute of Physics, AS of the Czech Republic, Na
Slovance 2, 182 21 Prague 8, Czech Republic
The calculation of random field distribution function in
the relaxor ferroelectrics was performed in the statistical
physics framework. The point charges and electric dipoles
randomly distributed in Burns reference phase were
considered as the main sources of random electric field. The
influence of the surfaces was calculated in the model of
imaginary charges and dipoles distributed in all the space.
The contribution of these real and imaginary sources of
random field was taken into account. The characteristic
features of calculated random field distribution function
namely its half-width and the most probable electric field
value were shown to be dependent both on the field sources
parameters and on the dielectric permittivity of the
surrounding media and ferroelectric material. Since the
latter is known to depend drastically on the film thickness
and temperature the size and temperature dependence of
random field arises. In particular it was shown the decrease
of random field strength in the thin films comparatively to
that in the bulk. This speaks in favour of statement that the
degree of disorder in the thin films is smaller than in the
bulk. The developed theory forecasts the possibility of
transformation of the most disordered dipole glass state in
the bulk relaxor into mixed ferro-glass (FG) phase in the
film as well as FG phase in the bulk relaxor into
ferroelectric phase in the film.
Comparative Analysis of Averaging
Procedures for Two-component
Composites: Example of Porous
Ceramics
S. V. GLUSHANIN
1,2
, V. YU. TOPOLOV
1
AND
V. K. YATSENKO
2
1
Department of Physics, Rostov State University, 5 Zorge
St., 344090 Rostov-on-Don, Russia. E-mail:
topolov@phys.rsu.ru
2
Institute of Physics, Rostov State University, 194 Stachki
Ave., 344090 Rostov-on-Don, Russia. E-mail:
glushanin@newmail.ru
By now for piezoelectric composites with 3-0 and 3-3
connectivities there are different procedures of averaging
the effective physical properties that are based on self-
consistent methods [1, 2], Bannos unit-cell model [3, 4],
matrix method [4, 5], etc. Accuracy of methods being
applied for the two-component piezoelectric system with
hard difference in elastic, dielectric and piezoelectric
constants of components is not yet clear. On example of
porous PZT-type ferroelectric ceramics some averaging
procedures were applied for evaluation of the effective
piezoelectric coefficients, dielectric permittivity,
electromechanical coupling factors, and other parameters
depending on the volume concentration of pores and their
microgeometry. Our resultes are used for prognostication of
effective electromechanical properties of PZT ceramic -
polymer, PZT ceramic porous polymer and PZT
ceramic air composites with different connectivities.
[1] H. J. Huang, J. S. Yu, Compos. Eng. 4 (11), 1169-1182
(1994).
[2] Grekov, Kramarov, Kuprienko, Mekhanika Kompo-
zitnykh Materialov. N

1, 62-69 (1989). (in Russian).
[3] H. Banno, Ceram. Bull. 66 (9), 1332-1337 (1987).
[4] V.Yu. Topolov, S. V. Glushanin, J. Phys. D: Appl.
Phys. 35 (16), 2008-2014 (2002).
[5] E. Akcakaya, G. W. Farnell, J. Appl. Phys. 64 (9), 4469-
4473 (1988).
10
th
139
Dielectric and Pyroelectric
properties of NaK-L-Malic acid
single crystals
GNANASUNDARAM ARUNMOZHI
1
, E. DE MATOS
GOMES
1
, J.A. MENDES
1
, P.M.VILARINHO
2
, A.
CRIADO
3
1
Department of Physics, University of Minho, Campus de
Gualtar, Braga 4710, Portugal.
2
Departamento de Fisica de la Materia
Condensada,Universidad de Sevilla, 41080 Sevilla,
Spain
3
. Departamento de Engenharia Cermic e do Vidro,
Universidade de Aveiro, Portugal.
Dielectric and pyroelectric properties of Sodium
potassium malate, NaK-L-Malic acid (NaKM) single
crystals are reported in this communication. In the earlier
communication on the synthesized salt of the title
compound, DSC, dielectric and X-ray diffraction studies
were reported [1]. Small crystals of NaKM were grown
from saturated solutions at room temperature by slow
evaporation. Crystals grew with morphology identical to
UlMA (Urea L-Malic acid crystals)[2].
The dielectric and pyroelectric properties were studied
perpendicular to the monoclinic b-axis from 290K to 375K.
Dielectric analysis carried out at a constant heating rate of
0.2K/min showed a marked anomaly at 365K, which agrees
well with the DSC studies. A broad envelope was observed
in the temperature range 300K to 340K, accounting for the
anomalies observed in the DSC in this temperature range.
Samples were initially heated through the transition
temperature and then allowed to cool to room temperature
under a poling field (33V/cm). Pyroelectric measurements
were carried out at a constant heating rate of 1.5K/min and
the pyrocurrent measured. The spontaneous polarization
calculated from the measured pyrocurrent was found to be
45C/cm
2
. The spontaneous polarization studied on three
different samples showed similar values. Lower dielectric
permittivity and significant spontaneous polarization makes
this a promising material for potential applications. The
results and analysis of the dielectric and pyroelectric
properties of NaKM crystals in relation with the crystal
structure will be presented in detail.
This work has the financial support of FCT and POCTI
under the project POCTI/33657/FIS/2000
[1] G.Arunmozhi, E. de Matos Gomes, M.
Belsley,A.Criado, S.Perez-Garrido and F.Proena., 6th
European Conference on Polar Dielectrics held in Sept
2002 in Aveiro, Portugal .
[2] V.K.Dixit, S.Vanishri, H.L.Bhat, E.de M.Gomes,
M.Belsley, G.Arunmozhi, V.Venkataramanan,
F.Proena, A.Criado., to be published in Journal of
Crystal Growth (2003)
Pyroelectric Properties of AspTGS
Crystals
GNANASUNDARAM ARUNMOZHI, E. DE MATOS
GOMES, J.L. RIBEIRO, J.A. MENDES
Gualtar, Braga 4710, Portugal.
Triglycine sulphate (TGS) crystals have interesting
pyroelectric properties [1]. It exhibits a second order phase
transition with the Curie point at 49
o
C. The crystal belongs
to monoclinic system with the space group P21 in the
ferroelectric phase and P21/m in the paraelectric phase.
Doping of TGS with chiral compounds has been practiced
to overcome depolarization effects observed with time in
TGS [2]. In the earlier communication the low frequency
dielectric properties of TGS doped with a new dopant L-
asparagine and its influence on the dynamics of the TGS
system was reported [3]. Substitution of glycine with L-
asparagine was accounted for the decrease in the dielectric
permittivity of the doped crystal.
In this work, the pyroelectric properties of AspTGS is
reported. Crystals were grown by a slow cooling technique
from saturated TGS solution doped with 10 mole% of
L-asparagine. Small plates were prepared by cleaving the
crystal normal to the polar axis. Samples were heated
through the transition temperature and allowed to cool to
room temperature under a poling field greater than the
coercive field of the samples (450V/cm). At a constant
heating rate of 1.5K/min, the pyroelectric current was
measured with a 617 Keithley electrometer coupled to a
computer. From the measured pyrocurrent, the spontaneous
polarization was computed and was found to be
2.85C/cm
2
. There is no significant increase in the
spontaneous polarization of the doped crystal compared to
TGS. Despite the decrease in the dielectric anomaly of the
doped crystal, there is no significant influence of the doping
on the spontaneous polarization, which can be related to the
lower replacement of glycine by asparagine molecules. The
results obtained on AspTGS and the analysis compared to
pyroelectric properties of TGS will be discussed in detail.
This work has the financial support of FCT and POCTI
under the project POCTI/33657/FIS/2000
[1] A.G.Chynoweth, Phys. Rev., 117 (1960)1235.
[2] P.J.Lock Appl. Phys. Lett., 19(1971)390.
[3] G.Arunmozhi, E. de Matos Gomes and J.L.Ribeiro., 6th
2002 in Aveiro, Portugal.
10
th
140
Synthesis, DSC, SHG and Dielectric
Studies on Salts of L-Malic Acid
ARUNMOZHI GNANASUNDARAM, E. DE MATOS
GOMES, C. SANTINHA, F.P. FERREIRA, A.J. PEREIRA,
M. BELSLEY
Gualtar, Braga 4710, Portugal
This work is in continuation of our earlier
communication on Sodium-potassium L-Malic acid, which
exhibited dielectric anomalies in the temperature range
290K to 375K[1]. In this communication, salts of L-Malic
acid such as Potassium L-Malic acid (KM), Ammonium L-
Malic acid (AM) and Lithium L-Malic acid (LiM) were
synthesized from aqueous solution. Preliminary studies
such as Differential Scanning Calorimetry, Second
Harmonic Generation and dielectric studies were carried
out on the synthesized salts. Lithium-L-Malic acid salt did
not reveal any anomaly above room temperature until the
decomposition temperature (430K). Ammonium-L-Malic
acid salt showed a broad anomaly around 360K which
agrees well with the DSC studies. In the case of Potassium
L-Malic acid salt, the presence of a broad anomaly was
identified between 300K and 330K and a sharp anomaly
was observed around 365K. The dielectric anomalies are in
accordance with the DSC and are also found to be similar to
the reported NaKM salt.
Kurtz test for SHG were performed on sieved powders
of known particle dimensions (100-180 microns) and
compared with KDP of same particle size. SHG intensity of
KM, LiM, AM, NaKM was found to be approximately
10%, 23%, 1% and 60% the intensity of KDP respectively.
Among the salts, NaKM shows very promising SHG
intensity and can be of potential use in Laser applications.
[1] G. Arunmozhi, E. de Matos Gomes, M. Belsley,
A.Criado, S. Perez-Garrido and F.Proena., 6th
2002 in Aveiro, Portugal.
DIELECTRIC PROPERTIES OF
Na
0.5
Bi
0.5
TiO
3
BaTiO
3
CERAMICS
J.R. GOMAH-PETTRY
1
, P. MARCHET
1
, A. SIMON
2
, R.
VON DER MHLL
2
, M. MAGLIONE
2
, J.P. MERCURIO
1
,
1
SPCTS, UMR 6638 CNRS, Facult des Sciences et
Techniques, 123, Av. A. Thomas, 87060 Limoges
Cedex, France , marchet@unilim.fr
2
ICMCB CNRS, 87 Av. du Dr Schweitzer, 33608 PESSAC
CEDEX, France, rvdm@icmcb.u-bordeaux.fr
At the present time, the most widely-used piezoelectric
materials belongs mainly to the PZT solid solution system
(1-x) PbTixO3 x ZrTiO3 . Because of the possible
evaporation of lead oxides during the sintering of such
ceramics, lead-free or low lead content piezoelectric
materials are actually extensively investigated in order to
replace PZT based ceramics. Sodium bismuth titanate,
Na0.5Bi0.5TiO3 (NBT) could be a good candidate for this
purpose as this lead-free compound is ferroelectric at room
temperature up to about 255C. As for PZT ceramics, the
formation of solid solutions could be a way to improve the
electrical properties of such materials.
Therefore the (1-x) Na0.5Bi0.5TiO3 x BaTiO3 system
was studied. NBT is rhombohedral at room temperature
even though BaTiO3 (BT) is tetragonal. X-ray diffraction
diagrams revealed the presence of two solid solution
domains, separated by a two- phase range. One domain
extends from 0 to 10 mol% BT and has the rhombohedral
symmetry of NBT, the other starts at 15 mol% BT and
has the tetragonal symmetry of BT.
The evolution of the lattice parameters with
composition was measured in order to study phase
transition temperatures. A monotonic decrease of the
transition temperature was observed from about 300C for
NBT to 110 C for BT.
The variations of the permittivity with composition
revealed a strong maximum ( 1600 1 kHz) in the
biphasic domain, whereas the observed values are close to
400 for the rest of the system, excepted close to BT where a
rapid increase was observed.
The evolution of the permittivity with temperature
showed two transitions for the NBT-rich materials, as
already observed for pure NBT (210C and 330C). Both
temperatures decrease rapidly as the BT content increases.
Only one transition was observed for the tetragonal BT-rich
ceramics, the temperature of which decreases with
increasing BT content from about 250C to 110C for pure
BT.
In addition, a relaxor like behaviour was observed when
increasing the Ba content, the maximum amplitude of
which (Tm,HF - Tm,LF) being located in the midrange of
compositions (50-70 mol.% BT). The origin of such a
behaviour might be in close connection with the disordered
occupation of the A site of the perovskite cell. Further
investigations are in progress in order to (1) determine the
temperature and frequency evolution of this phenomenon
(2) study the polar behaviour of such materials.
10
th
141
Electrical Properties of
Na
0.5
Bi
0.5
TiO
3
SrTiO
3
Ceramics
J.R. GOMAH-PETTRY
1
, P. MARCHET
1
, A. SALAK
2
,
V.M.FERREIRA
2
, J.P. MERCURIO
1
1
SPCTS, UMR 6638 CNRS, Facult des Sciences et
Techniques, 123, Av. A. Thomas, 87060 Limoges
Cedex, France : marchet@unilim.fr
2
Dep de Eng Cermica e do Vidro, Universidade de
Aveiro, 3810-193 Aveiro, Portugal salak@cv.ua.pt
At the present time, the most widely-used piezoelectric
material belongs mainly to the PZT solid solution system
(1-x) PbTixO3 x ZrTiO3 . Because of the possible
evaporation of lead oxides during the sintering of such
ceramics, lead free or low lead content piezoelectric
materials are actually extensively investigated in order to
replace PZT based ceramics. Sodium bismuth titanate,
Na0.5Bi0.5TiO3 (NBT) could be a good candidate for such
applications because this compound is ferroelectric at room
temperature up to about 255C. As for PZT ceramics, the
formation of solid solutions could be a way to improve the
electrical properties of such materials.
In opposition to previous studies using ferroelectric
compounds such as PbTiO3 or BaTiO3, it could be
interesting to study the influence of a non ferroelectic
compound such as SrTiO3 in the formation of solid
solutions and in their electrical properties. So the (1-x)
Na0.5Bi0.5TiO3 x SrTiO3 system was investigated. NBT is
rhomboedral at room temperature even though SrTiO3 (ST)
is cubic. X-ray diffraction diagrams revealed that two solid
solution domains exists for this system, separated by a
morphotropic phase boundary at about 25-26 mol% ST. In
the first domain, the rhomboedral symmetry of NBT
remains. The second domain have the cubic symmetry of
ST.
The variations of the permittivity with composition was
studied and revealed a rapid increase with a strong
maximum ( 2100 1 kHz) for the MPB, followed by a
slow decrease for the ST rich part of the system.
The evolution of the dielectric permittivity with
temperature was also studied. Two transitions were detected
for the NBT rich part of the phase diagram, as for pure
NBT for which two transitions can be observed at 210C
and 330C. These two transition temperatures decrease
rapidly with the ST content. Only one transition was
observed for the cubic ST-rich part of the system. This last
phenomenon is shifted to low temperatures with ST content
and the temperature of the maximum is rapidly located
below room temperature for ST contents larger than
50 mol% ST.
In addition, a relaxor like behaviour occurs when
increasing the Sr content, the maximum amplitude of which
(Tm,HF - Tm, BF) being located in the midrange of
compositions (40-50 mol.% BT). Further investigations are
in progress in order to determine the origin of such a
behavoiur and its connexion with the polar state of the
materials as a function of composition.
Influence of complex impurities on
dielectric properties of KDP crystal
S.V. GRABOVSKY
1
, I.V. SHNAIDSHTEIN
1
,
B.A. STRUKOV
1
, S.-H. JANG
2
, B. KAHR
2
1
Lomonosov Moscow State University, 119992 Moscow
Russia, bstrukov@mail.ru
2
University of Washington, 351700 Seattle WA USA
The problem of determining the nature of the influence
of complex impurity molecules on a ferroelectric phase
transition was stated by Blattner, Mattias and Merz [1].
They studied KDP crystals containing the organic dye
hematein [1] and showed unique evidence of influence of
nonisomorphic impurities on the properties of KDP crystal,
especially its ferroelectric phase transition temperature.
More recently, we found a number of another dyes with
nonisomorphic molecules which can be incorporated into
the certain growth sectors of the KDP crystal. It was
revealed that some dyes like hematein stain only the
prismatic growth sectors and others prefer the pyramidal
ones [2].
In this work we present the result of the study of
dielectric properties of KDP crystals grown on the point
seed from solutions contained organic dyes Chicago Sky
Blue (KDP+C), Amaranth (KDP+A), which stained
pyramidal sectors, and KDP crystal with inorganic
molecules K4[Ru2Cl10O], that were incorporated into the
prismatic growth sectors like hematein.
We investigated dielectric properties of different
growth sectors of these crystals and compared it with the
nominally pure crystals, grown by the same method. The
essential difference of dielectric properties of the prismatic
and pyramidal sectors in the polar phase of the pure crystals
and of the crystals stained by organic dyes was observed,
while no shift of the transition point was detected.
In polar phases of dyed pyramidal sectors of crystals
KDP+A and KDP+C, besides the trivial hysteresis of the
first order phase transition point, the temperature hysteresis
of dielectric constant resembled the global hystersis in
ferroelectrics with incommensurate phases was found.
The most interesting effects were observed in the
prismatic sectors of dyed crystals KDP+A and KDP+R. The
large increase of domain contribution to the dielectric
constant in comparison with another crystals was observed
in KDP+A. In the prismatic sector of KDP+R the domain
contribution to the dielectric constant was suppressed but
the temperature of the phase transition was shifted by 0.5 K
towards low temperatures in comparison with pure crystal.
Such a result is in accordance with results for system
KDP+hematein [1], where shift of Tc attained 2 K also for
the prismatic sector. In this report we discuss the possible
mechanisms of influence of nonisomorphic impurities on
the properties of KDP crystal.
This work was supported by the Russian Foundation
for Basic Research (Project 02-02-16261).
[1] H. Blattner, B. Matthias and W. Merz, Helv. Phys. Acta
19, 415 (1946) [2] J.A. Subramony, S.-H. Jang, B. Kahr,
Ferroelectrics 191, 293 (1997)
10
th
142
Amplitudon Mode in Deuterated
Thiourea by Raman Scattering
IVAN GREGORA, JIRKA HLINKA AND
BOHUSLAV BREZINA
Institute of Physics AS CR, Na Slovance 2, 18221 Praha,
Czech Republic. gregora@fzu.cz
Recently, we have succeeded to grow large and high
quality single crystal of fully deuterated thiourea,
convenient for coherent neutron scattering investigations.
Among others, it allowed us to elucidate the nature of the
quasi-elastic diffuse scattering in this material and to
determine the dispersion of phason relaxation frequency
[1]. Unfortunately, the phason branch in this crystal is
heavily overdamped, and subsequent attempts to observe
inhomogeneous underdamped phasons by inelastic neutron
scattering have met with severe difficulties [2]. Thus,
although it is quite plausible that the phason response can
be well described as overdamped harmonic oscillator, the
dispersion of phason oscillatory frequency could not be
determined from the neutron scattering data.
In order to get further insight in the incommensurate
dynamics of thiourea, we have investigated also the
amplitudon mode in the deuterated thiourea by polarised
Raman spectroscopy. The experiment and data analysis
were performed in a similar way as our previous
investigation of amplitudon mode in the crystal of
deuterated betaine calcium chloride dihydrate (BCCD)[3].
From this measurement, we were able to obtain temperature
dependence of both damping and oscillator frequency of the
amplitudon mode. Using these results and assuming that the
phason damping is roughly comparable to that of
amplitudon, we were able to estimate the dispersion of
phason oscillatory frequency and compare it with the results
known from other incommensurate dielectrics.
[1] J. Hlinka, J. Petzelt, B. Brezina, and R. Currat: Phys.
Rev. B 66, 132302 (2002).
[2] J. Hlinka, R. Currat, I. Gregora, J. Petzelt and
B. Brezina: to be published
[3] I. Gregora, J. Hlinka, and V. Vorlicek: Ferroelectrics
240, 117 (2000).
Amplitude-Dependent Internal
Friction in SrTiO
3
in a Vicinity of
the Ferroelastic Phase Transition
S.A. GRIDNEV
1
, V.V. LEMANOV
2
AND E.V. UKHIN
1
1
Voronezh State Technical University, 394026 Voronezh,
Russia
2
A.F. Ioffe Physical-Technical Institute, 194021 St.-
Petersburg, Russia
The strontium titanate SrTiO3 is known to be an
incipient ferroelectric and improper ferroelastic crystal
undergoing a ferroelastic phase transition at TC=110 K with
symmetry change from cubic Pm3m (T > TC) to tetragonal
I4/mcm. Though the elastic and anelastic properties of the
crystal SrTiO3 in a vicinity of TC are investigated within
more than 25 years, however, experiments were in most
cases carried out at high frequencies (f > 10 MHz). Only
recently a number of papers was published, in which
acoustic properties of SrTiO3 were studied using low
frequency experiments (f = 1-20 Hz). It was revealed, that
the movement of ferroelastic domain boundaries, which
arise in strontium titanate at the ferroelastic phase
transition, gives the main contribution to anomalies of the
internal friction and elastic modulus near TC and that values
of low-frequency elastic properties and mechanical losses
both in ferroelastic and in paraelastic phases essentially
depend on external mechanical stress, applied across a
sample.
The measurements of the internal friction Q
-1
(a
reciprocal quality factor) and shear modulus were carried
out using the setup based on the inverted torsion pendulum
with oscillation frequency about 15-20 Hz.
A very strong anisotropy of elastic and anelastic
properties in the crystal SrTiO
3
measured at a high level of
a vibrational stress below the ferroelastic Curie temperature
in a sample [110] has been observed.
It was found out that the amplitude dependence of an
internal friction in the sample [110] is complex and the
physical mechanism responsible for it should be related to
dislocation and domain wall dynamics. Detailed analysis of
amplitude-temperature spectra of the internal friction
enables us to separate the components related to
dislocation-point defect as well as domain boundary-point
defect interactions. Thermally activated interactions are
considered to be the basis of this result. Within the
framework of a thermally activated approach the force of
interaction between a domain boundary and a point defect
has been estimated.
There is the experimental evidence of the dislocation
mechanism responsible for the Q
-1
dependence on the strain
amplitude in a sample [100]. A similar law observed in a
sample [100] and in the paraelastic phase of a sample [110]
is a consequence of the same dislocation-point defect
interaction for micro- and macro-deformations. The value
of the dislocation deformation may be as small as 10
-5
if we
assume a power relationship between the internal friction
and the strain amplitude.
The work was partly supported by the Russian
Foundation for Basic Research under grants No 01-02-
16097 and No 03-02-06000-___ as well as by the Ministry
of Education of the Russian Federation under grant No
202.03.02.038.
10
th
143
X-ray Photoelectron Spectroscopy
of Ferroelectrics
J.GRIGAS
1
AND E.TALIK
2
1
Faculty of Physics, Vilnius University, Sauletekio 9/3,
2040 Vilnius, Lithuania. E-mail: jonas.grigas@ff.vu.lt
2
Institute of Physics, Silesian University, Universytetska 4,
40 007 Katowice, Poland
X-ray photoelectron spectroscopy is widely used for
solids surface investigations. Due to the reduced co-
ordination number, core-electron binding energies, Eb, are
different for surface and bulk atoms. Bulk sensitive X-ray
photoelectron spectroscopy enables to study the surface
valence changes, which affect the core-level Eb shift with
respect to bulk atoms.
Bulk-sensitive X-ray photoelectron spectra (XPS) of the
valence band and core levels of the semiconductors
ferroelectrics SbSI and incommensurate TlInS2 single
crystals are measured with monochromatized Al K
radiation in the energy range 0 - 1400 eV in paraelectric,

ferroelectric and incommensurate phases. Experimentally
obtained binding energies are compared with the results of
theoretical ab initio calculations of bulk and surface atoms.
The valence band of SbSI consists of s-band (Sb 5s,S 3s
and I 5s) and p-band (Sb 5p and S 3p). Large shifts (3-5 eV)
in the core-level binding energies of all surface atoms
relative to bulk atoms, which show a dramatic dependency
on surface crystallography, have been observed in SbSI
(Figure 1). The shifts are toward higher/lower binding
energies for the surface cations/anions. This is the first
observation of so large XPS shifts in solids. The mechanism
of the large XPS shifts in SbSI crystals is discussed.
The obtained chemical shift of Sb (+0.8 eV), I (-0.8 eV) and
S (-3 eV) suggests charge transfer from Sb to S and I.
Figure 1. Split into surface and bulk spin-orbit doublet
of Sb 3d5/2 (529 eV) and 3d3/2 (538 eV) in ferroelectric (215
K) and antiferroelectric (330 K) phases.
The first observation of the resolved splitting of the
XPS in the incommensurate phase of TlInS2 crystals is also
observed and discussed.
Luminescence in SrTiO
3
and
LiNbO
3
Crystals under High
Density Pulsed Electron Beam
Excitation
L. GRIGORJEVA
1
, D. MILLERS
1
, V. TREPAKOV
2,3
,
S. KAPPHAN
4
1
Institute of Solid State Physics, University of Latvia,
Kengaraga 8, LV-1063, Riga,Latvia, lgrig@latnet.lv
2
Institute of Physics AS CR, 182 21 Prague 8, Czech
Republic
3
A. F. Ioffe Physical-Technical Institute, 194 021, St-
Petersburg, Russia
4
FB Physik, University of Osnabrueck, 49069 Osnabrueck,
Germany
The time-resolved luminescence in SrTiO
3
and
LiNbO
3
single crystals was studied under pulsed electron
beam excitation. The excitation density was up to ~20
MW/cm
2
, pulse duration 10 ns.
SrTiO3 single crystals (undoped, Nb and Pb doped)
were studied. The luminescence spectrum under steady
state x-ray excitation shows the known 2.4 eV emission
band whereas under pulse electron beam excitation
spectrum is strongly different.
The luminescence spectra under pulsed electron beam
excitation for all SrTiO3 crystals are the same at room
temperature consisting of the main band peaking at ~2.8 eV
and do not change at least down to 90K. It is suggested that
this luminescence is intrinsic. Another band was observed
at spectral region <1.2 eV. The luminescence rise is fast and
follows to the excitation pulse. Main fraction of
luminescence (up to ~90%) decays during the first 50 ns
after excitation pulse switching off. The fraction of
luminescence intensity is temperature dependent and
increase at higher temperatures. The luminescence spectra
of LiNbO3 strongly depend from crystal composition
(congruent, stoichiometric) and impurities content [1].
However in the all crystals the luminescence band at 2.7 eV
was observed and the properties of band observed are
similar to that at 2.8 eV band for SrTiO3. This luminescence
in LiNbO3 has a fast rise observed during the irradiation
pulse and slower one follows the fast decay. Luminescence
at 300K became undetectable within ~40 ns delay after
excitation pulse. The luminescence intensity dependence on
the temperature is similar to that observed in SrTiO3. These
similarities indicate that the luminescence mechanism in the
both crystals has the similar nature. It is suggested that as in
SrTiO3 as in LiNbO3 crystals excited electrons and holes
became temporary trapped within oxy-anion complexes at
low temperatures. Formation of the charge-transfer vibronic
exciton [2] is suggested as a possible mechanism of this
trapping and the exciton radiative decay - as origin of
luminescence.
Acknowledgment This work was supported by
PST.CLG.9775 and Latvian SC grant 01.0813.
[1] L.Grigorjeva, V.Pankratov, D.Millers, G.Corradi,
K.Polgr, Ferroelectrics, 257, p.281, 2001.
[2] V.S.Vikhnin, R.Eglitis, S.Kapphan, G.Borstel,
Phys.Rev.B, 65, p.104304, 2002.
525 530 535 540 545 550
Surface
Bulk
215 K
330 K
Sb 3d
Binding energy (eV)
I
n
t
e
n
s
i
ty

