Advanced Nano - and Piezoelectric Materi - and Their Applications

MATERIALS SCIENCE AND TECHNOLOGIES
ADVANCED NANO- AND

PIEZOELECTRIC MATERIALS
AND THEIR APPLICATIONS
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ADVANCED NANO- AND

PIEZOELECTRIC MATERIALS
AND THEIR APPLICATIONS
IVAN A. PARINOV
EDITOR
New York
Copyright 2014 by Nova Science Publishers, Inc.

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CONTENTS
Preface
Chapter 1
Chapter 2
vii
Compatibility of Chemical Elements on Grain
Boundaries and Its Influence on Wear Resistance
of Polycrystalline Materials
Yu. F. Migal, V. I. Kolesnikov
and E. S. Novikov
Development and Study of Silicon Dioxide
Nanostructured Films Forming on
Semiconductor Structure Surface
V. V. Polyakov
Chapter 3
Methods to Study Modified Aluminum Silicates

V. A. Yavna, A. S. Kasprzhitskiy
and G. I. Lazorenko
Chapter 4
Investigations of Defect Formation

during Sapphire Crystal Growth
S. P. Malyukov, Yu. V. Klunnikova
and I. A. Parinov
Chapter 5
Chapter 6
Physics and Design of Multi-Functional Ceramic Materials

with Special Electrical and Magnetic Properties
L. A. Reznichenko, A. G. Abubakarov, K. P. Andryushin,
I. N. Andryushina, V. A. Alyoshin, N. A. Boldyrev,
I. A. Verbenko, S. I. Dudkina, A. A. Pavelko, A. V. Pavlenko,
H. A. Sadykov, M. V. Talanov, S. V. Titov, V. V. Titov,
A. V. Turik and L. A. Shilkina
New Model for Piezoelectric Medium with Voids
for Application to Analysis of Ultrasonic Piezoelectric
Transducers and Porous Piezocomposites
G. Iovane and A. V. Nasedkin
19
61
89
109
145
vi
Chapter 7
Chapter 8
Index
Contents
Comparative Study of Parametric Methods
for Online Estimating the Frequency
and Amplitude of Quartz Oscillators
A. V. Nikitin and S. V. Iushanov
The Limits of Measurements Accuracy
Parameters of Electromagnetic Oscillations
in Piezoelectric Materials
V. K. Ignatjev, A. A. Orlov
and D. A. Stankevich
171
205
239
PREFACE
The advanced materials and devices, fabricated on the base of nanotechnological and
piezoelectric approaches and developed theoretical and experimental methods and also
mathematical modeling, are very quickly introduced in numerous application areas of the
modern science, techniques and technologies. There is a great interest to similar studies,
which expand scientific knowledge on physical world, control and predict development of
very fine processes and transformations occurring during processing, loading and work of
modern materials and devices under critical conditions. The studied specimens demonstrate a
broad spectrum of properties in scale from nanometers up to macroscopic range. The
discussed devices and goods possess very high accuracy, longevity and extended possibilities
to work in wide temperature and pressure ranges; they demonstrate characteristics directly
defined by developed compositions, technical and technological solutions. This edited book is
divided into eight chapters.
Chapter 1 imitates the strengthening processes of the grain boundaries, based on the
model polyatomic clusters consisting of atoms of iron and other elements. The used quantumchemical approach allows one to systematize atomic interactions on the grain-boundary
surfaces, estimate the compatibility of various elements with iron on these surfaces, and
connect this compatibility with the Mendeleev's periodic law. The calculation results are
compared with the known experimental data and confirmed with the researches performed by
using the methods of Auger and X-ray electron spectroscopy. The dependences obtained can
be considered as a theoretical base for the prediction of strength properties of the
polycrystalline materials with different compositions of alloying and impurity elements. The
studied potential energy curves corresponding to the movement of atoms on iron surface
could be useful for designing the compositions of multi-layer coats on steel.
Chapter 2 is devoted to the experimental investigations, mechanism and processing
methods of SiO2 nanostructured films formed on Si and SiC surfaces by rapid thermal
annealing and gas-phase photo-decomposition with presentation of technical solutions and
equipment for the formation of nanosized silicon dioxide films. The films obtained can be
used for technology of forming the hybrid systems of microfluidic structures in the
implementation of planar processing by batch methods, microfluidic structures of channels by
surface passivation etc.
Chapter 3 presents the theoretical and experimental studies of properties of the nanoscale
layered aluminum silicates, when they are intercalated by metal ions. There are determined
the interaction mechanisms between layered aluminum silicates and nanoscale additives and
viii
Ivan A. Parinov
explains the nature of certain physical properties of these objects. Tthe sorption capacity,
mechanical and electrical properties are studied with comparison of theoretical calculations
performed by the methods of molecular modeling using density functional theory and
molecular dynamics, the modern experimental spectroscopic methods are applied to the study
of electronic structure of these objects. These comparative results reveal correlations of
micro- and macro-properties of the samples.
Chapter 4 discusses the mathematical simulation of the stress and bubbles formation in
sapphire crystals with consideration of the heat and mass transfer at all stages of sapphire
crystal production by estimating the large number of influence factors on crystal growth and
quality and determining the main causes of the defect structure formation in the solid phase.
Moreover, the preliminary results of study of different defects in sapphire polished and nonpolished samples were obtained by means of various experimental methods.
Chapter 5 considers ceramics as physical objects on the base of statistical approach. The
studied objects are the macro- and microheterogeneous (colloidal) ceramic materials with
different types of microheterogeneity (crystal-layer in the ferroelectric ceramics and
antiferromagnetic - ferromagnetic separation in multiferroics). The phenomena of dielectric
relaxation and retardation, electric effect are described together with crystallographic
characteristics of specific multicomponent compositions. Particular attention is paid to the
relationship of the crystallographic characteristics for these objects with their macroscopic
responses. In the context of multifractal investigations of ceramic materials, lead-free
ferroelectric ceramics, solid solutions of lead zirconate-titanate, multiferroics, different solid
solutions of multiple components were studied, with obtaining the results of multifractal
parameterization performed during the different stages of ceramic preparation (synthesis,
sintering, source components thermodynamic history, phase states and doping). The
dielectric and pyroelectric properties of multicomponent PbTiO3 PbZrO3 PbNb2/3Mg1/3O3
solid solutions were also investigated with revealing in the temperature dependences of
dynamic pyroelectric current the additional low-temperature peaks, corresponding to the
rhombohedral-tetragonal phase transition.
Chapter 6 generalizes the model of the piezoelectric medium with damping properties
and the Cowin-Nunziato model of the elastic medium with voids. In the generalized CowinNunziato model, the field functions of mechanical displacements, electric potential and
function of the porosity change are considered with formulations of the generalized continual
statements for piezoelectric bodies with voids or porous and finite element approximation in
the expanded and reduced forms. The mathematical properties of the natural frequencies and
eigenvectors for piezoelectric bodies with voids are also investigated for different types of the
boundary conditions, including the boundary conditions of mechanical and electric contact
types. Some theorems are established on changes of the resonant frequencies with changes of
the boundary conditions and material properties. For numerical analysis, the finite element
approximations of the problems have been obtained for piezoelectric bodies with voids. The
efficiency of the proposed model and finite element approximations is verified by the analysis
of a focusing spherical device, made from porous piezoceramics and emitting ultrasonic
waves in surrounding acoustic medium. Modal, harmonic and transient analysis for single
piezoelectric emitter and full transducers, loaded on the acoustic medium, is carried out.
Chapter 7 treats the methods for online estimating the frequency and amplitude of the
quasi-harmonic oscillations of studied generator and some features of its implementation. The
Preface
ix
comparative analysis of their accuracy and statistical characteristics as well as guidance on

the application of these methods to study the properties of quartz oscillators, are presented.
Chapter 8 deals with fundamental restrictions on quality of piezoelectric devices,
standard quantum limits of measurement errors of electromagnetic oscillations in
piezoelectric devices. The methods of advancing phase and frequency stability for oscillations
in piezoelectric resonators are studied. The low limit for estimation error of signal parameters
in resonators and filters by modern methods of digital processing signals based on RaoKramer inequality are obtained.
This collection continues the ideas our before-published books developing the theoretical,
model and experimental studies of nanomaterials, piezoelectrics, other related structures and
their applications. The chapters have been prepared by internationally recognized teams from
Russia and Italy in the field of investigations of different ceramics, nanomaterials, composites
and novel devices designed on their base.
The book addresses to students, post-graduate students, scientists and engineers, taking
part in the development and research of piezoelectrics and nanomaterials.
Ivan A. Parinov (Ed.)

Rostov-on-Don, April 2014
Head of Laboratory
Vorovich Mechanics and Applied Mathematics Research Institute,
Southern Federal University,
200/1, Stachki Ave., 344090,
Rostov-on-Don, Russia
Tel: 7-863-2975224
Email: ppr@math.rsu.ru, parinov_ia@mail.ru
In: Advanced Nano- and Piezoelectric Materials

Editor: Ivan A. Parinov
ISBN: 978-1-63321-239-8
2014 Nova Science Publishers, Inc.
Chapter 1
COMPATIBILITY OF CHEMICAL ELEMENTS ON

GRAIN BOUNDARIES AND ITS INFLUENCE ON WEAR
RESISTANCE OF POLYCRYSTALLINE MATERIALS
Yu. F. Migal1*, V. I. Kolesnikov2 and E. S. Novikov2
1
Southern Scientific Centre of Russian Academy of Sciences2,

2
Rostov State Transport University, Rostov-on-Don, Russia
ABSTRACT
To simulate the processes occurring on grain boundaries, we considered polyatomic
clusters consisting of iron atoms and other elements. The quantum-chemical approach
was used that allowed us to carry out the systematization of atomic interactions on grain
boundary surfaces, estimate the compatibility of various elements with iron on these
surfaces, and connect this compatibility with Mendeleev's periodic law. The results of
calculations are consistent with the known experimental facts and confirmed by the
studies performed using the methods of Auger and X-ray photoelectron spectroscopy.
The obtained dependences can be considered as the theoretical base for the prediction of
strength properties of polycrystalline materials with different composition of alloying and
impurity elements. Moreover, we investigated the curves of potential energy
corresponding to the movement of atoms on the iron surface. These curves can be useful
for the designing of compositions of nanostructured multilayer coatings on steel.
1. INTRODUCTION
It is well-known that the wear resistance of steel and other polycrystalline materials is
determined, in many aspects, by the properties of boundaries between the grains of surface
layers. Although the structure of surface layers can differ considerably from the structure of
*
41, Chekhov Avenue, 344006, Rostov-on-Don, Russia. E-mail: ymigal@mail.ru