(
a
.
u
.)
10
th
144
Investigation of Polarization
Switching Processes in FRAM
Capacitors Using Scanning Force
Microscopy
A. GRUVERMAN,
1
B. J. RODRIGUEZ,
1
A. I. KINGON,
1
J. S. CROSS,
2
Y. HORII
2
1
North Carolina State University, Raleigh, NC 27695-
7920, USA
2
Fujitsu Laboratories Ltd, Atsugi 243-0197, Japan
Ferroelectric capacitors are a key element of a new
generation of ferroelectric random access memory (FRAM)
devices, which combine nonvolatility with high operation
speed, unlimited endurance and low power consumption.
Integration of ferroelectric films into high-density memory
devices requires substantial improvement in the
understanding of the size-dependent properties of these
materials as well as development of new characterization
tools suitable for FRAM device testing. In this paper, recent
advances in high-resolution characterization of FRAM
capacitors by means of piezoresponse force microscopy
(PFM) have been reviewed. PFM has been used in
conjunction with the conventional ferroelectric P-V testing
technique to perform nanoscale investigation of the imprint,
retention and switching behavior of integrated PLZT-based
FRAM capacitors. The PFM approach allowed us to
characterize the spatial variations of properties within
individual capacitors as well as capacitor-to-capacitor
variations. Mapping of polarization distribution in the poled
capacitors as well as local hysteresis loop measurements
revealed a significant difference in imprint and switching
behavior between the peripheral and inner parts of the
capacitors. Effects of the film/electrode interface as well as
processing and stress conditions on imprint and retention
behavior have been investigated. PFM results have been
related to the results of P-V hysteresis measurements. It has
been shown that the switching and imprint behavior of the
FRAM capacitors is a complex combination of electrical
and mechanical effects.
Doping-Dependent Properties in
Photorefractive Congruent
Sr
x
Ba
1-x
Nb
2
O
6
: Ce, Cr Crystals.
A. GUBAEV
1
, R. DEMIRBILEK
1
, R. PANKRATH
1
,
S. KAPPHAN
1
, I. KISLOVA
2
, B. PEDKO
2
,
V. TREPAKOV
3
1
FB Physik, University of Osnabrueck, Barbarastr. 7,
49069, Osnabrueck, Germany. E-mail:
Airat.Gubaev@uos.de.
2
Dept. of Physics, Tver State University, Sadovij per. 35,
170002, Tver, Russia.
3
A.F. Ioffe Physical-Technical Institute, 194021,
St.-Petersburg, Russia.
Sr
x
Ba
1-x
Nb
2
O
6
(SBN) for the congruent mixture x=0.61,
where melt and crystal have the same composition,
allowing to grow large homogeneous crystals, is one of the
most promising photoreflactive materials [1] for various
nonlinear optical applications due to its large electro-optical
coefficients and intriguing photorefractive properties. These
properties may be distinctly enhanced by doping with Ce or
Cr [2], and already a small amount of dopants is influencing
optical, dielectric and pyroelectric properties and shifts the
the ferroelectric transition temperature T
C
. Because for
many applications it is important to retain the crystal in a
proper monodomain ferroelectric state above room
temperature, the doping effects should be well known for an
optimization. We report on results of optical absorption
measurements performed in the UV-FIR region,
luminescence spectra, and dielectric permittivity
measurements taken in the temperature range 2-400 K for
Sr
0.61
Ba
0.39
Nb
2
O
6
as a function of the Ce and Cr dopant
concentration. In accordance with [3], addition of a small
amount of Ce, Cr (about 20000 pmm per formula unit)
decreases T
c
below room temperature. Nature and details of
the properties observed are discussed and compared with
recent theoretical and experimental data.
This work has been supported by DFG/Grad.Koll
695/1, by DFG (KA501/8-1), NATO-CLG 977348 and
RFBR 03-02-17589 Grants.
1. P. Guenter and J. Huignard, Top. in Appl. Phys.:
Photorefr. mat. 61/62 (Springer/Berlin) (1998).
2. M.Gao, R.Pankrath, S.Kapphan, V.Vikhnin. Appl.Phys.
B68, 849 (1999).
3. S. Kapphan, B. Pedko, V. Trepakov, M. Savinov, R.
Pankrath, I. Kislova. Rad. Eff. and Defects in Solids,
157, 1033 (2002).
10
th
145
Study of Types of Equivalent
Circuit Models for Piezoceramics
With and Without Losses
A. GUISADO
1
, A. M. GONZLEZ
2
, E.M. ALCOCER
1
AND J.A. PREZ
1
1
Dpto. ICS. EUIT Telcomunicacin (UPM).
aguisado.ics.upm
2
Dpto. Fsica Aplicada EUIT Telcomunicacin (UPM)
In this work, we present a comparative study between
two different models of piezoelectric ceramic elements to
implement with PSpice, and working in a frequency range
close to the resonance for the thickness extensional mode.
The two models are the lossesless Leachs [1] one and
the Pttmers one, which includes losses in the transmission
line.
We do the simulations using a multilayered system and
analyse the accuracy of both of models of equivalent
circuits for the frequency and time response. In the case of
time response, we do a comparative with the experimental
results obtained by Pttmer[2]. We also present a
modification of this model using the ABM (analog
behavioural modelling) facility included in Pspice.
References
[1] W. Marshall Leach, Jr., Controlled-Source Analogous
Circuits and SPICE Models for Piezoelectric
Transducers, IEEE Trans. Ultrason., Ferroelect.,
Freq. Contr., vol. 41, no. 1, January 1994.
[2] A. Pttmer, P. Hauptmann, R. Luckum, O. Krause, and
B. Henning, SPICE Model for Lossy Piezoceramic
Transducers, IEEE Trans. Ultrason., Ferroelect.,
Freq. Contr., vol. 44, no. 1, January 1997.
Preparation of Nanocrystalline
Pb(Zr
0.52
Ti
0.48
)O
3
by Sol-Gel Method
HONGXIA GUO, YAYAN LIU *, BAISHENG DOU,
JIANKE XIA
Changchun Institute of Applied Chemistry, Chinese
Academy of Sciences 130022, hxguo@ciac.jl.cn,
yyliu@ciac.jl.cn, lanwang0188@sina.com
By a sol-gel method nanocrystalline Pb(Zr0.52Ti0.48)O3
(PZT) was prepared with lead acetate, zirconymitrate and
tetra-n-butyle. It was investigated the infection of the
volume ratio of HOCH2CH2OCH3 to H2 O to the
crystallization temperature of precursor PZT and the PZT
product size. As a result, both the crystallization
temperature of precursor PZT and PZT product size were
increased with the increase of V(C3H8O2)/ V(H2O) ratio.
When V(C3H8O2)/ V(H2O)=4.47 the gel was formed
moderately quick, and the granularity of fined
nanocrystalline PZT was even. The diameter of final
nanocrystalline measured by atomic force microscopy
(AFM) was ranged in 60~70nm. The crystallization
temperature of precursor PZT was 443 , and the
crystallization reaction was completed at 500 by DTA and
TG. The sol-gel reaction process was monitored by FT-IR
and XRD.
Keywords
Pb(Zr0.52Ti0.48)O3, nanocrystalline, sol-gel process
10
th
146
Domain Wall Orientations in
Sn
2
P
2
S
6
Type Ferroelectrics
M.I. GURZAN, D.I. KAYNTS, A.A. HORVAT
Institute of Solid State Physics and Chemistry, Uzhgorod
National University, 46 Pidhirna St., Uzhgorod, 88000,
Ukraine, e-mail:kaynts@uzh.ukrtel.ua
Static domain structure in uniaxial ferroelectric Sn2P2S6
have been studied by etching technique. These materials are
proper uniaxial ferroelectrics with a second-order phase
transition 2/m m, occurring at 337 K, that defines an
existence of the optically identical antiparallel 180
domains at the room temperature.
It is shown that static equilibrium domains are formed
mainly by two kinds of the walls. First ones are inclined
relative to spontaneous polarization vector on an angle
about 18 degree (charged walls), and second one are
parallel to the symmetry plane.
Charged walls existence well corresponds to the
directional light scattering by domain walls observed earlier
[1], as well as dielectric data. The formation of such kind of
domains in Sn2P2S6 is interpreted as a result of competition
between the electric and elastic contributions in a total
energy of the inter-domain boundaries supposing the
screening of these charged walls by movable charge
carriers.
The presence of the charged domain walls correlates
with the difference in the dielectric and optic parameters of
the Sn2P2S6 measured in single- and polydomain samples.
1. A.A.Grabar, J. Phys.: Condens. Matter., V. 10, 2339
(1998)
Behaviour of the Specific Heat of
ABBO
3
Complex Perovskites at
Low Temperatures
S. GVASALIYA
1, 2
, S. LUSHNIKOV
2
, Y. MORIYA
3
,
H. KAWAJI
3
, T. ATAKE
3
, M. SMIRNOV
4
, AND
V. KAZIMIROV
5, 6
1
Laboratory for Neutron Scattering, ETHZ & PSI, CH-5232
Villigen PSI, Switzerland,
Email: severian.gvasaliya@psi.ch
2
Ioffe Physical Technical Institute, 194021, St. Petersburg,
Russia, E-mail: sergey.lushnikov@mail.ioffe.ru
3
Tokyo Institute of Technology, 4259 Nagatsuta- cho,
Midori-ku, Yokohama, 226-8503 Japan
4
Fock Institute of Physics, Saint-Petersburg University,
194508 Petrodvoretz, St.-Petersburg, Russia
5
University of Virginia, Department of Physics,
Charlottesville, VA 22903, USA
6
FLNP, JINR, 141980, Dubna, Moscow Region, Russia
It is well established now that at low temperatures
amorphous solids exhibit nearly universal behaviour of
various properties like heat capacity, thermal conductivity,
and dielectric susceptibility. Low temperature properties of
partially disordered crystals are less studied. Complex
perovskites of ABBO3 type are the crystals with the
disorder in B- sublattice. Crystals of PbMg1/ 3Nb2/3O3
(PMN) and PbMg1/3Ta2/3O3 (PMT) are the well-known
relaxor ferroelectrics, while BaMg1/3Ta2/3O3 (BMT) is the
crystal with low dielectric permittivity. Here, we present the
results of measurements of the specific heat of PMN, PMT,
and BMT crystals and comparison of different model
approaches to the describing of experimental data at low
temperatures. Precise specific heat measurements between
13 and 300 K were performed using a homemade adiabatic
calorimeter. The measurements between 2 and 50 K were
made by a relaxation method using the PPMS (model 6000,
Quantum Design Inc.). Results are in a good agreement
with the data obtained by the adiabatic calorimetry. Figure
shows the experimental data at T<30 K as well as the
approximation of them for PMN in the framework of (i)
Debye model - dotted line (ii) using the sum of fracton
contribution and phonon contribution derived from shell
model calculations solid line. The shell-model
calculations were performed using the LADY toolkit [1],
parameters were taken from [2]. In report we plan to
discuss: 1) behaviour of the specific heat of PMN, PMT,
and BMT 2) different ways to describe low temperature
specific heat of PMN (shell-model calculations, two-level
systems, Einstein model, fracton approach). Work was
partially supported by RFBR grant 02-02-17678.
[1] M.Smirnov, V. Kazimirov Preprint JINR E14-2001-
159. [2] S. Gvasaliya et al. Ferroelectrics 283 (2003) 31.
10
th
147
Neutron and Raman Scattering
Study of PbMg
1/3
Ta
2/3
O
3
Relaxor
Ferroelectric
S. GVASALIYA
1,2
, S. LUSHNIKOV
2
, B. ROESSLI
1
,
R. KATIYAR
3
1
Laboratory for neutron scattering, ETHZ & PSI, CH-5232,
Villigen, Switzerland; severian.gvasaliya@psi.ch
2
Ioffe Physical Technical Institute, 194021, St.Petersburg,
Russia; E-mail: sergey.lushnikov@mail.ioffe.ru
3
Univ. of Puerto Rico, P.O. Box 23343, San Juan, USA
Despite the intense research, nature of ferroelectric state
appearing at low temperatures in relaxor ferroelectrics is
still far from being understood. Crystal of PbMg1/3Ta2/3O3
(PMT) is a relaxor ferroelectric with mean Curie
temperature Tcm~170 K. In our report, we present results
of studies of PMT crystal by neutron and Raman light
scattering. Neutron scattering studies were performed on
the 3-axis spectrometer TASP located at the cold neutrons
guide of SINQ (Switzerland). Neutron diffuse scattering
(DS) was studied in the temperature range 20295 K.
Raman light scattering (RLS) studies were performed using
a TR-64000 spectrometer in the range 30285 K. Raman
spectra were excited with an Ar+ laser. The same single
crystal of PMT was used in the experiments. We found that
the DS scattering in PMT can be adequately described by a
Lorentz function. Therefore, we analysed temperature
dependence of the DS in terms of the integrated intensity
(S) of a Lorentzian and the correlation length , which is
inverse of the half width at the half maximum of a
Lorentzian. Among the results of RLS experiments it was
found that the shape of the high-frequency mode of A1g
symmetry (~800cm
-1
) is strongly temperature-dependent.
Thus, the useful parameter to follow the temperature
evolution of the A1g mode was found to be its integrated
intensity (A). Figure shows the temperature dependence of
S and A (note that A normalised to the unity). It is clearly
seen that A has pronounced peak in the range 80-220 K. In
the same temperature range S linearly increases with
decreasing of the temperature. Indicated temperature range
corresponds to the region of strong frequency dispersion of
the dielectric permeability of PMT. In the report we plan to
discuss: 1) correlation of the behaviour of the diffuse
scattering and A1g mode in PMT crystal; 2) particular role
of the oxygen in this correlation 3) behaviour of DS in PMT
and in other relaxors. This work was performed in part at
the spallation neutron source SINQ, Paul Scherrer Institut,
Villigen (Switzerland) and partially supported by RFBR
grant 02-02-17678
10
th
148
25.0
-25.0
-20.0
-15.0
-10.0
-5.0
0.0
5.0
10.0
15.0
20.0
5 -6 -5 -4 -3 -2 -1 0 1 2 3 4
Polarization ( C/cm
2
) vs. Voltage (V)
25.0
-25.0
-20.0
-15.0
-10.0
-5.0
0.0
5.0
10.0
15.0
20.0
5 -6 -5 -4 -3 -2 -1 0 1 2 3 4
25.0
-25.0
-20.0
-15.0
-10.0
-5.0
0.0
5.0
10.0
15.0
20.0
5 -6 -5 -4 -3 -2 -1 0 1 2 3 4
Polarization ( C/cm
2
) vs. Voltage (V)
Effect of Electric Field on
Hydrostatic Piezoelectric Coefficients
of Single Domain PZN-PT Crystals
P. HANA
1
, L. BURIANOVA
1
, E. FURMAN
2
, S. ZHANG
2
,
T.R. SHROUT
2
, L.E. CROSS
2
1
Technical University of Liberec, Department of Physics and
International Center for Piezoelectric Research, Halkova
6, CZ-461 17 Liberec 1, Czech Republic,
petr.hana@vslib.cz
2
Materials Research Institute, University Park, PA 16802, The
United States of America
The effect of dc bias electric field on the hydrostatic
piezoelectric coefficient dh in Lead Zinc Niobate - Lead
Titanate (PZN:PT) single crystal solid solutions in the vicinity
of the morphotropic phase boundary (MPB) is studied. The
hydrostatic measurements can be very important to gain
insight into these materials. In particular, the discrepancy
between sum of piezoelectric coefficients d33 + 2 d31 vs.
hydrostatic dh coefficient measured directly suggests the
importance of extrinsic contributions.
Limiting values of measured hydrostatic piezoelectric
coefficients dh for high electric fields are compared with
calculated theoretic values from the Landau - Devonshire -
Ginzburg (LGD) phenomenological theory.
The influence of complicated microstructure within the
single domain region is studied. Such microstructure could
possibly account for the inability of the LGD phenomenology
to give correct electric field bias dependence of dielectric
constant.
References
[1] Zhi Yu, Chen Ang, E. Furman and L.E. Cross, Appl. Phys
Letters 82, 5 (2003) 790.
[2] J. Yin and W. Cao, J. Appl. Phys. 92, 1(2002) 444.
[3] V. Yu. Topolov and A. V. Turik, Phys. Sol. State 43, 6
(2001) 1117.
[4] S. Stotz, Ferroelectrics 76 (1987) 123.
Aqueous CSD of ferroelectric
(Bi,La)
4
Ti
3
O
12
(BLT) thin films
A. HARDY
1
, D. NELIS
1
, G. VANHOYLAND
1
,
M.K. VAN BAEL
1
, J. MULLENS
1
, L.C. VAN POUCKE
1
, J.
DHAEN
2
, D.J. WOUTERS
3
1
Laboratory of Inorganic and Physical Chemistry, IMO
2
IMO-IMOMEC, B-3590 Diepenbeek
Limburgs Universitair Centrum, B-3590 Diepenbeek, Belgium
3
IMEC, B-3001 Heverlee-Leuven, Belgium
e-mail: an.hardy@luc.ac.be
Lanthanum substituted bismuth titanate, a layered
perovskite material, is studied since 1999 for application as
non-volatile FRAM [1]. Here an aqueous chemical solution
deposition (CSD) route is presented for the fabrication of BLT
thin films. The precursors are trimetallic aqueous solutions,
which lead to homogeneous, amorphous gel films upon
evaporation of the water. Hydrolysis of the metal ions is
prevented by complexation with appropriate chelating agents
[2]. Separate monometallic solutions of Bi
3+
, La
3+
and Ti
4+
are prepared. In this way, different Bi4- xLa xTi3O12
compositions are easily attainable by mixing the monometallic
precursors in the desired ratios. Several layers of these
precursors are spin-coated onto platinized silicon wafers,
which are first subjected to an intense chemical cleaning
procedure [3]. Preliminary investigations of the thermal
treatment settings show the necessity of intermediate crystal-
lization steps at a
relatively high
temp-erature
(650C) in order
to obtain a high
film density and a
ferroelectric
response (see
Figure).
However t hi s
also has an adverse effect on the orientation of the films as it
results in preferential c-axis orientation. This is a possible
explanation for the lower Pr value observed, compared to
random and a- or b-axis oriented films [4]. The emphasis in
this research is placed on the relation between precursor
chemistry and film properties such as microstrucure,
orientation and ferroelectric behavior, while a lot of attention
is devoted to the reproducability of the results. Therefore, the
films are characterized at different stages of the heating
scheme by means of fourier transform infrared spectroscopy
(FTIR), scanning electron micro-scopy (SEM) and X-ray
diffraction (XRD). Some preliminary results on ferroelectric
properties are reported.
[1] B.H. Park, B.S. Kang, S.D. Bu, T.W. Noh, J. Lee, W. Jo,
Nature, 401 (1999) 682 [2] A. Hardy, D. Mondelaers, M.K.
Van Bael, J. Mullens, L.C. Van Poucke, G. Vanhoyland, J.
D'Haen, Journal of the European Ceramic Society, in press
[3] M.K. Van Bael, D. Nelis, A. Hardy, D. Mondelaers, D.
Van Werde, J. D'Haen, G. Vanhoyland, H. Van Den Rul, J.
Mullens, L.C. Van Poucke, F. Frederix, D.J. Wouters,
Integrated Ferroelectrics, 45 (2002) 113 [4] H.N. Lee, D.
Hesse, N. Zakharov, U. Gosele, Science, 296 (2002) 2006
10
th
149
Anelastic Relaxation of Ferroelastic
Domain Walls in LaAlO
3
RICHARD HARRISON, SIMON REDFERN, EKHARD SALJE
Department of Earth Sciences, University of Cambridge,
Downing Street, Cambridge CB2 3EQ,
rjh40@esc.cam.ac.uk
The low-frequency mechanical properties of single crystal
LaAlO3 have been investigated as a function of temperature,
frequency, and applied force using the technique of dynamical
mechanical analysis in three-point bend geometry. LaAlO3
undergoes a cubic to rhombohedral phase transition below 550
C. The mechanical response in the low-temperature
rhombohedral phase is shown to be dominated by the anelastic
motion of transformation twin domain walls, resulting in a
factor of ten decrease in the storage modulus relative to the
high-temperature cubic phase (super-elastic softening) and a
significant increase in attenuation. Super-elastic softening is
observed down to 200 C, below which temperature the
mobility of the domain walls decreases markedly, causing a
rapid increase in storage modulus and a pronounced peak in
attenuation (anelastic relaxation). The frequency and
temperature dependence of the internal friction associated with
the relaxation has been studied in detail, and reveals the
presence of three distinct relaxation peaks. Activation energies
for each peak have been determined using the peak-shift
method. The largest peak has an activation energy of 0.8 eV
and is associated with movement of domains walls in the bulk
of the sample. At higher temperatures there is a second peak
with similar activation energy, possibly related to the
formation and retraction of needle domains at the sample
surface. A third low-temperature peak has an activation energy
of 0.9 eV. This may be related to the interaction between
domain walls and oxygen vacancies.
Detailed analysis of the dynamic force-deflection curves
reveals three distinct regimes of mechanical response. In the
elastic regime, the domain walls are pinned and unable to
move. The elastic response is linear with a slope determined
by the intrinsic stiffness of the lattice, the initial susceptibility
of the pinning potential, and the bending of twin walls
between pinning sites. In the super-elastic regime, the domain
walls unpin and displace by an amount determined by the
balance between the applied and restoring forces. The value of
the apparent super-elastic modulus is shown to be independent
of the spontaneous strain, and hence independent of
temperature. At high values of the applied force, adjacent
domain walls come into contact with each other and further
super-elastic deformation is possible only by the formation
and retraction of needle domains (saturation). The strain in the
saturation regime scales with the spontaneous strain and the
resulting modulus is strongly temperature dependent.
19
F-NMR Study in Phase Transition
of [(CH
2
OH)
3
CNH
3
]
2
SiF
6
JUNKO HATORI, YASUMITSU MATSUO,
ZBIGNIEW CZAPLA
1
, MASARU. KOMUKAE,
TOSHIO OSAKA AND SEIICHIRO IKEHATA
Department of Applied Physics, Faculty of Science, Tokyo
University of Science,1-3 Kagurazaka, Shinjuku-ku,
Tokyo, 162-8601, Japan
1
Institute of Experimental Physics, M. Borna 9 University of
Wroclaw, Poland E-mail : PXA07656@nifty.ne.jp
It is known that many crystals with the (CH2OH)3CNH3
ion show the structure without the symmetric center.
Therefore, in these crystals the development to the new
electro-optical material is expected. Recently, it was found
that the [(CH2OH)3CNH3]2SiF6 crystal, which is one of those
type crystals, undergoes the phase transition at around 178 K.
However, the mechanism of this phase transition has not been
made clear. In the present work, we have examined the
dynamics of the SiF6 ions below room temperature by means
of the spin-lattice relaxation time T1 and the NMR absorption
line of
19
F nucleus, in order to investigate the mechanism of
this phase transition.
It was found that the
19
F-NMR line width becomes narrow
with increasing temperature above 77 K, and becomes
constant above Tc=178 K (Fig. 1). This narrowing of the line
width is caused by the rotation of SiF6 ions in the high-
temperature phase. Moreover, we observe a large anomaly in
T1 at around Tc=178 K. This result also indicates that the
dynamics of the SiF6 ions changes at Tc. It is deduced from
these results that the motion of SiF6 ions is closely related to
the appearance of the phase transition at 178 K.
Figure 1 Temperature dependence of
19
F-NMR Line
width
10
th
150
Modification of the Polarization
under Cationic Competition
R. HAUMONT
1
, B. DKHIL
1
, J.M. KIAT
1,2
,
A. AL-BARAKATY
3
, L. BELLAICHE
3
, H. DAMMAK
1
1
Laboratoire Structures, Proprits et Modlisation des
Solides, Ecole Centrale Paris, CNRS-UMR8580, Grande
Voie des Vignes 92295 Chtenay-Malabry Cedex, France
-haumont@spms.ecp.fr
2
Laboratoire Lon Brillouin, CE Saclay, CNRS-UMR12,
91191 Gif-sur-Yvette Cedex, France
3
Department of physics, University of Arkansas, Fayetteville,
Arkansas 72701, USA
A global picture for the structural evolution in the relaxor -
ferroelectric solid solution (PbSc1/2Nb1/2O3)1-x - (PbTiO3)x,
namely PSN-PT is proposed. Thanks to X-Ray profile analysis
and Rietveld neutrons powder refinement, a monoclinic phase
has been evidenced in the morphotropic region (i.e. x 0.43).
This lower symmetry phase bridges the rhombohedral
Ti-poor phase (x 0.26) with the tetragonal Ti-rich phase
(x 0.55), in a similar way as in PMN-PT or PZN-PT. For
weak titanium concentration, we observe a macroscopic
rhombohedral state with local monoclinic symmetry resulting
from the combination between Pb and Sc/Nb/Ti shifts along
[001] and [111] directions respectively. Cationic competition
with Ti-doping increases the coherence length of this short
ranged monoclinic phase which becomes long ranged in the
morphotropic region.
This intermediate monoclinic phase is in complete
agreement with our first-principles calculations which predict
a Pm or a Cm space groups. It has been showed that these
ones are very close to each other in the free energy space, and
a minor change of atomic distribution and/or a slight
modification in composition is enough to alter the space group
of the monoclinic ground-state. Finally, in Ti-rich region, the
monoclinic ground state is destroyed in favor of a tetragonal
phase. Random fields due to the cationic distribution and the
competing orderings of the polarization along multiple
direction on a mesoscale are found to play a key role on the
ground states and their associated electromechanical
properties.
Relaxor-Ferroelectric Transition in
Lead-based Piezoelectric Perovskites
R. HAUMONT
1
, B. DKHIL
2
, J.M. KIAT
1,2
1
Laboratoire Structures, Proprits et Modlisation des
Solides, Ecole Centrale Paris, CNRS-UMR8580, Grande
Voie des Vignes 92295 Chtenay-Malabry Cedex, France
-haumont@spms.ecp.fr
2
Laboratoire Lon Brillouin, CE Saclay, CNRS-UMR12,
91191 Gif-sur-Yvette Cedex, France
Many lead-based relaxor-PbTiO3 system such as PMN-
xPT, PZN-xPT or PSN-xPT exhibit a similar phase diagram:
for Ti-poor region, we observe a rhombohedral ground state
associated to a relaxor behaviour, while for Ti-rich region,
close to the PT compound, a tetragonal phase associated to a
normal ferroelectric behaviour takes place. Between these
regions, all those solid solutions show a Morphotropic Phase
Boundary (MPB) where ultra-high dielectric and
electromechanical properties are observed. Besides, the
crystallographic structure in the MPB is monoclinic, i.e. the
polarization vector is no longer constrained to lie along a
symmetry axis, as in the rhombohedral and tetragonal
structures, but instead can rotate within a monoclinic plane.
This poster intends to look at how the relaxor behaviour
transforms into a normal ferroelectric one. Our diffraction data
show for instance that lead atoms though polar nanoregions
play a crucial role. Moreover, closely related to these polar
nanoregions, our data show how the monoclinic phase takes
place and bridges the rhombohedral and the tetragonal
phases.
10
th
151
Low-Temperature Fabrication and
Properties of PMN-PZT Ceramics
Using LiBiO
2
Sintering Aid
T. HAYASHI, T. HASEGAWA, J. TOMIZAWA AND
Y. AKIYAMA
1
Department of Materials Science, Shonan Institute of
Tecnology, Fujisawa, Kanagawa 251-8511, Japan
Email:hayashi@mate.shonan-it.ac.jp
1
R&D Center, RICOH Co., Ltd., Shinei-cho, Tuzuki-
ku,Yokohama 224-0035, Japan
Lead-containing perovskites ceramics have excellent
piezoelectric properties and are widely used in various
applications such as stack-type actuators, ultrasonic motors
and piezoelectric transformers. Most of these ceramics
generally have been sintered above 1100C. However, these
sintering temperature are too high in case of fabrication of
multi-layered device with internal electrode. Ag-Pd alloy are
generally used as internal electrode, which contains very
expensive Pd metal. Low-temperature processing makes it
possible to use Ag-Pd electrode with lower Pd content, and
also decrease environmental pollution due to vaporization of
PbO.
In this work, low-temperature sintering of 0.375Pb
(Mg1/3Nb2/3)O3-0.625Pb(Zr0.4Ti0.6)O3 (PMN-PZT) powders
using a LiBiO2 sintering aid was investigated. PMN-PZT
powders with particle size of approximately 210nm were
prepared using solid state reaction between PbO and both of
MgNb2O6 and Zr0.4Ti0.6O2 fine powders synthesized by
hydrothermal process, which could be densified into sintered
bodies at 850C for 2 h with a relative density of
approximately 95%. The addition of LiBiO2 sintering aid
promoted the lower-temperature sintering and the grain
growth of PMN-PZT ceramics. 1wt% LiBiO2-added PMN-
PZT ceramics fabricated at 800C with relative density of 95%
exhibited the electromechanical coupling factor (kp) of 40.2%,
and the specimens fabricated at 1000C exhibited the kp value
of 51.8% and longitudinal strain of 0.17% under the applied
electric field of 40kV/cm.
Preparation and Properties of
V-doped (Bi, Nd)
4
Ti
3
O
12
Ferroelectric
Thin Films by Chemical Solution
Deposition Method
TAKASHI HAYASHI, NAOYA IIZAWA, DAICHI TOGAWA,
MIO YAMADA
1
, WATARU SAKAMOTO
2
AND SHIN-ICHI
HIRANO
1
Department of Materials Science, Shonan Institute of
Technology, 1-1-25 Tsujido-Nishikaigan, Fujisawa,
Kanagawa 251-8511, Japan.
hayashi@mate.shonan-it.ac.jp
1
Department of Applied Chemistry, Graduate School of
Engineering, Nagoya University, Furo-cho, Chikusa-ku,
Nagoya 464-8603, Japan.
2
Center for Integrated Research in Science and Engineering,
Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-
8603, Japan.
Bismuth titanate (Bi4Ti3O12; BIT)-based ferroelectric thin
films, where the Bi-site ions are doped by lanthanoid ions
(La
3+
or Nd
3+
) and Ti-site ions by other ions with higher
charge valence (V
5+
or W
6 +
), have been investigated as a
promising non-volatile ferroelectric random access memories
(NvFRAM). In this work, vanadium-doped (Bi, Nd)4Ti3O12
(BNTV) thin films were prepared on Pt(200 nm)/TiOx(50
nm)/SiO2/Si substrates by chemical solution deposition (CSD)
method. BNTV thin films crystallized at 600 and showed a
higher crystallinity than BNT thin films. They exhibited a high
(117) preferred orientation. BNTV thin films consisted of a
dense microstructrue with grain sizes of approximately 150-
250 nm. 600-annealed BNTV thin films showed a well-
saturated P-E hysteresis loop. The Pr and Ec values of the
BNTV thin films were 11.5 C/cm2 and 96 kV/cm,
respectively. The polarization values of the BNTV thin films
decreased by 18% after the fatigue measurement with 1010
switching cycles, while that of the BNT thin films decreased
by 30%. Ferroelectric property was little changed by
vanadium doping, but fatigue property of BNT was improved.
10
th
152
Saturation Effects in Ferroelectric
and Ferroelastic Phase Transitions
STUART HAYWARD, SIMON REDFERN, EKHARD SALJE
Department of Earth Sciences, University of Cambridge,
Downing Street, Cambridge CB2 3EQ, United Kingdom.
(sah21@esc.cam.ac.uk)
The saturation of order parameters in phase transitions at
low temperatures can arise from two mechanisms; true
saturation of the order parameter (for example, because
complete order is attained in an order-disorder process), and
quantum mechanical saturation, where zero-point effects
prevent increases in the order parameter on cooling. The
effect of these two processes on graphs of order parameter
versus temperature and on phase diagrams in a range of phase
transitions is described. Whereas the limit of a truly saturated
order parameter is a degree of order (and hence, a spontaneous
polarisation or strain), quantum mechanical saturation is
characterised by a saturation temperature S. The saturation
temperature is related to the soft mode associated with the
phase transition, and so provides an insight to the phase
transition mechanism. Unlike the transition temperature, S
appears not to be modified by variables such as pressure or
chemical composition.
Compounds with the perovskite structure, such as SrTiO3,
BaTiO3 and KTaO3 undergo a number of ferroelectric and
ferroelastic phase transitions, allowing S values to be
compared. Whilst the ferroelectric transitions in SrTiO3 and
KTaO3 both have S = 20 K, ferroelectricity in BaTiO3 has a
much higher saturation temperature (S = 160 K, as shown in
the phase diagram in Figure 1).
Figure 1 Comparison of experimental phase diagram of
BaTiO3 [1], with a modified Landau potential [2].
In KDP type ferroelectrics, both forms of saturation are
observed. Where the ferroelectric transition temperature is
reasonably large, the spontaneous polarisation reaches its true
saturation limit. If the transition temperature is reduced (for
example, by applying hydrostatic pressure), the quantum
mechanical saturation becomes the dominant effect.
1. Ishidate T, Abe S, Takahashi H and Mri N 1997 Phys.
Rev. Lett. 78 2397. 2. Hayward SA, Salje EKH 2002 J. Phys
Condens. Matter 14 L599
Dielectric Response of Highly
Ordered Pb(Sc
1/2
Nb
1/2
)O
3
under
Hydrostatic Pressure
ANDRZEJ HILCZER
1
, MAREK SZAFRANSKI
1
,
WOJCIECH NAWROCIK
1
AND CLAUDE CARANONI
1
Institute of Physics, Adam Mickiewicz University,
Umultowska 85, 61-614 Poznan, Poland
AHILCZER@AMU.EDU.PL
2
Laboratory L2MP-CNRS, Faculty of Sciences and
Techniques Saint Jerome, University Aix-Marseille III,
13397 Marseille, Cedex 20, France
Pb(Sc1/2Nb1/2)O3 belongs to the subgroup of ferroelectric
relaxors that undergo a spontaneous transition to the normal
ferroelectric state and their degree of order can be controlled
by thermal treatment [1]. The disordered materials posses very
large dielectric constants and exhibit diffuse, rounded
dielectric anomaly [2]. The anomaly is highly dispersive
below the temperature Tm of the permittivity maximum, Tm is
shifted towards higher temperatures as the applied frequency
increases. Above Tm the permittivity does not obey the Curie-
Weiss law, and though the dielectric polarization is equal to
zero its random mean square value persists to a temperature of
a few hundreds K above Tm. The properties of the relaxors are
related to their heterogeneous structure: the nonpolar, highly
polarizable matrix contains both chemical and polar
nanodomains. By diverse chemical substitution or/and thermal
treatment the degree of crystalline disorder can be changed
and thus the properties can be controlled to some extent. An
alternate way of tuning the properties of relaxors was
indicated by Samara who applied hydrostatic pressure for this
purpose [3].
In this paper we discuss the effect of hydrostatic pressure
on the dielectric response of Pb(Sc1/2Nb1/2)O3 with the degree
of order S = 0.9. At atmospheric pressure two dielectric
anomalies were observed in this material. A broad anomaly
near TI = 375 K is related to the paraelectric relaxor phase
transition while the second one, at TII = 353 K, can be ascribed
to the relaxor normal ferroelectric phase transition.
Hydrostatic pressure induces a downward shift of both
dielectric anomalies, but with different slopes:
dTI/dp = 5.8 K/100 MPa and dTI I/dp = 3.8 K/100 MPa,
resulting in a decrease of the temperature range in which the
relaxor phase can exist. A simple approximation of our results
to higher pressures, above 1 GPa, indicates the existence of a
critical point near pc 1.16 GPa, where the transition lines
should meet. Thus, it can be expected that the relaxor
behaviour is suppressed under pressures above pc. A similar
effect of pressure was observed in other highly ordered
perovskite relaxors [4].
[1]. N. Setter, L. E. Cross, J. Appl. Phys. 51, 43-56 (1980).
[2]. L. E. Cross, Ferroelectrics 151, 305 (1994).
[3]. G. A. Samara, Phys. Rev. Lett. 77, 314-317 (1996).
[4]. N. Yasuda, H. Ohwa, J. Oohashi, K. Nomura, H.
Terauchi, M. Iwata, Y. Ishibashi, J. Phys. Soc. Jpn. 66, 1920-
1923 (1997).
0 2 4 6
0
100
200
300
400
classically
expected
critical point:
(6.5 GPa, 130 K)
rhombohedral
orthorhombic
tetragonal
cubic
T

/

K
p / GPa
10
th
153
Effect of Hydrostatic Pressure on the
Dielectric Behaviour of Polymer
Relaxors
BOZENA HILCZER, EWA MARKIEWICZ, CZESLAW
PAWLACZYK , MARCIN KRUPSKI
Institute of Molecular Physics, Polish Academy of Sciences,
Smoluchowskiego 17, 60-179 Poznan, Poland, e-mail:
bhilczer@ifmpan.poznan.pl
Giant electrostriction, as well as broad and dispersive
dielectric anomaly, characteristic of ferroelectric relaxors,
reported in radiation-modified P(VDF/TrFE) copolymers have
attracted an attention in recent years [1-3]. The relaxor
properties of ferroelectric perovskites are related to a complex
heterogeneity: the presence of random fields and polar
nanodomains [4]. Our results of IR and NIR Raman studies
showed that in fast electron irradiated P(VDF/TrFE) the C=C
and conjugated C=C bonds (sources of random fields) cut the
ferroelectric all-trans conformations into short-range trans
coherence (polar nanoclusters) [5]. The relaxor-like dielectric
response of the copolymers damaged by fast electrons is a
result of an overlapping of the dielectric anomaly,
characteristic of the ferroelectric-paraelectric transition (at TC)
with that of the glass transition (at Tg), as well as the dielectric
dispersion enhanced by the contribution of polar clusters.
We studied the effect of hydrostatic pressure on the
dielectric behaviour of P(VDF/TrFE)(50/50) film exhibiting
different dielectric response: i) dispersive dielectric
permittivity nearly temperature independent in the range 250-
350 K and ii) the response with separated anomalies at the
Curie point and at the glass transition. Pressure causes an
upward shift of both TC and Tg, similarly to the pressure-
i nduced ef f ect repor t ed f or noni r r adi at ed
P(VDF/TrFE)(52.8/47.2), (64.6/35.4) and (70/30) copolymers
[6,7]. The pressure results also in a decrease of the real and
imaginary part of the permittivity and moreover, the frequency
of the maximum absorption decreases and the frequency
dispersion increases. The decrease in the dielectric compliance
we relate to the hindrance of the motion of the dipolar groups
in the amorphous and the crystalline phases of the copolymers
and the changes in the dielectric absorption to an increase in
the activation energy of the relaxation processes.
References
[1] B. Daudin, J.F. Legrand, J.Appl.Phys.70:4037 (1991),
[2] Q.M. Zhang, V. Bharti, X. Zhao, Science 280: 2101
(1998),
[3] Z.-Y. Cheng, V. Bharti, T.-B. Xu, S. Wang, Q.M. Zhang,
J.Appl.Phys. 86: 2208 (1999),
[4] L.E. Cross, Ferroelectrics 151: 302 (1994),
[5] B. Hilczer, H. Smogr, J. Goslar, S. Warcho_, Radiation
Effects and Defects in Solids, in press,
[6] N. Koizumi, N. Haikawa, H. Habuka, Ferroelectrics 57: 99
(1984),
[7] G.A. Samara, F. Bauer, Ferroelectrics 171: 299 (1995)
Polar Nanoregions in Perovskite
Relaxor Crystals by Neutron
Scattering
JIRKA HLINKA
1
, STANISLAV KAMBA
1
, JIRI KULDA
2
AND
JAN PETZELT
1
1
Institute of Physics AS CR, Praha, Czech Republic
2
Institute of Laue-Langevin, Grenoble, France
Polarization inhomogenieties, persisting above Currie
temperatures of Ti doped PbMg1/3Nb2/3O3 PbZn1/ 3Nb2/3O3
relaxor crystals (PMN:PT, PZN:PT) are usually discussed in
terms of so called polar nanoregions (PNRs). Polar
nanoregions plays certainly important role in relaxor
properties of these crystals and perhaps also in their "giant
piezoelectricity" and "waterfall phenomena". Up to date, the
most direct evidence of polar nanoregions comes from diffuse
scattering (DS) observed in neutron and X-ray scattering
experiments. Among others, the neutron scattering
experiments provided the nanometric size correlation length as
a function of temperature, relative atomic displacements
associated with the local dipolar moment and information
about anisotropy of PNRs.
However, only a little is known about characteristic
relaxation frequency associated with this DS, although several
recently proposed models actually assume or imply DS being
quasi-elastic. In order to better understand the dynamics of
PNRs, we have undertaken high resolution inelastic neutron
scatering study of PZN-8%PT single crystal at high flux
neutron reactor of ILL Grenoble. By using cold neutrons, we
have repeated some previous measurements at significantly
better energy resolution (8 GHz).
Obtained results allows to discard some recent promising
models in which the diffuse scattering stems from acoustic
modes coupled to overdamped soft modes. It also rules out
possibility that the relaxation time corresponds directly to the
critically temperature-dependent relaxation frequency seen in
the Brillouin experiments. On the other hand, our results
indicate that the correlation time scale of the DS corresponds
to relaxations seen in dielectric spectroscopy (relaxation
frequency associated with DS is not higher than 1GHz at
500K in PZN-8%PT). These results could be helpful for
quantitative understanding the unusual properties of the
perovskite relaxor crystals in general.
10
th
154
Thin Films of Bi
4-x
R
x
Ti
3
O
12
(R=Sm, Nd) Fabricated by Sol-gel
and Pulsed Laser Deposition
X. B. HU, A. GARG, J. WANG AND Z. H. BARBER
Department of Materials Science and Metallurgy, University
of Cambridge, Pembroke Street, Cambridge, CB2
3QZ,UK E mail:xh204@cam.ac.uk
Thin films of Bi4-xRxTi3O12 (R=Sm, Nd) have been shown
to demonstrate excellent fatigue resistance and a large
spontaneous polarization. To study the origins of such
desirable behavior for nonvolatile ferroelectric random access
memory (Nv-FRAM) applications, thin films of Bi4-xRxTi3O12
of variable compositions have been fabricated using two
different techniques: sol-gel and pulsed laser deposition,
which give rise to rather different film structures. Film
structure and properties have been studied as a function of the
processing parameters for both techniques. The ferroelectric
properties of these films have been characterized, and
comparison made with similar compositions in bulk ceramic
form. The observed behavior has been correlated with the
doping effects of Sm
3+
and Nd
3+
in the layered structure of
Bi4Ti3O12,. Other parameters that can affect the ferroelectric
properties of thin films are also considered, including the film
texture, film thickness, grain orientation, and interaction with
substrates and metal electrodes.
High-k HfO
2
Gate Oxide for CMOS
Applications
CHEOL SEONG HWANG,
1*
, MOONJU CHO,
1
HONG BAE PARK,
1
JAEHOO PARK,
1
SUK WOO LEE,
1
JONG-CHEOL LEE
2
AND SE-JUNG OH
2
1
School of Materials Science and Engineering and Inter-
university Semiconductor Research Center, Seoul National
University, Seoul 151-742, Korea
*
cheolsh@plaza.snu.ac.kr
2
School of Physics and Center for Strongly Correlated
Materials Research, Seoul National University, Seoul 151-
742, Korea
HfO2 gate dielectric thin films were deposited on bare-Si,
Al2O3- and Si3N4-passivated Si wafers using an atomic-layer-
deposition (ALD) technique at different temperatures (200 ~
400
o
C) with different thicknesses (2 ~ 15 nm). The HfO2
films were grown using HfCl4 and H2O or O3. 1~2-nm-thick
Al2O3 buffer layers were ALD grown at 400
o
C using
trimethylaluminium and O3, and some of the Al2O3 films were
NH3 plasma-treated to improve the thermal stability. Si3N4
films were also grown by another ALD technique. Thermal
annealing of the dielectric film stack at temperatures ranging
from 400
o
C to 1000
o
C under a pure N2 atmosphere resulted in
an increased equivalent-oxide-thickness due mainly to the
interfacial oxidation and Si-diffusion. The interfaces have a
high density of the fixed charges resulting in a flat-band
voltage shift. Si3N4 served as a good oxidation and Si-
diffusion barrier. However, the high interface state density
was problematic. Al2O3 also worked as the reaction barrier to
a certain degree. High temperature (>800
o
C) annealing
induced SiO2 formation and intermixing between the HfO2
and Al2O3 layers, which resulted in an increase in the
equivalent-oxide-thickness. The film stack showed a minimal
hysteresis (<15mV) behavior in the capacitance - voltage
curve and a flat-band voltage shift of 0.6 0.9 V by the
negative fixed charges at the Al2O3/SiO2 interface after
annealing at temperatures > 500
o
C. The variation in fixed
charge density as a function of the annealing temperature was
also investigated. The thermal stability and interface quality
was improved by a proper nitridation of the Al2O3 layer. A
minimum equivalent-oxide-thickness of 1.26 nm with a
leakage current density of 8x10
-6
A/cm
2
at 1 V was obtained
with the poly-Si electrode even after annealing at 1000
o
C for
10 sec.
10
th
155
LC Alignment Effects for a Nematic
Liquid Crystal on a-C:H Thin Film
as Working Gas at Bias Condition
J.-Y. HWANG
1
, C.-J. PARK1, D.-S. SEO
1
, S.-J. ROH
2
AND
H.-K. BAIK
2
1
Department of Electrical & Electronic Engineering, College
of Engineering, Yonsei University, 134 Shinchon-dong,
Seodaemoon-ku, Seoul 120-749, Korea E-mail:
dsseo@yonsei.ac.kr
2
Department of Materials Engineering, College of
Engineering, Yonsei University, 134 Shinchon-dong,
Seodaemoon-ku, Seoul 120-749, Korea
In this paper, we studied the nematic LC aligning
capabilities using the new alignment material of a-C:H thin
film as working gas at 30W rf bias condition. A high pretilt
angle of about 5by ion beam(IB) exposure on the a-C:H thin
film surface was measured. A good LC alignment by the IB
alignment method on the a-C:H thin film surface was observed
at annealing temperature of 250C, and the alignment defect of
the NLC was observed above annealing temperature of 300C.
Consequently, the high LC pretilt angle and the good thermal
stability of LC alignment by the IB alignment method on the
a-C:H thin film surface as working gas at 30W rf bias
condition can be achieved.
This work was supported by National Research
Laboratory program (M1-0203-00-0008).
UV-Exposure Effect on
Ferroelectricity of the Sol-gel
Processed PZT Thin Film
JAE-YEOL HWANG
1,2
, SANG-A LEE
2
,
CHAE-RYONG CHO
1
, AND SE-YOUNG JEONG
2
1
Korea Basic Science Institute, Busan branch, Korea
2
Department of Physics, Pusan National University, Korea
wolfhhh@pnu.edu
The Pb(Zr0.52Ti0.48)O3 thin films were prepared by sol-gel
method. Before final annealing, the spin-coated PZT thin films
were treated by the UV-photolysis process. The PZT thin
films with UV-photolysis process were exhibited higher
remnant polarization (Pr) and lower coercive field (Ec) than
those of not-treated one. The UV-photolysis process made it
possible to lower crystallization temperature and stabilize film
surface. The variation of the chemical bonding states in the
surface region due to the UV exposure were characterized by
x-ray photoelectron spectroscopy (XPS). The fatigue and
retention behavior of the film were also investigated. It is
assumed that the UV-treatment are very effective to enhance
ferroelectric properties and electrical properties. It is expected
to enable high reliability to fabricate ferroelectric thin film
devices.
10
th
156
Smart Material Formation on
Non-flat Surface with Use of Spray
Coating Method
M. ICHIKI, L. ZHANG, Z. YANG, T.IKEHARA AND
R. MAEDA
National Institute of Advanced Industrial Science and
Technology, 1-2 Namiki, Tsukuba, Ibaraki, 305-8564,
Japan. E-mail:ichiki-m@aist.go.jp
Conventional LSI fabrication technology has been
developed mainly onto the flat surface, e.g. Si-wafer. On
the other hand there has been increasing demands for three
dimensional manufacturing techniques for realization of
highly integrated and complicated devices. Chemical
solution deposition (CSD) could be useful for smart
materials except for step coverage. On the other hand
chemical vapor deposition (CVD) is suitable for step
coverage but not enough for many other process factors at
present. Therefore SCM is considered to be suitable for
these purposes. In this method fine liquid particles of smart
materials are ejected by a jet stream of carrier gas onto
substrate. SCM has advantages both in high quality
formation of chemical solution deposition and also in three-
dimensional fabrication including step coverage coating. It
is possible to make additional deposition onto deep-etched
base plate, coating onto the cylindrical non-planar surface
and micro molding. SCM enables us to make can be
formation of structure in both dry and wet condition in
accordance with control of process condition of deposition.
Gas-deposition method, which is dry deposition process
with use of fine particle, is also suitable for additional
fabrication but has risks of micro-damage or anchoring to
the substrate. SCM with electrostatic force has been
proposed for film formation

but can not be used widely
compared with SCM without electrostatic force (our
approach). Our results show the advantages of spray
coating method compared with other conventional PVD and
CVD technology. The formed film has almost the same (at
least not inferior) properties as that formed other process.
The crystalline structure is proved to be perovskite single
phase. Ferroelectric property of the film is also confirmed.
Charge Ordering and Polar
Properties in LuFe
2
O
4
NAOSHI IKEDA, HIIROYUKI OHSUMI AND
MASAICHIRO MIZUMAKI
Japan Synchrotron Radiation Research Institute 1-1 Koto
Mikazuki-cho Sayo-gun, HYOGO Japan, 679-5198.
ikedan@spring8.or.jp , ohsumi@spring8.or.jp,
mizumaki@spring8.or.jp
LuFe2O4 is a member of RFe2O4 family (R=Y or Dy to
Lu) in which an equal amount of Fe
2+
and Fe
3+
coexist on a
triangular plane. As the deviation of the iron valence from
average is 0.5 and +0.5 for Fe
2+
and Fe
3+
, respectively, the
configuration of the iron ions on triangular plane shows the
frustration in its free energy. It is considered that the
frustration effect dominates the ordering process of iron
ions in RFe2O4. In LuFe2O4 the two dimensional ordering
of iron charges appears below 500K and it develops to three
dimensional at 330K. The ferrimagnetic ordering is
observed below 250K.
The ordering of iron charges on LuFe2O4 was
confirmed with the resonant X-ray diffraction experiment
near the iron K absorption edge at a synchrotron beamline
BL02B1 in SPring8. The characteristic enhancenment of
the energy dependence of the diffraction intensity proves
that the ordered iron ions form a triple times super-structure
cell on triangular lattice. Our conclusion is that the charge
configuration on the ordered super cell become polar. We
suppose that the charge frustration originates such polar
super-cell formation.[1]
Our interest is to reveal the polar nature of the charge
ordering in LuFe2O4. The dielectric response of LuFe2O4 is
described by the electric hopping process among Fe
2+
and
Fe
3+
which coincides with the inverting process of the polar
charge region.. The temperature variation of the AC
dielectric constants shows a characteristic dispersion[2].
In order to prove the polar nature of the charge ordreing
on triangular plane, we are surveying the external electric
field responce of the charge ordering structure through the
resonant X-ray diffraction experiment.
We had heated the sample above the three dimensional
charge ordering temperature 500K without electric field
then cooled the sample under electric field along a-axis
until room temperature. Before the field cooling treatment
the appearance rule of the superlattice spot was described as
n/3 n/3 n+1/2, where n and m were integer. After the field
cooling the appeared index has changed to n/3 n/3 3m+1/2,
where n and m were integer in hhl plane (h>0). The super
lattice spot shows the characteristic variation in the energy
dependence of the diffraction intensity. These facts suggests
that the charge super cell is polar and it has the helical
arrangement along the c-axis in the single domain state.
[1] N. Ikeda et al. Ferroelectrics 272(2002) 309.
[2] N. Ikeda et al. J. Phys. Soc. Jpn., 63(1994)4556.
10
th
157
Microstructure-Property
Relationship in Dielectric Ceramics
Containing (Nb,Ti)O
6
Octahedra
Y. IQBAL AND I. M. REANEY
Department of Engineering Materials, University of
Sheffield, Mappin Street, Sheffield, UK.
Environmental concerns over Pb and Bi have led to the
search for new dielectric materials which do not contain
these elements. The most likely ions other than Bi and Pb to
give rise to good dielectric properties are Ti
4+
and Nb
5+
since these are highly polarisable, particularly when in
octahedral coordination. Two compositional series have
therefore been investigated: (1-x)Sr4Nb4O14 - xTiO2 and
(1-y)Sr4Nb4O14 ySrTiO3. The addition of TiO2 to
Sr4Nb4O14 significantly increased r from ~45 for x = 0 to
~500 for x=0.67. However, the permittivity for x = 0.67
was decreased as the frequency approached 10MHz and
ceramics were clearly two phase. The addition of SrTiO3 to
Sr4Nb4O14 resulted in the formation of single phase (by X-
ray diffraction) compounds up to y = 0.67. This was
commensurate with an increase in r from 45 (y = 0) to 68
(y = 0.67). The MW properties of the latter series are
currently being investigated.
Theoretical Consideration on the
90
o
Domain Walls in Tetragonal
Ferroelectrics
Y. ISHIBASHI
1
AND E. SALJE
2
1
Aichi Shukutoku University, Nagakute-cho, Aichi
Prefecture 480-1197, Japan, yishi@asu.aasa.ac.jp
2
Department of Earth Science, Cambridge University,
Downing Street, Cambridge CB2 3EQ, United
Kingdom ekhard@esc.cam.ac.uk
It is known that there are two types of domain walls in
the tetragonal perovskite oxide ferroelectrics, i.e., 180
o
walls and 90
o
walls. There are only few theoretical
analyses on the 90
o
walls[1, 2], though the 180
o
walls have
been very much studied. On the other hands, it has been
found that more 90
o
walls appear in ferroelectric thin films
fabricated on some substrates, likely due to the mismatch of
strains between films and the substrates, and it has become
more important than before to understand physical
properties of the 90
o
walls.
The most substantial difference between the 180
o
walls
and the 90
o
walls is that in the former the modulation of
polarization takes place transversally, while the latter it
does longitudinally, and therefore in the latter it is
indispensable to take into account of the depolarization
field effect. Regarding this, it can be easily guessed that
the larger the anisotropy in the local potential energy, the
larger the amplitude of the modulation and therefore the
depolarization field effect.
References
1. Y. Ishibashi: J. Phys. Soc. Jpn. 62, 1044 (1993).
2. Y.Ishibashi and E. Salje: J. Phys. Soc. Jpn. 71, 2800
(2002).
10
th
158
Low-frequency Elastic and
Anelastic Properties of the Ceramic
PbFe
0.5
Nb
0.5
O
3
Ferroelectric-
Ferroelastic with Magnetic
Ordering
O. N. IVANOV, E. A. SKRIPTCHENKO,
M.E. PRYAKHINA
Voronezh State Technical University, Moskovskii prospekt
14, 394026 Voronezh, Russia. gridnev@ns1.vstu.ac.ru
The mixed perovskite-type oxide PbFe0.5Nb0.5O3 is
known to be as one of typical ferroelectrics with magnetic
ordering. For this compound antiferromagnetic spin
ordering arises below the Neel temperature TN=143 K and
ferroelectricity-ferroelasticity takes place below the Curie
temperature TC =383 K. The aim of present work is to find
and study the peculiarities of the low-frequency (f10 Hz)
elastic and anelastic properties of the ceramics
PbFe0.5Nb0.5O3 within the temperature range including the
Curie and Neel temperatures.
The ceramic samples were prepared by the solid-state
reaction of the appropriate amounts of PbO, Fe2O3 and
Nb2O5. Technology with two-stage annealing was applied
(stage I: T=1250 K, t=4h and stage II: T=1370 K, t=2h).
Internal friction Q
-1
and shear modulus G was measured by
the inverted torsion pendulum for cooling mode.
Step-like change of the G (T) dependence was observed
in the vicinity of TC. Such kind of elastic anomaly is a
characteristic of improper ferroelastic phase transitions. A
slight curvature in the G (T) dependence was found at TN.
This elastic anomaly could be induced by the
magnetostriction. The maxima of internal friction near the
Curie and Neel temperatures corresponding to the elastic
anomalies were observed as well. The possible reasons of
the anomalies found in elasticity and anelasticity of the
ceramics PbFe0.5Nb0.5O3 are discussed.
This work was supported by the Ministry of Education
of the Russian Federation under grant No UR.01.01.016.
Magnetically Ordered Ferroelectric
Complex Metal Oxides: A neutron
Powder Diffraction Study
S. A. IVANOV
1
, S.-G. ERIKSSON
2
, R. TELLGREN
3
,
H. RUNDLF
3
1
Karpov' Institute of Physical Chemistry, Moscow, Russia
e-mail: ivan@cc.nifhi.ac.ru
2
Department of Inorganic Chemistry, University of
Gothenburg, Sweden
3
Institute of Chemistry, Uppsala University, Uppsala,
Sweden
The electronic properties of complex perovskites are
dependent on the adopted atomic structure and an
understanding of the crystal chemistry of these compounds
is crucial in the development of novel materials with an
unusual combination of dielectric and magnetic properties.
In this study, we have paid attention to 1:2 ordered
perovskites, and will report the temperature evolution of
their nuclear and magnetic structures. NPD studies have
been carried out to study the magnetically ordered
ferroelectric materials with perovskite-related structure
A3Fe2BO9 (A=Pb,Sr,Ca,Ba; B=W,Te), prepared by solid
state route. It was shown that this class of the so-called
ferroelectric magnets exhibits both electric-dipole and
magnetic ordering within a definite temperature range.
NPD patterns have been collected at the Swedish
Research Reactor R2 (Studsvik) at different temperatures in
the range 10 to 1000 K. The data were analyzed with the
FULLPROF software in order to characterize the
temperature-induced phase transformations, and to
determine the nuclear and magnetic structures. By replacing
Pb by Sr, Ba or Ca the different types of lattice distortions
of the initial cubic perovskite cell was found (tetragonal for
Sr, hexagonal for Ba and monoclinic for Ca compounds).
The size of the involved A-type cation is directly related to
different types of structural distortions. The structural
peculiarities of distorted phases are discussed and possible
mechanisms of phase transitions are presented.
It was found that for the Pb compound the Fe and
W(Te) cations are randomly distributed over the B sites
while in the case of Sr and Ca compounds a partial
crystallographic order was established. Tc values appear to
depend mainly on the nature of the A-cation (ion size and
electronic configuration) and degree of cation ordering of
Fe/W(Te).
The ordering of magnetic moments of Fe in these
systems are analyzed. And all the compounds show G-type
of magnetic structure. Magnetic properties would be more
sensitive to the content of W cations in comparison with Te
ones. The correlation between ferroic distortions and the
magnetic ordering is also briefly discussed.
The financial support for this research from Swedish
Royal Academy of Sciences and Russian Foundation for
Basic Research (project N 00-03-32578) is gratefully
acknowledged.
10
th
159
Crystal Structure and Ferroelectric
Phase Transitions of KTiOPO
4
Doped with Nb and Sb
S. A. IVANOV
1
, S. STEFANOVICH
1
, S.-G. ERIKSSON
2
,
V. VORONKOVA
3
, V.YANOVSKII
3
, T. LOSEVSKAYA
3
,
R.TELLGREN
4
, H. RUNDLF
4
1
Karpov' Institute of Physical Chemistry, Moscow, Russia
2
Department of Inorganic Chemistry, University of
Gothenburg, Sweden
3
Department of Physics, Moscow State University,
Moscow, Russia
4
Institute of Chemistry, Uppsala University, Uppsala,
Sweden
Crystals of KTiOPO4 (KTP) have a unique combination
of physical properties such as non-linear optic (NLO),
ferroelectric (FE), and superionic(SI)). In an attempt to
understand the role of Nb and Sb doping in KTP on FE and
NLO properties, a series of neutron powder diffraction
(NPD) and second harmonic generation (SHG) studies were
initiated. KTNP crystals with 2, 3, 10, or 15% Nb and
KTSP crystals with 5 or 10% Sb were grown using a flux
method. The powder specimens were prepared from single
grystals by grinding.
NPD patterns have been collected at the Swedish
Research Reactor R2 (Studsvik) at different temperatures
below and above Tc. The NPD patterns were analyzed with
the FULLPROF software in order to characterize the
temperature-induced phase transformations. From sequental
Rietveld refinements the correct symmetry of ferroic phases
and polar atomic displacements associated with the
ferroelectric phase transitions were studied as a function of
temperature.
All the structures are found to be orthorhombic (space
group Pna21 at T<Tc and space group Pnan at T>Tc) and
are isostructural with KTP. The substitution of Nb for Ti
leads to expansions along the a- and b- axis and a
contraction along the c- axis. Nb atoms strongly favor the
Ti(1) sites reducing the octahedral distortion. The charge
balance was kept by creation of vacancies preferentially at
the K(1) site. The major atomic displacements associated
with the FE transitions were used for estimation of the
spontaneous polarization. Moreover, above Tc a partial
disorder of K cations was found. Finally, the possible type
of phase transition (displacive or order-disorder) is briefly
discussed.
The financial support of this research from the Swedish
Royal Academy of Sciences and the Russian Foundation for
Basic Research (project N 00-03-32578) is gratefully
acknowledged.
Switching Processes in DTGS Crystals Irradiated by High-
current Pulsed Electron Beam.
V.V. IVANOV
1
, V.V. MAKAROV
1
, E.A. KLEVTSOVA
1
,
T.A. MARKOVA
1
, S.I. TUTUNNIKOV
2
, V.V. EFIMOV
2
1
Tver State University, Tver, Russia,
E-mail: Vladimir.Ivanov@tversu.ru
2
Joint Institute for Nuclear Research, Dubna, Russia
Of great importance are the measurements of the
polarization reversal occurring after some type of external
influence electric field, temperature, mechanical strain.
Relaxation switching processes in DTGS crystals irradiated
by high-current pulsed electron beam were studied. The
method combining the measurements of dielectric
permittivity, polarization, coercive field and tan with
Barkhausen effect method observation has been employed.
Investigations performed in a wide range of electric field
strength (up to 0.5 kVcm
-1
) and temperatures (from 20C
to 60C).
The total Barkhausen jumps number dependences and
differentiate distribution in irradiated DTGS crystals during
of changing electric state by branch of hysteresis loop were
obtained. The total Barkhausen jumps number at the
polarization reversal were studied. The time dependence of
the Barkhausen jumps number in DTGS crystals irradiated
by high-current pulsed electron beam at the different
radiation dose were observed.
The Tikhonov regularization method was applied in the
analysis of the experimental data to obtain the distribution
function of relaxation time of switching processes.
Switching processes in DTGS crystals irradiated by high-
current pulsed electron beam are discussed by dielectric
viscosity model.
10
th
160
Peculiarities of light scattering near
domain-domain phase transition
S. V. IVANOVA
Leninsky Physical Institute RAS, Moscow, 119991,
Leninsky pr.53, email: ivanova@sci.lebedev.ru
The ferroelectric crystal barium sodium niobate, (BSN,
Ba2NaNb5O15) with tetragonal tungsten bronze type of
structure has been the subject of studies for its potential
tecnical applications because excellent non-linear optical
and electrooptical properties. BSN to show some peculiar
phenomena in the incommensurate (IC) phase such as the
memory effect, which are closely related to a phase
transition from a normal tetragonal phase to an IC one at
300C. Single crystals were grown by the Czochralsky
method perpendicular to the ferroelectric c-axis. The
samples (3x4x5mm) oriented along the crystallographic
aces were placed in focused light beam ( = 514.5 nm,
P = 30 300 mW) ). The length of the focused beam in
crystal was 3 mm and transverse diameter of the light spot
was 20m. The direction of laser beam in different
experiments was parallel and perpendicular to optical axis
of crystal. Crystal was mounted in an oven which had four
windows that allowed visual observation of the sample. The
patterns of scattering light were observed on the screen in
far field (about 200 cm from the sample). The elastic light
scattering was studied by means monochromator DFS-12.
In this work thermal evolution of the scattering radiation,
passed through crystal, was studied in temperature range of
20 - 500C. When the temperature is lowered from 500C
to 20C, the light scattering pattern exhibit two different
continuous changes in far field: the round-like form was
observed from 500 to 300C, the elongated rounds was
shown from 300 to 270C. When the temperature is
lowered to 230C the pattern changes and exhibits fine
stripes. At these temperature earlier was discovered the
phase transition of second order. Features of elastic light
scattering in IC phase of BSN that appear in the cooling and
heating processes were investigated at different geometry of
experiments. There is correlation between the behaviour of
light scattering in far field and anomalies on the curves of
elastic light scattering. Mori et al. [1] have found that the IC
structure in the temperature range between 300 and 270C
is constituted of a complicated array of two type of
ferroelastic microdomains with a size of about 20 nm.
When the temperature is lowered to 260C the domain
structure exhibit two different continuous changes. One is
the decrease in volume of one of the two types of
microdomains, and the other is the formation of elongated
rectangular domain structure. When the temperature is
further lowered to around 230C, the domain structure
abruptly changes into a large scaled domain structure of the
ferroelastic phase with the orthorhombic symmetry. The
size of the domain was estimated to be about 1m on
average. The most important feature of this change is that
the domain-structure change never accompanies a change in
point group symmetry. From the reversibility, the domain-
structure change around 230C could be called the
domain-domen structure transition.
[1] S. Mory, et al. Evolution of a ferroelastic domain
structure in an incommensurate phase of barium sodium
niobate,Phys. Rev. B, 52, pp. 57-68, 1995.
Annealing Effect of the Phase
Transition in PbIn
1/2
Nb
1/2
O
3
Crystal
M. IWATA
1
, S. KATAGIRI
2
, H. ORIHARA
2
, I. SUZUKI
1
,
M. MAEDA
1
, H. OHWA
3
, N. YASUDA
3
AND
Y. ISHIBASHI
4
1
Department of Electrical and Computer Engineering,
Nagoya Institute of Technology, Nagoya 466-8555,
Japan
2
Department of Applied Physics, School of Engineering,
Nagoya University, Nagoya 464-8603, Japan
3
Electric and Information Department, Gifu University,
Gifu 501-1193, Japan
4
Department of Communications, Aichi Shukutoku
University,Nagakute-cho, Aichi 480-1197, Japan
A lot of lead-based Perovskite-type ferroelectrics
Pb(B,B')O3 show the relaxor behaviour characterized by the
diffuse phase transition. The essence of the diffuse
transition is considered to be on the spatial fluctuation of B-
site cations which brings about small polar region and
distribution of the transition temperature. As for the
compositional fluctuation, it was reported that the chemical
ordering of B-site cations can be controlled by relevant
thermal treatment in some relaxor ferroelectrics such as
Pb(In1/2Nb1/2)O3 (PIN), Pb(Sc1 / 2Nb/2)O3 (PSN) and
Pb(Sc1/2Ta/2)O3 (PST).
1,2)
PIN crystal, which has different chemical ordering in
the arrangement of In
3+
and Nb
5+
on the B-site obtained by
different thermal treatment, can be classified into three
groups, which are called "the ordered PIN", " the disordered
PIN" and "the partially ordered PIN". The ordered PIN
shows a first order phase transition from the paraelectric
phase to the antiferroelectric phase at about 160C, the
disordered PIN shows the relaxor behaviour characterized
by a dielectric dispersion below 50C, and the partially
ordered PIN shows a broad peak of dielectric constant
without dielectric dispersion at about 90C. Ohwa et al.
reported the experimental results of the polarizing
microscopic observation in PIN crystals with different
thermal treatment and the local dielectric measurement in
the partially ordered PIN.
In the present study, we have investigated the annealing
effect of the phase transition in PIN crystal by means of the
dielectric constant measurement, the D-E l oop
measurement and the polarizing microscopic observation.
Using the same sample plate of the PIN, it has been
observed that antiferoelectric transition gradually changes
into the diffuse phase transition as the annealing
temperature increases. On the basis of the observation by
optical microscope, the annealing effect of the diffuse phase
transition in the relaxor has been discussed.
1) P. Groves: J. Phys. C: Solid State Phys. 19 (1986) 5103.
2) P. Groves: J. Phys. C: Solid State Phys. 19 (1986) 111.
3) H. Ohwa, M. Iwata, H. Orihara, N. Yasuda and
Y. Ishibashi: J. Phys. Soc. Jpn. 69 (2000) 1533.
10
th
161
Raman Studies of Pb
1-x
Sr
x
TiO
3
Ceramics and Composites
M. JAIN
1
, YU. I. YUZYUK
1
, R.S. KATIYAR
1
,
Y. SOMIYA
2
, A.S. BHALLA
2
1
Department of Physics, P.O. Box 23343, University of
Puerto Rico, San Juan PR-00931, USA
Email:rkatiyar@rrpac.upr.clu.edu
2
Materials Research Institute, The Pennsylvania State
University, University Park, PA-16802, USA
Raman spectra of solid solutions of (Pb1-xSrx)TiO3 for
x=0.7 (PST30), x=0.8 (PST20) and a composite of PST20
with MgO have been investigated. The ceramics were
prepared by the conventional solid state reaction method.
Raman data showed that all PST compositions studied were
cubic at room temperature. Phase transition was observed
by dielectric and Raman measurements for PST20 and
PST30 ceramics at 60
o
C and 10
o
C, respectively.
Moreover, Raman measurements revealed well pronounced
soft-mode behaviour below the Curie temperature in both
the compounds and the composite PST20:MgO. At the
transition temeprature, dielectric constants are 38,500 and
29,000 for PST20 and PST30 ceramics respectively, with
loss tangents in the range of 0.002-0.003. The addition of
MgO in the PST20 ceramic was found to reduce the
dielectric constant and the phase transition became diffused.
We believe that nano-polar regions exist in PST20 and
PST30 compositions. In the PST20:MgO composite
diffused phase transition and dilution of dielectric
properties occured. The effects of nano-polar regions and
the inhomogeneous strain inside the composite material
generated by intergrain clamping or due to other point
defects (like oxygen vacancies), are discussed in this paper.
Dielectric Properties at the
Successive Phase Transitions in
[4-NH
2
C
5
H
4
NH][SbCl
4
]
RYSZARD JAKUBAS
1
, GRAZYNA BATOR
1
AND
ADAM PIETRASZKO
2
1
Faculty of Chemistry, University of Wroclaw, Joliot-Curie
14, 50-383 Wroclaw, Poland,
rj@wchuwr.chem.uni.wroc.pl
2
Institute of Low Temperature and Structure Research,
Polish Academy of Sciences, 50-950 Wroclaw, Poland,
4-ami nopyri di ni um t et rachl oroant i monat e(III)
(4 APCA), [4-NH2C5H4NH][SbCl4], is a member of the
family of general formula RaMbX3b+a (where R = organic
cations, M = Sb, Bi and X = Cl, Br, I) [1]. The crystal
structure of 4-APCA is made of polyanionic chains of
(SbCl4
-
) and the 4-aminopyridinium cations connected via
weak hydrogen bonds to the chlorine atoms [2]. 4-APCA is
a very unique structurally incommensurate (IC)
ferroelectric crystal. It undergoes very complex sequence of
phase transitions : at 304 K from paraelectric phase (I) to
modulated commensurate phase (II), at 270.5 K to
ferroelectric incommensurate phase (III), at 248 K to
second ferroelectric commensurate phase (IV) and at 240 K
to nonpolar phase (IV). The ferroelectric phase transition
(IIIII) is accompanied by a distinct dielectric anomaly,
700 at 100 kHz. Dielectric dispersion was found to occur
in single crystals of [4-NH2C5H4NH][SbCl4] at radio-
frequencies in the range of 200 Hz 1 MHz. The dielectric
dispersion is monodispersive in the commensurate phase
(II) (270.5 304 K) except for the close vicinity of Tc, for
T > Tc +1 K (Tc = 270.5 K). An apparent critical slowing
down is found with 1 10
-4
s just above Tc. Dielectric
behaviour of the crystal in an electric bias field is studied
and analysed.
References
[1] R. Jakubas and L. Sobczyk: Phase Transitions 20 163
(1990).
[2] R. Jakubas, Z. Ciunik and G. Bator : Phys. Rev. B67
024103 (2003).
[3] A. Pietraszko et.al. sent for publication in J. Phys.:
Condens. Matter.
10
th
162
Ferroelectric Properties of SBN
Thin Films Deposited by Ion Beam
Sputtering
JAE HOON JANG
1
, SUNG WON JUNG
1
,
JEONG-JOO KIM
2
, SANG-HEE CHO
2
, AND
HEE YOUNG LEE
1
1
Department of Materials Science and Engineering,
Yeungnam University, Gyeongsan 712-749, KOREA.
hyulee@yu.ac.kr
2
Department of Inorganic Materials Engineering,
Kyungpook National University, Daegu 702-701,
KOREA.
SrxBa1-xNb2O6 (SBN) thin films were deposited on two
different types of Pt/Ti/SiO2/Si(100) substrates by ion beam
sputter deposition (IBSD) technique. Ceramic targets with x
values corresponding to 0.25, 0.30 and 0.60 were prepared
by the conventional mixed-oxide ceramic process. Base
chamber pressure was kept well below 10
6
torr, while
working pressure was on the order of 10
4
torr. Substrates
were heated during deposition typically in the range of 400
to 500
o
C. X-ray diffraction (XRD) and a field-emission
scanning electron microscope (FE-SEM) were used to
determine the crystallinity and microstructure of the
samples.
It was found that the film orientation was strongly
dependent upon t he subst r at e used, i . e.
Pt(111)/Ti/SiO2/Si(100) or Pt(100)/Ti/SiO2/Si(100), and the
presence of seed layer. D-E hysteresis loop for Pt/SBN30/Pt
capacitor sample was saturated after annealing treatment in
air at 750
o
C, with remanent polarization (2Pr) value of
about 22_C/cm
2
and coercive field (Ec) of 128 kV/cm.
Relative permittivity and leakage current characteristics
were also determined from C-V and I-V measurements.
Inverse Database of Phase
Transitions in Crystals with a
Single Phase Transition
V. JANOVEC
1
, P. TOMASZEWSKI
2
, L. RICHTEROV
3
,
Z. KLUIBER
4
1
Technical University of Liberec, Hlkova 6, 461 17
Liberec 1, Czech Republic, janovec@fzu.cz ,
2
Institute of Low Temperature and Structural Research,
PAN, P. Nr 1410, Wroclaw 2, 50-950 Poland,
3
Comenius University, Faculty of Mathematics and
Physics, Mlynska dolina F1, 842 15 Bratislava,
Slovakia,
4
Comenius University, Faculty of Mathematics and
Physics, Mlynska dolina F1, 842 15 Bratislava,
Slovakia,
We report on a database of selected ferroic phase
transitions arranged according to symmetry reduction at the
transition and present some overall conclusions on the
population (percentage) of various kinds of transitions in
crystals with a single phase transition.
Tomaszewskis database of structural phase transitions
[1] and its updated version [2,3] (containing about 6400
phase transitions in about 3450 crystalline materials) are
arranged according to chemical formulae of crystals. From
these data we have selected about 300 crystals with a single
phase transition and with reliable data on space-groups and
lattice parameters of the parent and ferroic phases. Then we
have rearranged this small database 1 according to
symmetries of the parent (prototypic) and ferroic phase.
From this inverse small database 1 some general
conclusions for crystals with a single transition can be
deduced, e.g.
A . population of observed full, partial and non-
ferroelastic phase transitions,
B . population of observed full, partial and non-
ferroelectric phase transitions,
C. combinations of two preceding divisions,
D. population of equitranslational and several types of
non-equitranslational phase transitions,
E . percentage of symmetry reductions for which no
crystal with corresponding phase transition has been
found.
The inverse database can be helpful in search for
materials with similar phase transitions and may also serve
as an impetus for a deeper study of structural instabilities of
crystals.
[1] P.E. Tomaszewski (1992), Phase Transitions 38, 127-
228.
[2] P.E. Tomaszewski (2002). "Golden Book of Phase
Transitions" (Phase transitions database PTDB-2002);
manuscript (2002).
[3] P.E. Tomaszewski (2003). to appear in Phase
Transitions.
10
th
163
Displacements of Atoms in Domain
Walls of Tetragonal Perovskite
Crystals
V. JANOVEC
1
, M. GROCKY
2
, V. KOPSKY
3
,
Z. KLUIBER
4
1
Technical University of Liberec, Hlkova 6, 461 17
Liberec 1, Czech Republic
2
Faculty of Mathematics and Physics, Charles Univ.,
Ke Karlovu 5, 121 16 Prague 2, Czech Republic,
mari.mail@centrum.cz
3
Institute of Physics, CAS, Na Slovance 2, 182 21
Prague 8, Czech Republic
4
High School of Christian Doppler, Zborovsk 45,
150 00 Prague 5, Czech Republic
We demonstrate what information on microscopic
structure of domain walls can be deduced from symmetry
analysis and compare this treatment with usual
thermodynamic theory of domain walls.
Atomic displacements and/or ordering of atoms in a
domain wall are confined by symmetry of the wall
expressed by a layer group. This confinement determines
relations between displacements of atoms at different
positions and specifies (completely or partially) the
direction of atomic displacements in the wall. These
deductions describe topology of the displacement field but
do not yield numerical values of atomic displacements.
The main advantage of this approach is that it is not
restricted by any approximation or by simplifying models,
needed in usual treatments, and its conclusions are,
therefore, definitive. Other positive feature is that the
structure of domain walls of any (even one-atomic-layer)
thickness can be examined and, further, information about
atomic displacements of particular atoms is given directly
and not indirectly via an order parameter as in a
thermodynamic theory.
We have analyzed the displacement field of ferroelastic,
ferroelectric and antiphase domain walls in tetragonal
phases of BaTiO3 and of SrTiO3. Typical results in a
graphical representation demonstrate significant changes of
the microscopic wall structure with orientation and position
of the wall in crystal lattice. Examples also illustrate basic
distinction between symmetric-asymmetric and reversible-
irreversible domain walls.
A comparison between symmetry analysis and Landau-
type thermodynamic theory of domain walls shows
advantages and drawbacks of both approaches.
Dynamics of Domain walls in
Ferro-electrics and
Magneto-electrics
T. JANSSEN
Institute for Theoretical Physics, University of Nijmegen,
Nijmegen, The Netherlands. e-mail ted@sci.kun.nl.
Domain walls are static excitations in ferro-electrics,
which may be set in motion by external forces or internal
strain. This movement can be described in terms of a non-
linear dynamical system. The mobility depends strongly on
the underlying microscopic structure and may become large
in the case of weakly modulated aperiodic phases. The
conditions under which a low internal friction may be found
will be discussed.
For magneto-electric materials the coupling between
the magnetic and electric order parameters may lead to
breather solutions.
The dynamics of the domain wall is illustrated by
means of simple models.
10
th
164
Breakdown of the Electrostatic
Approximation for Polarization
Waves Propagating in Ferroelectric
Layers
JEAN-PIERRE JARDIN AND PHILIPPE MOCH
LPMTM, CNRS, Universit Paris-Nord, Av. J.-B.Clment,
93430 Villetaneuse, France;
e-mail: moch@galilee.univ-paris13.fr
The polarization waves propagating in a semi-infinite or
in a thin film layer are described using a Landau model for
the free energy including spatial dispersion and appropriate
surface energy terms [1] with realistic numerical values [2].
The retardation arising from the Maxwell equations is
explicitely taken in account. Concening the surface
localized modes in the paraelectric phase, the electrostatic
approximation provides satisfactory results as long as the
surface wave vector k significantly overpasses /c where
is the radial frequency and c is the light velocity in the
surrounding medium. In most cases the retardation effect
practically only consists in the presence a cut-off wave
vector at /c. However, this cut-off does not occur for the
fundamental even Transverse-Electric (TE) mode in a thin
film, the frequency of which vanishes when k decreases
down to 0. The far infra-red optical properties are also
studied in various conditions of illumination : it is shown
that optical measurements could provide information about
the above mentioned dispersion and surface terms.
References
[1] J.-P. Jardin, P. Moch and V. Dvork, J. Phys.:Condens.
Matter, 14, 1745 (2002)
[2] W.L. Zhong, Y.G. Wang, P. L. Zhang, B.D. Qu, Phys.
Rev. B50, 698 (1994)
Progressive Loss of Ferroelectricity
under Bipolar Pulsed Fields and
Experimental Determination of
Non-switchable Polarization in
Au/Ba
0.5
Sr
0.5
TiO
3
/SrRuO
3
Thin Film Capacitors
*
A. Q. JIANG
1
J. F. SCOTT
1
AND J. M. GREGG
2
1
Symetrix Centre for Ferroics, Department of Earth
Sciences, University of Cambridge, Downing Street,
Cambridge CB2 3EQ, UK.
*
ajia00@esc.cam.ac.uk
2
Condensed Matter Physics and Material Science Research
Division, School of Mathematics and Physics, The
Queens University of Belfast, Belfast BT7 1NN, UK.
Interfacial passive layers have often been invoked to
interpret both the reduced dielectric permittivity and tilted
P-E hysteresis loops found in thin film electroceramics.
1-3
The interfacial influence is believed to be significant even if
the passive layer is very thin. Of particular relevance here is
the hypothesis that interfacial non-switchable polarization
could play a part, and also explain the voltage offset
observed in many P-E hysteresis loops.
4
Our experiments
on a 175nm-thick Ba0.5Sr0.5TiO3 film integrated into a
Au/Ba0.5Sr0.5TiO3/-SrRuO3/MgO capacitor structure show
that the film is the mixture of ferroelectric and paraelectric
at room temperature, as confirmed by a novel plot of
capacitances with decreasing dc voltage versus increasing
dc voltage. The similar mixed phases was also observed on
SrTiO3 thin films.
5
The volume concentration of the
ferroelectric phase reduces with increasing switching
number of bipolar pulsed fields, but recovers gradually after
pulsing has ceased, associated with an increase of dielectric
permittivity of the capacitor. D-V hysteresis loops at
various relaxation times for the switched capacitor intersect
with two fixed points. The gradient of the line joining these
two points was found to be equal to the paraelectric
dielectric permittivity. Non-switchable polarization and
paraelectric dielectric permittivity were determined to be
3.37 C/cm
2
and 255, respectively. This supplies ideal
conditions to model the importance of one genuine passive
layer on domain switching. The coercive voltage of domain
switching is found to decrease with increasing
concentration of paraelectric phase, and obeys the
relationship Ec
t
=(1+d/l)
-1
Ec
f
, where d and l the thicknesses
of constituent paraelectric and ferroelectric layers,
respectively.
1. L.J. Sinnamon et al. Appl. Phys. Lett. 78, 1724 (2001).
2. A.M. Bratkovsky and A.P. Levanyuk, Phys. Rev. B 63,
132103 (2001).
3. A.K. Tagantsev et al. J. Appl. Phys. 78, 2623 (1995).
4. P.K. Larsen et al., J. Appl. Phys. 76, 2405 (1994).
5. U. Robels et al. J. Appl. Phys. 77, 4002 (1995).
10
th
165
Investigation of Crystal Growth,
Structure and Properties of
Na
0.5
Bi
0.5
TiO
3
-xBaTiO
3
Crystals
Near the Morphotropic Phase
Boundary
Q. JIANG
1
, P.A. THOMAS
1
, VICTORIA SHUVAEVA
2
AND
A.M.GLAZER
2
1
Physics Department, University of Warwick, Coventry
CV4 7AL, UK, Email: Q.Jiang@warwick.ac.uk
2
Clarendon Laboratory, Parks Road, Oxford OX1 3PU, UK
Over the years, morphotropic phase boundary(MPB)
ferroelectric materials have attracted much attention due to
their large piezoelectric coefficients, both for applications
and for a fundamental understanding of the phenomenon.
Although the Pb-based MPB crystals, such as
(1-x)Pb(Mg1/3Nb2/3))3-xPbTiO3 ( PMN- xPT) and
(1-x)Pb(Zn1/3Nb2/3)O3-xPbTiO3 (PZN-xPT) have shown
superior piezoelectric properties, it can be difficult to obtain
compositionally uniform crystals. Among non-Pb-based
MPB crystals, there are technical difficulties in growing
(1-x)Na0.5Bi0.5TiO3-xK0.5Bi0.5TiO3(KNBT) crystals near the
phase boundary at x~0.6. However, for morphotropic
(1-x)Na0.5Bi0.5TiO3- xBaTiO3(Ba:NBT), since a small range
of concentration x=0-8% will cover both tetragonal and
rhombohedral phases, it is expected that Ba:NBT will
display the crystallisation behaviour of NBT. In this work,
both self-nucleation and Bridgeman methods were
employed for crystal growth of Ba: NBT. The phase
boundary is determined to be between x=0.06-0.08. The
phase transitions of both tetragonal and rhombohedral
Ba:NBT were investigated by impedance analysis and
birefringence imaging using the Metripol.
1
The domain
switching characteristics are also investigated by observing
both the switching current and ferroelectric hysteresis
tracing.
Reference
1. M.Geday, J.Kreisel, A.M.Glazer, K.Roleder,. Journal of
Applied Crystallography, 33 (2000) 909-14
Relaxor-like Behavior of
Pb
.5
Ca
.5
TiO
3
Thin Films
R. JIMENEZ, C. ALEMANY, M.L. CALZADA,
J. MENDIOLA
Inst. Ciencia de Materiales de Madrid, CSIC, Cantoblanco,
Madrid 28049, Spain, riqjim@icmm.csic.es
Single phase thin films of ferroelectric Pb.5Ca.5TiO3
were deposited onto Pt/TiO2/SiO2/Si(100) substrates by
spin-on sol-gel process. This is the first time, to the
knowledge of the authors, that relaxor properties are
reported for with this composition. The films show a
diffusivity in the phase transition and a frequency
dispersion of the temperature of the dielectric constant
maxima, Tm. From polarization- temperature measurements,
remanent polarization persists well above the phase
transition (close to 273 K). These all properties are
characteristics of relaxor ferroelectrics and confirms that
previously proposed suggested by Ranjan et al. (1) for bulk
ceramics of the same composition. The Vogel-Fulchner
relation is fulfilled for the frequency dependence of the
temperature of the maximum of dielectric constant, Tm., as a
verification of the relaxor nature of the films. As usually
detected in thin films, diffusivity of the dielectric constant
is very large, the maximum, Tm, is shifted at higher
temperatures and its values lowered with respect to the bulk
ceramic counterpart. These differences can be adscribed to
the stress state of the films ( 200 MPa) and to the
influence of the electrode-film interfaces (dead layer).
[1] R. Ranjan, N.Singh, D. Pandey, V. Siruguri, P.S.R.
Krishna, S.K. Paranjpe, A. Banerjee, Appl. Phys.
Lett.,70 (24), 3221 (1997)
10
th
166
An Activation Energy for Domain
wall Switching based on Nucleation
Limited Switching Kinetics
D. J. JUNG
1
, M. DAWBER
1
, F.D. MORRISON
1
,
A. RUEDIGER
1
, J.F. SCOTT
1
, H.H. KIM
2
AND
KINAM. KIM
2
1
Department of Earth Sciences, University of cambridge,
Downing Street, CB2, 3EQ, UK, Email:
djun01@esc.cam.ac.uk
2
Advanced Technology Development Team,
Semiconductor R&D Division, Samsung Electronics
Co. LTD. San#24, Nongseo-Ri, Kiheung-Eup,
Youngin-City, Kyunggi-Do, Korea, Email:
khhsun@samsung.co.kr
An activation energy for domain switching is extracted
and explained in terms of the Du and Chen model of
switching kinetics[1], which is based on the idea that
switching of ferroelectric domain is limited by the critical
energy for domain nucleation. The measured coercive field
of the PZT capacitors[2] in this study strongly depend on
both frequency and temperature, suggesting that the
nucleation limited model, one of the models to describe
switching process in ferroelectric thin film is more
applicable than a domain wall motion limited model. We
studied the switching behaviours of domains in PZT
capacitors and thin films with a ribbon style geometry[3].
Domain relaxation, a key problem from a device
reliablity perspective is closely linked to switching kinetics.
In addition, the dependence of coercive field on frequency
is an important characteristic of a ferroelectric device for
both practical and fundamental reasons. Practically, if the
coercive field increases substantially with increased
switching frequencies ferroelectric devices operating at
high frequencies will require higher and possibly
impractical switching voltages. We are able to probe the
switching dynamics of ferroelectric thin films by the
behaviour of coercive field against frequency. In order to
understand better the switching dynamics in ferroelectric
thin films in general we conducted measurements with a
variety of frequencies, temperatures, and applied electric
fields, which allow us to understand switching in a more
universal manner.
[1] X. Du and I. Chen, Mat. Res. Symp. Proc. 493 311
(1998)
[2] H.H. Kim et. al., Symp. on VLSI Tech. Dig. pp.210-211
(2002)
[3] D.J. Jung et al., 1 5
t h
Int. Symp. on Integrated
Ferroelectrics (2003)
10
th
167
Anisotropy of Piezo-, Elasto- and
Acoustooptic Properties of
Incommensurate Cs
2
HgCl
4
Crystals
as Perspective Acoustooptic
Material
MYKOLA KAIDAN, ANA ZADOROZHNA,
YURIY BILOBRAN, ANATOLIY ANDRUSHCHAK,
MYHAJLO KLYMASH, ANDRIY KITYK
1
Lvivska Politechnica National University, 12 S.Bandery
Str., Lviv, Ukraine, anat@polynet.lviv.ua
Institute for Computer Science, Technical University of
Czestochowa, Al. Armii Krajowej 17, 42-200,
Czestochowa, Poland
According to our previous investigations and
calculations the incommensurate Cs2HgCl4 crystal is
perspective acoustooptical material [1]. Therefore it is
actually to investigate the spatial distribution of piezo-,
elasto- and acoustooptic
effects in these crystals.
In [1] we determined
all of the absolute
piezooptic coefficients
i m on laser interfero-
meter (=0,6328m) by
new two-fold measure-
ments method [2] and
calculated all of the
elastooptic coefficients pin
for Cs2HgCl4 crystals (see
Table), according to well-
k n o wn r e l a t i o n
pin=imCmn ( a l l
components of the elastic
const ant Cmn w e r e
calculated from our acoustical measurements the ultrasonic
waves velocities on the such samples [3]). Using filled
matrix of im and pin the indicative surfaces for longitudinal
or transverse piezo- and elastooptic effect and their
stereografic projections were constructed for Cs2HgCl4
crystals by means of created computer program. For this at
first the analytical relations, which necessary for indicative
surfaces construction in the biaxial crystals, were found.
For each surface we have determined their extremes and
calculated the anisotropy power. On the basis of elaborated
software the spatial anisotropy of pef effective acoustooptic
coefficient and M=p
2
ef n
6
/v
3
well-known acoustooptic
quality parameter were analyzed and their extreme values
for different forms of light diffraction on the acoustic wave
in the Cs2HgCl4 crystals were calculated.
[1] Kaidan M.V., et al. (2002). Applied Optics, 41, 5341.
[2] Andrushchak A.S., et al.. (2002). Visnyk of theLvivska
Politehnika National University. Electronics, 455,
110.
[3] A.V.Kityk, et al. (1998). Phys. stat. sol. (b), 210, 35.
Thermal Conductivity and Thermal
Expansion of Ceramics PZT in the
Region of Phase Transition
S.N. KALLAEV
1
, G.G. GADJIEV
1
, I.K. KAMILOV
1
,
M.M. KHAMIDOV
2
, S.A. SADICOV
2
1
Institute of Physics, Daghestan Scientific Center, Russian
Academy of Sciences, 367003 Dagestan, Russia, e-
mail: analit@dinet.ru
2
Daghestan State University, 367025 Dagestan, Russia.
In the present work the results of experimental
investigations of thermal properties (thermal conductivity
and thermal expansion) ferroelectric ceramics PZT-19 are
given on the basis of solid solutions of PbZrO3 PbTiO3 in
the temperature ranges 293-750K. It is known, that there is
a temperature area with tetragonal - rhombohedral structure
morphotropic region in ceramics PZT-19 at transition
(T 600K) from cubic to a ferroelectric phase.
As a result of examinations the following is revealed:
-the thermal conduction of a piezoelectric ceramics PZT
grows with increase of temperature, i.e. it has a character
appropriate to random systems;
-the thermal expansion coefficient in the area of a
ferroelectric phase with advancement of temperature falls,
i.e. the negative linear expansion coefficient is observed;
-in field of structural phase transition (T 610K) to a
polar state are observed the anomalies on temperature
dependences of thermal conductivity and thermal expansion
in modes of cooling and heating;
-in temperature ranges 520-610K (morphotropic region)
temperature dependences of thermal conductivity and the
thermal expansion have nonlinear anomalous character.
The analysis of the obtained experimental results is
carried out in view of structural reorganization in the area
of wash-out phase transition. The effect of optical
oscillations, interphase boundaries and electrical domain
structure on behaviour of thermal conduction is considered.
It is noted, that the anomal temperature dependence of
thermal expansion coefficient below T 620K can be
stipulated by strong dipole - dipole interaction in random
systems, which occurs owing to displacement of sublattices
and reorganization of domain structure at to ferroelectric
state.
Temperature hysteresis, which is peculiar to
incommensurate systems and stipulated by fastening of
domain walls (pining-effect) and interphase boundaries
on structure inhomogeneities and grain boundaries is
observed in temperature range of the existence of
morphotropic region.
Also the effect of sample shape thermal memory is
found at investigations of thermal expansion PZT-19.
im
im
, p
in
or in Br=10
-12
m
2
/N
11 2,40,4 0,40
12 17,50,9 0,40
13 14,80,9 0,39
21 -1,40,3 0,26
22 11,80,8 0,29
23 16,60,9 0,34
31 -1,70,3 0,17
32 7,30,6 0,19
33 12,60,8 0,24
44 -11,01,8 -0,034
55 -5,81,1 -0,026
66 -10,41,6 -0,032
10
th
168
Features of Electrical Properties of
Glassy SbSI
S.N. KALLAEV
1
, A.A. AMIROVA
1
,
A.M. DZHABRAILOV
1
, A.A. BABAEV
1
, S.A.
SADYKOV
2
, G.K.SAFARALIEV
2
Academy of Sciences, Makhachkala, 367003
Daghestan, Russia
e-mail: analit@dinet.ru
2
Daghestan State University, Makhachkala, 367025, Russia
The great attention to chalcogenide glassy materials is
caused by specifity of their energy spectrum and a number
of properties, which are not observed in the appropriate
crystal analogues. Characteristics of such materials is the
infringement of the distant order, which renders essential
influence on dynamics of nuclear structure and electrical
properties. One of the sample of such system is glassy SbSI.
The interest to connections SbSI is caused by that they have
simultaneously semi-conductor and ferroelectrics
properties.
In spite of crystal analogue the glassy systems Sb-S-I
are weakly investigated. Therefore, the present work is
devoted to research of electrical properties (dielectric
constant and polarization ) of glassy SbSI in wide
temperature range.
It is revealed, that at cooling in a temperature point
Tc~198K the brightly expressed anomaly of dielectric
constant and polarization , characteristic for structural
phase transition of the fist-order occurs. The size of a
temperature hysteresis is approximately 12K. The large size
of a temperature hysteresis can be caused by strong defect
of a glassy materials.
The occurrence of polarization at temperature Tc
testifies that low-temperature phase is polar, i.e. at the T=Tc
the transition in a condition of dipole glass is carried out.
It is necessary to note, that in glassy SbSI in
comparison with its crystal analogues is displaced not only
temperature of phase transition in range of low
temperatures (on size ~ 97 ), but also changes
(qualitatively and quantitatively) character of anomaly of
dielectric constant .
Thus, the results of research of dielectric properties
testify that the phase transition of the first-order in a polar
condition (dipole glass) is realized in glassy SbSI at
T=198K.
Critical Behaviour of a Heat
Capacity in the Region of
Incommensurate Phase Transition
of SC(NH
2
)
2
Crystals
S.N. KALLAEV, I.K. KAMILOV, A.M. ALIEV, SH. B.
ABDULVAGIDOV, A.A. AMIROVA, A.B. BATDALOV
Academy of Sciences, Makhachkala, 367003
Daghestan, Russia, e-mail: analit@dmet.ru
The theory of Landau is usually attracted for
interpretation of anomalies of a heat capacity in succession
transitions of normal- incommensurate-polar phases,
because of its simplicity. However thermodynamic model
Landau qualitatively reproduces an anomalous part of a
heat capacity only in a temperature range transition of a
first order incommensurate - ferroelectric phase.
Experimental examinations of various physical properties in
a transition range of a II-order normal- incommensurate
phases demonstrate essential diversions from the theory
Landau. According to this the detection of a role of
fluctuation effects at transitions in disproportionate phases
in various crystals has fundamental importance.
In this work the detailed experimental study of critical
behaviour of specific heat in the region of incommensurate
phase transition on an example of a crystal SC (NH2)2 by
method of an ac-calorimetry is carried out. The crystals SC
(NH2)2 has phase transitions in a incommensurate phase
at Ti=202K and in a ferroelectric phase at the Tc =169K.
To elucidate the possible nature of deviations from the
Landau theory, Levanyuk et al. [1] developed the method
for analysis of the experimental data in the region of
structural transitions on the basis of fluctuation theory.
According to [1], the experimental temperature dependence
of heat capacity can be represented as the sum of Landau
and fluctuation contributions:
C
+
= Cb+
+