2, Narodnogo Opolcheniya Square, 344038, Rostov-on-Don, Russia
Yu. F. Migal, V. I. Kolesnikov and E. S. Novikov
inner domains of polycrystals, the mechanisms of destruction of surface and inner domains
have much in common. One of the causes of failure of polycrystals mentioned in the literature
is the grain boundary segregation. This phenomenon is caused by transition of atoms of
alloying and impurity elements from the bulk of grains to their boundaries. As a result, the
intergranular boundaries weaken. This idea was suggested long ago, but in spite of numerous
experimental studies of the grain boundary segregation the connection between this
phenomenon and the mechanism of destruction of polycrystalline materials have yet to be
completely clarified.
There are various points of view on how the segregated atoms promote failure (see, e.g.
[1-5]). One of the hypotheses is based on the fact that during the process of segregation the
metal-metal bond is substituted by a weaker or stronger bond of metal-segregated atom [1].
To prove this hypothesis, the estimates of the energy necessary for the rupture of bonds
between grains were obtained in [6] using the approach of ideal solutions and theory of pair
connections. Note that in [6] the data were used that concerned only the enthalpy of
sublimation and the sizes of atoms of investigated substances.
Figure 1 represents a plot of grain boundary embrittlement constructed by using the data
of [6] for the basic materials (matrix) and segregated elements. If iron is used as the matrix
then all the elements, located above the dotted line on this plot (for example, carbon and
molybdenum), increase the strength of bonds between the grains, and the elements located
below (for example, phosphorus, copper and sulfur), on the contrary, reduce the strength of
bonds (these elements also embrittle iron). The degree of this effect depends on the distance
between the point corresponding to the element and the dotted line. The available
experimental data, related to embrittlement, confirm the results of these estimations (see [6]).
This fact gives the reason to suppose that the magnitude of the binding energy of atoms in
many respects determines the ability of segregated atoms to weaken or strengthen grain
boundaries. Nevertheless, in view of the assumptions, forming the basis of the estimations,
this conclusion needs experimental substantiation and/or additional study.
The overwhelming majority of publications during two last decades, concerned the
problem of segregation, were the works of experimental character in which considerable
advance in studying the properties of grain boundaries was achieved (see, e.g., [7, 8]).
However, the chemical bond and purposeful formation of any atomic structures on the
boundaries were not investigated in those works. We suppose that today such problems can
be successfully investigated via quantum chemistry methods.
Quantum chemistry methods based on the approximation of the density functional theory
(DFT) and appeared in recent decades allow for more accurate analysis (than in [6]) of atomic
interactions affecting metal destruction. These methods are effective for investigating various
phenomena wherein chemical interactions can be observed. However, the works, where these
and similar quantum-chemical methods are applied to reveal the connection between the
phenomenon of grain boundary segregation and the problem of destruction and wear
resistance of metals, are still rare. The segregation of only some elements was considered in
them (see, e.g. [3-5] where the segregation of the H, B, C, S, P, Mn and some other elements
was studied). In our opinion, to understand the problem more deeply, it is necessary to
perform a more systematic analysis and investigate a large group of segregated elements.
Compatibility of Chemical Elements on Grain Boundaries
Figure 1. Plot of grain boundary embrittlement constructed by using data from [6].
In our study of segregation we used the ADF software [9] based on the DFT
approximation. It allows one to investigate the compounds of transitional elements including
hundreds of atoms. This is important for applications in case of steel. We studied the
interactions between grains in the presence of segregated atoms by means of model
polyatomic clusters. This analysis has shown that the appearance of segregated atoms on
grain boundaries is not an accompanying effect but one of the main causes of the weakening
of the strength of the bond between grains and the subsequent destruction of surface layers of
metal [10].
It is also shown below, that the quantum-chemical approach allows us to carry out the
systematization of atomic interactions on grain-boundary surfaces, estimate the compatibility
of different elements with iron on these surfaces and connect this compatibility with
Mendeleevs periodic law.
2. CHOICE OF CLUSTER MODEL

It is obvious that full quantum-chemical analysis of a polycrystal being a non-uniform
macroscopic system is practically impossible because of a huge number of atomic interactions
in the system. The way out of this situation is the selection of some microscopic part (a
polyatomic cluster) of a polycrystal, for which the phenomenon of interest could be studied in
detail. As an alternative, the so-called zone approach can be used where the grain boundary
surface is assumed to be periodic and infinite. However, within this approach it is difficult to
estimate the energy of a chemical bond between interacting fragments. That is why we choose
the cluster model.
A polyatomic cluster simulating the segregation in a polycrystalline material should
evidently include some amount of matrix atoms (from the adjacent layers of two neighboring
grains), as well as segregated or diffused atoms located on the boundary. The cluster size
should be large enough to more precisely reproduce the basic qualitative and quantitative
features of the segregation. However, the practice of quantum-chemical calculations shows
that in many cases the clusters with rather small sizes can reproduce the features of the
studied phenomenon on qualitative or semi-quantitative levels (see, e.g. [11]). We have
selected the binding energy Eb of a cluster and interatomic distances as calculated
characteristics. The energy Eb, obtained through the ADF package and taken modulo,
approximately represents the energy necessary for the breaking of all bonds in the cluster. As
the size of the cluster increases the binding energy Eb(1) per atom should monotonically
increase, and the interatomic distances should approach the values specific for crystal lattice
of iron.
The results of calculations of the dependence of Eb(1) on the number n of atoms in a
cluster are represented in Figure 2. It can be seen from the figure, that as the n value changes
from 2 up to 8 the binding energy grows rather quickly. But when n = 18, the dependence
Eb(1) on n is stabilized. Taking this result as the ground, we suppose that the cluster with n =
18 can be considered as the minimal cluster which can be used for investigating the
phenomena related to variations of the element composition in steel. Using the clusters of
similar size will allow us to study the changes of the binding energy caused by the grain
boundary segregation. This conclusion is preliminary because the estimations given above do
not account for the features of grain boundary segregation. We shall conclude finally, after
comparison of the results obtained with known data, on the sizes of clusters suitable for study
of this phenomenon.
When modeling the conditions under which segregation occurs we used a well-known
fact that on the narrowest portion of the boundary between grains in a polycrystal (that is, in
the place of grain contact), the width of the boundary is of the same order as a lattice constant.
It has allowed us to consider the following simple model of a boundary, where the atoms of
the middle layer are replaced with segregated atoms in 18-atomic iron cluster (Figure 3). Two
upper and two lower layers simulate the upper and lower grains of the polycrystal,
respectively, and the middle layer corresponds to the boundary between the grains. In the case
of high purity metal, the model cluster contains only Fe atoms.
Figure 2. Dependence of the binding energy per atom on the number of atoms in a cluster.
Figure 3. The minimal cluster that allows reproducing semi-quantitatively the interaction of segregated
atoms with steel grain surface. Big particles correspond to Fe atoms, and small ones show segregated
atoms.
Of course, such a model does not take into account the variety of conditions that are
significant in segregation and wear resistance (including, e.g. grain surface irregularities, the
nonparallel nature of surfaces, dislocations etc.). The main purpose of the model proposed is,
firstly, to evaluate the effect of the closest atomic surrounding on the chemical bond between
segregated atoms and matrix atoms in the place of grain boundary, and, secondly, to
determine, how the bond affects the strength of microscopic domains and surface layers of
polycrystals.
If all atoms of the two upper layers in this model are removed then the remaining atoms
(the lower layers + the layer of impurity atoms) imitate the phenomenon of adsorption on the
(100) surface of iron. The results of calculations, related to two similar phenomena, namely
the segregation of elements on a grain boundary and the adsorption on a free surface of iron,
are presented in the next section. We suppose that the comparison of these results will help us
to explain, why the conclusions obtained in [6] by using the sublimation data (the
phenomenon typical for outer surfaces), are valid for the phenomenon of grain boundary
segregation typical for inner surfaces in polycrystals.
3. CALCULATIONS OF BINDING ENERGY OF CLUSTERS CONTAINING

ADSORBED AND SEGREGATED ATOMS
We performed calculations of binding energy Eb of clusters, which contain adsorbed and
segregated atoms of chemical elements with atomic numbers from 1 to 54 (from hydrogen to
xenon). These additional atoms were located either on the outer surface of a cluster (in the
case of adsorption) or in the middle layer (in the case of segregation). In both cases, the
position of additional atoms was over the centers of squares of iron atoms (the fourfold
position) or over the centers of the sides of these squares (the twofold position).
Note that results of calculations of binding energy of any model system greatly depend on
the approximations used. We can compare only results, obtained using the same
approximations. Within the DFT approach, a number of schemes with different level of
approximation are used. The simplest of them is the LDA (local density approximation).
More complex schemes, united under the GGA name, differ by account of the non-local
interactions. In this work, the binding energy of all considered systems calculated uniformly
by means of the TZ2P basis, an option of the frozen inner electrons (option Small) and the
GGA-BLYP approximation (see [9]).
To evaluate the strength of bond of different atoms with iron, we can compare Eb values
for clusters containing adsorbed atoms and clusters consisting only of iron atoms. It can be
assumed, that adsorbed atoms substitute iron atoms in a cluster of a greater size, if adsorbed
atoms are arranged over the centers of squares (i.e. in the positions, which are similar to those
of iron atoms in a matrix). In such cases, it is easy to determine which bond is stronger: Fe-Fe
or Fe-X (the symbol X denotes both adsorbed and segregated atoms). Obviously, the stronger
bond corresponds to a cluster with a greater modulo binding energy.
The values of Eb for clusters with adsorbed atoms are listed in Table 1. It follows from
the data that the atoms of carbon, nitrogen, vanadium, chrome and manganese have stronger
connections with iron surface than iron atoms with each other. On the other hand, the atoms
of lithium, sulfur, aluminum and copper have weaker connections with iron surface.
The results of calculations for the clusters containing segregated atoms are presented in
Table 2. It follows from the data that the atoms of carbon, nitrogen, chrome and manganese
bind the iron grains together more strongly, since the binding energy of the clusters
containing these atoms is lower than the binding energy of the same-sized cluster consisting
of pure iron. Conversely, the atoms of lithium, silicon, phosphorus, sulfur, copper, and nickel,
though they can have chemical bonds with iron, nevertheless, weaken the bonds between the
grains since the binding energy of the corresponding clusters is lesser than the binding energy
of a pure iron cluster. Evidently, the weakening of the intergranular bonds in surface layers
decreases steel wear resistance.
The correspondence between the binding energy of a cluster and the strength of grain
bonds is confirmed by the calculations of energy Ed, which is necessary for dividing a cluster
into two parts imitating the grains in a model cluster (see Figure 4). The values of this
quantity determined by the simple equation:
Ed Es E g Ea ,
(1)
where Es is the binding energy of a segregative cluster including two grains and a boundary
layer between them, Eg is the binding energy of a cluster consisting of only one grain, and Ea
is the binding energy of an adsorptive cluster consisting of a grain and a boundary layer. By
using the same equation, it is possible to calculate the energy necessary to disjoin a cluster of
pure iron, supposing that the 18-atomic cluster Fe2Fe6Fe2Fe6Fe2 divides into two parts
Fe2Fe6Fe2 and Fe6Fe2.
In this way, we can evaluate the binding energy of two iron grains separated by atoms of
different elements. The results of such calculations are presented in Table 3 and Figure 5.
Table 3, formed similarly to Mendeleevs periodic table, actually reflects the compatibility of
different elements with iron on its grain surfaces. For elements from the beginning of a
period, the bond with iron is weak as compared with Fe-Fe bond, and, as the atomic number
grows, the bond first increases, and then, for the second half of the period, it decreases. The
bond becomes weaker while moving along a group. It means that the properties of the
chemical bond of different elements with iron on inner surfaces are in periodic dependence on
the nuclear charge of atoms, and this corresponds to the periodic law.
Table 3 shows that the elements having the weakest bond with iron are alkaline and
alkaline-earth metals, and also inert gases. These elements mostly soften steel. Moreover, the
elements from the middle of the third period (Si, P, S) are softening elements. As it is well
known phosphorus and sulfur entered into steel deteriorate its properties. It is caused by small
values of binding energy of these elements with iron (experimental and theoretical study of
this problem in connection with a wheel-rail system has been performed using the methods of
X-ray electron spectroscopy and Auger-electron spectroscopy and quantum chemistry, see
[10]).
Table 1. Binding energy of adsorptive clusters Fe2Fe6X2 (eV)

I
1
2
3
4
II
H
-63.7
Li
-61.4
Na
-59.9
K
-59.5
Be
-65.0
Mg
-60.4
Ca
-62.1
Cu
-63.7
III
Rb
-59.5
Ag
-62.1
B -71.2
Zn
-60.3
Ti
-72.0
Ga
-65.0
Y
-68.2
Cd
-59.9
Ge
-68.8
As
-69.7
Se
-66.3
0
He
-55.5
Ne
-55.8
Ar
-55.9
Fe
-74.0
Co
-72.9
Ni
-67.0
Br
-64.7
Tc
-78.8
Te
-66.5
VIII
F
-67.5
Cl
-66.8
Mn
-75.0
Mo
-77.0
Sb
-68.1
VII
O
-73.0
S
-69.0
Cr
-75.0
Nb
-76.6
Sn
-67.1
VI
N
-76.4
P
-71.4
V
-74.5
Zr
-73.3
In
-63.9
C
-75.1
Si
-70.0
Al
-65.5
Sc
-68.2
Sr
-61.7
IV
Kr
-56.0
Ru
-73.2
I
-63.6*
Rh
-70.5
Pd
-63.1
Xe
-55.3*
Table 2. Binding energy of segregative clusters Fe2Fe6X2Fe6Fe2 (eV)
1
2
3
4
I
H
-129.4
Li
-120.6
Na
-117.7
K
-116.9
Cu
-125.7
Rb
-116.9
Ag
-122.4
II
Be
-127.6
Mg
-120.8
Ca
-121.8
Zn
-121.4
Sr
-121.1
Cd
-120.4
III
B
-138.7
Al
-127.6
Sc
-129.8
Ga
-126.6
Y
-129.3
In
-125.0
IV
C
-143.2
Si
-133.3
Ti
-135.9
Ge
-130.3
Zr
-136.2
Sn
-128.1
N
-140.9
P
-134.9
V
-140.0
As
-130.9
Nb
-141.2
Sb
-129.1
VI
O
-136.5
S
-131.2
Cr
-141.7
Se
-125.9
Mo
-142.8
Te
-126.9
VII
VIII
0
He
-113.0
Ne
-112.5
Ar
-112.4
F
-125.9
Cl
-124.1
Mn
-141.9
Fe
-140.2
Co
-137.7
Ni
-130.9
Br
-121.2
Tc
-145.1
I
-122.0*
Kr
-112.1
Ru
-139.2
Rh
-135.0
Pd
-125.3
Xe
-112.2*
10
Figure 4. Dividing a cluster into two parts imitating grains in model cluster.
By comparing the characteristics of atoms in adsorptive and segregative states, it is

possible to make a conclusion that atoms weakly bonded with a free iron surface also weakly
interact with iron on a grain boundary. Evidently, it is possible to suppose, that the bond
strength depends in greater degree on the type of atoms bonded together than on the number
and location of atoms of the nearest surrounding. Although the dependence of bond on the
surrounding undoubtedly exists, we can ignore this fact on the qualitative level. Moreover, the
bond strength is a rather stable quantity with respect to the methods of the estimation. In
particular, this conclusion is confirmed by the fact that the results of calculations qualitatively
agree with the results of [6], in spite of significant difference in the approaches.
The above-mentioned results explain why the clusters of rather small sizes allow for the
modeling of changes of the grain bond strength during grain boundary segregation.
Taking into account all these facts it is possible to formulate the following important
conclusion: the elements, whose energy of binding with iron is much lesser than the energy of
the Fe-Fe bond, reduce the wear resistance of steel. If these atoms appear on boundary
between two grains in surface layer of polycrystal their weak bond with iron is the essential
factor influencing the strength of this layer.
Table 3. Energy necessary for dividing segregative clusters Fe2Fe6X2Fe6Fe2 (eV)

I
1
2
3
4
II
H
9.9
Li
3.4
Na
2.0
K
1.6
Be
6.8
Mg
4.6
Ca
3.9
Cu
6.2
III
Rb
1.6
B
11.7
Al
6.3
Sc
5.8
Zn
5.3
Sr
3.6
Ag
4.5
IV
C
12.3
Si
7.5
Ti
8.1
Ga
5.8
Y
5.3
Cd
4.7
N
8.7
P
7.7
V
9.7
Ge
5.8
Zr
7.1
In
5.3
VI
O
7.8
S
6.4
Cr
10.9
As
5.4
Nb
8.8
Sn
5.2
VII
Se
3.8
He
1.7
Ne
1.0
Ar
0.7
Fe
2.6*
Co
9.0
Ni
8.1
Br
0.8
Tc
10.5
Te
4.6
F
2.7
Cl
1.6
Mn
11.1
Mo
10.0
Sb
5.2
VIII
Kr
0.3
Ru
10.2
I
2.6*
Rh
8.7
Pd
6.4
Xe
1.1*
12

14
Energy of dividing, eV
12
10
8
6
4
2
0
11
16
21
26
31
36
41
46
51
Atomic number of X
Figure 5. Dependence of energy needed for dividing the segregative clusters Fe2Fe6X2Fe6Fe2 on atomic
number of X.
Despite the fact that our calculations are approximate, the results obtained confirm the
known experimental facts and correspond to the periodic law. We suppose that more accurate
calculations will confirm the obtained dependence of hardening (or softening) properties of
elements on the nuclear charge of atoms. This dependence can be the theoretical base for the
prediction of strength properties of polycrystalline materials with different alloying
components.
4. CALCULATIONS OF BINDING ENERGY OF CLUSTERS CONTAINING

SEGREGATED ATOMS OF TWO ELEMENTS
Now, we shall consider the possibility of reducing the negative effects of atoms of
softening elements on wear resistance of steel. The way for solution of this problem, the most
obvious from the chemical point of view, is the introduction of atoms increasing the binding
energy between grains and thus neutralizing the effect of atoms of the softening elements into
the composition of a metal. Such additional atoms can wholly or partially force out the atoms
of softening elements from the grain boundary surface (see Figure 6) depending on the
activity of the atoms.
Table 4 represents the computation results of the binding energy of segregative clusters
containing two types of segregants. From these data, it follows that boron atoms are able to
block the exposure of sulfur and phosphorus atoms to the grain-boundary surface. Carbon and
nitrogen atoms are able to block sulfur atoms. The investigation in this area is going on.
13
Figure 6. Cluster containing two types of segregants. Boron atoms (small dark spheres) force out sulfur
atoms (light spheres) from grain boundary.
Table 4. Binding energy of segregative clusters containing two types of segregants

Grain
composition
Segregated
layer
Fe6S2
Fe6BS
Fe6P2
Fe6BP
Fe6S2
Fe6CS
Fe6S2
Fe6NS
Fe6S2
B3
SBS
B3
PBP
C3
SCS
N3
SNS
Cu3
Binding energy of clusters, eV

full clusters without
lower grain
lower grain
127.44
68.11
49.80
126.95
70.75
49.14
133.59
71.64
52.21
131.67
73.19
51.58
131.86
74.88
49.80
130.11
73.19
52.75
131.59
76.35
49.80
129.08
71.70
52.76
115.46
59.34
49.80
Binding
energy of
grains, eV
9.53
7.06
9.74
6.90
7.18
4.17
5.44
4.62
6.32
Note that the hardening elements introduced into steel can dissolve in a volumetric phase
of iron (i.e. within grains) and a part of these elements remaining on the surfaces of the grains
may be too small and thus insufficient for steel hardening. From this point of view, the
alloying of steel by boron appears to be the most effective because boron, having a smaller
value of Ed than carbon, dissolves in steel much worse than carbon. If steel is alloyed by
boron in amounts providing the filling of grain boundaries (in actuality, it is the 100-th
fraction of percent of the total volume of a sample), it is possible to expect an essential
increase of steel wear resistance. However, if a greater amount of boron is added, some boron
atoms will penetrate into iron grains and there will appear compounds of boron with iron,
carbon and other metals inside them that is borides and carbides. These compounds are
considerably lesser strong than iron and the properties of steel will deteriorate. Thus, it is
possible to raise the strength of steel only by adding small concentrations of boron.
14
At present, we carry out the experimental testing this phenomenon. Within the framework
of the grant of JSC Russian Railways, we develop the method of diffusive introduction of
boron into the surface layers of railway wheels. The purpose of this method is the creation of
a surface layer with increased wear resistance. It is like somewhat to the known thermochemical technology of boriding. Due to this technology, the chemical compounds of boron
with iron and carbon appear on a steel surface that provides high hardness and high fragility.
The method developed by us does not lead to increased fragility.
5. POTENTIAL ENERGY CURVES FOR ADSORBED

AND SEGREGATED ATOMS
The adduced above values of the binding energy of clusters correspond to the separation
of grains in the direction perpendicular to the grain boundary surface. In this case, there is no
work to do in order to overcome the friction forces between grains. Under real conditions, at
least, some part of grains moves with a shift relatively to each other during the destruction of
polycrystalline material. To take into account the additional losses of energy appearing in this
case, it is necessary to consider a relief of potential energy for impurity atoms moving along a
grain boundary surface.
To calculate this quantity for a model cluster, we assumed that the coordinates of all Fe
atoms are fixed and the atoms of investigated elements can move along and perpendicularly
to a grain surface (Figure 7). The trajectory of an atom should correspond to minimal values
of energy, as the atom moves from one equilibrium position to other.
Figure 7. Coordinates describing the displacement of atoms on iron surface.
15
Figure 8. Relief of the potential energy for elements of the first and second periods.
Figure 8 shows the calculated curves describing the relief of the potential energy E(x),
where x is the coordinate of adsorbed atom on surface. We can see that the steepness of the
relief for various elements can differ noticeably. The relief for hydrogen is mostly flat. The
energy of its interaction with an iron surface practically does not depend on the position of
hydrogen atom on the surface. Evidently, it corresponds to the known fact that hydrogen does
not create stable compounds with iron. For elements of the second period of Mendeleev's
periodic table the steepness of the relief increases as the atomic number of an element grows.
An important quantitative characteristic of the relief of the potential energy E(x) is the
second derivative d2E/dx2 at the equilibrium position. The greater this derivative is, the
steeper is the relief of E(x) and the more difficult it is to displace the atom from the
equilibrium position. The values of this derivative for the case of adsorbed and segregated
atoms are present in Figure 9.
This figure shows that the steepness of the relief for elements from the beginning and the
end of a period is comparatively small, and is greater for elements from the middle of the
period. This fact correlates with the behavior of energy of the binding of atoms with a surface
studied above. Namely, atoms of elements, which separate with difficulty from iron surface in
the perpendicular direction, also cannot freely move in parallel directions. It signifies, in
particular, that if a certain element has a property to strengthen the bond between iron grains,
this property does not depend on the direction of a destroying action.
16
Figure 9. Values of the second derivative d2E/dx2 (a.u./2) for elements adsorbed (light columns) and
segregated (dark columns) on iron surface.
The degree of steepness of the relief of the potential energy of adsorbed or segregated
atoms can be an essential factor influencing the stability of a layer containing these atoms.
When the size of the atoms exceeds the size of iron atom then the order and symmetry of
atomic arrangement in a layer will be lower than in the iron lattice. It can lead to the rise of
energy of the layer. Since some atoms will not be in positions with minimal energy, then the
steeper is the relief, the larger store of energy has the layer. Such an increase of energy leads
to additional mechanical stresses in the layer. Some insignificant thermal or mechanical loads
can lead to essential structure rearrangement of the layer.
The practical consequence of the above consideration is the necessity to take into account
the steepness of the relief of the potential energy for designing multi-layer coatings. Such
coatings should have intermediate layers of soft materials, i.e. such materials, where atoms
have a relatively flat relief of potential energy on the surface of the base metal. The relief is
flat enough for some transition metals in Figure 9 (copper, titanium, vanadium). Probably,
this explains the fact that these metals are widely used for intermediate coatings on steel.
CONCLUSION
The results of quantum-chemical calculations performed show the following:
1) Using polyatomic clusters with the number of atoms equal to 18 or more allows us to
study the changes of energy of the bond between segregated atoms and surfaces of
iron grains on qualitative and semi-quantitative levels. This fact indicates that the
bond of atoms of various elements with iron surface is reproduced well by model
clusters with a rather small number of interacting atoms.
17
2) The comparison of the binding energy of clusters, representing adsorptive and