-1/2
at T>Ti
C

-
= Cb+C L +
-

-1/2
at T< (1)
where Cb is the regular part of heat capacity, CL is
the heat capacity jump at T = Ti (according to Landau),
=T/Ti-1 is the reduced temperature,
+
and
-
are constants,
and the ratio
+
/
-
is 2 for the XY-type systems and
2 2 for the Ising systems.
As with the temperature dependences of birefringence
obtained in [1], Eq. (1) with CL = const and
= const
properly approximates experiment only if Cb const (this
imposes a limitation on the domain of applicability of the
Landau theory). We will assume that the regular part can be
represented as a polynomial suitable for the description of
empirical data on the thermal characteristics of solids in a
limited T range on the order of Debye temperature:
Cb = C0+C1 t +C2 t
2
,
where t = T- Ti . In this case, Eq. (1) approximates well
the experimental dependences in the region from 1 t <
70 K and -2 K < t -20 K.
According to Eq. (1), the ratio of critical amplitudes
+
/
-
derived from the measurements of heat capacity (
+
=
0.0598 0.0033 and
-
= 0.0862 0.0038 for T> Ti and T<
Ti , respectively) is equal to 1.441, which corresponds to the
theoretical estimate 2 for the XY-type systems. [1] N. R.
Ivanov et al., Ferroelectrics 96, 83 (1989).
10
th
169
Low-temperature Dielectric
Response of Relaxor Ferroelectrics
and Related Materials
STANISLAV KAMBA, IVAN RYCHETSKY,
ALEXEJ PASHKIN, VIKTOR POROKHONSKYY,
VIKTOR BOVTUN, MAXIM SAVINOV,
POLINA SAMOUKHINA, JAN PETZELT
Institute of Physics, Academy of Sciences of the Czech
Republic, Na Slovance 2, 18221 Prague 8, Czech
Republic, kamba@fzu.cz
This paper reviews characteristic low-temperature
dielectric response of relaxor ferroelectrics PbMg1/3Nb2/3O3,
and (Pb1-xLax)(ZryTi1-y)1-x/4O3,
[ 1 ]
solid solutions of
PbMg1/3Nb2/3O3-PbTiO3, PbZn1/3Nb2/3O3-PbTiO3, BiScO3-
PbTiO3, and disordered Bi1.5ZnNb1.5O3 pyrochlore
[2]
in the
frequency range of 100 Hz 100 THz. In all the listed
materials a dielectric relaxation appears in the microwave
and THz region at high temperatures, which softens and
broadens on cooling. Distribution of relaxation frequencies
below room temperature is very broad (several orders of
magnitude) and at low temperatures (in relaxors below the
freezing temperature) it results in nearly frequency
independent dielectric losses (1/f noise) which can be seen
from sub-Hz up to THz range. Dielectric relaxation in
relaxors has origin in dynamics (breathing and flipping) of
polar-nanoclusters. In the other materials it describes an
anharmonic motion of disordered ions. The broad
distribution of relaxation frequencies stems from structural
inhomogeneities (e. g. Mg
2+
and Nb
5+
in the perovskite B
sites), which cause random fields and have influence on the
distribution of activation energies for hopping of ions in the
A sites. The lowest relaxation frequency corresponds to
hopping of ions over the highest potential barrier. The
magnitude of frequency-independent losses decreases
exponentially on cooling, however remains still appreciable
at helium temperatures. Landau-type thermodynamic model
based on the perovskite structure near morphotropic phase
boundary was proposed for calculation of the energy
barriers for polarization reversal near the polar-cluster
boundaries. This model explains the broad distribution of
relaxation frequencies and related frequency independent
losses at low temperatures. Additional dielectric relaxation
was observed in the ferroelectric phase of the above-
mentioned solid solutions in the frequency range of 10
8
-10
9
Hz. The relaxation frequency is temperature independent,
i.e. the relaxation does not describe a thermally activated
process and is probably caused by a sound generation due
to ferroelectric-ferroelastic domain motion in the high-
frequency electric field. In relaxors breaking the
translational symmetry causes activation of phonon density-
of-states in submillimetre spectra. Besides of it, the TO1
optical mode softens to the Burns temperature, below which
the polar nanoclusters appear. However, contribution of
polar phonons to static permittivity below the Burns
temperature is by one or two orders of magnitude lower
than the contribution of relaxations.
References
1. S. Kamba et al., J. Phys.: Condens. Matter 12, 497 (2000)
2. S. Kamba et al., Phys. Rev. B 66, 054106 (2002)
Temperature Dependence of
Microwave and THz Dielectric
Response in Sr
n+1
Ti
n
O
3n+1
(n=1-4)
STANISLAV KAMBA
1
, ALEXEJ PASHKIN
1
,
VIKTOR BOVTUN
1
, DMITRI NOUJNI
1
, JAN PETZELT
1
,
ANNA-KARIN AXELSSON
2
, NEIL MCN ALFORD
2
,
P.L. WISE
3
, IAN M. REANEY
3
1
Republic, Na Slovance 2, 18221 Prague 8, Czech
Republic, kamba@fzu.cz
2
Physical Electronics and Materials, South Bank
University, 103 Borough Road, London SE1 0AA, UK