segregative complexes of one-type elements, points to the correlation between the
energy of Fe-X bond appearing at the adsorption of an element X on iron surface and
the energy of Fe-X-Fe bond appearing at the grain boundary segregation.
3) If the energy of Fe-X bond is greater modulo than the energy of Fe-Fe bond then the
element X increases steel wear resistance in the segregation process. Thus, the
strength of the bond of segregated atoms with iron atoms inside the surface layer of
metal is an essential factor influencing wear resistance.
4) The calculations have revealed the periodic dependence of the energy of binding of
atoms of different elements with a grain surface on their atomic number. This fact
complies with the periodic law and can be considered as the theoretical base for the
forecasting of strength properties of steel with different composition of alloying and
impurity elements.
5) If a certain element can strengthen the bond between iron grains then this property
does not depend on the direction of a destroying force.
6) Multilayer coatings on metals should have the first layer from materials whose atoms
have a flat relief of the potential energy on the surface of the base metal.
ACKNOWLEDGEMENTS
The work was carried out with the financial support from Russian Foundation for Basic
Research (project codes 07-08-00525, 08-08-00759, 11-08-00640) and Open Joint Stock
Company Russian Railways (2012, grant for young scientists Improvement of wear
resistance of rolling surface of wheels).
REFERENCES
[1]
Briggs, D.; Seah, M. P. Practical Surface Analysis by Auger and X-Ray Photoelectron
Spectroscopy, John Wiley & Sons, Ltd.: Chichester, 1990.
[2] Painter, G. S.; Averill, F. W. Physical Review Letters, 1987, vol. 58, 234-237.
[3] Yang, R.; et al. Journal of Physics: Condensed Matter, 2003, vol. 15, 8339-8349.
[4] Braithwaite, J. S.; Peter, R. Acta Materialia, 2005, vol. 53, 2715-2726.
[5] Gesari, S. B.; et al. Applied Surface Science, 2007, vol. 253, 5939-5942.
[6] Seah, M. P. Acta Metallurgica, 1980, vol. 28, 955-962.
[7] Lejcek, Pavel. Grain Boundary Segregation in Metals, Springer: 2010, pp. 1252.
[8] Herbig, M.; et al. Phys. Rev. Lett., 2013, accepted paper (19 December 2013).
[9] te Velde, G.; et al. Journal of Computational Chemistry, 2001, vol. 22, 931-967.
[10] Kolesnikov, V. I.; et al. Journal of Friction and Wear, 2010, vol. 31, 11-22.
[11] Lebedev, M. V. Physics of the Solid State, 2006, vol. 48, 164-171.

ISBN: 978-1-63321-239-8
Chapter 2
DEVELOPMENT AND STUDY OF SILICON DIOXIDE

NANOSTRUCTURED FILMS FORMING ON
SEMICONDUCTOR STRUCTURE SURFACE
V. V. Polyakov*
Department of Nanotechnology and Microsystems, Southern Federal University,
Taganrog, Russia
ABSTRACT
The study is devoted to SiO2 nanostructured films formed on Si and SiC surfaces.
The films were formed by rapid thermal annealing and gas-phase photo-decomposition.
The films can be used for technology of forming the hybrid systems of microfluidic
structures in the implementation of planar processing by batch methods, microfluidic
structures of channels by surface passivation etc. In this study, the experimental results
are discussed, and the processing mechanisms and methods for SiO 2 nanostructured films,
formed on Si and SiC surfaces are considered. Some technical solutions, based on using
the equipment for silicon dioxide nano-structured films, are suggested.
1. INTRODUCTION
To achieve a higher integration, reliability, durability and quick response of integrated
circuits, it is necessary to reduce the temperature and duration time of technological
operations of oxide formation on semiconductor structure surfaces, which are implemented in
the processing of the integrated circuits.
Corresponding author: Email: vpolyakov@sfedu.ru.
20
V. V. Polyakov
The most promising technique, providing the reduction of thermal operation duration
time is rapid thermal annealing (RTA). The most wide-spread regime is a heat balance one
with thermal annealing pulse duration from several seconds to tens of seconds, based on the
use of infrared radiation halogen lamps. The temperature of silicon dioxide nanostructured
films formed can be reduced by applying optical radiation for initiation of chemical reactions
in the gas phase and structural transformations in the surface layer of the semiconductor. The
resonant excitation and selective break of molecule chemical bonds by optical radiation of
UV-range reduces both temperatures in the gas phase and surface temperature during the
deposition process.
A great experience in application of coherent (laser) and non-coherent radiation sources
for semiconductor devices and integrated circuit technology has been gained over the last
years [1 8]. The peculiarity of this technological process is the requirement to take into
account the optical characteristics of the considered semiconductor; the most important of
them are reflection and absorption coefficients.
The study results in rapid thermal annealing of silicon and silicon carbide structures
explaining the temperature dependences of the integrated absorption coefficient during
annealing of doped layers, and contact spray-metal system are reported in references [3 5, 9,
10]. It is shown, that the investigation results are significantly influenced not only by the
power density but the spectrum of the radiation source, as well.
During the radiation stimulation of thermal annealing of silicon dioxide films on the
silicon, the light in dielectrics is hardly absorbed. The main absorption occurs in the
semiconductor [11 13]. The interface along dielectric surface determines the rate of
reflected radiation that depends, besides other things, on silicon dioxide film thickness. In this
case, the characteristics of luminous flux, which comes through dielectric, are also found by
the film thickness. Due to the absorptive capacity of the layer with thickness of d1 is
determined by the Bouguer Lambert law, then the fraction of the absorbed radiation can
be defined by the expression [11]:
|
(1)
where R1 and R2 are the SiO2 semiconductor and SiO2 air interface reflection coefficients,
respectively, = 2nd1cos is the difference of ray lengths, n is the refraction in dioxide film,
is the angle of incident ray and d1 is the oxide thickness, 0 is the value of incident
radiation.
The spectral characteristics of silicon dioxide films are present in Figure 1. As it could be
seen from Figure 1, the local absorption for SiO2 is observed in the short- and long-wave
radiation region. Therefore, at the time of processing the semiconductor structures, containing
local dielectric films, on the surface of the wafers, it is important to take into account the
complex nature of the absorption, reflection and transmission of silicon dioxide films.
Furthermore, during the rapid thermal annealing (RTA) the film of the dielectric can
serve as an anti-reflecting coating. Consequently, the semiconductor regions with different
Development and Study of Silicon Dioxide Nanostructured Films
21
thickness of dielectric films are annealed differently. This effect will be particularly
noticeable in case of small spans of radiation. These features of SiO2 films absorption and
transmission must be considered in case of choosing the optimal treatment regimes of
semiconductor structures used in the integrated circuits and micro-systems [14 17].
During the stimulated by radiation thermal annealing of semiconductor structures,
depended on the radiation source type, we use a wavelength range from vacuum ultraviolet up
to the far infrared radiation. Then for actual structures of integrated circuits and
microsystems, in case of use of SiO2 films with 0.05 - 1.0 m of thickness, we should
consider the optical characteristics of SiO2 films and their impact on distribution of the
temperature fields in the structures.
Uniformity of the temperature distribution on the surface of the wafers in the process of
pulse treatment is a critical factor for use of rapid thermal annealing technology for
fabrication of the integrated circuits and microsystems. The rapid thermal annealing is
achieved by corresponding designing of heating chamber. However, even in case of radiation
of wafers surface by luminous flux, due to different optical and thermal characteristics of
local regions, significant temperature gradients may arise in the wafer, which, in turn, cause
excessive mechanical stresses. The mechanical stress relaxation may cause both line and
point defect formation [18 20]. The concentration of point defects could be reduced under
certain conditions, but line defects, particularly dislocations, have a high resistance. Finally, it
may result to impossibility to fabricate the accepted integrated circuits and microsystems.
Therefore, in the case of implementation of the stimulated by radiation thermal annealing in
the processing technology of integrated circuits and microsystems, we should carry out a
careful control and selection of treatment regimes that would avoid dislocations [21, 22].
Figure 1. Spectral dependences of absorption (), reflection (R) and transmission () coefficients for
Si2: 1 absorption, 2 transmission, 3 reflection.
22
V. V. Polyakov
2. CHARACTERISTICS OF SILICON DIOXIDE NANOSTRUCTURED

FILMS FORMED BY DIFFERENT METHODS
2.1. Characteristics of Processing SiO2 Films during Rapid
Thermal Annealing
In most cases, for forming the silicon dioxide films with stable electrical and physical
parameters, a 1000-1200 temperature range is used [23, 24]. At higher temperatures, the
initial stage of 57 nanometer film growth is quite rapid, which does not allow one to
precisely control the oxidation process. Application of low temperatures (lesser than 1000 )
in fabrication of oxides by means of rapid thermal annealing is limited no so strongly by the
quality of the films, as by their slow growth (see Figure 2, curve 2).
This can be avoided by using the oxidant atmosphere of dry oxygen (96 97 %) and
ozone (3.4 %) mixture [24], which reduces the oxidation temperature to 600 900 C by
increasing the rate of silicon dioxide formation and in comparison to usual thermal oxidation;
it occurs up to 300 % (see Figure 2, curve 3). Application of other gases (N2, HCl, H2 etc.)
instead of ozone produces a little effect on oxidation rate, but reduces the heterogeneity and
improves electrical parameters of thin films [25].
One way to stabilize the characteristics of the obtained oxide is annealing that impacts the
alterations in the fixed charge in the oxide and mechanical stresses at Si SiO2 interface [25
27]. Regardless of the oxidation temperature, the greatest reduction of fixed charge is
observed at temperatures above 1000 C in vacuum, in various gases (N2, H2, Ar etc.), as well
as in gas mixtures. Mechanical stresses, according to [26], are relaxed at the temperature
above 1100 C within 10 15 s. For example, annealing process of thin films (~ 15
nanometers) was carried out in [23, 28 32] for 10 30 s at 1000 1200 C, that made
possible to form oxides, which, by their electrical parameters, are equal to the films,
fabricated by thermal method. In reference [29], silicon oxidation in dry oxygen was
alternated with annealing in argon at 900 C. Furthermore, we could observe the dependence
of the oxide thickness on the annealing time between cycles of oxidation. It is assumed that a
very rapid growth of the oxide (see Figure 2, curve 4) is related to the stress relaxation and
perhaps with change of the charge states that affect the film growth rate.
As it is known, thin oxide under the conditions of thermal oxidation grows much faster
than it is described by Deal-Grove model [33]. So, for the theoretical justification of the oxide
growth kinetics, a number of models based on bulk diffusion of charged particles or neutral
pairs as well as on electron tunneling effects, building-up an electron cloud layer, generating
elastic stresses on the oxide structure changing, has been developed [30, 31, 34 36].
However, none of these mechanisms can fully explain the experimental data.
The impact of oxide fabrication technology on the growth rate of films can be revealed
by comparing the oxide growth curves in studies on silicon oxidation by rapid thermal
annealing method [23, 37, 38] and thermal oxidation [32, 39]. In the case of substrate heating
up by non-heterogeneous sources, the silicon dioxide film of 10 20 nm thickness grows 5
10 times faster than under the conditions of usual thermal oxidation. It is assumed that there
are several ways for oxidation forming reaction occurring. In case of rapid thermal treatment,
23
it is very possible that we should consider two independent and parallel processes, namely
photo-stimulated and thermally-stimulated oxidations.
Photo-stimulated reaction during rapid thermal annealing may be considerably complex,
its occurring depends on power and implemented radiation sources, as effects of radiation on
solids, and gases cause generation of physical and chemical processes that are determined by
the properties of the irradiated material and photon energy [31, 35]. In the case of silicon
oxidation by rapid thermal annealing method, the 2 SiO2 Si system, that gained energy
from outside, tends to relaxation that, most probably, is obtained through the set of reactions,
causing oxide growth dynamics.
The possible effect of oxidation due to the photo-stimulation is dissociation of oxidant in
gas phase effected by photons with energy of 5 electron volts with emergence of atomic
oxygen that, in turn, reacting with molecular oxygen, forms ozone. The ozone molecules,
adsorbing on the hot surface of the substrate, dissociate into molecular and atomic oxygen.
The latter, due to the smaller size, quickly reaches a Si SiO2 interface and efficiently
includes into the oxide lattice, which leads to the increase in the growth rate of the silicon
dioxide [24]. In the spectrum of widely used for rapid thermal annealing halogen or xenon
lamps the fraction of photons with energy above 5 electron volts is considerably small, so the
concentration of atomic oxygen in the oxidant atmosphere can be neglected. On the contrary,
the use of excimer sources with the emission spectrum, shifted to short-wavelength band, led
to a significant increase in the atomic oxygen and ozone concentration in the atmosphere
oxidant, whose impact on the dielectric growth process was shown in works [24, 31]. In the
case of presence of 4.3 % ozone fraction in the dry oxygen, the 300, 250 and 50 % increase in
the oxide growth rate for temperatures of 600, 800 and 950 C, respectively, in comparison
with usual thermal oxidant was observed.
Figure 2. Dependence of oxide thickness on the time of oxidation 900 C: 1 usual thermal oxidation
in dry 2; 2 oxidation by rapid thermal annealing method in 2; 3 oxidation by rapid thermal
annealing method in 2 + 3; 4 alteration of oxidation stages in 2 and annealing in Ar at 1150 C.
24
V. V. Polyakov
It is assumed that the acceleration of the oxide growth is caused by the presence of
atomic oxygen at Si SiO2 interface. The atomic oxygen is formed by dissociation of the
adsorbed ozone molecules on the hot substrate surface. Moreover, in the region of low
temperatures, when molecular oxygen weakly reacts with silicon (energy of activation of the
reaction is Ea = 1.7 eV [26, 39]), atomic oxygen will be effectively involved into the oxide
formation (Ea = 0.22 eV [24]), and with rising temperature a usual thermal oxidation reaction
starts to prevail. If we use other gases as additives to the oxygen atmosphere, it is important to
consider their dissociation processes that, in some cases have a rapid character [31]. Light
flux, passing through the oxidant atmosphere, reaches Si SiO2 system, where part of the
radiation is absorbed, that leads to heating up the silicon substrate [3, 25]. In general, the
degree of absorption depends on the substrate doping level and the photon energy. It is
characterized by the following basic types: free carrier absorption, its own absorption and
ionization state absorption [40].
The prevalence of various absorption types for the substrate with different conductivity at
the 1.3 and 1.55 m wave lengths in the temperature range of 400 900 C is analyzed in
[41]. For low-alloyed silicon wafers in the above mentioned temperature range, at the 1.55
m wave length, a free carrier absorption was prevailing; and at 1.33 m its own absorption
was prevailing. It probably has an impact on the character of occurring in silicon the
photochemical processes and, consequently, on the silicon dioxide forming, which is most
clearly observed during irradiation of Si SiO2 system with short-wave optical radiation [31,
32, 42]. In reference [31], the region of thermally oxidized silicon sample was treated by the
514 and 488 nm tunable wavelength laser, at the same time there was an increase in the 20 %
(514 nm) and 25 % (488 nm) growth rate of oxide. The change of the laser radiation power
also accelerated the oxide growth. It was registered that the oxidation rate increasing depends
on doping level of the substrate, in addition for p-type wafers this effect is maximum, while
for n-type is minimal.
Under irradiation we could observe change of the surface state density at the oxide
semiconductor interface and the accumulation of negative charge in the silicon dioxide film
that was caused, as we suggest, by the over-barrier injection of electrons from SiO2 [42]. In
this case, the formation of the charged atomic or molecular particles of oxygen in the oxide
film is caused by the transition of electrons from the silicon carrier band (CB) to the CB of
SiO2 so as it follows at subsequent reaction with molecular oxygen. At the same time, the
electrons could flow over more than 3.15 electron volt height barrier [32, 40] (see Figure 3).
But the most likely, it is the emission of electrons to the SiOx transition layer, i.e. between Si
and SiO2 and that is determined by reconfiguration of the silicon crystal structure into SiO2
structure. The SiOx thickness is to be into range from several angstroms up to 30 ,
depending on the oxide history and thickness [26].
The barrier between the CBs of Si and SiO is smaller than one electron volt, so the
photoemission of electrons from the silicon to the transition layer will be effective. Under
these conditions the SiOx layer shall be saturated with free carriers that may be trapped on
positively charged traps and react with molecular oxygen, if we take into account the electron
affinity energy (Ee) of 1.46 and 0.4 electron-volt for O and 2 respectively, according to the
following scheme [24, 30, 32]:
2 + e = O 2 (Ee = 0.4 eV),
25
O 2 + e = O + O + e ( Ee 1.5 eV),
O 2 + hv = O + O (hv > 1.5 eV),
O +e = O ( Ee > 1.46 eV).

The flow of oxidant charged particles to the Si SiOx interface is determined by
concentration gradient and volume charge electric field assisted drift. Thus, similar to the case
of dissociation of molecular oxygen in the gas phase, atomic oxygen moves to the Si SiO2
interface and reacts with the silicon to form silicon dioxide. This reaction proceeds at
temperatures below 800 850 more effectively than standard reaction [30, 32].
By analyzing the photo-stimulated reactions, it is necessary to take into account the
concentration and depth of electron penetration into the dielectric, and the rate of atomic
oxygen diffusion to the Si SiO2 interface.
Oxide growing on a silicon surface also affects the absorption of radiation by the
substrate. The presence of the dielectric film helps to change the radiation absorption
coefficient in the substrate by 10 30 % due to antireflective effect at Si SiO2 interface. It
requires taking into account the refractive index of silicon and silicon dioxide, the film
thickness and the radiation wave length [43]. The radiation absorption by silicon dioxide in
the 200 6000 nm wave-length range is relatively slight. It is determined by the presence of
impurity centers in the SiO2 band gap and is equal to 0.01 % of silicon absorption. The
absorption of radiation by the film within oxidation process increases due to the presence
therein of the oxygen atoms or molecules, as well as free electrons from silicon. Band-gap
absorption of silicon dioxide may be neglected, since it corresponds to the bonding energy of
the Si O that is equal to 9 electron volts [40].
Figure 3. Band diagram of SiO2 Si structure: E0 is the vacuum level, Eco is the oxide carrier band level,
ef
EcSi is the silicon carrier band level, EvSi is the silicon valence band level, Ev is the effective valence
level; EVo is the oxide valence band level, SiOx is the variable composition oxide [40].
Thus, obtainment of high-quality dielectric by rapid thermal annealing method is

associated with the control over all fabrication stages of oxidation process and the best choice
26
V. V. Polyakov
of equipment, i.e. radiation sources. By means of varying their parameters we can change the
photo-stimulated reaction occurring, achieving the desired growth rate and acceptable
parameters of forming dielectric [44]. The possibility of the oxidation temperature reducing
makes rapid thermal annealing method really promising for use in low-temperature
technology of modern integrated circuits and microsystem fabrication.
To improve CMOS VLSI performance we need gate dielectric with a required thickness
of 5 10 nm. Experimentally we can get ultra-thin oxide of high quality. However, the
repeating occurrence of the results is no high enough. This is due to the lack of a common
theoretical framework that would explain the mechanism of thin oxide formation, as well as
the factors affecting the dielectric growth rate.
The basic model of thermal oxidation offered by Deal and Grove [33] describes relatively
well the growth of the silicon oxide thickness of 30 2000 nm in the range of partial
pressures of (0.1 1.0) 105 Pa at 973 1473 K temperature, in atmosphere consisting of
dry oxygen, or water vapor. However, the Deal Grove model does not describe correctly the
growth of the films with thickness lesser than 30 nm. The main distinction of the proposed
model from the Deal Grove model is the suggestion to dissociate the molecular oxygen in
the growing oxide by means of electrons moving from the silicon, and the use of infrared
heaters as a heat source that allowed taking into account the role of the thermo- and photostimulated oxidation reaction. The spectral range of the radiation falls on the 1.1 m wave
length with photon energy of 1.2 electron volts. Since the silicon band gap is 1.12 electron
volts, the silicon substrate effectively absorbs photons of these energies on its own charge
carriers. In the silicon subsurface layer the electron cloud is formed and electric field that is
associated with the photo EMF effect, is generated. At the initial stage of the oxidation the
energy barrier between the silicon and growing oxide is equal to 1 2 electron volts that, in
turn, facilitate the efficient transfer of electrons from the silicon conduction band to the
silicon dioxide conduction band. Then, with increasing oxide thickness the barrier grows to 3
electron volts and electron flux weakens [30, 45].
Schematically, the silicon oxidation reaction is shown in Figure 4. In a simple way, the
kinetics of oxide growth is described by three fluxes: (i) the oxidant flux from the gas phase
to the substrate surface; (ii) the oxidant flux to the Si SiO2 interface; (iii) the flux associated
with the oxidation reaction. During rapid thermal annealing electrons, moved to oxide and
described by Fe flow, are involved in the dissociation of the part of oxidant flux. As it follows
from reference [30], even during usual thermal oxidation at temperature of 1173 K, there are
electrons that have moved to the oxide. During photo-stimulated process their number
increases dramatically.
The penetration depth of the electrons in the oxide is determined by the mean free path,
x0 (Figure 4). Distribution of electrons in energies in the oxide is similar to the distribution of
photons in the spectrum of the radiation source. Consequently, we can estimate the
concentration of electrons with energy sufficient for dissociation of molecular oxygen: O2 + e
= O 2 (0.4 eV). Then O 2 metastable molecule dissociates: O 2 + hv O + O (> 1 eV) [24].
Part of molecular oxygen, which has reached the interface, reacts with silicon according the
Deal-Grove model [33].
27
Figure 4. Schematic presentation of oxidation reaction [24].
Thus, the oxidation reaction of silicon is represented by five fluxes:

(1) F1 is the oxidant flux from the gas phase to the surface of silicon:
F1 = h(C* C0),
(2)
where h is the transition coefficient from the gas phase, C* is the oxidant
concentration on the outer surface of the oxide, C0 is the equilibrium concentration of
the oxidant in the oxide.
(2) F2 is the flux of molecular oxygen through the oxide to the dissociation interface:
F2 = D0(C0 0' )/(x x0),
(3)
where D0 is the molecular oxygen diffusion coefficient, 0' is the oxidant

concentration at the dissociation interface.
(3) F31, F32 are the fluxes of molecular oxygen and dissociation products:
F31 = D1(C1 1' )/x0; F32 = D2(C2 2' )/x0,
(4)
where C1 = n 0' , C2 = 0' (1 n) are the concentration of molecular oxygen, and the
dissociation products immediately after dissociation oxidant under condition that 0' =
= C1 C2; 1' and 2' are the concentration of oxygen molecules, and the dissociation
products at the interface. The following interface conditions must be observed:
'
1 0 , at n 1;
'
0 , at n 0,
28
V. V. Polyakov
where n is the dissociation constant (probability). If n = 1, then the oxidation of
silicon is reduced to the thermal reaction, if n = 0, then the oxidation is reduced to
photo-stimulated reaction. If 0 < n < 1, then there is a mixed oxidation type.
Total flux is defined as
F3 = F31 + F32.
(5)
Consequently, the flux system F3 shall be represented as follows

D1 (nC 0' C1' )
;
x0
F3
'
'
D1 [C 0 (1 n) C 2 ] .
x0
(6)
Into framework of description of the dissociation products F32, for the diffusion flow
of F32, it is assumed that the restricting factor is the rate of diffusion of the neutral
oxygen, which is characterized by the diffusion coefficient D2. Oxygen ions quickly
reach the Si SiO2 interface, drifting along direction of the electric field.
(4) F41, F42 are the oxidation reactions describing, respectively, the transformations:
Si + O2 SiO2 and Si + O + O SiO2 + e and defined as
F41 = k1 1' ; F42 = k2 2' ,
(7)
where k1, k2 are the constants of the chemical reaction velocities.