3
University of Sheffield, Department of Engineering
Materials, Sheffield S1 3JD, UK
Microwave, near-millimetre and infrared dielectric
response of Srn+1TinO3n+1 (n=1-4) Ruddlesden-Popper
homologous series was studied in temperature range
between 10 and 300 K. Resonant cavity method, time-
domain THz transmission and infrared reflectivity were
used in the respective spectral ranges. At room temperature
increasing the number of perovskite layer n in the
Srn+1TinO3n+1 series results in higher polarizability of the
lattice and softening of the lowest frequency phonon mode,
which is responsible for the observed increase in
microwave permittivity, dielectric loss and temperature
coefficient of resonance frequency with n. Sr2TiO4 and
Sr3Ti2O7 do not show any remarkable changes in phonon
frequencies on cooling, therefore their microwave
permittivity remains temperature independent. Softening of
the polar optical modes were observed on cooling in
Sr4Ti3O10 and Sr5Ti4O13 which explains the monotonous
increase of microwave permittivity at low temperatures
(similar to incipient ferroelectric SrTiO3). Microwave
dielectric loss depends non-monotonously on temperature
suggesting weak dielectric relaxation connected with
defects.
10
th
170
Optical Study of Long-range Order
Destruction in Pb
1-x
Ba
x
Sc
1/2
Nb
1/2
O
3
(PBSN) Relaxor Ferroelectrics
L.S. KAMZINA
1
, I.P. RAEVSKII, V.V. EREMKIN,
V.G. SMOTRAKOV
1
A.F.Ioffe Physico-Technical Institute RAS, 194021, St.-
Petersburg, Russia, e-mail: kamzin@spb.cityline.ru
Institute of Physics, PSU, 344090, Rostov-on-Don, Russia
The influence of partial substitution of Pb for Ba ions
on stability of relaxor state and on destruction of long-range
order in relaxor ferroelectrics Pb1-xBaxSc1/2Nb1/2O3, where
x=0 (PSN), x=0.04 (PBSN-4), x=0.06 (PBSN-6) and
x=0.08 (PBSN-8), has been investigated. The methods used
are the measurements of optical transmission (OT), small-
angle light scattering (SALS) and birefringence (n) as a
function of temperature at different amplitudes and regimes
of electric field application.
It was shown, that in materials with 0x0.04 in
absence of an electric field are still kept features of both the
normal ferroelectric and the relaxor behavior. The
spontaneous phase transition (SPT) from the relaxor to a
macrodomain state occuring in PSN and PBSN-4 at
temperatures below Tmax is accompanied by onset of n
and sharp maximum of SALS intensity, which indicates the
percolation nature of this transition.
The further increasing of Ba contents up to 6% has
resulted in disappearance of SPT and display only of
relaxor properties. No sharp changes were observed in the
temperature dependences of OT, SALS intensity and n in
PBSN-6 with no electric field. However, the development
of long-range order was observed under the electric field. A
very weak electric field ~0.4 kV/cm is sufficient to induce
the kinetic phase transition in macrodomain state. It was
shown, that the process of destruction of the induced
ferroelectric state is a first-order phase transition which is
accompanied by anomalously narrow peak in SALS
intensity, passes on percolation type and does not depend
on heating rate of crystal. It was found that the temperature
dependences of n induced by an electric field in PBSN-6
solid solution crystals differ for various regimes of electric
field application. The boundaries of induced ferroelectric
state stability are determined at different regimes of electric
field application and E-T phase diagram is constructed.
The conclusion about the presence of spontaneous-
polarized microregions which develops in cubic nonpolar
matrix was made. The sizes and the volume fraction of
these polar regions are determined. The physical nature of
induced ferroelectric phase in PBSN-6 solid solution is
compared with one in typical relaxor PbMg1/3Nb2/3O3
(PMN).
Experiment of Physical Properties
on Vacuum Evaporated Parylene
Polymer Thin Film
S. S. KANG
1
, B. Y. CHA
1
, D. G. LEE
1
, K. H. LEE
1
,
J .H. KIM
2
, AND S. H. NAM
2
1
Department of Biomedical Engineering, College of
Biomedical Science and Engineering, Inje University,
Korea (kss94@drworks1.inje.ac.kr)
2
Medical Imaging Research center of Inje University,
Korea (jhkim@physics.inje.ac.kr)
Parylene is the generic name for members of a unique
polymer series. The basic member of the series, called
parylene N, is poly-para-xylylene, a completely linear,
highly crystalline material. Due to the uniqueness of the
vapor phase deposition, the parylene polymers can be
formed as structurally continuous films from as thin as a
fraction of a micrometer to as thick as several mils.
The barrier and dielectric properties of parylene make it
the premium coating for electronics exposed to
environmental threats such as moisture condensation, harsh
chemicals, or corrosive gases. Parylene is used on
electronics ranging from advanced military and aerospace
electronics to general-purpose industrial products.
In this work, we have investigated the physical
properties of vacuum evaporated parylene polymer thin
film, which include the resistivity and deposition rate
according to parylene dimer quantities.
The parylene polymers are deposited from the vapor
phase by a process which in some respects resembles
vacuum metallizing. Unlike vacuum metallization,
however, which is conducted at pressures of 10
-5
torr or
below, the parylenes are formed at around 0.1 torr. Parylene
is applied at room temperature with deposition equipment
that allows control of both coating rate and ultimate
thickness. Polymer deposition takes place at the molecular
level as the chemical, in dimer form, is vaporized under
vacuum and heat to a dimeric gas, then pyrolized to cleave
the dimer to its monomeric form, and finally deposited as a
transparent polymer film.
The measured resistivity was about 1-410
5
-cm. And
deposition rate according to a weight of parylene dimer
varied from 0.8 to 0.9 m/g. From these results, we can
optimize the thickness of parylene polymer thin film as
blocking layer of amorphous selenium based flat panel
digital x-ray imager.
10
th
171
Erasure Effect of Latent Charges
on Au/a-Se/poly-para-xylylene/ITO
X-ray Detector
S. S. KANG
1
, J. Y. CHOI
1
, G. W. JANG
1
, G. H. LEE
1
,
J.H. KIM
2
, AND S. H. NAM
2
1
Department of Biomedical Engineering, College of
Biomedical Science and Engineering, Inje University,
Korea (kss94@drworks1.inje.ac.kr)
2
Medical Imaging Research center of Inje University,
Korea (nsh@bme.inje.ac.kr)
Introduction
A flat panel digital x-ray detector using amorphous
selelnium (a-Se) has developed for general radiography. An
a-Se based detector consists of a-Se layer as electron-hole
pair (EHp) generation layer and poly-para-xylylene layer as
the protection layer of a high electric field. Charges that are
generated from x-ray absorbtion by a-Se move under the
applied electric field. Negative charges will move in the
direction of the top positive electrode and will stop and
accumulate at the selenium-poly-paraxylylene interface.
This nonuniform charge accumulation causes a non-
uniform sensitivity within the x-ray imaging system that
produces the ghost image.
In this work, we investigated the erasure effect of latent
charges on a-Se-parylene interface. Erasure of an x-ray
imaging device was performed by applying high voltage
and erasing light simultaneously.
Experimental
For fabrication of chlorinated 0.3% As:Se alloy which
can be used in x-ray medical imaging, small amounts of As
(0.3wt%) and Cl (30ppm) are added to enhance the
conducting and thermal properties of a-Se (99.999%:
Nippon Rare Metal Co.). The a-Se photoconductive layer
was prepared by the thermal evaporation of a-selenium onto
ITO (Indium Tin Oxide) glass. Typical pressure during the
vacuum deposition process was 2x10
-5
torr. The thickness
of evaporated a-Se film was 200m. Polyparaxylylene
(10m thickness) as a dielectric layer was coated on the
evaporated a-Se layer by parylene peposition system (PDS
2060, SCS Co., USA). Finally, an Au (99.99%, Cerac Co.)
electrode for measuring I-V was deposited by thermal
evaporator.
The experimental setup for I-V measurements was
composed of a electrometer (Keithley 6517A, USA) for
measuring x-ray induced charges, a power supply (EG&G
558H, USA) for applying high electric field. A Shimadzu
TR-500-125 was used as a x-ray generator to measure x-ray
sensitivity. The light used for erasure had a spectral
emission of 200-800 nm, and a luminance of 5-500 cd/m
2
.
Results and Discussion
The digital x-ray detector comprises a-Se photoconductor
overcoated with a layer of poly-paraxylylene. In this work,
we completely eliminated the negative charges at the
interface by switching the high voltage from positive to
negative polarity during the erasuring.
Experimental results showed that the erasure method
using a combination of high voltage and light remained
unchanged x-ray sensitivity, and eliminated a ghost image
for pre-exposure.
Initial Excitation Process of
Ferroelectric B
2
Soft Mode in
KD
2
PO
4
J. KANO, Y. TSUJIMI, K. A. NELSON
1
AND T. YAGI
Research Institute for Electronic Science, Hokkaido
University, Sapporo 060-0812, Japan
1
Department of Chemistry, Massachusetts Institute of
Technology, Cambridge, Massachusetts 02139, USA
In order to establish the complete description of the
dynamics of the electric polarization fluctuation in the
ferroelectric phase transition, the response function G(t) of
the ferroelectric B2 soft mode of KH2PO4 (KDP) has been
measured directly in the time domain by the impulsive
stimulated Raman scattering with a heterodyne detection
method (HD-ISRS).[1] HD-ISRS system gives the time
dependence of the B2 mode with an excellent signal to noise
ratio near the ferroelectric phase transition temperature Tc.
The initial excitation process with the time scale of m 100
femtosecond was firstly discovered in G(t), and the
relaxation process with a relaxation time followed with
the initial excitation process showed a critical slowing-
down above Tc.[1]
In the present study, the isotope effect on G(t) was
investigated in KD2PO4 (DKDP) by HD-ISRS. Both the
initial and relaxation processes are successfully detected in
addition to a 180 cm
-1
lattice mode as shown in Fig.1. The
time dependence of the 180 cm
-1
mode was first observed in
the present study. The excitation process of the B2 mode is
clearly distinguished in the observed data shown in Fig.1.
The isotope effect on is confirmed by the analysis of the
B2 mode. On the other hand, the effect on m is not
observed; m 100 femtosecond also is obtained for DKDP.
These results indicate that the initial excitation process is
essentially mechanical one where D (H) atoms play a minor
role
Fig.1. The time dependence of HD-ISRS signal of DKDP.
[1] J. Kano et al.:Ferroelectrics. 272, 57 (2002).
10
th
172
Phase Tunable SAW Device on
LiNbO
3
Substrate
KUO-SHENG KAO
*1
, CHUNG-JEN CHUNG
1
,
YING-CHUNG CHEN
1
AND CHIEN-CHUAN CHENG
2
1
Department of Electrical Engineering, National Sun Yat-
Sen University, Kaohsiung, Taiwan, R.O.C.
*Corr. author mail: d8831802@student.nsysu.edu.tw
2
Department of Electronic Engineering, De Lin Institute of
Technology, Tucheng, Taipei, Taiwan, R.O.C.
Within the last decade, great and important progresses
in delay line devices were made. Delay line devices are
often adopted to make the signals delayed for a certain
time. Signal delay can be achieved via two methods. One is
electromagnetic delay line, and the other is acoustic delay
line. These devices exist in precise oscilloscope, PAL color
television system, electronic calculators, and wireless
communication system for different applications. The
velocity of SAW propagating on various piezoelectric
substrates is between 2,000~6,000 m/s, which is much
slower than the electromagnetic wave. Under the same
operation frequency, it just needs no more than 1cm crystal
propagation length for SAW to obtain 1~3 ms time delay.
Therefore, SAW device is suitable for applications with
larger time delay.
Lithium Niobate (LiNbO3) is an attractive piezoelectric
material due to its high electromechanical coupling
coefficient (K
2
). It is extensively fabricated to be surface
acoustic wave (SAW) devices that are used as filters,
resonators, and sensors. The integrated-optics-grade
congruent z-cut LiNbO3 (Crystal Technology, USA) with
double side polished is used as substrate. The center
frequency of the SAW filter is 189.1 MHz for the
propagation along the y-axis on z-cut LiNbO3. The external
electrical field between top and bottom electrodes is applied
by DC power supply from 500~500V. The parameters of
the device such as S21, phase shift and time delay were
measured to investigate the effect of biasing external
electrical field.
The measurement in time domain using a Hewlett-
Packard (HP) 8720 network analyzer is carried out at the
fixed center frequency of the device in order to investigate
its effects on SAW signal. The phase-shift varies with
different biasing voltage at fix center frequency in time
domain. It is obvious that the positive biasing voltage
causes positive phase shift, and negative biasing voltage
causes negative phase shift. The result reveals that the
phase shifts of signal vary linearly with the variation of
biasing voltage.
References
[1] L. Reindl, C. C. W. Ruppel, S. Berek, U. Knauer, M.
Vossiek, P. Heide and L. Oreans, IEEE Trans.
Microwave Theory and Tech., 49, 787 (2001).
[2] A. Springer, W. Gugler, M. Huemer, R. Koller and R.
Weigel, IEEE Trans. Microwave Theory and Tech., 49,
754 (2001).
LiTaO
3
Thin Films Prepared by a
Diol-Based Sol-Gel Process and
Crystallized by Conventional and
RTA Process
MING-CHENG KAO
1
, YING-CHUNG CHEN
1
,
CHIH-MING WANG
2
AND HONE-ZERN CHEN
3
1
Department of Electrical Engineering, National Sun
Yat-Sen University, Kaohsiung, Taiwan.
2
Department of Electrical Engineering, Cheng-Shiu
Institute of Technology, Kaohsiung, Taiwan.
3
Department of Electrical Engineering, Hsiuping Institute
of Technology, Taichung, Taiwan.
The properties of ferroelectric thin films can be
dependent on the preparation and crystallization method.
This study is focused on the crystallinity, dielectric and
ferroelectric properties of LiTaO3 thin films prepared by a
diol-based sol-gel method and crystallized by conventional
and RTA (Rapid Thermal Annealing) process. The gel
systems used 1, 3-propanediol, HO(CH3)2OH solvents other
than ethanol to increase the thickness of crack-free single-
layer coating and obtain the chemically homogeneous oxide
films with high quality. Films were heat-treated using a
conventional furnace and RTA processes at heating rates of
5
o
C/min and 1800
o
C/min, respectively. For the former
process, films were crystallized at 700
o
C for 1 h, and 700
o
C
for 2 min for the latter process.
Based on the results, c-axis orientation of the films
crystallized by the RTA process presented better
crystallization than films crystallized in a conventional
furnace. The film with RTA process exhibited a dense
microstructure, but not for the conventional furnace
process. The relative dielectric constant (r) and dielectric
loss factor (tan) of the films treated by the RTA process
were 40 and 0.08, respectively. These values are larger than
those of the films crystallized in a conventional furnace of
r=32 and tan=0.004. The remanent polarization (Pr) and
the coercive field (Ec) of the films crystallized in a
conventional furnace were about 2.4 C/cm
2
and 87 kV/cm.
On the other hand, for LiTaO3 films crystallized by the
RTA method, the remanent polarization (Pr) and the
coercive field (Ec) were about 10.7 C/cm
2
and 45 kV/cm,
respectively.
References
[1] M. C. Kao, M. S. Lee, C. M. Wang, H. Z. Chen , and Y.
C. Chen, Jpn. J. Appl. Phys. 41, 2982 (2002).
[2] S. D. Cheng, Y. Zhou, C. H. Kam, X. Q. Han, W. X.
Que, Y. L. Lam, Y. C. Chan, J. T. Oh, and W. S. Gan,
Mater. Lett. 44, 125 (2000).
[3] P. J. Retuert, P. G. Kneuer, O. Wittke, R. E. Avila, and
G. J. Piderit, J. Mater. Res. 10, 2797 (1995).
[4] W. S. Hu, Z. G. Liu, and D. Feng, J. Appl. Phys. 80,
7089 (1996)
10
th
173
Leakage Current Mechanisms in
Rapid Thermal Annealed LiTaO
3
Thin Films Prepared by a Diol-
Based Sol-Gel Method
MING-CHENG KAO
1
, YING-CHUNG CHEN
1
,
HONE-ZERN CHEN
2
CHIH-MING WANG
3
AND YI-JU LI
1
1
Department of Electrical Engineering, National Sun
Yat-Sen University, Kaohsiung, Taiwan.
2
Department of Electrical Engineering, Hsiuping Institute
of Technology, Taichung, Taiwan.
3
Department of Electrical Engineering, Cheng-Shiu
Institute of Technology, Kaohsiung, Taiwan.
Lithium tantalite (LiTaO3) is a ferroelectric material,
which has a rhombohedral structure with point group 3m
and high Curie temperature (approximately 650C). It can
be applied in optoelectronic devices, surface acoustic wave
devices and pyroelectric detectors due to its unique
pyroeletric, piezoelectric, electro-optic and nonlinear
optical properties. In this study, we report the electrical
properties of LiTaO3 thin films on Pt(111)/SiO2/Si(100)
substrates, prepared by the sol-gel method and rapid
thermal annealing (RTA) in the oxygen atmosphere with
the heating rate of 600~3000C/min. The microstructure
and leakage current of lithium tantalite (LiTaO3) thin films
were investigated to understand the mechanism of the
leakage current.
The leakage current density (J) of LiTaO3 thin films
decreased with the increase of heating rate from 9.6810
-8
A/cm
2
for 600C/min to 4.3410
-8
A/cm
2
for 3000C/min.
It is due to the decreased porosities of films with the
increased heating rate according to the surface
morphologies. It was found that the leakage current was
affected not only by the microstructure but also by the
interface between the Pt electrode and LiTaO3 thin films.
Moreover, it was found that more than one conduction
mechanism is involved in the range of electric field used in
the experiment. In the low electric field region, the leakage
current was controlled by Poole-Frenkel emission. On the
other hand, the mechanism can be explained by Schottky
emission from the Pt electrode in the high field region.
References
[1] J. F. Scott, C. A. Araujo, B. M. Melnick, L. D.
McMillan, R. Zuleeg, J. Appl. Phys. 70, 382 (1991)
[2] H. Hu, S. B. Krupanidhi, J. Mater. Res. 9, 1484 (1994).
[3] M. C. Kao, M. S. Lee, C. M. Wang, H. Z. Chen, and Y.
C. Chen, Jpn. J. Appl. Phys. 41, 2982 (2002).
[4] Y. Fukuda, K. Aoki, K. Numata, A. Nishimura, Jpn. J.
Appl. Phys. 33, 5255 (1994).
Photo Dissociation of
Blue-light-induced VIS-Centers in
SBN:Ce, Cr and in BCT:Fe Into
Small Polarons at Low
Temperatures
S. KAPPHAN
1
, A. GUBAEV
1
, I. KISLOVA
1
,
A. KUTSENKO
1
, R. PANKRATH
1
, V. VIKHNIN
2
1
FB Physik, University of Osnabrueck, Barbarastr. 7,
49069 Osnabrueck, Germany.
E-mail: Siegmar.Kapphan@uos.de.
2
A.F.Ioffe-Phys.Tech. Inst., RAS, 194021, Saint-
Petersburg, Russia.
The promising photorefractive single crystal systems
SrxBa1-xNb2O6 (SBN, congruent composition x=0.61) and
Ba1-yCayTiO3 (BCT, congruent y=0.23), can be doped with
polyvalent ions like Fe, Cr, Ce to enhance and optimize
their photorefractive properties. Illumination with blue Ar
+
-
laser light at low temperature creates light-induced NIR and
VIS absorption bands [1]. The light induced charge
transport from the doping ions and trapping in shallow
polaronic states has been identified to constitute the
underlying process and first step leading to the build-up of a
space charge field (under spatially inhomogeneous
illumination), which is then modifying the refractive index
via the electro-optic effect.
The lifetime of the polaronic centers at low temperature
is rather long, allowing to study their dynamics with various
spectroscopic techniques. The NIR absorption has been
identified as being due to electron polarons (Nb
4+
in SBN,
Ti
3+
in BCT) and their properties have been investigated in
some detail [2]. The VIS-Centers are less well understood
and their nature is still under discussion [3]. We could show
that illumination with red Kr
+
-laser light (647 nm) leads to
a dissociation of the VIS-Centers and a simultaneous build-
up of a transient NIR-polaron absorption. These features
give new insight into the dynamic nature of these VIS-
Centers, which are currently being discussed as either
bipolarons (in analogy to such centers in LiNbO3) or
polarons trapped at charged centers, or charge transfer
vibronic exitons (CTVEs) being trapped at charged centers
[4].
This work has been supported by DFG/Grad.Koll 695/1
and by NATO-CLG 977348
References
1. M.Gao, S.Kapphan, R.Pankrath. J. Korean Phys. Soc. 32,
542 (1998).
2. M.Gao, R.Pankrath, S.Kapphan, V.Vikhnin. Appl.Phys.
B68, 849 (1999).
3. M.Gao, S.Kapphan, R.Pankrath, X.Feng, Y.Tang,
V.Vikhnin. J. Phys. Chem. Solids, 61, 1775 (2000).
4. V.Vikhnin, S.Avanesyan, H.Liu, S.Kapphan. J. Phys.
Chem. Solids, 63, 1677 (2002).
10
th
174
Construction and Testing of
Hydrophone Arrays Assembled
from PZT Ceramic Foams
H. KARA
1
, R. RAMESH
1
, R. STEVENS
1
, C. R. BOWEN
1
,
N. JAYASUNDERE
2
AND V. HUMPHREY
2
1
Materials Research Centre, Department of Engineering &
Applied Science, University of Bath, Bath BA2 7AY,
UK. H.Kara@bath.ac.uk
2
Department of Physics, University of Bath, Bath BA2
7AY, UK.
Porous PZT and PZT-polymer 3-3 piezocomposites
have been shown to display very high hydrophone figure of
merit (FOM) compared with that of dense PZT [1,2].
Experimental studies on wide range of porous and polymer-
filled PZT composites have shown optimum values of FOM
around 80% porosity [3]. Analytical [4,5] and finite element
models [5] on 3-3 PZT composites show similar results.
Polymer impregnation degrades the FOM, hence sensitivity
due to high stiffness of polymer. High porosity content also
cause problems in design stage where high capacitance
values are needed to improve signal to noise ratio [4].
We have constructed a hydrophone array from
reticulated PZT ceramic foams (PZT-air piezocomposites)
for low frequency shallow water receiving applications. The
array was assembled from 18 identical pieces in 3x3
configuration in electrically series connection. The
hydrophone array was tested for receiving sensitivity and
compared with the sensitivities of a single element PZT-air
and dense PZT hydrophones. The dense PZT hydrophone
displayed strong radial resonances while the array
hydrophone showed a flat response from 20kHz to 100kHz
frequency range measured. This indicates that the radial
resonance is suppressed by the porosity present in the PZT-
air piezocomposites allowing a broadband response. The
sensitivity of the array hydrophone was around
200 dB re 1V Pa
-1
.
References
[1] K. Rittenmyer et al. Piezoelectric 3-3 Composites,
Ferroelectrics, 41, pp. 189-195 (1982).
[2] M. J. Creedon and W. A. Schulze, Large Area
piezocomposite Arrays From Distorted Reticulated
Ceramics, Proceedings of the 10
th
IEEE International
Symposium on Applications of Ferroelectrics, pp.527-
530 (1996)
[3] H. Kara et al. Porous PZT Ceramics for Receiving
Transducers, IEEE Transactions on Ultrasonics,
Ferroelectrics and Frequency Control, Accepted for
publication.
[4] C. R. Bowen et al. "Analytical Modelling of 3-3
Piezoelectric Composites", Journal of the European
Ceramic Society, 21(10-11), pp.1463-1467, (2001).
[5] R. Ramesh et al. "The Dielectric, Mechanical and
Piezoelectric Properties of 3-3 Piezoelectric
Composites", Ferroelectrics, vol.273, pp.383-388,
(2002).
Curie Temperature Shift for Cubic
BaTiO
3
in Single Ion Model
FARUK KARADAG
1
, OLEG E. KVYATKOVSKII
2
,
AMIRULLAH M. MAMEDOV
1
1
Cukurova University, Adana/Turkey, fkaradag@cu.edu.tr
2
A.F. Ioffe Physico-Technical Institute, St. Petersburg,
Russia, Kvyatkoskii@pop.ioffe.rssi.ru
In this paper, we present the results of cluster ab initio
calculations of the local force constants k
loc
(s) ,i.e. harmonic
parameter a in accordance by using result of [1], performed
for the Ti atom in the cubic BaTiO3.
Our calculation shows that the local force constants a
are positive and large compared to the atomic force
constant for the perovskites kat = e
2
/(r0)
3
2V/
2
, where r0
is the B-O bond length, as well as in comparison to the
k
loc
(s) for cations in typical ionic crystals. The values of
k
loc
(B) are the largest for the oxide of titanium, which is
indicative of the stabilizing effect the B-O bond covalency
exerts on the stability of the central position of these atoms
in the (BO6)
n-
octahedron. These results suggest that the
assumption of the B atoms in the paraelectric phase of
perovskite ferroelectrics being off-center. Our result present
the value of V0 for Ti sublattice calculated using the
corresponding values of Born effective charges found in
[2]. We predicts that the ferroelectric instability of cubic
paraelectric phase at low temperatures and in accordance
with equation for T0
cl
gives positive value for the
ferroelectric phase transition temperature. It should be
emphasized that in the framework of purely empirical
approach all of these properties are postulated. Thus the
conclusions based on ab initio calculations are originally
discovered here
The microscopic approach under consideration also
allows us the possibility to consider an influence of
quantum statistics on the Curie temperature in ferroelectric
perovskites and estimate the quantum shift of Curie
temperature in BaTiO3. The observation of isotopic shift on
Curie temperature in BaTiO3 under isotopic substitution
48
Ti
46
Ti or
48
Ti
50
Ti [3] and the results of Monte Carlo
simulations of the effects of quantum fluctuations on the
ferroelectric phase transition temperatures in BaTiO3 [4]
make this problem very interesting.
[1] O. E Kvyatkovskii, Solid State Com.117, 455-459,
2001.
[2] W. Zhong, R.D. King-Smith and David Vanderbilt,
Phys Rev. Lett, 72, 3618, 1994
[3] T. Hidaka, K. Oka, Phys. Rev.B, 35 (16), 8502, 1987
[4] W. Zhong, David Vanderbilt, Phys. Rev.B, V 53 N.9,
1996
10
th
175
Frequency Dependence of
Microwave Quality Factor of Doped
BaSrTiO
3
Ferroelectric Ceramics
S.F. KARMANENKO
1
, A.D. KANAREIKYN
2
,
E.A.NENASHEVA
3
, A.I. DEDYK
1
, A.A. SEMENOV
1
1
Electrotechnical University , St. Petersburg 197376, Russia
2
Euclid Concepts LLC, 5900 Harper Rd. Solon OH 44139
USA
3
GIRICOND Institute, 194223, St. Petersburg, Russia.
SFKarmanenko@eltech.ru
The purpose of this work was a study of microwave
(MW) properties of BaSrTiO3 ferroelectric ceramics doped
by alkaline elements (BSM) that are intended for
applications in tunable accelerator structures and switching
devices for linear colliders. Measurements of dielectric
characteristics of sintered BSTO ceramics were carried out
at low frequencies 1 kHz; 1 MHz, and at two microwave
bands 3 13 GHz, and 27 37 GHz. The copper
electrodes were deposited on the both sides of thin ceramic
disks by magnetron sputtering. The thickness of the BSM
disks was about 500 m, and Cu-electrodes - 3 m. The
following characteristics were measured: the temperature
dependencies of capacitance C(T) and the dielectric loss
tangent tan (T), capacitancevoltage characteristics C(U).
The tunab-ility factor was evaluated by the expression of
K= C(0)/C(Umax), where Umax maximal voltage applied to
the electrodes (maximum electrical field was Ema x 1
V/ m). Low frequency measurements showed that
ordinary BaSrTiO3 (BST) samples had dielectric
permittivity of = (13001450) and tunability factor of _
1,1 (Ema x 1 V/m). BSM ceramics demonstrated
practically the same tunability as BST samples, but value
varied in the range 440 500. Dielectric loss factor of BSM
samples had lower value of tan = (10
3
310
4
) in
comparison with BST ceramics 510
3
. The temperature
dependencies C(T) of BSM ceramics had rather wide
maximum at 170 200. Three techniques of electrode-less
MW measurements were used: (A) -waveguided round
dielectric resonator for 3 - 11,5 GHz ; (B) - rectangular
cavity resonator for 9 - 12 GHz with tunable dimensions;
and (C) the same resonator type for 27 - 37 GHz. In the
techniques (B) and (C) an internal wall of reflective
resonator was replaced by the sample to be tested. The (B)
type had a possibility to use an electrode on one side of
rectangular ceramic sample - 25170,5 mm. Electrode
could be patterned as the interdigital structure in order to
apply electrical field to ceramic sample. The typical value
of quality factor of BSM ceramics measured by (A) and (B)
method was (150 - 200); the method (C) gave 100-120,
nevertheless the samples with higher Q0 value were also
detected. The frequency dependence demonstrated non-
linear character indicates various dominate physical mech-
anisms of MW dielectric losses in BSM ceramics, which
are discussed. An estimation of MW dielectric losses for
investigated BSM ceramics showed rather low values of tan
= 0,005 0,01 for wide frequency region of 10 37 GHz.
The low loss factor and high tunability coefficient allow us
to utilize the BSM ferroelectric ceramics for tunable
accelerating structures of the Argonne Dielectric Wakefield
Accelerator. The same BSM ceramics could be used for
high power 11.42 GHz switches for the future linear
colliders. This work is partly supported by the DoE SBIR.
Oriented BaSrTiO
3
[100] & [110]
Ferroelectric Films Grown on
Alumina Substrates
S.F. KARMANENKO
1
, YOUNG-JEI OH
2
,
A.S.GORDEICHUK
1
, A.A. MELKOV
1
1
Electrotechnical Univ., St.-Petersburg 197376, Russia
2
Korea Inst. of Science and Technology, Seoul 136-791,
Korea armanenko@mail.eltech.ru
Alumina (Al2O3) is a commonly used in
radioelectronics polycrystalline substrate due to universal
combination of high dielectric characteristics, physical and
mechanical properties, and low cost. Therefore a possibility
to deposit on alumina substrates highly-oriented thin films
with nonlinear physical parameters attracts an attention of
physicists and engineers.
The oriented BaxSr1xTiO3 (BSTO, x = 0,5 0,6)
ferroelectric thin films were grown in the process of RF
cathode reactive sputtering [1] at oxygen pressure (10 20)
Pa. The temperature of the substrates was varied from 650
up to 850
0
_; and growth rate - from 1 to 3 nm/min. The X-
Ray Diffraction (XRD) analysis showed that
crystallographic orientation of BSTO films was dependent
on the deposition process regimes. At rather low values of
substrate temperature and oxygen pressure (no more 15 Pa)
and high enough deposition rates, the formation of [100]
preferable orientation occurred on alumina substrate,
whereas the films of [110] orientation were formed at high
oxygen pressure (higher than 20 Pa), the substrate
temperature more than 750
0
C, and deposition rate lower
1.5 nm/min, respectively. Weak intensive BSTO peaks -
(110) and (111) were observed together with main {k00}
peaks in the XRD patterns of the first type. The diagrams of
BSTO/alum structure presented in Figure showed a strong
peak of perovskite BSTO phase (110) only. All other peaks
correspond to polycrystalline alumina..
XRD pattern of [110] orieneted BSTO film grown on
alumina substrate. The dielectric characteristics and
tunability in paraelectric phase of variously oriented BSTO
films were investigated on RF and microwaves. The [100]
oriented BSTO films had high tunability coefficient K
more than 2 in electrical field ~10 V/m, and rather high
level of dielectric losses - tan 0,01 at 1 MHz and 0,03 at
30 GHz. In comparison with BSTO films of alternative
orientation the [110] oriented BSTO films had reduced K
(about 1,2) and lower tan (< 510
4
and 0,01), respectively.
Both kinds of BSTO films investigated in this work have
own field of applications in radioelectronics and microwave
hybrid integrated circuits.
1. Karmanenko S.F. et al. -J. of physics: Condensed Matter,
2002, v.14, 6823-6831
20 30 40 50 60
0,00
0,25
0,50
0,75
1,00
alum
BSTO(110)
I
n
t
e
n
s
i
t
y
,

a
r
b
.
u
n
i
t
s

2 Co(K
a
)
10
th
176
Charge Density Study on the
Ferroelectric Phase Transition of
Litium Tantalate by MEM/Rietveld
Method
HIROFUMI KASATANI
1
, HAYATO OOTAKA
1
,
SHINOBU AOYAGI
2
, AKIHIRO KIMURA
3
AND
YOSHIHIRO KUROIWA
3
1
Shizuoka Institute of Science and Technology, 2200-2
Toyosawa, Fukuroi,Shizuoka 547-8555, JAPAN:
kasatani@ms.sist.ac.jp
2
SPring-8, JASRI, 1-1-1, Kouto, Mikazuki-cho, Sayo-gun,
Hyogo 679-5198, JAPAN
3
Department of Physics, Faculty of Science, Okayama
University, Tushima, Okayama 700-8530, JAPAN
Lithium tantalate (LiTO3) is one of the typical
ferroelectric materials with which many researches have
been done in respect of the basic properties and
applications. In industry, it is widely used as surface
acoustic wave filter, piezo-electric and pyroelectric
materials. In recent years, it is expected also as an optical
device material for the next-generation of the light
information communication. The basic physical properties,
e. g. dielectric, elastic and optical propeties, have been
investigated since the discovery of ferroelectricity by
Matthias and Remeika in 1949.[1,2] However, the structural
study of this substance is seldom done after the 1970s.[2]
The recent development for the method of crystal
structure analysis by X-ray diffraction enables us to clarify
the nature of the atomic bond in the experimentally
obtained, electron density distribution. The precise
visualization has been recently attained by the combination
of the synchrotron radiation (SR) powder diffraction
experiment and t he MEM(Maximum Entropy
Method)/Rietveld analysis.[3] We have learned that this up-
to-date method is very efficient in order to clarify the
relations between structural characteristics and the unique
ferroelectric property of LiTaO3.
The SR powder experiment of LiTaO3 crystal was done
at BL02B2 of SPring-8 in Japan using high energy X-ray
with 30 keV (0.41 ). The Rietveld analyses were carried
out for the data obtained every 100 K in the temperature
range from 100 K to 1000 K. The subsequent MEM
analysis was performed to clarify the precise electron
density distributions of the ferroelectric phase at 300 K and
the paraelectric phase at 1000 K. The clear crystal
structures are evidenced at electron density levels, which
charaterize the ferroelectricity and the phase transition in
LiTaO3.
[1] Matthias, B.T., Remeika, J P.: Phys. Rev. 76 (1949)
1886.
[2] Landolt-Bornstein Springer-Verlag Berlin Heidelberg
New York 2001 and 2002, Vol. III/36A1
[3] M. Takata et al.: Z. Kristallogr. 216, (2001) 71.
Raman Spectroscopy of Bulk and
Integrated Thin-Layer
Ferroelectrics
R.S. KATIYAR, YU.I. YUZYUK
Department of Physics, University of Puerto Rico, San
Juan, Puerto-Rico 00931-3343, USA
email:rkatiyar@upracd.upr.clu.edu
Ferroelectric thin films are very attractive materials for
practical applications in micromechanics, nanoelectronics,
and optoelectronics. The origin of the size-dependent
ferroelectric properties remains a challenging problem, and
requires a better understanding as to what extent the bulk
physical properties can be used for design of thin-layer
devices. We have used micro-Raman spectroscopy to
investigate a number of ABO3 ferroelectric perovskites
(A = Ba, La, Pb, Sr, and B = Ti, Zr), Aurivillius-type
Bi-layered compounds (SrBi2Ta2O9, Bi4Ti3O12) and their
solid solutions prepared in bulk, thin film and nano-
crystalline forms. The influence of various factors, such as
particle size, compositional homogeneity, film thickness,
processing conditions, post deposition treatment,
hydrostatic and two-dimensional (2D) stresses on the lattice
dynamics ferroelectric materials in relation to their phase
transitions was investigated. The size dependent Raman
spectra were studied in the broad temperature intervals for
A and B substituted polycrystalline compounds. The size
effect on the ferroelectric transition temperature in lead
based perovskites is discussed. Systematic studies of the
film thickness dependent stresses in PT and PZT films
revealed strong dependence upon the lattice parameters of
the film and the substrate. The mismatch of the thermal
expansion coefficients of the film and substrate may induce
significant 2D clamping and determines the domain state in
the epitaxial ferroelectric film. The 2D stresses imposed by
the substrate increase remarkably the Curie temperature and
even change the entire phase transition sequence in thin
films, creating new phases that are not present in bulk
materials. To clarify the factors determining stress
formation we have studied stress relaxation in partially
unsupported and completely free-standing areas of the
epitaxial BST film. It is shown that the E(TO) soft mode
can be used as very sensitive internal probe of 2D clamping
imposed by the substrate. Raman studies of SrBi2Ta2O9
based solid solutions revealed very strong dependence on
dopants resulting in structural modifications. A-site
substitution in strontium bismuth tantalate induces a
relatively linear variation of the ferroelectric transition
temperature compared to the B-site substituted ones. The
structure - property correlations will be discussed in
comparison between bulk, thin film, and nano-crystalline
forms of these materials.
10
th
177
(a) (b) (c)
Pt substrate
Bi-rich layer
with rough surface
Bi-deficient layer
with smooth surface
Stoichiometric SBT
Current Status of Bi-based
Precursors for Integrated
Ferroelectrics
KAZUMI KATO
1,2
, KAZUYUKI SUZUKI
1
, DESHENG FU
1
,
KAORI NISHIZAWA
1
, TAKESHI MIKI
1
1
National Institute of Advanced Industrial Science and
Technology, 2266-98 Anagahora, Shimoshidami,
Moriyama-ku, Nagoya 463-8560, Japan
kzm.kato@aist.go.jp
2
Frontier Collaborative Research Center, Tokyo Institute of
Technology, 4259 Nagatsuda, Midori-ku, Yokohama
226-8503, Japan
Bi-based layer-structured ferroelectrics (BLSF) are
promising materials for development of high performance
devices such as ferroelectric random access memories,
piezoelectric devices and condensers. In the devices, the
ferroelectrics are integrated as in shape of thin or thick
films on silicon semiconductors and are connected to other
functional components via electrodes and related materials.
In such precisely-designed structure, the ferroelectric films
should be synthesized at much lower temperatures to
prevent introducing thermal damages such as undesirable
diffusion and interface reactions. Moreover, the BLSF films
have some serious problems relating to phase purity,
stoichiometry and microstructure. It is inevitable to solve
the problems for development of the high-density devices
for new generation. Chemistry of precursors should be
clearly understood because it gives a key to solve the
problems. Bismuth-2-ethylhexanoate and bismuth-
triethoxide are competitively used as starting chemicals to
prepare the precursors for the BLSF films. As the two
chemicals have entirely distinguishable reactivity, they
proceed toward oxides unexpectedly through different
routes. Bismuth-2-ethylhexanoate decomposes thermally to
oxides in oxygen-rich ambient. In contrast, bismuth-
triethoxide hydrolyzes to hydroxides and then transforms to
oxides by condensation at relatively low temperature. Each
elemental reaction leads characteristic crystallization
behavior and results in microstructural evolution in the
BLSF films. In this paper, we pick up some unique Bi-
based multi-component precursors and discuss the detail
chemistry. The molecular structure and reactivity of the
precursors are analyzed using FT-IR and NMR, and the
resultant BLSF films are characterized by XRD, AFM,
SEM, TEM, a LCR meter and a ferroelectric test system.
Finally, importance of design of precursors would be
addressed for low temperature integration of BLSF films on
silicon semiconductors.
This work is financially supported by the ISTF
Program of METI in Japan.
[1] K. Kato, et al., Appl. Phys., 88, 3779-3780 (2000).
[2] K. Kato, et al., Appl. Phys. Lett., 78, 1119-1121 (2001).
[3] K. Kato, et al., J. Appl. Phys., 89, 5088-5092 (2001).
[4] K. Kato et al., Appl. Phys. Lett., 79, 397-399 (2001).
[5] K. Kato et al., Jpn. J. Appl. Phys., 40, 5580-5584
(2001).
[6] K. Kato et al., Appl. Phys. Lett., 81, 3227-3229 (2002).
[7] K. Kato, et al., Jpn. J. Appl. Phys., 41, 6829-6835
(2002).
Formation of Ultrathin SrBi
2
Ta
2
O
9
Films using Protective Layers
YOSHIHITO KAWASHIMA AND HIROSHI ISHIWARA
Technology, 4259 Nagatsuta-cho, Midori-ku,
Yokohama-shi, Kanagawa-ken 226-8503, JAPAN
E-mail: ykawa@neuro.pi.titech.ac.jp
Introduction
SrBi2Ta2O9 (SBT) is one of the most promising
materials for non-volatile ferroelectric random access
memories (FeRAM) due to its fatigue-free property.
However, it is difficult to form thin SBT films with sub-100
nm in thickness because of their rough surface
morphologies
1)
. In this work, in order to form sub-100 nm-
thick SBT films steadily, we use Bi-deficient SBT layers as
protective layers deposited on the Bi-rich layers, because
the surface of the former is much smoother.
Experiment
A Bi-rich SBT layer was deposited by spin-coating
sol-gel solution on Pt/Ti/SiO2/Si structure and annealed in
RTA for 1 min at 750 C. This first layer has rough
morphologies as shown in fig. 1 (a). Next, a Bi-deficient
SBT layer was deposited on the first layer and annealed in
the same way. The second Bi-deficient layer has a smoother
surface than the first layer, as shown in fig. 1 (b). After
formation of Pt top-electrode, crystallization annealing was
conducted for 30 min at 750 C in oxygen flow. During this
process, excess Bi atoms in the first layer were found to
diffuse to the second layer and an SBT film with a uniform
composition and smooth surface was obtained as shown in
fig. 1 (c). The total thickness of the SBT film was about 50
nm.
Result and Discussion
It was found from P-V hysteresis property that the
remanent polarization (Pr) value of a 50-nm-thick SBT film
was 8.3 C/cm
2
and its coercive voltage (Vc) was 0.34 V,
and that the Pr value saturated at a voltage of 1 V. Leakage
current density at the saturation voltage of 1 V was on the
order of 1x10
-7
A/cm
2
. Squareness of the hysteresis loop in
this film was not degraded compared with a thicker SBT
film formed by a conventional sol-gel method.
1 ) S. Narayan, C. A. Araujo et al., Integrated
Ferroelectrics, (1999), Vol. 25. 169
Fig.1 Formation Process
10
th
178
Phase Diagram of the Ferroelastic-
Superionic Cu
6
PS
5
Br
1-x
I
x
Solid
Solutions
1
D.I. KAYNTS,
2
I.S. GIRNYK,
2
O.M. KRUPYCH
1
Institute of Solid State Physics and Chemistry, Uzhgorod
National University, 46 Pidhirna St., Uzhgorod, 88000,
Ukraine, e-mail:kaynts@uzh.ukrtel.ua
2
Institute of Physical Optics, 23 Dragomanov Str., 79005,
Lviv, Ukraine, e-mail:vlokh@ifo.lviv.ua
Cu6PS5Br1-xIx solid solutions belong to the argyrodite-
type structures crystals family and they are known as fast-
ion conductors and ferroelectrics-ferroelastics. The
Cu6PS5Br pure crystals possesses ferroelectric-ferroelastic
phase transition (PT) with the change of symmetry
F43mCc at T c=(268 2)K and superionic one at
Ts=(1737)K as well as Cu6PS5I pure crystals perhaps
possesses ferroelectric-ferroelastic PT with the change of
symmetry F43mCc at Tc=269K and superionic one at
Ts=(1705)K.
The concentration-temperature phase diagram of the
Cu6PS5Br1-xIx (x=0, 0.25, 0.5 and 1) solid solutions was
obtained by studying of the optical birefringence, thermal
expansion and domain structure. It was shown that solid
solutions with x=0, 0.25, 0.5 possesses ferroelectric-
ferroelastic PT and superionic PT as well as Cu6PS5I pure
crystals do not undergo ferroelectric-ferroelastic PT. The
lower temperature of ferroelectric-ferroelastic PT is
determined as Tc=218K and belong to solid solutions with
x=0.5. The triple point on the x, T-phase diagram with
approximately coordinates (0.5;218K) was found. In this
point three lines of PT are concurrated: at x<0.5 - line of the
2-nd order ferroelectric-ferroelastic PT and line of the 1-st
order superionic PT and at x>0.5 - line of the 1-st order
superionic PT. Probably at x=0.5 morphotropic phase
boundary between ferroic (Cc) and superionic (F43m)
phases exist.
The ferroelectric-ferroelastic domain structure in
Cu6PS5Br1-xIx solid solutions crystals was investigated
using a polarizing microscope. Four types of domain walls
are found out. These domain walls separate at least six
orientation states. The founded domain walls were
classified as W and W` walls. The critical exponents of
order parameter were determined on the base of
temperature behavior of birefringence. The temperature
hysteresis of Ts and jump like change of thermal expansion
at Ts shows that superionic PT is of the first order in all
studied solid solutions.
Electrode-less Technique of
Ferroelectric Film Study at
Microwaves
VICTOR KAZMIRENKO, YURIY POPLAVKO
1
,
BEOMJIN KIM, AND SUNGGI BAIK
2
1
National Technical University of Ukraine, 37, Peremogy
Ave, Kiev, 03056, Ukraine; e-mail: poplavko@ieee.org
2
Pohang University of Science and Technology, Pohang,
Republic of Korea; e-mail: nima@postech.ac.kr
1. Thin film, rigidly bounded with substrate, is a
complicated 2D physical object. Film dielectric properties
*=+j are of interest because they represent alterations
in the polarization processes in a film to compare with bulk
ferroelectric. In this connection, microwave data specify
important fundamental (lattice) polarization of film.
Besides, paraelectric film is promising material in
microwave electronics to use bias electric field for (Eb)
tuning. Moreover, as paraelectric so ferroelectric films are
basic material for high operation speed memories that work
at very high frequencies, up to the microwave band.
Therefore, microwave investigation of integrated film is
currently urgent question.
2. Problem of film microwave study consists in too
small film thickness. At the normal incidence, film of 1m
or less cannot be noticed by transmitted microwaves. To
force microwave to propagate along film, the metallic
electrodes are usually used. However, due to decreased
skin-layer, ferroelectric-metal interface has too big loss that
shades film properties.
3. Proposed microwave method of film investigation
does not require electrodes deposition, so film dielectric
constant () and loss () can be obtained at various stages
of film processing. The objects of study are films deposited
on substrates. The film-on-substrate sandwich is centrally
located in the rectangular waveguide, Fig. 1. Vector
network analyzer is utilized to obtain sample scattering
parameters, from which film ' and " are calculated using
elaborated software.
4. In a paraelectric phase, used for tuned devices,
microwave loss is much lower that in the ferroelectric one,
and microwave absorption is derived from the damping of
soft lattice vibration mode as well from polar phase
fluctuations above the Curie point (clusters). Microwave
methods are very sensitive to the ferroelectric f i l m
properties because film shows microwave dispersion of *
conditioned by the domain wall vibrations. It means that
domain switching possibility is tied with microwave ' and
". Namely, while film processing, the appearance of
capable for switching ferroelectric domains corresponds to
the microwave loss " maximum.
Fig. 1. Thin films test fixture, and example of data
processing.
10
th
179
Contemporary Waveguide
Technique for Ferroelectrics Study
at Microwaves
VICTOR KAZMIRENKO AND YURIY POPLAVKO
National Technical University of Ukraine, 37, Peremogy
Ave, Kiev, 03056, Ukraine; e-mail: poplavko@ieee.org
An improved manner of microwave measuring of
materials with large dielectric constant is presented.
Transmission/ reflection and short-circuited line reflection
techniques supported by dielectric transformers are adapted
to modern wideband microwave equipment (Vector
Network Analyzer). Correspondent software for fast
automatic instrumentation is elaborated and tested. An
exactness and validity of experimental methods are
analyzed. 1. Relaxor ferroelectrics are an important object
in solid state physics because of their broad-smeared phase
transition accompanied by diffused and large maximum of
. To distinguish several mechanisms of polarization, the
relaxor has to be studied at extremely different frequencies.
The investigation at centimeter and millimeter waves can
define the lattice vibration (fundamental) contribution to the
dielectric constant that is usually shaded by other
polarization mechanisms. That is why, accurate data of
microwave = - j are of importance to describe relaxor
physical properties. 2. Because of very high usually
conducted by high loss factor, microwave measuring of
ferroelectric materials is quite unconventional. Opened
microwave systems such as resonators or microstrip line
suffer from approximations, while coaxial line is
uncomfortable to make samples of cylinder or disk form
from studied ceramics or crystals. Moreover, dielectric
properties of ferroelectric crystals might be strongly non-
isotropic, and, by reason of this, the one-directional electric
field is required for their investigations. These requirements
can be satisfied in the waveguide. Our work indicates that
conventional rectangular waveguide is quite appropriate for
ferroelectrics study at frequencies of 10
10
10
11
Hz. 3. At
present time, a contemporary technique, employing
Network Analyzer (NA) to obtain scattering parameters
frequncy dependence, is elaborated only for materials with
2 10. Cardinal distinction of ferroelectric is their
microwave = 10
2
10
4
. In relaxors and ferroelectrics this
big is accompanying with a large loss (tan ~ 0.05 1).
At the present work, NA-supported technique is improved,
taking into consideration ferroelectric materials distinctions,
and using vast possibilities of present-day microwave
equipment. 4. The major problem of high- dielectric
microwave study is a poor interaction of electromagnetic
wave with studied specimen. Because of significant
difference in the wave impedance, most part of
electromagnetic energy reflects from air-dielectric
boundary, and can not penetrate the specimen. That is why,
short-circuited waveguide method exhibit lack of
sensitivity. If the loss of dielectric is also big, the sample of
a few millimeters length looks like endless. For the same
reason, in the transmission experiment, only a small part of
electromagnetic energy passes through the sample to output
that is not sufficient for network analyzer accurate
operation. This problem is solved by the matching dielectric
plates practice. Many reference ferroelectrics and some
relaxors are studied.
ENDOR of Fe
3+
in Near-
Stoichiometric LiTaO
3
DAVID J.KEEBLE AND MONICA LOYO
Carnegie Laboratory of Physics, Faculty of Engineering and
Physical Sciences, University of Dundee, Dundee
DD1 4HN, UK. D.j.keeble@dundee.ac.uk
Lithium tantalate is an attractive optoelectronic material
due to favourable non-linear optical properties and a large
electro-optic effect. Advances in crystal growth have
allowed stoichiometric LiTaO3 to be grown, in contrast to
the commonly available lithium deficient congruent
material (Li/[Li+Ta]~0.485)[1]. Iron is a common impurity
ion but is of specific importance in LiTaO3 as it gives rise
to a photorefractive effect that has been successfully used
for non-volatile holographic storage.
Recent 9GHz ENDOR experiments on near-
stoichiometric LiTaO3:Fe
3+
are reported in the plane
perpendicular to the c-axis. The results provide insight on
the local environment of the ion and aide the interpretation
of detailed EPR studies on the same crystals.
[1] Y. Furukawa, K. Kitamura, E. Suzuki, and K. Niwa, J.
Crystal Growth 197, 889 (1999).
10
th
180
Hydrogen in PbTiO
3
:
Muon Spin Rotation and
Relaxation Experiments
D.J. KEEBLE
1
AND S.F.J. COX
2
1
Carnegie Laboratory of Physics, Faculty of Engineering
and Physical Sciences, University of Dundee, Dundee
DD1 4HN, UK. D.j.keeble@dundee.ac.uk
2
ISIS Facility, Rutherford Appleton Laboratory, Chilton
OX11 0QX, UK.
The role of hydrogen in ferroelectric oxides has been
the subject of intense recent interest due, in part, to
degradation issues involved in fabrication of ferroelectric
non-volatile memories. Recent ab initio calculations have
studied H incorporation in PbTiO3 and have proposed that
H can act as a shallow donor impurity[1]. These results are
consistent with behaviour predicted for a wide range of
oxides[2]. Atomic muonium is the analogue of atomic
hydrogen in which the proton is replaced by a positive
muon (+). The muon mass is 1/9th that of H; both have
near identical Bohr radius and binding energy in their
vacuum states. Muonium adopts the same sites with
essentially identical local structure to those occupied by
hydrogen.
Measurements reported here were performed at the
pulsed muon beam facility at ISIS using a mosaic of
PbTiO3 single crystals. PbTiO3 powders were also studied.
The linewidth of the muon magnetic resonance was
observed to broaden significantly below about 50 K and is
consistent with the formation of a paramagnetic state with a
very weak binding energy and with a electronmuon
contact hyperfine less than 0.01% of the free muonium
value. Dynamic processes cause averaging and prevent
precise determination of the hyperfine constant. The decay
of muon spin magnetism in zero field and the suppression
of this decay with applied longitudinal magnetic field
provide insight on the fluctuation processes.
[1] C.H. Park and D.J. Chadi, Phys. Rev. Lett. 84, 4717
(2000)
[2] C. Kilic and A. Zunger, Appl. Phys. Lett. 81, 73 (2002)
New Relaxor Perovskite Derived
from Ba(Ti
1-X
zr
x
)0
3
by Cationic
Heterovalent Substitution in the
12 C.N Crystallographic site
A. KERFAH
1
, K. TAIBI
1
. A. GUEHRIA-LAIDOUDI
1
,
A. SIMON
2
AND J. RAVEZ
2
1
Faculte de Chimie, U.S.T.H.B., BP 32 El-Alia,
Bab-Ezzouar, Alger, Algerie.
E-mail: taibikameldz@yahoo.fr
2
I.C.M.C.B.-C.N.R.S., 87 Avenue du D'A. Schweitzer,
33608 Pessac, France.
Materials with ferroelectric relaxor behavior are of
great interest for applications [1,2]. In complex perovskite
(ABBO3), the relaxor behaviour appears usualy in lead-
based compositions (A = Pb) which present inconvenience
due to the toxicity of PbO. Researchs are now oriented to
environment friendly applications. In this way, ceramics
with composition Ba(Ti1-xZrx)03 have evidenced of relaxor
type for 0.26 < x < 0.40. In this case, the ionic substitution
is homovalent and occurs in the 6 C.N crystallographic site
(B-site) [3]. The aim of the present work concerns the
dielectric study of some compositions of perovskite type
derived from Ba(Ti1-xZrx)03 system by heterovalent
substitution in the 12 CN crystallographic site (A-site). This
study concerns the Ba1-xA2x/3(Ti0.7Zr0. 3)03 systems
(A = Y, La, Bi).
The various compositions were obtained by solid state
reaction. Dielectric measurements performed on ceramic
disks, show that the temperature and frequency variations
of the real part of permittivity are typical of relaxor
behavior for each investigated composition ( x < 0.2 ). For
all samples, the relaxor characteristics are evidenced.
Regarding relaxor characteristiscs in the case of
dodecahedral site substitution, this evolution is weaker than
that noticed in the case of the octahedral site substitution.
In the other hand, Tm is higher for Y than La or Bi
according to the increase of Tc as the size decreases in the
perovskite compounds. Nevertheless, the fact that the value
of Tm is higher for Bi than for La is not related to the steric
effect ( rY
3+
= 1.02 A ; rLa
3+
= 1.16A and rBi
3+
= 1.17A, in
8CN). The real cause is related to the lone pair which leads
to the non spherical and strongly polarized cation Bi
3+
.
Although the values of Tm are relatively far from room
temperature, these new materials can be used friendly for
environment.
References
[1] L.E. Cross, Ferroelectrics, 151,305 (1994)
[2] K. UCHINO, Ferroelectrics, 151, 321 (1994)
[3] J. Ravez and A. Simon, Eur. J. Solid State taorg. Chem.,
34, 1199 (1997)
10
th
181
Phase Transitions and Properties of
K
3
Nb
3
B
2
O
12
Single Crystals and
their Solid Solutions
E.P. KHARITONOVA, V.I. VORONKOVA, AND
V.K. YANOVSKII
119992, Physics Department, Moscow State University,
Moscow, Russia; harit@crysc24.phys.msu.ru
K3Nb3B2O12 (KNB) single crystals are of interest as
materials with unique combination of ferroelectric,
ferroelastic and superionic properties. These properties are
determined by peculiarities of their atomic structure
consisting of rigid framework from NbO6 octahedra and
plane BO3 groups with wide channels occupied by labile K
ions. In the present work single crystals of KNB and their
solid solutions with a various degree of substitutions K
+
by
Na
+
or Rb
+
, Nb
5+
by Ta
5+
or Sb
5+
, and B
3+
by Si
4+
are grown
and their phase transitions and physical properties are
investigated. It is shown that KNB crystals undergo to
several phase transitions (the temperature is indicated in
o
C):
which are accompanied by intensive anomalies of dielectric
permeability 33 and by changes in domain structure. The
high -temperature phase is hexagonal one with the point
group 2m, phase has symmetry 3m or 2m, other low-
temperature phases are monoclinic or triclinic. The
phase transition is anti- or ferroelectric, whereas other
transitions have mixed ferroelectric-ferroelastic nature.
Electric conductivity 33 of KNB crystals is near to
10
-5
Ohm
-1
cm
-1
at 300
o
C with a sharp drop at
transition. The doping of KNB crystals by the above
elements leads to important changes of physical properties
and phase transitions temperature, up to 200
o
C and more for
some instances. The Sb-doping raises the conductivity 33
on 1-2 order of magnitude. The room-temperature dielectric
permeability 33 of Si-doped crystals increases in six times.
At the substitution of Nb by Ta the anomalies of dielectric
permeability gradually become diffuse and dissappear
which can be explaned by decomposition of these solid
solutions at low temperatures. Possible structural
mechanisms of phase transitions in KNB crystals may be as
follows: distortions of NbO6 octahedra and displacement of
Nb
5+
cations, deformations of BO3 groups, and shifts of K
+
ions in wide channels. The first mechanism seems to play
the principal role at , and transitions,
while the other two mechanisms affect mainly low-
temperature transitions. It is evidenced by strong influence
of Ta- and Sb- substitutions on high-temperature transitions
whereas Na-, Rb- and Si-substitutions influence mainly on
low-temperature ones. The full substitutions of B by Si is
possible and K3Nb3Si2O13 single crystals are grown and
studied. They have hexagonal growth form but at the room
temperature have lower symmetry and are divided into
domains. These crystals are characterized by high dielectric
permeability 33 which is about 4000 at room temperature
and rises with temperature. Authors are grateful to the
RFBR for financial support of this work.
Local Electromechanical Properties
of Ferroelectric Relaxors Studied by
Piezoresponse Force Microscopy
A. KHOLKIN
1
, V. SHVARTSMAN
1
, M. WOITAC
2
,
J. SALDAA
3
, S. VAKHRUSHEV
4
, AND A. SAFARI
5
1
Department of Ceramics and Glass Engineering,
University of Aveiro, 3810-193 Aveiro, Portugal
2
Faculty of Chemistry University of Wroclaw, Joliot-Curie
14, 50-383 Wroclaw, Poland
3
University of Technology Hamburg, Harburg Denickestr.
15, 21073 Hamburg, Germany
4
A. F. Ioffe Physico-Technical Institute, Politekhnicheskaya
26, 194021 St. Petersburg, Russia
5
Department of Ceramics and Materials Engineering,
Rutgers University, New Jersey 08854, U.S.A.
The local electromechanical properties of relaxor single
crystals, ceramics and thin films (PMN, PMN-PT, PZN-PT)
are investigated by Piezoresponse Force Microscopy (PFM)
sensitive to local vibrations of the surface induced by
electric field applied by the sharp PFM tip. Even in pure
relaxor compositions, where the macroscopic polarization
should be absent, stable domain contrast can observed due
to the local piezoelectric effect. This was especially notable
in thin films where locally polarized areas could occupy
entire grains or grain agglomerates [1]. Thus on the
nanoscale level the material behaves as a composite with
local ferroelectric regions embedded in the non-polar
matrix. This can be described as a local relaxor-to-
ferroelectric phase transition or self-polarization effect.
Local hysteresis measured in all investigated compositions
is attributed to extremely high electric field that may shift
the phase diagrams of relaxors, so that the ferroelectric
phase can be induced at elevated temperatures. The data on
single crystals confirm that the domain contrast is an
intrinsic property and can be, in principle, related to locally
ordered region (nanoclusters) [2]. The correlation analysis
is used to extract important information on local
polarization and its behavior with temperature The stability
of the induced polarization is investigated in time domain in
an attempt to access characteristic relaxation times at the
nanoscale. The nature of the observed effects is discussed
from the point of view of current theoretical understanding
of polar state in relaxors and PFM instrumentation
References
1. V. Shvartsman, A. Yu. Emelyanov, A. L. Kholkin, and
A. Safari, Appl. Phys. Lett. 81, 117 (2002).
2. S. B. Vakhrushev, A. A. Naberezhnov, B. Dkhil, J.-M.
Kiat, V. Shvartsman, and A. L. Kholkin, AIP
Proceedings (Proceedings of the Fundamental Physics
of Ferroelectrics 2003; Williamsburg, February 2003).
(submitted).
10
th
182
Preparation of Si-added SrBi
2
Ta
2
O
9
Ferroelectric Thin Films by
RF Magnetron Sputtering at
High Temperature
S. KIKUCHI
1,2
AND H. ISHIWARA
2
1
R&D Association for Future Electron Devices, 2-9-14
Toranomon,Minato-ku,Tokyo 105-0001, JAPAN
2
Technology, 4259 Nagatsuta, Midori-ku, Yokohama,
226-8503, JAPAN, kikuchi@neuro.pi.titech.ac.jp
Recently, we developed novel ferroelectric materials by
adding dielectric bismuth silicate (Bi2SiO5, BSO) to typical
ferroelectric materials such as PbZrxTi1-xO3(PZT),
SrBi2Ta2O9 (SBT) , and Bi4Ti3O12(BIT), and demonstrated
that these materials exhibited excellent ferroelectric
properties.
1)
In this work, we prepared Si added SBT ferroelectric
thin films using an RF magnetron sputtering system with a
106mm ceramic BSO-SBT target. SBT films of 200nm
thickness were formed by RF magnetron sputtering on
Pt/Ti/SiO2/Si substrates. The substrate was heated from
400C to 700C to crystallize SBT films. Sputtering power
and Ar/O2 pressure were varied from 50W to 100W and
from 0.5Pa to 5.0Pa respectively. The deposition rate was
controlled from 2.5nm/min to 8.5nm/min. Pt top electrodes
of 100um in diameter were formed by electron-beam
evaporation. It was found that the Si-added SBT films were
crystallized at deposited temperatures between 500C and
600C, which was much lower than the conventional
annealing temperature (800C) of the films deposited at
room temperature. Figure shows the P-E hysteresis loops of
Si-added SBT films deposited at 550C. As can be seen
from this figure, Si-added SBT films deposited at low
temperature were comfirmed to show ferroelectric
behaviors.
Applied Field (kV/cm)
This work was performed under the auspices of the
R&D Projects in Cooperation with Academic Institutions
(Next-Generation Ferroelectric Memory) supported by
NEDO (New Energy and Industrial Technology
Development Organization in Japan) and managed by FED
(R&D Association for Future Electron Devices).
1) T.Kijima, H.Ishiwara : Jpn. J. Appl. Phys. Vol.41 (2002)
No.6B pp.L716 - L719
Influence of Uniaxial Pressure on
the Phase Transition in Glycine
Phosphite
TOSHIO KIKUTA,
1
YASUHIRO TAKEMOTO,
TOSHINARI YAMAZAKI AND NORIYUKI NAKATANI
1
Department of Electric and Electronic Engineering,
Faculty of Engineering, Toyama University, Toyama
930-8555, Japan. tkikuta@eng.toyama-u.ac.jp
Glycine phosphite (NH3CH3COOHH2PO3, abbreviated
as GPI) is one of hydrogen bonded ferroelectrics and
undergoes the second order phase transition at TC = 224.7 K
[1-3]. Since the temperature of the phase transition shifts to
322K by substitution of deuterium for hydrogen [3,4], it is
expected that the hydrogen bonds may play an important
role for the phase transition in GPI. To investigate the
influence of the hydrogen bonds on the phase transition,
application of pressure to the crystal is one of the effcient
way, as a hydrogen bond is weak in intermolecular forces.
Effect of hydrostatic pressure on the dielectric properties in
GPI and deuterated GPI has been reported [5,6].
Tempreature of the phase transition decreases with
increasing pressure with a slope dTC
H
/dp = 11.0 K/kbar for
GPI and dTC
D
/dp = 5.0 K/kbar for deuterated GPI,
respectively.
Influence of uniaxial pressure on the phase transition in
GPI crystal and several partially deuterated GPI crystals
have been studied by measurement of the dielectric
properties. The pressure was applied to the crystal along
the three principal axes a, b and c*, while temperature
dependence of the dielectric constant along the b-axis was
measured. It has a tendency that temperature of the
dielectric peak shifts towards lower temperature with
increasing uniaxial pressure. For example, the uniaxial
pressure dependence of the each principal axes on the phase
transition temperature in 75% deuterated GPI crystal is
dTC
D75%
/dpa = 0.3 K/kbar for the a-axis, dTC
D75%
/dpb =
3.0 K/kbar for the b-axis and dTC
D75%
/dpc* = 1.5 K/kbar
for the c*-axis, respectively.
References
[1] M. T. Averbuch-Pouchot, Acta Cryst. C 49, 815 (1993).
[2] S. Dacko, Z. Czapla, J. Baran and M. Drozd, Physics
Letters A 223, 217 (1996).
[3] J. Baran, G. Bator, R. Jakubas and M. _led_, J. Phys.:
Condens. Matter 8, 10647 (1996).
[4] J.Baran, M. _led_, R. Jakubas and G. Bator, Phys. Rev.
B 55, 169 (1997).
[5] N. Yasuda, T. Sakurai and Z. Czapla, J. Phys.: Condens.
Matter 9, L347 (1997).
[6] N. Yasuda, K. Kaneda and Z. Czapla, J. Phys.:
Condens. Matter 9, L447 (1997).
10
th
183
Study of Ferroelectric Phase
Transition in Multilayered
Langmuir-Blodgett Thin Films of
P(VDF-TrFE 80:20) and
P(VDF-TrFE 50:50)
JIHEE KIM, MATT POULSEN, STEPHEN DUCHARME,
SHIREEN ADENWALLA
Department of Physics and Astronomy, Center for
Materials Research and Analysis, University of
Nebraska, Lincoln, USA, jhkim@unlserve.unl.edu
The phase transition and dielectric properties of
multilayer films of copolymers of vinylidene fluoride with
trifluoroethylene have been studied in order to investigate
interactions between two different copolymers with distinct
ferroelectric-paraelectric phase transition temperatures. The
phase transition temperatures of multilayered films of
P(VDF-TrFE 80:20) and P(VDF-TrFE 50:50) were
determined using dielectric and x-ray diffraction
measurements. The measured phase transition temperatures
are dependent on the repeat period of the mixed-multilayer
films and ranged between the phase transition temperature
of each copolymer, 57
o
C~131
o
C. The observation indicates
an interaction between the two copolymers resulting in the
multilayer films behaving like hybrid copolymer films. To
complement the structural measurements dielectric
measurements have been also performed on a similar
system of multilayered films.
Work at the University of Nebraska was supported by
the USA Department of Energy, the USA Office of Naval
Research, and the Nebraska Research Initiative.
Ultra Thin Pb(Zr,Ti)O
3
Films and
Pt Electrode for High Density
FeRAM Devices
SEUNG-HYUN KIM
1
*, JUNG-HOON YEOM
1
,
CHANG-YOUNG KOO
1
, CHEOL SEONG HWANG
2
,
AND JOWOONG HA
1
1
INOSTEK Inc., 356-1 Gasan, Keumchun, Seoul 153-802,
KOREA
2
School of Mat. Sci. and Eng., Seoul National University,
KOREA
Ferroelectric random access memories (FeRAM) are
well known to have a number of distinct properties such as
fast programming, high write endurance, low voltage
operation and low power read/write properties that make
them most attractive candidates for standard non-volatile
technologies. For realization of 32 Mb FeRAM devices, the
requirements for the ferroelectric capacitor became
stringent [1-3]. The requirement includes higher remanent
polarization (Pr, > 30 C/cm
2
) in order to compensate for
the small amount of charge due to the reduced size of
capacitors and integration-related degradation of the Pr,
lower thermal budget (< 600
o
C, a few min.) in order to
maintain the low resistance of the buried-contact plug, and