Total flux:
F4 = F41 + F42.
(8)
From the condition of stationarity F31 = F41 and F32 = F42. Thus,
1'
nC 0' D1 and ' (1 n)C0' D2 .

1
x0 k1 D1
x0 k 2 D2
(9)
The oxide growth rate will be ascertained by differential equation:

dx F ,
dt N1
(10)
where N1 is the amount of oxidant molecules included into the unit volume of the
oxide, and F is the flow satisfying the stationarity condition: F = F1 = F2 = F3 = F4
One of the difficulties arising from the using of the model is determination of the
molecular oxygen concentration C* on the surface of the oxide. In the case of
dissociation, Henry law can be written as follows:

(C*)m = K1P,
29
(11)
where K1, P are the proportionality coefficient and oxidant pressure, respectively, m
is the ratio of the matter molecular weight in the gas phase to average molecular
weight of dissociation oxidation products in oxide. We may assume that m n. If m
= 1 then Equation (11) transforms into Henry law.
(5) The electron flux Fe into oxide. Electron concentration in SiO2 is ascertained by the
ratio: n0x = (nf + nt)G [43], where G is the function, which takes account the oxidation
conditions and the state interface; nf, nt are the concentrations of photo- and
thermally stimulated electrons in the conduction band of silicon.
In the oxidation process, three stages of dielectric growth should be observed:
(i) extremely thin oxide layer at the moment when the dissociation of molecular oxygen
proceeds on the surface of growing silicon dioxide (x = x0);
(ii) the average thickness oxide (x > x0);
(iii) extremely thick oxide layer, if x >> x0; in this case value of x0 could be neglected,
assuming that the dissociation of the oxidant occurs at the Si SiO2 interface.
For the first case the model can be simplified by assuming that at the initial stage of
oxidation the restricting factor is the chemical reaction rate at interface, then
dx F4 nk1C0 (1 n)k 2 C0 ,
dt N1
N1
(12)
x nK L' t (1 n) K L'' t ,
(13)
so
where K L' , K L'' are the linear growth rate for photo- and thermally stimulated reactions. From
the experimental curves of oxide growth using rapid thermal treatment, shown in [30, 45],
and thermal oxidation [33], we find K L' = 2.4 m/h at = 1173 and K L'' = 0.021 m/h. By
assuming that each electron, injected into the oxide at the initial stage of growth (x 0), will
participate in the oxygen ionization and n0 x CO 1016 cm3 [30, 45], the probability is
2
n 1. With growth of the oxide, according to Reference [46], the potential barrier Ep at the
interface increases and the concentration of electrons in the oxide decreases. By using these
suggestions, we can submit the schedule for growth of silicon dioxide at the temperature of
1173 K (see Figure 5)
In the case of using short-wavelength light sources the model can be complicated, if we
take into account the dissociation of molecular oxygen in the gas phase volume. Atomic
oxygen in the presence of oxidizing atmosphere in the volume of 3-4 % increases the rate of
oxidation by about of 10 % [24]. Presence of atomic oxygen in the oxidizing atmosphere in
the volume of 3-4 % increases the rate of oxidation by about of 10 % [24].
30
V. V. Polyakov
Figure 5. Dependence of the oxide thickness (x) to oxidation time (t) at 1173 K. The numbers
correspond to: 1, 4 calculation by Deal-Grove theory [33]; 2, 2 calculations by using Equation (13)
with the growth of Ep, if x 4 nm and x 15 nm, respectively, and 3 experiment [35].
Thus, with implementation of rapid thermal annealing the usual thermal oxidation
reaction of silicon is complicated for the photo-stimulated component that significantly
complicates the calculation of the model. Probability of it or that the reaction takes place is
determined by value of n, which is strongly dependent on the oxidation conditions, the type of
used lamps and the substrate, so the oxide growth rate may vary within wide limits. However,
at all other the same parameters, a thin dielectric grows faster at rapid thermal annealing than
in the case of a usual thermal oxidation.
2.2. Processing Dielectric Thin Films SiO2 on SiC by Thermal Oxidation