lower height of total capacitor stack (< 300 nm) due to the
difficulty in obtaining steep etching slope of the capacitor
for successful node separation. To solve these drawbacks, it
is highly required to achieve high quality PZT films having
sub-100 nm thickness on ultra-thin electrode (sub-50 nm) at
low annealing temperature.
Recently, we have fabricated high-quality (111)-
oriented PZT (Zr/Ti = 35/65) films by newly developed
chemical solution deposition method. Sub-70 nm PZT thin
films are investigated. All processes are performed at 550
o
C low annealing temperature. In this research, the variation
in the crystalline quality of Pt electrode with its thickness
was studied in detail and their influences on ferroelectric
properties of PZT films are reported. The influence of
thickness scaled PZT thin films on the ferroelectric
performance was also investigated. Our results suggest that
with stringent process control, well-prepared sub-70 nm
PZT thin films on 30 nm-thick Pt electrode can be achieved
excellent ferroelectric performance and provide the
possibility to realize 32Mb FRAM devices and beyond.
References
[1] K. Kim, Integrated Ferroelectrics, 36, 21 (2001).
[2] W.L. Warren, H.N. Al-Shareef, D. Dimos, B.A. Tuttle,
and G.E. Pike, Appl. Phys. Lett. 68, 1681 (1996).
[3] S-H. Kim, D-S. Lee, C.S. Hwang, D-J. Kim, and A.I.
Kingon, Appl. Phys. Lett. 77(19), 3036 (2000).
10
th
184
High Performance Pb(Zr,Ti)O
3
Thin Films for Piezo-Sensors and
Uncooled IR Detectors
SEUNG-HYUN KIM
1
*, JEONG-SUONG YANG
1
,
JUNG-HOON YEOM
1
, CHANG-YOUNG KOO
1
, EUIJOON
YOON
2
AND JOWOONG HA
1
1
INOSTEK Inc., 356-1 Gasan, Keumchun, Seoul 153-802,
KOREA email : shkim@inostek.com
2
School of Mat. Sci. and Eng., Seoul National University,
KOREA
For systematic evidences for composition dependent
piezoelectric and pyroelectric properties, we have
performed extensive study based on experimental results of
the piezoelectric and the pyeroelectric properties, and
related dielectric and ferroelectric properties of PZT films
with three different compositions (Zr/Ti =30/70, 52/48 and
70/30). All PZT films were reasonably well-textured (111)
orientation for the investigated compositional range.
However, it was observed that Zr-rich compositions were
less well oriented when compared to those having
tetragonal symmetry. With increasing Ti-content, larger
remanent polarization and higher coercive voltage were
observed. The squareness of polarization hysteresis loop
was maximized in Ti-rich composition. The remanent d33
values were maximized near the MPB composition, while
pyroelectric figure of merit near the tetragonal composition.
It was shown that the piezoelectric coefficient and the
pyroelectric figure of merit were dependent on the dielectric
properties of the films. This result indicated that there exist
almost identical mechanisms governing bulk and thin PZT
films. The maximum dielectric constant was achieved near
the MPB composition, showing same trend with bulk PZT
ceramics. It was observed that the morphotropic PZT films
with high dielectric constant and low pyroelectric figure of
merit showed the largest piezoelectric coefficient values,
while the tetragonal PZT films with low dielectric constant
and high remanent polarization values showed the largest
pyroelectric figure of merit compared to other composition.
Crystal Structure and Phase
Transitions in [(CH
3
)
2
NH
2
MeCl
4
Crystals
L. KIRPICHNIKOVA
1
, A. PIETRASZKO
2
, A. SHELEG
3
1
Institute of Crystallography Russian Acad. Sci., 117333
Moscow, Russia, E-mail:luba@ns.crys.ras.ru
2
Insttitute of Low Temperature and Structural Research
Polish Acad. Sci., 50-950 Wroclaw, Poland,
E-mail: adam@int.pan.wroc.pl
3
Institute of Solid State and Semiconductor Physics NAS,
220072 Minsk, Belarus,
E-mail: sheleg@ifttp.bas-net.by
The (CH3)2NH2Al(SO4)26H2O, (CH3)2NH2H2PO4, [1,2]
ferroelectric crystals has complicated system of hydrogen
bonds, which largely determined the way to bind its
building blocks into framework. The [(CH3)2NH2] (DMA)
ion pay an important role in the processes of formation of
polar ferroelectric phases in this compounds. The
[(CH3)2NH2]2CoCl4 and [(CH3)2NH2]2CuCl4 crystals [3,4]
possess incommensurate and ferroelectric phases. Results
of our investigation of crystal structure and dielectric
properties of [(CH3)2NH2]2CuCl4, [(CH3NH2]2CoCl 4 and
new compound [(CH3)2NH2CdCl4 are reported. Our study
allow us to obtain crystallographic data, change the
symmetry of phase and propose the mechanism of phase
transitions.
References
L. Kirpichnikova, A.Pietraszko, K.Lukaszzzewich, et.al
Cristallography Reports,39, 1078 (1994)
A. Pietraszko, D.Kucharczyk et.al. Journ. Molecular
Structure 508, 139 (1999)
Z. Bobrova, V.Verikash et.al Krystallografyia 32, 255
(1987)
V. Vasilev, V.Rudjak et.al Sov.Solid State Physics, 29,
1539 (1987)
10
th
185
Theoretical Analysis, X-ray and
Optical Research of Domain
Structure in [(NH
4
)
1-x
Rb
x
]
3
H(SO
4
)
2
Mixed Crystals.
L. KIRPICHNIKOVA
1
, V. SHAKHMATOV
2
,
A. PIETRASZKO
3
, M. POLOMSKA
4
, B. HILCZER
4
1
Institute of Crystallography Russian Acad., Sci.,117333
Moscow Russia, E-mail: luba@ns.crys.ras.ru
2
Joint Institute for Nucleas Reserch, 141980 Dubna,
Moscow Reg. Russia, E-mail: shakh@thsun1.jinr.ru
3
Institute of Low Temperature and Structural Research
Polish Acad., Sci., 50-959 Wroclaw, Poland,
Email: adam@int.pan.wroc.pl
4
Institute of Molecular Physics Polish Acad.,Sci., 60-179,
Poznan, Poland E-mail:B.Hilczer@ifpan.poznan.pl
The [(NH4)3H(SO4)2 crystals below reversible
superprotonic-ferroelastic phase transition R3/m (I) -A2/a
(II) exhibit four phase transitions. The Rb3H(SO4)2 crystals
undergo one irreversible phase transition to superprotonic
phase. The mixed [(NH4)1-xRbx]3H(SO4)2 are very sensitive
to RbNH4 substitution: rubidium ions replacing
ammonium ions brings about the stabilization of phase II.
The temperature of superprotonic phase transition increase
with increasing Rb content and compounds with x > 0.5
exhibit two superprotonic phases. In the present work we
present the results of detail studies the domain structure
evolution, X-ray investigation and theoretical analysis on
the basis phenomenological theory of high temperature
phase transition in the mixed [(NH4)1-xRbx]3H(SO4)2
crystals. One can calculate the spontaneous deformation as
a temperature function using temperature dependence of
unit cell parameters. The transition process to superprotonic
phase is more complicated than has been describe in the
literature.
Domain Structure and Theoretical
Analysis of CsDSO
4
Crystals
L. KIRPICHNIKOVA
1
, V. SHAKHMATOV
2
,
M. POLOMSKA
3
, B. HILCZER
3
1
Institute of Crystallography Russian Acad., Sci., 117333
Moscow, Russia, E-Mail: luba@ns.crys.ras.ru
2
Joint Institute for Nuclear Research, 141980 Dubna,
Moscow Reg., Russia,
E-mail: Shakh@thsun.jinr.ru
3
Institute of Molecular Physics Polish Acad., Sci., 60-179
Poznan, Poland
E-mail: B.Hilczer@ifpan.poznan.pl
According to [1,2] CsDSO4 (CDS) crystals have one
improperferroelastic-superprotonic phase transition I4/amd
P2/c. Recently we report [3] that there exists an
intermediate phase in the vicinity Ts and a hypothetical
cubic phase -prototype. The present study was undertaken
for further study of the domain structure of CDS crystals on
plates with different orientation subjected to mechanical
tests and generalization and systematization of the observed
changed. A theoretical analysis on the basis
phenomenological theory is proposed. A more detail
analysis of domain structure and the theoretical analysis
provide the better understanding of the processes occurring
in the vicinity of the phase transition, which accompanied
by disappearance of considerable spontaneous deformation
and appearance large conductivity.
References
A.I.Baranov, L.A.Shuvalov et. al., Sov. Phys. Crystallogr.,
29, 706 (1984)
B.V.Merinov, A.I.Baranov et. al., Sov. Phys. Crystallogr.,
32, 47, (1987)
L.Kirpichnikova, M.Polomska, B.Hilczer, Ferroelectrics,
221, 85 (1999)
10
th
186
Relaxor Ferroelectrics
From Random Field Models to
Domain State Physics
W. KLEEMANN
1
, J. DEC
1,2
, TH. WOIKE
3
,
R. PANKRATH
4
,
1
Angewandte Physik, Universitt Duisburg-Essen, D-47048
Duisburg, Germany;
wolfgang@kleemann.uni-duisburg.de
2
Physics Department, University of Silesia, PL 40-480
Katowice, Poland
3
Institut fr Mineralogie, Universitt zu Kln, D-50674
Kln, Germany
4
Fachbereich Physik, Universitt Osnabrck, D-46069
Osnabrck, Germany
Substitutional charge disorder giving rise to quenched
random-fields (RFs) is probably at the origin of the peculiar
behavior of relaxor ferroelectrics, which are primarily
characterized by their strong frequency dispersion of the
dielectric response and by an apparent lack of macroscopic
symmetry breaking at the phase transition. By cooling in an
external electric field, however, the response becomes
ferroelectric-like and the thermoremanent polar-ization
vanishes at a well-defined transition temperature. Spatial
fluctuations of the RFs correlate the dipolar fluctuations and
give rise to polar nanoregions in the paraelectric regime.
The dimension of the order parameter decides upon whether
the ferroelectric phase transition is destroyed (e.g. in cubic
PbMg1/3Nb2/3O3, PMN) or modified towards random-field
Ising model behavior (e.g. in tetragonal Sr1-xBaxNb2O6,
SBN, x 0.4) [1]. Frustrated interactions between the polar
nanoregions in cubic relaxors give rise to cluster glass
states as modeled by the spherical random bond-R F
modeling [2], while freezing into a domain state takes place
in uniaxial relaxors. Convincing evidence of paraelectric
nanoregions has been obtained e.g. from precursor tails of
the linear bi-refringence [3] and from both optical [4] and
dielectric second harmonic response [5]. Below Tc frozen-in
nanodomains have been evidenced indirectly by dynamic
light scattering [6] and directly by piezoresponse force
microscopy [7] as well as by relaxational and creep-like
dielectric response of pinned domain walls [8]. It is noticed
that the field-induced creep is replaced by slow relaxation
after aging within the ferroelectric phase [9] or after cluster
formation in the paraelectric phase. Interestingly, despite its
long-range dipolar interaction, the uniaxial relaxor SBN
exhibits non-classical critical behavior as expressed by
critical exponents 1.8 [1], 0.1 [10] and 0 [11].
Very probably this is a consequence of the reduced
correlation length of the order parameter due to the
abundant charge disorder.
[1] W. Kleemann et al., Europhys. Lett. 57 (2002)14 [2]R.
Blinc et al., Phys. Rev. Lett. 83 (1999) 424[3] P. Lehnen et
al., Eur. Phys. J. B 14 (2000) 633 [4] P. Lehnen et al.,
Ferroelectrics 268 (2002) 113 [5] J. Dec et al., Phys. Rev.
Lett. (submitted) [6] W. Kleemann et al., Phys. Rev. Lett.
86 2001) 6014 [7] P. Lehnen et al., Phys. Rev. B 64 (2001)
224109 [8] W. Kleemann et al., Phys. Rev. B65 (2002)
220101 [9] W.Kleemann et al., Ferroelectrics (in press) [10]
R. Blinc et al., Phys. Rev. B 64 (2001) 134109 [11] Z.
Kutnjak and W. Kleemann, unpublished
Theoretical Study of Flexoelectric
Effect Based on a Simple Model of
Ferroelectrics
A. KLIC AND M. MARVAN
Rep., Na Slovance 2, 18221 Praha 8,
e-mail: klic@fzu.cz
Charles University, Faculty of Mathematics and Physics,
V Holesovickch 2, 18000 Praha 8,
e-mail: marvan@kmf.troja.mff.cuni.cz
By flexoelectric effect is called linear relation between
polarization and gradient of deformation Pl = ijkl i j/xk
(ij - tensor of small deformation, xk - space co-ordinate).
The upper limit of the flexoelectric coefficient ijkl for
ordinary dielectric was formerly theoretically estimated as
e/a of the order of 10
-10
C/m [1] where e is elementary
electric charge and a is lattice constant. The recent
experimental investigation [2,3,4] shows that the
flexoelectric coefficient of ferroelectric relaxors PMN and
BST is about four orders of magnitude higher than the
previously theoretically estimated value. As it is shown in
the present work the limit e/ a is not general. In
ferroelectrics with orientation mechanism of dielectric
properties the gradient of deformation plays the role of an
effective electric field. In our simple model it has the value
Eeff (a
2
/e)grad (where is the spring constant). It
means that P = Eeff and the effect can be expected as
relatively large at temperatures close to the phase transition.
This work was supported by the Grant Agency of the
Czech Republic (Project No. 202/03/0551 and
202/02/0238/A)
[1] Tagantsev A K, Phys. Rev. B 34, 5883 (1986)
[2] Ma W and Cross L E, Appl. Phys. Lett. 78, 2920 (2001)
10
th
187
Semiadiabatic High-Field
Polarization Respose In
Ferroelectrics II: Size Effects
E. KLOTINS
1
, J. HLINKA
2
AND E. KAUPUZS
3
1
Institute of Solid State Physics, 8 Kengaraga Str., LV 1063
Riga, Latvia, klotins@cfi.lu.lv
2
Institute of Physics, Praha
3
Institute of Mathematics and Computer Sciences, Riga
Spatial extension and size effects are at the core of
nonconservative energy functional based models claiming
to describe non-linear and non-adiabatic dielectric response
in ferroelectrics [1]. The standard technique comprises
Fourier transformation of the energy functional, Fokker-
Planck scheme, and the diagram technique for spatially
temporal correlation functions of polarization [2]. Spatial
resolution of the energy functional is determined by
incorporating periodic boundary conditions with maximum
cutoff for the wave number. We report an extension of this
approach applicable to finite size objects for which the
transformation is derived from basic functions defined
within a finite x [-L,L] region. As a result, the
transformation is discrete within an arbitrary region and
accounts for finite size by definition. Only the zero order
term is necessary to model the polarization kinetics of the
region as a whole the spatial extension being given by terms
of higher order. Finally, as the main result of this work, the
Fokker-Planck scheme becomes size specific. We
exemplify this approach for the quartic prototype model and
demonstrate its term-by-term transformation within a finite
size region. We show the coefficients at spectral amplitudes
and at the diffusion term in Fokker-Planck equations
becoming size specific and the barrier height in the energy
landscape diminishing with reducing the size. A
cooperative effect, essential in the context of technological
applications, is the increase of relaxation rate with reducing
the size.
[1] E. Klotins, J. Hlinka and J. Kaupu_s , Semiadiabatic
highfield polarization respose in ferroelectrics I:
Hysteresis and nonlinear susceptibility (this conference)
[2] J. Kaupuzs, phys. Stat. Sol. (b) 195, 325 (1996)
The Phase Transition of PbHPO
4
Under High Pressure
Y. KOBAYASHI
1
, S. ENDO
1
, M. MATSUSHITA
2
,
F. ONO
2
, K. DEGUCHI
3
AND T. YAMANAKA
4
1
Rcesearch Center for Materials Science Conditions, Osaka
University, Toyonaka, Osaka, 560-8531, Japan,
2
Department of Physics, Okayama University, Okayama,
Okayama 700-8530, Japan,
3
Department of Materials Science, Shizuoka Institute of
Science and Technology, Fukuroi, Shizuoka 437-8555,
Japan,
4
Department of Earth and Space Science, Gradutate School
of Science, Osaka University, Toyonaka, Osaka, 560-
0043. nakamoto@rcem.osaka-u.ac.jp
Lead hydrogen phosphate, PbHPO4 (LHP), undergoes a
phase transition from Phase I to Phase II at TC=310K under
atomospheric pressure. The low-temperature ferroelectric
phase (Phase II) with pseudo-one dimentional hydrogen-
bonded structure has a space group of PC. On the other
hand paraelectric phase (Phase I) has generally been
assumed to have P2/C. 1) From dielectric measurement, TC
is gradualy lowered with increaseing pressure and when TC
goes down to room temperature, the transition pressure has
been determined to be 0.125GPa.2, 3) The phase transition
was no more observed over 3 GPa.
In the present work, x-ray powder diffraction study of
LHP was carried out under hydrostatic conditions at room
temperature using a diamond-anvil cell and an imaging
plate at Photon Factory, KEK, Japan. We could not detect
any difference in the diffraction patterns of Phase II and
Phase I with increaseing pressure up to 5.6 GPa. By further
compression a new pressure-induced phase (Phase III)
appear at about 6.5 GPa as shown in Figure. Phase III is
stable within the present pressure region up to 17 GPa.
During decompression cycle, phase III is converted back to
the original phase I at 0.7 GPa.
Figure: Upper and low diffraction patterns are represented
by Phase III (at 11 GPa) and Phase II (at 0.1 MPa),
respectively
[1] T. J. Negran et. al.: Ferroelectrics, 6(1974)179.
[2] V. P.Mylov et. al.: Sov. Phys.-Crystallogr. 24(1979)738.
[3] N. Yasuda et. al.: Japan. J. Appl. Phys. 17(1978)103
10
th
188
Ferroelectric and Piezoelectric
Properties of
0.24PZN 0.384PZ 0.376PT
Thin Films Crystallized by
Hot Isostatic Pressing
MASAFUMI KOBUNE, SHINICHI KOJIMA,
ATSUSHI MINESHIGE, TETSUO YAZAWA,
HIRONORI FUJISAWA AND MASARU SHIMIZU
Himeji Institute of Technology, 2167 Shosha, Himeji,
Hyogo 671-2201, Japan.
kobune@chem.eng.himeji-tech.ac.jp
To develop the piezoelectric thin films with high
pe r f or ma nc e , a mor phous 0.24Pb(Zn1/3Nb2/3)O3
0.384PbZrO30.376PbTiO3 ( a-PZNZT) films were
deposited on PbTiO3(PT)/Pt(111)/SiO2/Si(100) substrates
by room-temperature sputtering. Subsequently, they were
crystallized at the fixed annealing temperature by varying
the pressure in the wide range by hot isostatic pressing
(HIP). The crystal structure and the orientation of the
obtained films are investigated. On the basis of the
measurements of ferroelectric and piezoelectric properties
for Pt/PZNZT/PT/Pt ca-pacitors, the HIP-pressure
dependence of their properties is revealed. A-PZNZT films
were deposited on PT(30nm)/Pt(200nm)/SiO2 (400nm)/Si
substrates by rf-magnetron sputtering without heat-ing the
substrates. The thickness of PZNZT films was 270 nm. As-
deposited films were HIPed at 500C for 1 h under mixed
gas (Ar/O2=80/20) pressure ranging from 1.0-176.5 MPa
after chemical-oxidation treatment. The crystal structure
and the ori-entation were investigated using an X-ray
diffractometer (XRD). The P-E characteristics and the
applied voltage dependence of piezoelectric coefficient d33
were measured using a ferroelectric film test system
(Radiant; RT66A) and a piezoelectric scanning force
microscopy (PFM) system, respectively. The crystalline
phase of the obtained films was the single-phase perovskite
structure. The films HIP-treated at the pressure of 1.8 MPa
showed almost completely (001)-orientation and their
degree of c-axis orientation, attained to 0.95. The
crystallinity in the pressure region over 8.8 MPa
significantly lowered with increasing pressure. The
spontaneous polarization, the remanent polarization and the
coercive field, which indicated almost sym-metric P-E
hysteresis loops, were Ps=36.8 C/cm
2
, 2Pr=23.2 C/cm
2
and 2Ec=86.7 kV/cm, respectively. The symmetric but-
terfly loops of d33 vs. applied voltage were observed in the
sam-ples HIP-treated at the pressure of 1.8-17.7 MPa.
Especially, the saturated d33 of the sample HIP-treated at
the pressure of 1.8 MPa was 70-80 pm/V. The
electromechanical coupling factor k33 which was calculated
using d33, Youngs modulus Y33
E
and die-lectric constant
33
T
was estimated to be 27-31%. Thus the opti-mal
crystallization pressure of PZNZT 24/38.4/37.6 films was
judged to be 1.8 MPa. The above excellent electrical
properties may be explained by the presumption that the
compensation for oxygen vacancies which partly exist in
the site of each vertex of the BO6 oxygen octahedron is
almost completely carried out at low temperature (500C)
under the appropriate high-pressure (1.8 MPa), resulting in
stabilization of the perovskite structure.
Self-Consistent Geometric Effect
at the Origin of the Isotope Effect
in KDP
J. KOHANOFF
1
, S. KOVAL
2
, R. MIGONI
2
AND
E. TOSATTI
3
1
Atomistic Simulations Group, Queen's University Belfast,
Belfast BT7 1NN, Northern Ireland
2
Instituto de Fisica de Rosario, Universitad Nacional de
Rosario, 27 de Febrero 210 Bis, 2000 Rosario,
Argentina
3
SISSA and ICTP, Strada Costiera 11, I-34014 Trieste, Italy
The debate on the origin of the huge isotope effect upon
deuteration in the ferroelectric transition of KH2PO4 (KDP)
has been open for the past four decades. Blinc's proton
tunneling model [1] and later improvements were able to
explain a 100 K increase in Tc in terms of tunneling of the
protons between deep wells. Alternatively, Sugimoto and
Ikeda succeded in rationalising the phenomenon, but in
terms of geometric (Ubbelohde) effects [2]. Their model
parameters and molecular dipoles depend on the isotopic
mass, but tunneling is not considered at all.
Here we present first-principles calculations on clusters
of different size, embedded in KDP and DKDP paraelectric
hosts, i.e. at different lattice parameters. We observed two
main phenomena. Firstly, the potential energy for collective
displacements along ferroelectric-like local modes exhibits
a double-well character only for large enough clusters, and
when the heavy atoms (K, P) are included. Secondly, the
depth of the potential wells for cluster motions depends
very strongly on the lattice constant, much more than the
global barrier for polarisation inversion. For the same
cluster size, the barriers for DKDP are one order of
magnitude larger than for KDP. This is an extremely non-
linear behaviour, which we modelled by a non-linear
Schrdinger equation on the collective motion of the atoms
in the cluster. In this model the cluster wave function
introduces a feedback onto the potential making it deeper
where the probability is larger. In this way, the isotope
effect can be explained as a self-consistent geometric effect:
the stronger localisation of the deuterons makes O-O
distances larger, thus creating a pressure that expands the
lattice, and this expansion reflects back onto a further
localisation of the wave function of the deuteron [3].
[1] R. Blinc, J. Phys. Chem. Solids 13, 204 (1960).
[2] H. Sugimoto and S. Ikeda, Phys. Rev. Lett. 67, 1306
(1991).
[3] S. Koval, J. Kohanoff, R.Migoni and E. Tosatti, Phys.
Rev. Lett. 89, 187602 (2002).
10
th
189
Terahertz Time Domain
Spectroscopy of Polariton
Dispersion in LiNbO
3
S. KOJIMA
1
, H. KITAHARA
2
, S. NISHIZAWA
3
AND
M.WADA TAKEDA
2
1
Institute of Materials Science, University of Tsukuba,
Tsukuba, Ibaraki 305-8573, Japan.
kojima@bk.tsukuba.ac.jp
2
Department of Physics, Faculty of Science, Shinshu
University, Matsumoto, Nagano 390-8621, Japan
3
Cooperative Research Center, Shinshu University, Nagano,
Nagano 380-8553, Japan
The recent progress in the generation of coherent
terahertz radiation enables the potential application for far-
infrared spectroscopy.
1-3
Using THz Time-Domain
Spectroscopy the intensity and phase of transmittance of an
x-plate of a ferroelectric lithium niobate crystal were
accurately measured in the frequency range between 0.09
and 2 THz. The lowest branch of phonon-polariton
dispersion was determined down to the very low frequency
of 0.09 THz, it cannot be attained by other experimental
methods.
For light polarization parallel to the z-axis (E//z) and
y-axis (E//y), low-frequency polariton branches of A1(z) and
E(y) symmetries were clearly observed separately. We have
determined the low-frequency phonon-polariton dispersion.
The obtained dispersion relation was well reproduced by
the phonon-polariton dispersion relation calculated on the
basis of Kurosawas formula. The observed dispersion
curve of A1(z) polariton shows no "avoided crossing" at
1.3 THz reported previously by Bakker et al.
4
as shown in
Fig.1. The real and imaginary parts of dielectric constants
have been determined from transmitted amplitude and
phase signals. The dielectric behavior in the frequency
region from sub-terahertz to terahertz is also discussed.
Fig. 1 Polariton dispersion of A
1
(z) symmetry.
References
1. S. Nishizawa et al.: Proc.1999 IEEE 7th Int. Conf. on
Terahertz Electronics (THz'99), P50, Nara, 1999.
2. S. Kojima, N. Tsumura, M. Wada Takeda and S.
Nishizawa: Jpn. J. Appl. Phys. 41 (2002) 7033.
3. S. Kojima, N. Tsumura, M. Wada Takeda and S.
Nishizawa : Phys. Rev. B67 (2003) 035102.
4. H. J. Bakker, S. Hunsche and H. Kurz: Phys. Rev. B48
(1993) 13524.
New Finding of Phase Transition
Feature in BaTiO
3
AKIRA KOJIMA
1
, YUKIO YOSHIMURA
2
,
HIROSHI SASOU
1
, NAOTOSHI TOKUNAGA
2
,
HIROSHI IWASAKI
2
AND KEN-ICHI TOZAKI
3
1
Department of Materials Science, The University of Shiga
Prefecture, Hikone, Shiga 522-8533, Japan
2
Faculty of Science and Technology, Ritsumeikan,
Kusatsu, Shiga 525-8577, Japan
3
Department of Physics, Faculty of Education, Chiba
University, Chiba 263-8522, Japan
There are huge amount of studies on phase transitions
of the typical ferroelectrics BaTiO3 for more than half a
century, but perfect understanding of the transition features
has not been obtained. In order to observe changes in
physical properties at the structural phase transitions
precisely, we have developed the "mK-stabilized cell"
1)
,
with which we can follow transient process under nearly
quasi-static condition not only on heating but also on
cooling with the temperature stability of +-0.20 mK and the
temperature resolution of 0.20 mK
2)
.
Samples used are single crystals from two different
sources grown by the top-seeded solution growth method.
These crystals are virgin samples in the sense with no
external electric field applied prior to measurements.
Different characteristics have been revealed at each
transition. Temperature width of the three phase transitions
differs remarkably. Compared to the width of the
uppermost temperature (403K) transition from the cubic
phase, that of the lower temperature transition is one order
small and that of the lowest temperature transition is one
order large. Most significant is the finding of a multi-step
feature at the uppermost temperature transition on cooling
in the measurements of exothermic heat, dielectric constant,
displacement current and ultrasonic resonance. These
results suggest that the transition from the paraelectric state
to the ferroelectric state is not so simple in real crystals as
the existing theories predict.
We have examined structural changes using X-ray
precession method in the temperature range from 420 K to
85 K. Paying attention to both the appearance of extra spot
and the splitting of Bragg spot, transition sequence has been
determined as follows: cubic coexistence of tetragonal
and monoclinic 1 monoclinic 2 orthorhombic. This is
entirely different from the widely accepted sequential
transition model proposed by Kay and Vousden
3)
.
References
1. A. Kojima et al., Rev. Sci. Instrum. Vol. 68, 2301 (1997).
2. A. Kojima et al., Proceedings of the 8th Temperature
Symposium (Chicago), August, 2002 (to be published).
3. H. F. Kay and P. Vousden, Phil. Mag., Vol. 40, 1019
(1949).
10
th
190
Effect of ECR Plasma Treatment on
Lithium Niobate Surface State
L.S. KOKHANCHIK, S.YU. SHAPOVAL, E.B. YAKIMOV
Institute of Microelectronics Technology, Russian
Academy of Sciences, Chernogolovka, Moscow
District, 142432 Russia, mlk@ipmt-hpm.ac.ru
Microwave plasma etching in the electron cyclotron
resonance (ECR) conditions finds the more and more
applications in microelectronics technology. The ECR
plasma has a lot of advantages as compared with other
methods of plasma discharge such as the high plasma
density, low operation pressure, low particle energy leading
to a decrease of surface damage etc. Plasma etching of
lithium niobate is now widely used in the formation of
acousto- and optoelectronic devices. Nevertheless the
question concerning the ECR plasma effects on the
properties of near surface layers has been still open,
especially if one takes into account a sensitivity of lithium
niobate to temperature, light, X-Ray and some other
excitations.Lithium niobate Z cuts from the Czochralski
grown crystal were used in this study. All investigated
samples contained large 180
o
domains with +C and C
orientation. The samples were mechanically polished before
etching and had not any surface relief. The lithium niobate
plasma etching was carried out in the mixture of SF6 and
Ar. During plasma treatment the layer with a thickness of
about 0. 3 m was removed. Surface characterization before
and after etching was carried out in the SEM-525M
(Philips) and JSM-840A (Jeol). Secondary electron (SE)
mode in the low accelerating voltage regime was used for
investigation that allowed to study surface roughness,
charge surface state, pulse electron emission and local
changing of surface pyroelectric potential during heating in
the SEM. It was shown that +C and C domains had
different surface relief after etching and different etching
rate. Besides, it is seen that the surface of negative domains
is smoother than that of positive ones. Although after
etching the samples were storied for a few days, the SE
signals from the domains of different polarity differs
significantly. The negative domains had positive charge of
subsurface layer while the positive ones have been charged
negatively after plasma treatment. Electron emission pulses
and sharp local surface pyroelectric potential changing on
C domain surface were observed in temperature range 40-
120
o
C before etching. No any pulses were detected after
treatment the same samples in the ECR plasma. As we
shown in the paper [1] the pulse emission and local surface
potential changing in lithium niobate during heating in the
SEM are associated with sample defect structure. It seems
that this phenomenon is very similar to Barkhausen effect
in ferroelectrics during heating [2]. The local pyroelectric
potential changing and simultaneous emission pulses
observed in the SEM could be explained by an appearance
of new domains in subsurface structure defect areas. The
ECR plasma surface treatment is appeared to reduce the
number of surface structural defects thus the emission
pulses are not observed during sample heating more. The
effects of ECR plasma etching on LiNbO3 surface obtained
in the investigation are discussed. [1] L. S. Kokhanchik, E.
B. Yakimov. Ferroelectrics. 1999. V 225. P.41-48. [2]
V.M.Rudyak. Prozessy perekljuchenija v nelineinyh
krystallah. M.: Nauka. Glavnaja red. fis.-mat. liter. 1986. P.
248.
Influence of the Electron
Irradiation in the SEM on Terbium
Molybdate Surface Potential State
L. S. KOKHANCHIK
1
, B. K. PONOMAREV
2
1
Institute of Microelectronics Technology, Russian
Academy of Sciences, Chernogolovka, Moscow
District, 142432, Russia mlk@ipmt-hpm.ac.ru
2
Institute of Solid State Physics, Russian Academy of
Sciences, Chernogolovka, Moscow District, Russia
The Scanning Electron Microscopy (SEM) allows not
only to observe domains in ferroelectrics but also to
investigate the physical properties of these materials. In this
work the electron beam of the SEM was used to modify and
to investigate the properties of the surface of ferroelectric
ferroelastic terbium molybdate.
The Tb2 (MoO4)3 samples of 3.5x4.5 and 2.2x2.2 mm
2
in size and with thickness about 1mm were cut
perpendicularly to the [001] axis that is parallel to the
spontaneous polarization Ps (0.0019 C.m
-2
). The
orthorhombic axes [100] and [010] were directed along the
sample diagonals in the (001) plane. The [010] axis is about
0,3% longer than the [100] axis. The ferroelectric structures
consisting of two or three 180
o
-domains were created in the
single domain samples by compressing them along the
[010] axis. These domains will be referred to as + and -
. We used two regimes of the electron beam interaction
with the sample surface in the SEM: a short time irradiation
at low energies (1-3 keV) and small beam currents (10
-11
A)
and a long time irradiation at larger currents (10
-10
A).
Beam energies were always smaller than 10 keV. Initial
surface potentials and those ones after the electron beam
irradiation were investigated in a secondary electron (SE)
mode.
At the beginning of the experiment positive domains
exhibit ~ 1.5 times weaker SE emission than negative ones.
The observed contrast is explained by the existence of the
electrostatic effective fields caused by the spontaneous
electric polarization and directed in the + and -
domains oppositely. The SE emission of domains was
evaluated for different beam energies. The results were
compared with the SE emission of domains from the Z cut
of LiNbO3 crystal of similar conductivity but with greater Ps
(0.71 C m
-2
). The intrinsic electrostatic fields were
calculated in both types of materials and domains.
Increasing the irradiation dose results in disappearing
the SE contrast between opposite domains. Furthermore the
inverse contrast is frequently observed after the storage of
the sample during several days at ambient conditions. The
inversion of the contrast is explained by redistribution of
electrons and holes. Due to the opposite directions of the
intrinsic electric fields the redistributions are different in the
+ and - domains. So the different amounts of the
electrons and the holes are accumulated in subsurface layers
of the domains. Domain wall image appears at stronger
surface charging. The wall image varies from dark to bright
depending on the electrical charge formed on the surface.
Increasing the accelerating voltage results in broadening of
the wall potential image from 2-3 to 50-60 microns. The
relation between the width of potential image and the real
width of the domain wall is discussed.
10
th
191
Recent Understanding the
Dielectric Relaxation Processes
and Dipolar Disordering in
High-Symmetry Relaxor System
Cd
2
Nb
2
O
7
N.N. KOLPAKOVA
1
, P. CZARNECKI
2
, W. NAWROCIK
2
,
M. P. SHCHEGLOV
1
, AND L. SZCZEPANSKA
3
1
A.F. Ioffe Physico-Technical Institute RAS, 194021 St.
Petersburg, Russia
2
A. Mickiewicz University, 61-614 Poznan, Poland
3
Institute of Molecular Physics PAS, 60-179 Poznan,
Poland (kolpakova@mail.ioffe.ru )
The Cd2Nb2O7 pyrochlore (CN) described by the high-
symmetry cubic space group Oh
7
Fd3m at RT is the first
example of the undiluted sol i ds that exhibits a relaxor
behaviour [1,2]. Earlier, the relaxor behaviour was known
only for a few mixed perovskites like PbMg1/3Nb2/3O3
(Oh
1
-Pm3m) [3]. The nature of disordered relaxor state as
well as the transition from a relaxor to glassy or
ferroelectric state are the basic questions of physics of
relaxor ferrroelectrics (RF), but still open for CN.
We report on unusual dielectric behaviour of CN over
the frequency range of 100 Hz to 13 MHz between 100 to
300 K. In addition to the dielectric relaxation at Tc=196 K
typical of ferroelectrics, two non-Debye type relaxation
processes develop in the system below Tc (around 190 and
150 K). The former is characterized by (i) the transition
from a relaxor to glassy state at Tfreez183 K in zero or a
weak bias electric field, (ii) slowing down of the relaxation,
and (iii) dramatic broadening in the dielectric absorption
and relaxation-time distribution at the low-frequency side
below Tfreez, typical of RF with glassy behaviour [3]. The
latter dominating around 150 K is characteristic of the
dipolar glass-forming systems in the ergodic state far above
Tglass (20 K): slowing down relaxation (non-Arrhenius
behaviour) and increasing asymmetry both in the dielectric
absorption peak and the relaxation-time distribution at the
low-frequency side with decreasing temperature, yet
without freezing the peak-absorption frequency.
Taking into account the specificity of the pyrochlore
structure, a mechanism is proposed that explains
(i) developing two different disordered states in CN
(relaxor, dipolar glass) separated by an incommensurate
phase, and (ii) an orientational dipole disorder in the
system. Characteristic features in dielectric behaviour of the
RF with pyrochlore and perovskite structure are briefly
reviewed.
The financial support by RFFI (Russia) under the
Grants 0002-16900, 0102-17877 and KBN (Poland),
Project 2P03B04722 is acknowledged.
[1] N.N. Kolpakova et al.. J. Exper. Theor. Phys. 94, 395
(2002). [2] N.N. Kolpakova et al., J Appl. Phys. 90, 6332
(2001). [3] L.E. Cross, Ferroelectrics 76, 241 (1987);
ibidem 151, 305 (1994).
Influence of External Fields on the
Properties of SrTi(
16
O
1-x
18
O
x
)
3
at
Oxygen Isotope Substitution
PEET KONSIN AND BORIS SORKIN
Institute of Physics, University of Tartu, Riia 142, 51014
Tartu, Estonia; E-mail: sorkin@fi.tartu.ee
The dynamical mechanism of the ferroelectric phase