There is a lot of methods for processing the dielectric thin films on semiconductor
surfaces [23, 36, 37, 39, 41 47]. Nowadays, several types of dielectric thin films on SiC
have been extensively used in processing the SiC-based electronic devices.
The oxidation of SiC and processing the nitride films on surface of SiC are commonly
used. Thermal oxidation of SiC is usually carried out in dry oxygen, wet oxygen and water
vapor [46, 48 63].
The experiments have proved that the oxidation process of SiC, as well as silicon
oxidation, is described by the Deal-Grove model [33]. The oxide thickness is a function of
temperature and oxidation time. It was determined that in oxidizing in wet oxygen, the
activation energy of linear component of the oxidation rate for (000 1 ) 6H-SiC is equal to 26
kkal/mole and activation energy of parabolic component of the oxidation rate is 48 kkal/mole.
By oxidizing in wet oxygen at temperatures from 980 C up to 1245 C, the activation
energy Ea of oxidation process equals 85 and 47 kkal/mole, respectively [51].
The main problem arising during the SiC oxidation is the presence of carbon in the oxide
being part of the metal-oxide-semiconductor structures. This leads to the degradation of
31
dielectric properties of the film. That is why the investigation of the oxidation mechanism as
well as the structure of the grown oxide on the surface of silicon carbide is essential to
understand and control electrical characteristics of the SiC-based devices [48 64].
Reference [65] suggests that there exist two main sources of high density of the electron
states in SiO2 films processed on 4-SiC, namely, the carbon sludge in the oxide film or the
interface and the structure defect on the part of SiO2 film at the film/silicon carbide interface.
According to [65], the carbon sludge is a source of electron states in the lower part of SiC
forbidden band, while silicon oxide structure defects cause defect states in the upper part of
SiC forbidden band [65].
As indicated in [66 70], high density of interfacial defects is due to compounds
containing carbon (such as Si4C2O2) or carbon clusters and/or sub-oxides (the presence of
under-oxidized silicon) at the interface [70]. As it was shown in Reference [66], the
concentration of excessive carbon at the interface is well lesser than 1015 cm2. Based on the
spectral analysis of electron energy loss, it was demonstrated that the concentration of carbon
at the interface SiO2/4H-SiC(0001) can be higher than in the oxide or SiC crystal. Carbonrelated defects at the interface SiO2/SiC were confirmed with data from electron paramagnetic
resonance while the presence of carbon clusters on the C-face of SiC was detected by means
of surface-enhanced Raman scattering [66].
Interfacial carbon-carbon bonds can act as interface traps due to defects at the interface
SiO2/4H-SiC. Reference [71] shows that the -face demonstrates higher density of interfacial
defects during high-temperature oxidation. By surface-enhanced Raman scattering it was
determined that the concentration of carbon clusters on the C-face of SiC is much higher than
on the Si-surface of SiC and these clusters most probably have the graphite-like nature [66,
67]. The carbon clusters contribute to the density of electronically-active interfacial states
(Dit) due to their graphite-like and therefore semimetallic nature [71]. A steep increase of Dit
in the conduction band Ec, especially for polytype 4-SiC, is determined by so-called
interfacial traps [72]. Their microscopic origin is not clear, yet. It is suggested [71] that they
are caused by the lack of oxygen.
These states act as interfacial electron traps and lead to leakage currents in MOS-devices
[71]. At the same time, it was shown in [72] that interfacial state density is higher for p-type
MOS-structures than for n-type MOS-structures.
A more detailed investigation of the (0001) Si-face revealed the absence of carbon
clusters as well as carbon contained in co-products, the latter ones are detected through
studies of the photoemission of ex-situ and in-situ grown samples SiO2/4H-SiC [73].
According to [73], the main reason of high density of the defects at the interface SiO2/SiC is
the presence of sub-oxide Si2O, apart from fully formed oxide SiO2. On the other hand, the
presence of carbon clusters as well as carbon contained in co-products on (001) C-face, nonpolar (10 1 0) and (11 2 0) surfaces is detected in the samples of SiO2/SiC grown in-situ within
2. Based on the research data, it was suggested that higher partial pressure of oxygen can
lead to interfacial carbon quantity reduction. As indicated in [73], for (000 1 ), (10 1 0) and
(11 2 0) surfaces under investigation, the initial oxidation stage is characterized by the
presence of sub-oxide SiO at the interface SiO2/SiC.
According to [71] for the Si-face of 4-SiC the initial oxidation stage is characterized by
the presence of two silicon suboxides with various degrees of oxidation: Si2O and SiO2.
However, on the initial oxidation stages one cannot neglect the contribution of sub-oxide Si2O
32
V. V. Polyakov
by estimating the oxide film thickness. The extension of oxidation time and the temperature
increase up to 800 C result to increasing in the proportion of SiO2. During long oxidation at
800 C neither carbon containing co-products, nor graphite-like carbon in oxide film are
detected at the interface or on the surface [73].
For non-polar (10 1 0) and (11 2 0) surfaces after the initial oxidation stage the presence
of under-oxidized silicon (Si2O, SiO) is observed at the interface SiO2/SiC, while for (000 1 )
polar surface only silicon sub-oxide Si2O3 or Si2O5 is observed [76].
For silicon carbide C-face at the initial oxidation stages sub-oxide SiO predominance is
observed. However, longer oxidation time results in SiO2 predominance in the same manner
as for the Si-face [73].
According to [69, 75], during silicon carbide oxidation the presence of free carbon is
observed at the interface SiC/SiO2.
Reference [76] shows that during oxidation of 6-SiC (000 1 )-(22) carbide surface at
1000 C, the interface contains Si2O3 and Si2O5 adsorbed layers. The temperature increasing
results in Si2O5 predominance.
Types of defects and their concentration at the interface SiC/SiO2 also depend on what
surface of silicon carbide has been oxidized [63]. Thus, the -face ((000 1 ) surface) is
characterized by a higher oxidation rate than the Si-face ((000 1 ) surface) approximately 10
times faster under high oxygen pressure ( 100 Torr). On the other hand, the -face ((000 1 )
surface) is characterized by a higher concentration of trap layers [63].
The SiC oxidation, using oxygen isotopes 16O2 and 18O2, gives a possibility to suggest a
SiC oxidation mechanism according to the surface used [85, 86]. The SiC surface was first
oxidized by isotopes 16O2, and then was affected by 18O2. In agreement with oxygen
adsorption/desorption dependence on oxidation rate and temperature [8], four processes were
revealed to occur during silicon carbide oxidation for the polar C-face: (i) oxygen adsorption
to the silicon adlayer, (ii) transfer to the back bond of the Si adlayer, (iii) oxygen desorption
from the silicate adlayer, and (iv) transfer from the silicate adlayer to the back bond of the Si
adlayer. The processes mentioned above are shown in Figure 6.
At the first stage of oxidation, molecule 2 is adsorbed on the SiC surface and dissociates
into separate atoms. After that, the formed oxygen atoms rearrange on the surface [78]. Labile
oxygen atoms are easily adsorbed at the upper bound of the Si adlayer. The back bond of the
Si adlayer is easily oxidized at the initial stage, when it is not completely oxidized, though the
potential barrier for the back bond oxidation is slightly higher than the one for oxygen
introduction into carbon-carbon bonds in the Si adlayer. However, the potential barrier for the
back bond oxidation is much higher, if Si atoms in the adlayer are almost oxidized. In the
case, when an oxygen atom is adsorbed at the back bond, one or two neighboring oxygen
atoms in the silicate adlayer are removed from the surface and/or ne oxygen atom is
embedded into the back bond by means of kinetic power transmission from the adsorbable
oxygen atom. Such a model suggests the existence of a much greater bond energy for the
bridging oxygen in Si-O-C bond [78], than it is required for the silicate adlayer surface.
Another process is possible: when an oxygen atom is adsorbed on the Si layer, a neighboring
oxygen atom can volatilize from the surface or be embedded into back bond of the Si adlayer,
getting kinetic power from the adsorbable oxygen atom. The second process is hardly
probable because the uppermost Si adlayer is almost completely oxidized. The Si adlayer
33
oxidation results in forming the Si2O3 silicate layer even at 500 C, provided that the silicate
layer is stable up to 1000 C [76, 79].
The total number of oxygen atoms, be adsorbed on an additional silicon layer, is constant
at oxidation temperatures from 500C up to 1000 C. In contrast, the total number of oxygen
atoms, embedded into the back bond of the Si adlayer, first increases quickly during the
oxidation in 18O2 at 900 C and then increases gradually, as the oxidation time increases. A
steep increase of the number of 18O2 atoms at the interface Si-face adlayer/SiC substrate
during the oxidation at 900 C for 5 minutes is described by oxidation mechanisms (2) and
(4) [76].
Reference [77] considers in depth the processes of interface formation for the non-polar
6-SiC (11 2 0) surface. As noted above, the perfect 6-SiC (11 2 0) surface is non-polar and
contains coplanar Si and C atoms with parallel zigzag chains of six-fold frequency.
By investigating the structure of the 6-SiC (11 2 0) surface, it was found that, an
additional Si layer is formed on the substrate at the silicon oxide/carbide interface similar to
the case with the polar surface [77].
Figure 6. Layout of possible oxygen adsorption and desorption processes [76].
Figure 7. Most probable atomic configuration of the oxidized at room temperature (11 2 0) surface.
Open black and grey circles represent Si, and atoms, respectively, big open circles represent Si
adlayer atoms. The clip shows two corner Si adatoms and the location of adsorbed O [77].
34
V. V. Polyakov
The oxidation of the specially cleaned 6-SiC (11 2 0) surface was carried out at room
temperature, 500, 600, 700 and 800 C [77].
Non-stoichiometric SiO2 layer is formed in the samples oxidized at room temperature.
Based on the experimental data [77], the most probable atomic configuration of the 6SiC (11 2 0) surface, oxidized at room temperature, was suggested in Figure 7. The adsorbed
oxygen atom (adatom) is located as a bridge between two corner atoms of the Si zigzag chain,
an additional oxygen atom is embedded into the back bond of one of the above-mentioned
corner adatoms, bonded to the second layer of Si atoms (see Figure 7).
The 100-120 nm thick ultrathin stoichiometric SiO2 layers are formed during thermal
oxidation at 500, 600, 700 and 800 C [80]. The authors note, that the best values of such
characteristics as dielectric constant, film density, root-mean-square roughness of the SiCSiO2 interface, effective oxide charge, leakage current density are observed during the
oxidation at 700 C.
To determine the oxidation kinetics the specially cleaned (11 2 0) surface was first
oxidized by isotopes 16O2 at room temperature, and then was affected by 18O2 at 600 C.
As it was shown in [77], the exchange reaction between the substrate and oxide atoms
occurs in the upper surface region, and in both cases the atoms of oxygen isotope penetrate
into the substrate in the same way, forming a silicate-like sub-oxide layer at the interface
SiO2/6H-SiC. This is to support that oxygen surplus, formed as a result of the exchange
reaction of oxygen on the surface, leads to the formation of CO molecules, desorbing from
the surface [77]. The deformation, caused by thermal oxidation on the surface of
oxide/substrate interface, was estimated. It was demonstrated that maximum compression
deformation of 2 % is induced under the oxide film and the deformation decreases gradually
with increase in depth approximately up to 1.5 nm of the Si-face [76, 77].
Reference [81] overviews the photoluminescence of the SiO2 layers, formed by the
anodic electrochemical oxidation of -Si films. It was demonstrated that the oxide film
thickness increases with increasing the sample oxidation time. However, all the silicon oxide
films kept traces of carbon uniformly distributed through the volume.
The authors of [81] suggest two explanations of the observed photoluminescence
mechanism:
(1) The electrochemical oxide, formed on the SiC film, contains certain local centers
(complexes). These centers determine the appearance of an impurity band in the
forbidden band as well as recommendation levels causing the observed
photoluminescence. The impurity band in its turn is lesser than 3.7 eV behind of
valence band. The width of the photoluminescence spectral band is determined by
the presence of several recommendation levels, as well as the oxide microporosity.
(2) The other possible explanation concerns the photoluminescence of small quantumdimensional SiC clusters, which can be present in the oxide volume after the
electrochemical etching.
Based on the results of the performed research, the authors of [81] concluded that the
carbon, affecting the photoluminescence spectrum characteristics, must be found within the
local centers with oxide structure defects.
35
The authors [82, 83] suppose that the revealed states are on nature similar to
paramagnetic centers Pb in the SiO2/Si system. In the SiO2/Si system, the paramagnetic
centers Pb, representing the oxidation defects centers of Si Si3 kind with silicon
dangling bonds give a main contribution to the surface states density at the interface SiO2/Si.
These centers are amphoteric in nature and the relevant states density has two peaks in the
silicon forbidden band. The peaks are almost symmetric with respect to the band midpoint:
the acceptor states are situated in the upper half of the band (maximum at Ev + 0.85 eV), the
donor states are situated in the lower half of the band (maximum at Ev + 0.25 eV). In addition,
the integrated states density and their density peak tailing depend on the crystallographic
orientation and SiC surface treatment conditions: states density is minimum on the welloxidized (000 1 )-oriented Si-face and maximum on the free (10 1 0)-oriented -face [82, 84].
Furthermore, each of SiC crystalline polytypes has a distinct oxidation rate under the
same oxidation conditions. For the various SiC polytypes, the oxidation rate on the (000 1 )
Si-face increases with decreasing the hexagonality percentage of the SiC polytype, while the
rate of oxide growth on the (000 1 ) C-face does not depend dramatically on polytype. As in
other semiconductors, conduction type, dopant density, surface roughness and crystalline
quality should also be expected to have an effect on the oxidation rate [48, 59, 62].
It is found that 3-, 4-, 6- and 15R-SiC polytypes have distinct oxidation rates on the
Si-face; the 3-SiC is oxidized approximately 20 % faster than 4-SiC.The 6- and 3-SiC
polytypes oxidation on Si- and C-faces differs according to the oxidation method.
In reference [54], a study of influence of the 6-SiC surface orientation on the oxidation
process was conducted. The samples were cut in the 1120 direction from the surface under
angles of 15, 30, 45 and 90. The concentration of donar dopant in the samples was equal
1018 1019 cm3. The oxidation time was defined so that provided a growth of the film to a
thickness over 300 at 1200, 1100 and 1000 C. This made it possible to measure capacity
voltage characteristics of the samples to a better quality. As a result, the research has found
that the linear component of the oxidation rate changed dramatically, when cutting at 30
from the 6-SiC {0001} surface. Such strong oxidation rate anisotropy leads to certain
difficulties in bird's beak length control in MOS IC topology with a thick protection layer
of silicon oxide. The activation energy of the oxidation rate linear component increases
steadily from the C-face to the Si-face. One of the causes of the activation energy change in
distinct surfaces is due to the difference between Si- and -face SiO2 atoms, which in turns is
caused by electronegativity difference between Si and [6].
The operating temperature of SiC oxidation usually lies within the range of 800 1800
C. In Reference [59], silicon carbide Si- and C-face polished samples (manufactured by
CreeResearchInc) were used as work materials to study kinetics of 6-SiC oxidation. The
plates had an epitaxial layer of 3 m thick so that to reduce concentration of defects and
oversee the doping process. The initial aluminum concentration on the Si-face was 1.31015
cm3 and 5.51015 cm3 on the C-face, the nitrogen concentration on the Si-face is 8.71015
cm3 and 5.81015 cm3 on the C-face.
During the oxidation process such techniques as dry oxidation at 1523 K, dry oxidation at
1523 K with addition of trichlorethane and pyrogenic wet oxidation were used.
36
V. V. Polyakov
Table 1. Effect of 6-SiC surface type and oxidation conditions on oxide thickness [59]
Wafer type
Polished surface
n-type
Silicon
p-type
Silicon
n-type
Carbon
p-type
Carbon
Dopant concentration, cm3

Oxidation time, min
Oxide thickness, nm:
Dry oxidation, 1523
Dryoxidation + trichlorethane, 1523
Wet oxidation, 1473
8.71015
50
44
1.31015
50
40
5.81015
10
51
5.51015
10
48
43
40
42
48
49
130
50
131
So, in order to obtain relatively similar oxide thicknesses, the Si-face plates were
oxidized for 50 minutes while the C-face plates were oxidized for 10 minutes. The oxidation
was followed by nitrogen annealing at the same temperature for 60 minutes. The n-type and
p-type samples were oxidized simultaneously. Silicon samples were also used to control the
oxidation process. The oxide thickness was measured by ellipsometer with a wavelength of
632.8 nm and an incident angle of 70 (the index of refraction for SiC was assumed to be
2.636). All the oxides thickness was between 40 and 50 nm, except for the wet oxidized Cface samples. Their thickness was 130 nm.
The values of thickness of the oxide layers, formed on the surface of silicon carbide, are
presented in Table 1. The table shows the effect of surface type on the oxidation rate. The
capacitor dependencies of the samples under investigation are shown in Figure 8 11 [59].
The authors of [59] found the 6-SiC oxidation rate dependence on partial pressure of
oxygen and water vapor. The oxidation was carried out within a pyrogen system, in which 2
and 2 reacted inside a reaction chamber. A thermocouple-sensing element was used to
measure the temperature during the oxidation process. The oxide thickness was measured by
using ellipsometry. P-epi plates on the Si-face of 6-SiC substrate with the acceptor dopant
concentration of 1.71016 cm3 were used to carry out the experiments. The temperature
remained constant at 1100 C in all circumstances. The same plate was re-oxidized after the
grown oxide had been etched away. The wafer oxidation was carried out at 1100 C for 6
hours. Silicon oxidation rate in wet oxygen as it is known to be higher than in dry oxygen.
The same principle is relevant to silicon carbide. In order to find out how the oxidation rate
changes depending on whether wet or dry oxygen is used, the oxidation was carried out at
over a full range of 2 and 2 flow rates. The oxide thickness dependence on partial pressure
of water vapor is shown in Figure 12.
The partial pressure of water was calculated by using the following formula:
p = f(H2O)/[f(H2O)+f(O2)],
(14)
where f(H2O) and f(O2) are the flow rates of water vapor and oxygen, respectively. In (14), it
is expected that 2 is exhausted by reaction with 2 to produce a 2 molecule. The
calculation data and the thicknesses of the oxide formed for various gas flow rates are listed
in Table 2. The maximum oxide thickness for silicon carbide is observed under partial
pressure of water of p = 0.15, while for silicon it is observed under pressure of = 1
(humidity 100 %). Therefore, it is possible to make a thick oxide controlling 2 and 2 flow
37
rates on the Si-face. Another parameter influencing the oxidation rate is the gas flow joint rate
(i.e. the rate of the flow, comprising water vapor and oxygen). For samples (1-4) from Table
2, there is an increase in oxide thickness with increasing the gas flow rate. However, the gas
flow rate of sample 5 is lower than the one of samples 1-4, while the oxide is thicker. Thus, it
may be concluded that the oxide thickness does not depend on the gas flow rate [62].
Apart from kinetic principles of silicon dioxide formation on SiC, dielectric material
electrophysical characteristics are of great interest. One of the most efficient methods of
dielectric coating qualimetry is the measurement of volt-farad characteristics of the dielectric
films formed. In reference [60] CMOS gates were formed by 450 nm thick polysilicon
deposition and doped by POCl3. The 200 nm thick aluminum was deposed by electron
deposition. Dry and wet etchin, by means of F4 within the lithographic process of aluminum
and polysilicon thin films formation were used to form round contacts. The contact diameters
of 100, 200, 400 and 1000 m were used. The back side was covered with aluminum (-type
samples) and nickel (n-type samples). The samples were then annealed in a vacuum oven at
773 .
Figure 8. Dependence of C/Cox on gate voltage for Si-face capacitor on n-type SiC with the oxides
formed by different methods. The gate area is 0.00126 cm 2 [59].
Figure 9. Dependence of C/Cox on gate voltage for C-face capacitor on n-type SiC. The gate area is
0.00126 cm2 [59].
38
V. V. Polyakov
Figure 10. Dependence of C/Cox on gate voltage for Si-face capacitor on p-type SiC. The gate area is
0.00126 cm2 [59].
Figure 11. Dependence of C/Cox on gate voltage for C-face capacitor on p-type SiC. The gate area is
0.00126 cm2 [59].
Figure 12. Oxide thickness under various partial pressures of water vapor. Oxidation time is 5 hours: 1
theoretical curve, 2 experimental curve [62].
39
Table 2. Oxide thickness dependence on gas flow rate [62]