transition in SrTi(
16
O1-x
18
Ox)3 induced by the isotope
exchange of
18
O for
16
O [1] is proposed. This mechanism is
based on the electron-lattice p-d coupling [2], TO and TA
phonon-phonon interactions and the quantum fluctuations
(zero-point motion). The lowest zone center mode F1u() in
the cubic phase splits into A2u + Eu modes in the tetragonal
phase and the Eu mode is the ferroelectric soft mode in
SrTi
18
O3 . The Eu(x,y) mode softens down to about 200
GHz with the decrease in temperature and splits into two
modes below Tc 24 K. One of these two modes, the A1(z)
mode hardens with the further decrease in temperature. In
an external electric field the enhancement of the dielectric
constant is found. The quantum phase transition can be
controlled in terms of the photo-induced effect by the laser
field. The photo-induced effect in the quantum dielectric
system, in our case, is caused by the creation of
photoelectrons in the electronic subsystem and the vertex
corrections in the electron lattice p-d coupling. It is shown
that the application of hydrostatic pressure on the
ferroelectric SrTi
18
O3 depresses Tc down to 0 K above pc =
0.7-0.8 kbar through the electron-lattice strain coupling.
At p > pc SrTi
18
O3 turns to a quantum paraelectric.
[1] M.Itoh et al., Phys. Rev. Lett., 82, 3540, 1999.
[2] P.Konsin, B.Sorkin, Ferroelectrics, 270, 399, 2002.
10
th
192
Dielectric Response in Amorphous
Materials Based on Polar Oxides:
PbTio
3
, PbFe
1/2
Nb
1/2
o
3
and
PbMg
1/3
Nb
2/3
o
3
L. KOROTKOV, S. GRIDNEV,
T. KLIMENTOVA,V. DVORNIKOV, YU. BARMIN,
S. KOZHUKHAR AND V. POSMETIEV
Voronezh State Technical University, 394026, Voronezh,
Russia
The crystalline compounds PbTiO
3
, PbFe
1/2
Nb
1/2
O
3
and
PbMg
1/3
Nb
2/3
O
3
are well known ferroelectrics of perovskite
family. The PbTiO
3
undergoes the abrupt first order phase
transition near 500
o
C, the PbFe
1/2
Nb
1/2
O
3
shows the
diffused transition in the vicinity of 110
o
C and the
PbMg
1/3
Nb
2/3
O
3
has a change of crystal symmetry below
0
o
C under d.c. field only.
The purpose of the present work is comparative
investigation of structural disordering influence on
dielectric properties of mentioned above compounds.
The samples of amorphous materials for experiments in
the form of plates with sizes of ~5x5 mm
2
in area and
0.5mm in thick were prepared by quenching of melt.
The temperature dependences of dielectric permittivity
/
and dielectric losses
//
were obtained using the
capacitance bridge at a frequency range of 10
3
-10
6
Hz.
Measurements were performed at cycling regime (with a
rate of ~ 2K/min) in such a way that the temperature of
largest heating (T
m
) in every next cycle was increased. The
X-ray diffraction study (MoK
- radiation) of a sample
structure was carried out before each annealing cycle.
It was revealed a considerable difference in dielectric
response from amorphous and crystalline states of all
compounds under study. Unlike crystalline materials the
characteristic maxima of
/
relating to corresponding phase
transition temperature have not observed in the amorphous
samples, the dielectric permittivity in them is increased
with temperature up to crystallization temperature.
However some peculiarities of
/
(T) and
//
(T) dependences
are found for noncrystalline PbTiO
3
, and PbMg
1/3
Nb
2/3
O
3
.
Probably their nature is due to a presence of polar
microregions and their interaction with mobile charge
carriers.
The long time thermal treatment of amorphous samples
results to forming of crystalline structure of perovskite type
and leads to appearance of characteristic maximum of
/
.
The work was supported by the Russian Foundation for
Basic Research (Grant N 02-02-16267)
Diagram of State for Ferroelectric -
Antiferroelectric Mixed System
N.A. KORYNEVSKII
Institute for Condensed Matter Physics, National Academy
of Sciences of Ukraine, Svientsitskii 1, 79011 Lviv,
Ukraine,
Institute of Physics, University of Szczecin, Wielkopolska
15, 70-451 Szczecin, Poland, E-mail:
koryn@icmp.lviv.ua
The model of ferroelectric - antiferroelectric mixed
system is suggested. Every site of the crystalline lattice is
occupied by a cluster of "spin" particles, the total
momentum of which has a possibility to be oriented only in
the one of two perpendicular directions: along z or along x
axis. The probability of the type of site occupation is
determined by a concentration n for z-type component and
(1-n) for x-type component. It is supposed that under
certain phase transition temperatures the ferroelectric
ordering in the first case and correspondingly antiferroelec-
tric ordering in the second case takes place in the crystal.
Both long and short range interparticles interactions are
taken into account. The last one has only a cluster character.
For calculation of the partition function of the investigated
mixed system the replica method is used [1,2]. The
systematic expansion of replica Hamiltonian is proposed
and corresponding coefficients are found. With the
accuracy up to second order of the expansion the expression
for free energy of mixed system is tested. The equations for
ferroelectric and antiferroelectric order parameters and
corresponding temperatures of phase transitions are
obtained and analyzed. The diagrams of state for the mixed
system are investigated in details. It has been shown that
ferroelectric - antiferroelectric phases do not exists
simultaneously, so no spin-glass type phase can be
observed. The behavior of paraelectric - ferroelectric and
paraelectric - antiferroelectric phase diagrams are closely
related to the percolation problem. Usually the critical
concentration nc for this two types of the crystal ordering is
common. For n > nc the ferroelectric phase can be realized,
and for n < nc vice versa the phase only. But for certain
values of interparticle interactions there exist a possibility
to observe a sequence paraelectric antiferroelectric
ferroelectric - ferroelectric or - antiferroelectric transitions:
paraelectric - of phase antiferroelectric ones. In this case
temperature region of the intermediate phase is not small
(about 10-20 K). The order of phase transition (first or
second) depend on both intensity of long and short range
interparticle interactions and concentration. Dielectric
susceptibility of the investigated system is calculated and its
behavior in a wide temperature and concentration regions is
discussed. The proposed model can be useful in the
problem of thermodynamics for the large class of KH2PO4
- NH4H2PO4 type mixed compounds.
References
1. V.J. Emery, Phys. Rev., B11, 3397 (1975).
2. A.N. Vasilev, PINPh, St.-Petersburg, 1998 (in Russian).
10
th
193
Growth, Microwave Properties and
Microstructure of Ba
0.05
Sr
0.95
TiO
3
Thin Films
I. KOUTSONAS
*1
, W.F. HU
1
, T.J. JACKSON
1
,
I.P. JONES
1
, M.J. LANCASTER
1
, G. PASSERIEUX
1
,
R.A. CHAKALOV
2
, R.I. CHAKALOVA
2
AND
C.N.W. DARLINGTON
2
1
School of Engineering, The University of Birmingham,
Birmingham, B15 2TT, UK.
*
I.Koutsonas@eee-fs7.bham.ac.uk
2
School of Physics and Astronomy, The University of
Birmingham, Birmingham, B15 2TT, UK.
The Curie temperature of Ba0.05Sr0.95TiO3 is close to 77
K, a convenient temperature for the operation of thin film
devices incorporating high temperature superconductors.
Bilayers of ferroelectric and superconducting materials can
be used in frequency agile microwave devices, the
sensitivity of the ferroelectric to a dc bias providing a
convenient means of tuning. The suitability of the
ferroelectric for application in a tunable capacitor or filter
may be assessed using the standard quality factor
K = (n-1)
2
/[ntan(0)tan()]; n = (0)/() is the ratio of
the real part of the permittivity in zero bias and in a bias
field and tan the corresponding loss tangent [1]. The
relationships between the growth and microstructure of
films and the quality factor are still not fully appreciated.
In this work YBa2Cu3O7-x/Ba0.05Sr0.95TiO3 bilayers were
prepared on single crystal (001) MgO by pulsed laser
deposition. A bandstop resonator in the form of an
interdigital capacitor was patterned in to the
superconducting (YBa2Cu3O7-x) layer [2]. The real part of
the permittivity of the ferroelectric layer, at temperatures
below 85 K, was determined from a comparison of the
resonant frequency of the device with the results of
simulations. The loss tangent was deduced from the depth
of the resonance. Films were prepared under a variety of
pulsed laser and oxygen annealling conditions in order to
determine the influence of the growth conditions on
dielectric properties. The cubic lattice parameters of the
Ba0.05Sr0.95TiO3 films were measured from least-squares
fitting to data obtained in a 4-circle X-Ray diifractometer.
The microstructure of selected samples was assessed using
transmission electron microscopy and correlated with the
growth parameters.
This work is funded by the UK EPSRC. We are
grateful for the expertise of Donna Holdom and Cliff Ansell
in lithography and fabrication.
References
[1] I.B. Vendik, O.G. Vendik, and E.L. Kollberg, IEEE
Transactions on Microwave Theory and Techniques
48(3), 802 (2000)
[2] H.T. Su, M.J. Lancaster, F. Huang, and F. Wellhfer,
Microwave and Optical Technology Letters 24(3), 155
(2000)
Amorphous Pb(FeNb)
0.5
O
3
:
Processing, Structure, Dielectric
and Magnetic Properties
SERGEY KOZHUKHAR, LEONID KOROTKOV,
VICTOR POSMET'YEV, VALERIY IEVLEV,
BORIS AGAPOV, DMITRIY URAZOV, YURI BARMIN
Voronezh State Tech. University, 14 Moskovskii Pr.,
394026, Voronezh, Russia, E-mail: victorvpo@mail.ru;
Web-site of Laboratory: http://web.vrn.ru/lamp
Crystalline Pb(FeNb)0,5O3 (PFN) is ferroelectric and
ferromagnetic at the same temperatures. So it is very
interesting object for solid state physics. Amorphous
ferroelectric-ferromagnetc is interesting especially.
We have obtained the samples of amorphous PFN using
rapidly quenching method with the temperature decreasing
rate of 10
3
K/s. Samples are plates, their thickness is
0.51.0 mm, area is about 1 cm
2
. We can obtain three-
layered structures 'amorphous-crystalline-amorphous' and
'crystalline-amorphous-crystalline' selecting the processing
conditions.
X-Ray diffraction study confirms that the samples are
really amorphous.
The composition was determined by the electron-probe
X-ray spectral microanalysis with the accuracy of 0.5 at.%.
The layers structure was studied using scanning
electron microscopy. Optical microscopy photos are
obtained also.
At last we have studied dlectric and magnetic properties
of amorphous PFN.
The work was supported by Russian Foundation for
Basic Research, Grants # 02-02-16267 and 03-02-06005.
10
th
194
The Effect of Humidity on the
Dielectric Response in Ferroelectric
Polymer Films Made by Langmuir-
Blodgett Deposition
KRISTIN L. KRAEMER, C. M. OTHON,
1
A.V. SOROKIN,
1,3
STEPHEN DUCHARME,
1
V.M. FRIDKIN,
1,2
M. BAI,
1
T. J. REECE,
1
MATT POULSEN,
1
B. W. PETERSEN
1
1
Department of Physics and Astronomy, Center for
Materials Research and Analysis University of
Nebraska, Lincoln, Nebraska, USA,
kkraemer@unlserve.unl.edu
2
Institute of Crystallography, Russian Academy of
Sciences, Moscow, RUSSIA
3
Department of Physics, Ivanovo State University,
Ivanovo, RUSSIA
Crystalline films of vinylidene fluoride copolymers
show an increase in capacitance when exposed to humidity.
Using dielectric measurements, the properties of the films
are studied. It has been observed that the change in
capacitance is linear with the change in relative humidity, at
a fixed temperature for films 2.5 to 15 nm thick.
Measurements show that the water is interacting in the bulk
of the film. Current work is being done to investigate the
H2O copolymer bonding properties, such as dipole-dipole
interactions.
Work at the University of Nebraska was supported by
the The Petroleum Research Fund, the USA National
Science Foundation, and the Nebraska Research Initiative.
New Quantum Monte Carlo
Method Using Phase-free Random
Walks with Slater Determinants
HENRY KRAKAUER
1
AND SHIWEI ZHANG
2
Dept. of Physics, College of William and Mary
1
, P.O. Box
8795, Williamsburg, VA 23187-8795, USA
1
krakauer@physics.wm.edu,
2
swzhan@wm.edu
In order to predict material properties across length
scales, it is critical to have robust and reliable calculations
at the fundamental atomistic scale. Density-functional
methods are very successful except for strongly correlated
materials, and even for weak to moderately correlated
materials, small errors can result in crucial and qualitative
differences in the predicted properties. An important
example of the latter occurs in ferroelectrics like PbTiO3
where errors as small as 1% in the calculated lattice
parameters (acceptable in many materials) can completely
erase the ferroelectric instability.
Quantum Monte Carlo (QMC) methods allow
essentially exact calculations of ground-state and finite-
temperature equilibrium properties of many-electron
systems, with algorithmic complexity scaling in principle as
a power law with system size. A principle difficulty has
been the complexity of the required trial wave functions in
the standard diffusion Monte Carlo (DMC) methodology.
Obtaining an adequate trial wave function is crucial to any
successful DMC calculations and often constitutes the bulk
of the effort.
We have developed a quantum Monte Carlo method [2]
using Hubbard-Stratonovich auxiliary fields. Aimed at
treating electron correlation in real materials, this is a
many-body method that shares much of the machinery of
standard density functional methods. The method projects
out the ground state by random walks in the space of Slater
determinants. An approximate approach is formulated to
control the phase problem with a trial wave function. The
formalism allows the use of any set of one-particle basis
functions. For periodic systems it allows arbitrary k-point
sampling with twisted boundary conditions. Using a plane-
wave basis and non-local pseudopotentials, we have applied
the method to atoms, molecules and bulk crystals with up to
about 200 electrons in the simulations. The trial wave
functions were chosen to be single Slater determinants
simply constructed from the occupied one-electron states
obtained from a density functional calculation, without any
further optimization. Calculated dissociation and cohesive
energies are in excellent agreement with experiment and are
comparable to the best existing theoretical results.
[1] This work was supported by the Office of Naval
Research and the National Science Foundation.
[2] S. Zhang and H. Krakauer, Phys. Rev. Lett., 2003, in
press.
10
th
195
The Effect of High-pressure on the
Peculiar Relaxor BaTi
0.65
Zr
0.35
O
3
J. KREISEL
1
*, P. BOUVIER
2
, M. MAGLIONE
3
,
A. SIMON
3
1
LMGP, ENS de Physique de Grenoble, France,
kreisel@inpg.fr
2
LEPMI, ENSEE Grenoble, France
3
ICMCB-CNRS, Pessac, Franc
So-called relaxor ferroelectrics (relaxors) have attracted
considerable attention since the recent discovery of ultra-
high strain and giant piezoelectric properties in relaxor-
based single crystals. However, the toxicity of lead-
containing oxides combined with its important vapor
pressure during processing causes an increasing interest in
environmental-friendly high-strain materials such as the
lead-free BaTi1-xZrxO3 (BTZ). On the way towards such
alternatives, Ravez and Simon studied various BaTiO3-
based materials and, in particular, their investigation of the
BTZ-phase diagram showed that BTZ ceramics exhibit
interesting relaxor-like properties for substitution rates
higher than x = 0.25 [1]. However, BTZ is an unusual
relaxor, compared to classic relaxors like PMN or NBT,
because it involves an homovalent Ti
4+
/Zr
4+
substitution on
the B-site and does not contain a lone pair element on the
A-site, revealing that the observed relaxation in BTZ is at
least intriguing.
Here we will present a high-pressure Raman
spectroscopy (HP-RS) of BTZ. As a matter of fact, HP-RS
is known to be an adapted technique for the understanding
of classic ferroelectrics (e.g. BaTiO3, PbTiO3, KNbO3) or of
BTZ-similar PZT. Very recently, HP-RS studies have been
extended to the class of relaxor ferroelectrics [2-3],
illustrating that the combination of the parameter high-
pressure with the local probe Raman spectroscopy is also an
effective technique to investigate the relaxor characteristic
nano-structure. In particular, it has been argued, that HP-RS
allows addressing the often long-standing and controversial
discussion about the justification of the denomination
relaxor for a given material.
Our HP-RS investigation shows that BTZ presents
important pressure-instabilities and undergoes at least 2
phase transitions in the 1 bar to 16 GPa range. Furthermore,
BTZ does not display the relaxor-typical high pressure
Raman signature which was earlier reported for PMN and
NBT [2-3]. The latter is an interesting experimental
evidence showing that BTZ is different and illustrates that
BTZ is not nano-structured, or at least very differently
compared to PMN- and NBT-type relaxors. In other words,
BTZ shows a dielectric relaxation (and is thus somehow a
relaxor) but is most probably not a relaxor in the sense of
NBT and PMN.
[1] J. Ravez and A. Simon, Eur.J.Solid State Inorg. Chem.
34, 1199 (1997). [2] J. Kreisel, A.M. Glazer, P.Bouvier and
G.Lucazeau, Phys. Rev. B 63, 174106 (2001). [3] J. Kreisel,
B. Dkhil P. Bouvier, and J.M. Kiat, Phys. Rev. B 65,
172101 (2002)
Effect of High Pressure on Relaxor
Ferroelectrics
J. KREISEL
1
*, P. BOUVIER
2
, B. DKHIL
3
,
B. CHAABANE
1,2,
A.M. GLAZER
4
, P.A. THOMAS
5
,
R. WELBERRY
6
1
LMGP, ENS de Physique de Grenoble, France,
2
LEPMI, ENSEE Grenoble, France
3
SPMS, Ecole Centrale Paris, France
4
Clarendon Laboratory, University of Oxford, UK
5
Department of Physics, University of Warwick, UK
6
Research School of Chemistry, Australian National
University
Relaxor ferroelectrics (relaxors) form a special class of
ferroelectric materials of which the understanding remains a
challenging problem. From an application point of view,
relaxor-based materials have been reported to exhibit near
structural phase boundaries outstanding electromechanical
properties, which point to a potential revolution in
electromechanical transduction for a large range of
applications. Here we present a discussion of high-pressure
investigations by Raman spectroscopy [1, 2], diffraction
and diffuse scattering of PbMg1/3Nb2/3O3 (PMN) and
Na1/2Bi1/2TiO3 (NBT), considered as model relaxor
materials. We show that an external pressure of several GPa
(as can be met in thin films) alters fundamentally the
structural and polar properties in relaxor ferroelectrics. The
observed pressure-dependent Raman spectra are very
unusual, pointing to a new relaxor-specific spectral
signature, and illustrate that the pressure-induced
fundamental modifications of the polar properties take
place at both cation sites of the perovskite structure,
although at different pressures. Furthermore, the observed
total suppression of the relaxor-characteristic X-ray diffuse
scattering with pressure (see Figure) points to a pressure-
induced crossover from short-to-long-range order. The
gradually decrease of the diffuse scattering can be
understood in terms of a pressure-induced reduction of the
mechanical strain between the average structure and the
polar nano-regions (2D in NBT and 3D in PMN). We
namely suggest that high pressure suppresses the local
competition between A-site and B-site displacements
(inhibiting initially a long range order), which then allows
the establishment of a new long-range structure. Although
high-pressure commonly tends to increase disorder in most
materials, the observed crossover from short-to-long-range
order might well be a general feature in relaxor
ferroelectrics under high-pressure.
Fig 1: Pressure-dependent evolution of the diffuse
scattering around the (300) reflection in PbMg1/3Nb2/3O3
[1] J. Kreisel et al. Phys. Rev. B 63, 174106 (2001).
[2] J. Kreisel et al. Phys. Rev. B 65, 172101 (2002).
10
th
196
Structure and Properties of
Tin-doped Potassium Titanil
Phosphate Single Crystals
O.D. KROTOVA
1
, N.I. SOROKINA
2
, LIU WEN
3
,
V.I. VORONKOVA
3
, V.K. YANOVSKII
3
.
1
Moscow State University, Faculty of Geology, Vorob'evy
Gory, Moscow, 119899, Russia,
e-mail: olga@geol.msu.ru;
2
Shubnikov Institute of Crystallography, Russian Academy
of Sciences, Leninskii pr. 59, Moscow, 117333, Russia,
e-mail: nsor@ns.crys.ras.ru;
3
Moscow State University, Faculty of Physics, Vorob'evy
Gory, Moscow, 119899, Russia,
e-mail: voronk@crysC24.phys.msu.ru.
Crystalline solid solutions having the structure of
KTiOPO4 (KTP) continue to attract attention of scientists.
These compounds are possessed of rare set of physical
properties. They are characterized by high ionic
conductivity, ferroelectric phase transitions and nonlinear-
optical properties. With aim of study of the characteristics
of atomic structure and physical properties of tin-doped
potassium titanil phosphate crystals we grew a series of
single crystals with different tin contents. In the present
work a sensitive studies of three single crystals KTP:Sn, by
X-ray structural analysis, were performed. Crystal
structures KTP:Sn containing 6, 53 and 75 at.% Sn are built
by a three-dimensional framework of (Ti,Sn)O6 octahedron
and PO4 tetrahedron, sharing their vertices. The framework
of the structure has wide, screw-like channels along the
c-axis, in which potassium cations are located. Least-
squares refinement of structures and analysis of difference
electron-density syntheses showed the presence of
vacancies in the potassium, phosphorus and oxygen
positions. Non-stochiometric composition by potassium,
phosphorus and oxygen ions content of single crystals
KTP:Sn may depend on a high temperature (1200-800
o
C)
of their growth. (Ti,Sn)O6 octahedrons in structure become
more symmetric depend on increase tin content in crystal.
As we have found decrease in distortion of (Ti,Sn)O6
octahedrons is more significant in crystals with tin content
less than 50%. This fact is conform to SHG intensity under
laser irradiation in crystals of solid solution KTP:Sn
decreases to about zero depend on increasing tin content. At
that, slump occur in 0-40% range of tin content in crystal.
Influence of Dead Layer
Capacitance on the Dielectric
Dispersion of PMN-PT Relaxor
Thin films
S.B. KRUPANIDHI AND APURBA LAHA
Materials Research Center, Indian Institute of Science,
Bangalore INDIA. Email: apurba@mrc.iisc.ernet.in
xPb(Mg1/3Nb2/3)O3 (1-x)PbTiO3 (x=0, 1, 0.8, 0.3)
(PMN-PT) relaxor thin films were deposited on platinum
coated silicon substrate using pulsed excimer laser ablation
technique. The substrate temperature and oxygen partial
pressure maintained during the deposition were in the range
of 600 to 750
o
C and 100 to 300 mTorr, respectively. The
dielectric properties of as deposited films were studied as a
function of frequency over a wide range of temperature.
The films exhibited a diffused phase transition together
with the frequency dispersion of dielectric constant in the
temperature zone higher than the temperature of dielectric
maxima (Tm). This dispersion in higher temperature (Tm)
was attributed to the effect passive layers to the overall
dielectric response of the heterostructure. These passive
layers could be formed at interfaces between the film and
electrodes and at the grain boundaries. The response from
the grain boundaries was minimized by controlling the
grain structure of the films. The interfaces between the
electrodes and film, especially the top electrode which was
deposited at room temperature, could be the main
influential region to promote the passive layer formation.
This problem was rectified by single step and multi step
post deposition annealing of top electrodes at different
atmosphere. The microstructure at both the interfaces was
also investigated by the scanning electron microscopy. The
films deposited at higher temperatures (>675
o
C) showed
diffused interface at bottom electrode. We have also
analyzed the thickness dependence of different parameters
of the ferroelectric hysteresis e.g. coercive field, remnant
polarization etc. to identify the passive layers.
10
th
197
Effects of Thermal Stabilities for
the Ultra Thin Chromium Layers
Applied on (Ba,Sr)TiO
3
Thin Films
MENG-WEI KUO
1
, BI-SHIOU CHIOU
1
, DER-CHI SHYE
1
,
JYH-SHIN CHEN
2
, AND HUANG-CHUNG CHENG
1
1
Department of Electronics Engineering and Institute of
Electronics, National Chiao Tung University, 1001 Ta
Hsueh Rds., Hsinchu, 30010, Taiwan R. O. C.
e-mail address 1:mwkuo.ee90g@nctu.edu.tw
2
Precision Instrument Development Center, National
Science Council, 20 R&D Road VI, Hsinchu Science-
Based Industrial Park, Hsinchu 300, Taiwan R. O. C.
(Ba,Sr)TiO3(BST) films were fabricatied on
Pt/Ti/SiO2/Si substrates using radio frequency magnetron
co-sputtering technique. In this work, the thermal-dielectric
properties of the BST capacitors without/with an ultra thin
(2nm) chromium(Cr) layer, which formed the
Pt / BST( 300nm) / Pt and t he Pt / BST( 150nm) /
Cr/BST(150nm)/Pt structures, were systematically studied.
Pt/BST/Cr/BST/Pt multifilms behave excellent thermal
stabilities in dielectric properties, leakage current and
power dissipation. The dielectric variation versus
temperature greatly decrease from 13% to 7% while the
ultra-thin Cr layer was applied on the BST film. Besides,
the leakage current and the temperature coefficient of
resistivity(TCR) of the BST film with an ultra thin Cr layer
are also much lower than those of the BST film without Cr
layer. Tangent-loss versus substrate temperature shows that
the power dissipation of BST/Cr/BST multi-film capacitor
is much better than that of BST mono-film capacitor, and
the phase shift of the resonance frequency was analyzed in
this study.
Keywords: BST, thermal coefficient of resistivity (TCR)
SR Diffraction Evidence for the
Covalent Bonding Nature and the
Ferroelectric Phase Transition in
Perovskite Oxides
YOSHIHIRO KUROIWA,
1,*
AKIHIRO KIMURA,
1
AKIKATSU SAWADA,
1
SHINOBU AOYAGI,
2
HIROSHI TANAKA,
3
EIJI NISHIBORI,
4
MASAKI TAKATA
4
AND MAKOTO SAKATA
4
1
Department of Physics, Okayama University, Okayama
700-8530, Japan, kuroiwa@science.okayama-u.ac.jp
2
Japan Synchrotron Radiation Research Institute,
Mikaduki, Sayo, Hyogo 679-5198, Japan
3
Department of Materials Science, Shimane University,
Matsue 690-8504, Japan
4
Department of Applied Physics, Nagoya University,
Nagoya 464-8603, Japan
The charge density study by X-ray diffraction plays a
crucial role to reveal the relationship between the crystal
structure and the ferroelectricity. In recent years, the
accuracy of experimentally obtained charge density
distributions has made spectacular advances by analyzing
the synchrotron-radiation (SR) powder diffraction data by
the MEM(Maximum Entropy Method)/Rietveld method [1].
We have also been studying the structural characteristics of
perovskite oxides using the method. Significant differences
of perovskite structures have been found at the electron
density levels. For example, in tetragonal PbTiO3, covalent
bonding nature on the Pb-O bond, which is strongly related
to the large spontaneous polarization and the phase
stability, is demonstrated in the experimentally obtained
charge density distributions, whereas such electron
hybridization is not observed on the Ba-O bond in
tetragonal BaTiO3 [2]. These results are consistent with the
first-principles calculations [3].In the present work, we
show several experimental facts to characterize the
relationship between the bonding electron nature and the
phase transition temperature of ABO3 cubic perovskite
oxides. For the purpose, the high energy powder diffraction
experiments are done at the synchrotron radiation facility,
SPring-8, to obtain the accurate charge density
distributions. For the series of cubic perovskite oxides
where the B site atom is replaced with the atom which
belongs to the same group in the periodic table, it is found
out that the perovskite oxide displaying the lower covalent
bonding electron density between the B and O atoms shows
a tendency to undergo the phase transition at lower
temperature or no phase transition. This is the direct
experimental evidence for the theoretical prediction to show
that the hybridization between the B and O atoms weakens
the short-range repulsions and allow the ferroelectric phase
transition. For example, the Nb-O covalent bonding
electron density in cubic KNbO3 is higher than that of Ta-O
bond in KTaO3, which is considered to be due to the
difference of the valence charge densities. In addition, in
the cubic perovskite oxides which undergo the phase trans-
ition at the Brillouin zone boundary, charge density
distributions around the O atoms tend to be elongated to the
directions perpendicular to the B-O bond.
[1] Takata et al., Z. Kristallogr. 216, (2001).
[2] Kuroiwa et al., Phys. Rev. Lett. 87, 217601 (2001).
[3]Cohen, Nature 358, (1992).
10
th
198
Optical Spectra, Properties and
First Principles Computations of
Ba(Fe,Nb)O
3
, Pb(Fe,Nb)O
3
and
Pb(Fe,Ta)O
3
A.B. KUTSENKO
1
, R. DEMIRBILEK
1
, A.I. GUBAEV
1
,
S.E. KAPPHAN
1
, I.P. RAEVSKI
2
, S.A. PROSANDEEV
2
,
B. BURTON
3
, L. JASTRABIK
4
, V.S. VIKHNIN
5
1
Physics Department, Osnabrueck University, Barbarastr.7
D-49069 Osnabrueck, Germany.
E-mail: Alexey.Kutsenko@uos.de
2
Physics Department, Rostov-Don State University, 344090
Rostov-na-Donu, Russia
3
National Institute of Standarts and Technology, Md.20899
Gaithersburg, USA
4
Institute of Physics AS CR, Na Slovance 2, 182 21 Prague
8, Czech Republic
5
A.F. Ioffe Physical-Technical Institute, 194021
St.-Petersburg, Russia
Ba(Fe,Nb)O3, Pb(Fe,Nb)O3 and Pb(Fe,Ta)O3, have a
similar perovskite type structure in which Fe and Nb(Ta)
occupy the B-site. In spite of similar composition, the
electric and dielectric properties of these perovskites are
very different. Ba(Fe,Nb) is known as a new representative
of high-k materials [1]. Pb(Fe,Nb)O3 is a ferroelectric
crystal with a high Curie temperature[2]. Pb(Fe,Ta)O3 was
recently shown to exhibit relaxor properties [3].
We have studied the optical properties of these
compounds by measurements with a high resolution Fourier
IR spectrometer (Bruker HR 120, max. resolution
0.002cm
-1
) in the spectral range from FIR (400cm
-1
) to UV
(45000cm
-1
). The dielectric measurements were done for
different frequencies and in a wide temperature range. We
also studied the dependence of conductivity on the electric
field as well as photo-conductivity. We have performed
first-principles computations of equilibrium coordinates in
these structures, computed the force constants, dynamical
matrices and ionic vibronic frequences and corresponding
eigenvectors. These data help to understand the origin of
the complex properties of these compounds and also to
develop phenomenological models.
This work has been supported by DFG/Grad.Koll
695/1, by DFG (KA501/8-1) and by NATO-CLG 977348
References
[1] I.P. Raevski, S.A. Prosandeev and L. Jastrabik J.
Applied Physics 93, 2878 (2003).
[2] Y. Park, Solid State Comm 113, 379 (2000).
[3] I. P. Raevski, V. V. Eremkin, V. G. Smotrakov, M. A.
Malitskaya, S. A. Bogatina, and L. A. Shilkina
Crystallography Reports 47, 1007 (2002).
Time-domain Terahertz
Spectroscopy of Ferroelectrics and
Related Materials
PETR KUZEL, ALEXEY PASHKIN, MARTIN KEMPA,
FILIP KADLEC, STANISLAV KAMBA AND JAN PETZELT
Institute of Physics, Academy of Sciences of the
Czech Republic, Na Slovance 2, 182 21 Praha 8,
Czech Republic
The time-domain terahertz (THz) transmission
spectroscopy has become recently a powerful tool for the
investigation of far-infrared and submillimeter dielectric
properties of dielectrics, semiconductors, superconductors
and liquids (see [1] and references therein). The technique
requires to measure the temporal profile of the electric field
of a THz pulse transmitted through the investigated sample.
The complex spectrum of this pulse is normalized by a
reference spectrum (obtained when the sample is removed
from the THz beam path) yielding thus a complex
transmission function of the sample. Finally, the complex
refractive index in the whole studied frequency range is
obtained numerically. Recently, we have developed a novel
experimental setup enabling us to obtain also the complex
reflection coefficient of the samples in the reflection
geometry. This extends the applicability of the method to
opaque materials and allows getting more precise results for
thin films.New results obtained using time-domain THz
spectroscopy will be demonstrated on several materials: (1)
In SrBi2Ta2O9 (SBT) the recently found soft phonon mode
[2] was confirmed in a thin film by means of both
transmission and reflection measurements. In addition,
central-mode type dispersion was detected in the mm wave
range, which is responsible for a strong dielectric anomaly
at the ferroelectric-paraelectric (ferroelastic) transition near
600 K. (2) The relaxor ferroelectric crystal
Pb(Mg1/3Nb2/3)O3 shows a strong dielectric dispersion
below the phonon frequencies. Our THz reflectivity and
transmission spectra (together with FTIR reflectivity data)
reveal a splitting of the relaxation mode on cooling. The
softer component (polar cluster-wall contribution) softens
to microwave range while the harder one (assigned
presumably to activation of phonon density of states)
hardens and becomes underdamped. (3) A pronounced
softening and broadening of the dielectric relaxation in
disordered cubic pyrochlore Bi1.5ZnNb1.5O7 ceramics was
found in the transmission spectra on cooling below room
temperature [3]. (4) THz transmission spectra of
Ruddlesden-Popper homologous series Srn+1TinO3n+1
(n = 14) manifest an increase of permittivity with the
number of perovskite layers n towards the value of SrTiO3
(n = ). A softening of the optical phonon mode similar to
that in SrTiO3 was observed in Sr5Ti4O13 (n = 4).
References
[1] M. C. Nuss, and J. Orenstein, Terahertz Time-Domain
Spectroscopy, in Millimeter and Submillimeter Wave
Spectroscopy of Solids, ed. G. Grner, Chap. 2, p. 7
(Springer-Verlag Berlin Heidelberg, 1998).
[2] S. Kamba et al. Appl. Phys. Lett. 81, 1056 (2002).
[3] S. Kamba et al., Phys. Rev. B 66, 054106 (2002).
10
th
199
Origin of Ferroelectricity in Doped
Quantum Paraelectrics
O.E. KVYATKOVSKII
A.F. Ioffe Physico-Technical Institute, St. Petersburg,
194021, Russia, Kvyatkovskii@mail.ioffe.ru
A theory of isotope effect displacive ferroelectrics (FE)
is developed. It is shown that ferroelectric (FE) lattice
instability induced by the isotope exchange is the
anharmonic and quantum effect and the associated FE
phase transition is the result of the suppression of the zero-
point atomic motion caused by the substitution of a heavy
isotope for a light one. A criterion for the isotopically
induced ferroelectricity is formulated. It is found that this
isotope effect may occur only in quantum paraelectrics with
nearly complete compensation of the harmonic contribution
into FE soft mode frequency by the zero-point motion
contribution. The isotope effect in SrTi(
16
O1-x
18
Ox)3
discovered recently is explained. It is shown that in KTaO3
the oxygen isotope exchange does not produce ferroelectric
state. A microscopic nature of ferroelectric phase transition
in solid solutions Sr1-xAxTiO3 (A= Mg, Ca, Ba, Pb, Cd, Zn)
and KTa1-xNbxO3 is elucidated. The off-center impurity
model is checked. Local potentials for the impurity atoms in
SrTiO3 and for Nb and Li atoms in KTaO3 are studied using
total energy cluster ab initio calculations. The results show
that all the impurity atoms except for Mg, Zn and Li atoms
move in single-well local potentials, corresponding
ferroelectric solid solutions are of displacive type and the
stability of their paraelectric phase is governed by
generalized force constant kf,ss associated with the FE soft
phonon mode. It is found that Zn and Mg in SrTiO3 and Li
in KTaO3 are off-center impurities. In the framework of FE
soft mode theory a virtual crystal approximation is
considered which enables kf,ss to be found. The critical
concentrations xc found in this approach for displacive solid
solutions KTa1-xNbxO3 and Sr1-xAxTiO3 are in a good
agreement with experimental data.

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B) in a hot press at 200 C,

radiation in the energy range 0 - 1400 eV in paraelectric,

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