Sample
1
2
3
4
5
6
7
8
9
10
11
Gas flow rate (l/min)

2
2
8
4.36
8
4.5
8
5
8
6
4
4
4
6
4
8
4
14
2
13
1
0
12.5
8
Partial pressure of water,

calculated by formula (14)
0.96
0.94
0.88
0.8
0.67
0.5
0.4
0.25
0.14
0.08
-
Oxide thickness (nm)

29
31.8
35
37
39
38.9
43.7
50.3
49 52
32
-
The measurements of volt-farad characteristics were performed in the dark, at room

temperature and a frequency of 1 MHz. By measuring, the voltage at the equilibrium point
changed from inversion/depletion to beneficiating. The hysteresis range was found to be
narrow, by changing voltage along both directions. After that, the capacities of contacts with
200 and 400 m diameters were measured to provide identical curves. In order to make the
certain resistance in series being insignificant, oxide capacities with 100 and 1000 m gates
diameters, respectively, were measured. Experimental studies showed that the leak pockets
are quite big, especially in the oxides, grown on p-type substrates.
In Reference [60], MOS capacitors, intended to study volt-farad characteristics, were
made using homo-epitaxial layers grown on (0001) Si-face of silicon carbonate plates of 4and 6-SiC polytypes. Boron-doped epitaxial layers of p-type and aluminum-doped epitaxial
layers of n-type were grown on strongly doped substrates of p- and n-type, respectively. The
thickness of epitaxial layer is 4 m. The concentration of dopants of the epitaxial layers
equals 21016 cm3 for -type and 21015 cm3 for n-type. Boron-doped epitaxial layers for ptype samples were used in the experiment, because they demonstrated better controllability
than aluminum-doped epitaxial layers. However, there is no substantial difference in the
interface SiO2/SiC properties between the boron-doped and aluminum-doped samples.
As a gating electrode, aluminum was deposed through a metal mask so as to form a
contact with diameter of 300 and 500 m. The contact being formed it was annealed by using
the gas mixture (N2:H2 = 9:1) at 400 C for 30 min.
Figure 13 illustrates voltage-capacitance characteristic curve under lack of light for MOS
4-SiC-based p-type capacitors for various oxidation processes [60]. The measured curves
show deep depletion due to the low intrinsic-carrier concentration owing to the large-band
gap.
Despite the flat band negative bias (Vfb), wet oxidation may diminish Vfb for the
samples oxidized in dry oxygen ambient.
40
V. V. Polyakov
Figure 13. High-frequency voltage-capacitance characteristic for MOS 4-SiC-based p-type capacitors
[60].
High negative value of Vfb in p-type MOS capacitors is generally due to holes being
captured by the deep donor-type interface states rather than owing the fixed charges.
Nevertheless, if the negative fixed charges are present at the surface, size shift of a flat band
can be reduced.
In recent years, there have been a lot of published papers on processing and using metalnitrides films. The conducting metal nitrides on SiC with chemical and physical properties
depending on their structure and stoichiometric properties are of particular interest. Among
these properties, we see high thermal, mechanical and chemical resistance, high electrical and
thermal conductivity and in certain cases catalytic reactivity [85].
The conducting metal nitrides are made with the use of physical and chemical vapor
plating technology. In classical non-organic chemistry they were formed with the elemental
reaction under growing temperatures and/or higher pressure in the convection furnace.
Moreover, fast thermal annealing is required to get the highest quality films.
In the paper [85], Si(100) wafers of 150 mm in diameter with thermally grown 100 nm
oxide were used to prevent interactions between metal-silicon and silicide formations.
Vanadium and niobium layers, as well as the vanadium titan composites, were processed by
means of high-vacuum electronic beam of power 4 kW.
Metal targets (Ti and V) of 99.0 % purity were used as a source of vaporization. Quartz
glass was fixed near a substrate at the distance of 30 cm from a metal source to control the
general thickness and plating speed of 5 nm/min. The multilayered coating of Ti/V consists of
different monolayers of each metal (12.6 nm thick Ti, and 10.0 nm thick V), according to the
stoichiometry ratio 1:1.The multilayered system was made by serial vaporization of the
corresponding metals.
Experiments on RTA were carried out under atmospheric pressure in nitrogen or
ammonium stream (1.5 l/min) with purity of gas 99.999%, using SHS 100-system of RTA
made by Stead-a.s.t [85] with the quartz chamber for substrate in hot wall of the quartz
reactor.
Such a RTA system allows heating thin film metals on substrate fragments (2 2) cm2
deposited on the graphite slab and heating from the top to bottom by the tungsten halogen
lamp matrix, achieving the heat rate from 50 up to 100 C/s. After heating and following
41
cooling the gas flux is set at 10 l/min. The samples were processed in the RTA system under
the temperature range from 400 up to 1200 C with processing time ranging from 5 up to 300
seconds and further cooling to room temperature under the prevailing gas ambient.
Temperature control during the RTA was performed using the pyrometry.
Additional external actions are often used to alter the defect state density on the threshold
SiO2/SiC.
So, the effect of the laser light leads to the interface DOS distribution on SiC/SiO2
threshold in the form of monoenergetic surface level [75]. This level changes dependence of
surface potential on electrical bias of the SiC/SiO2 composition, whereas its shadowing effect
leads to only separate areas of the voltage-capacitance characteristic being shifted in contrast
to the initial one.
The authors of the paper [75] explain the observed effect with the mono-energetic surface
layer, which exists in the form of a trap which exchange electron charge with SiC. At this
moment the maximum density of the surface states was Nss = 2.5 1011 eV/cm2.
Supplementary annealing of films is necessary for stabilization of parameters of dielectric
in the nitrogen or argon ambient [62].
The subsequent sample annealing in various nitrogen-containing gases allows improving
the quality of the interface due to the silicon oxynitride formation [69, 73, 86].
Most likely when nitriding the C-N bond is not formed, but either carbon is removed
possibly due to oxidation gain in NO, or SixNyCz layer is formed, by means of including
carbon in dielectric.
The surface-enhanced Raman scattering provides the unique physical and chemical
identification of the carbon clusters on the threshold after thermal oxidation and their
considerable alteration after annealing in the NO ambient [66]. Relying on surface-enhanced
Raman scattering data contrast and the phenomenological three-stage model, it was claimed
that carbon clusters formed on the thresholds are graphite-like structured carbon. In contrast
to the diamond-like structures with -bonds, the graphite-like carbon contains -bonds similar
to the interfacial defects [66].
Processing the (0001) Si-face of the silicon carbide in NO and (NH3) with the substrate
temperature being as high as 800 degrees leads to formation of the silicon oxynitride and
(Si3N4) [73].
In reference [61] the oxynitrides were grown up on the 6H-SiC surface by means of
either humidified N2O (N2O gas was passed through the deionized water at 95 C) or dry
N2O, following the wet oxidation. The silicon oxide/silicon carbide interface was
subsequently studied. It was stated in the work that the threshold of both types of oxidation
improves for p-SiC/oxide, but worsens for n-SiC/oxide, when compared to just dry oxidation
in N2O.
The process in use can be improved by means of removing the undesirable carbon
impurity from the surface owing to the wet ambient and, reducing the donor-type surface
states for MOS structures on p-6H-SiC, respectively. As for the MOS structures on the n-6HSiC hydrogen the -bound particles, incorporated into the structure under wet oxidation,
enhances the surface acceptor states. This allows wet oxidation in N2O to be used to provide
equal robustness for n- and p-silicon carbide MOS-structures.
In reference [61], a silicon wafer side 6H-SiC of n-and r-type, made by Cree Research,
was used for carrying out studies. The 5 m thick epitaxial layer was grown on strongly
42
V. V. Polyakov
doped SiC wafers. The epitaxial layer doping degree for both types of wafers was (4 1015)
cm3. The wafers were placed inside a quartz tube under 800 C. By rising the temperature up
to 1150 C, oxidation in dry (DN2OG) or wet (WN2OG)N2O atmosphere was carried out
during 4 hours with the speed of the gas flow being as high as 500 ml/min. The third sample
was oxidized first in dry N2O atmosphere during 2.5 hours, and then in dry N2O atmosphere
during 1.5 hours (DWN2OG) at the same temperature and speed of gas flow. After cooling in
N2 at the speed of 1 C/min up to 950 C, all the samples were subjected to annealing in N2 at
the speed of gas flow 1 l/min during 0.5 hours. Then aluminum was thermally deposited and
gate electrodes were formed at the area (1.14 103) cm2.
High-frequency voltage-capacitance characteristic was subsequently measured under
room temperature, the signal amplitude achieving 20 mV. The obtained results are depicted in
Figure 14 (for n-type SiC MOS) and Figure 15 (for -type SiC MOS) under lack of light.
In reference [56], the studies were carried out of the dielectric power temporal stability of
the MOS capacitors incorporated on the n-type 6-SiC wafers. The 25 nm thick oxide was
grown at the temperature of 1150 C in the atmosphere of wet oxygen. In the samples under
study, the break was observed at 145, 240 and 305 C. It is appeared that the studied samples
remain to be stable under temperatures as high as 150 C. The dielectric stability is broken at
the temperature of 250 C. This proves that SiC MOS devices cannot operate under these
temperatures.
Thus, to receive a high-quality dielectric SiC surface, all pollution or crystalline defects
would be cleared carefully, and oxidation modes also would be controlled additionally.
2.3. Silicon Dioxide Deposition with UV and Thermal Activation

The method of pyrolitic decomposition of the Si-organic compound along with thermal
oxidation is widely used in chips technology [87]. Films of silicon dioxide can be deposited
both with alloying additives, and without them. Undoped silicon dioxide is used as an
isolating film under multilevel metallization, as a masking coating. The doped films of silicon
dioxide are used as isolating, passivating, gettering layers (phosphor-silicate glass), and as the
diffusive sources doped with boron, phosphorus, arsenic, etc. [88]. The pyrolitic process
generally includes the following stages: feeding molecules or particles to the surface,
diffusion through the interfacial level, adsorption of molecules, reactive intermediates and
products of homogeneous decomposition, as well as chemical reaction, respectively, and
eventually a desorption and decomposition products sleeving.
The film deposition velocity under high temperatures is mainly limited by the velocity of
the homogeneous nucleation, which is often determined by the wastes of the reaction volume.
Under low temperatures the speed of process is determined by the velocity of heterogeneous
nucleation and by chemical reaction kinetics. The quality of the pyrolitic films is considerably
affected by the carrier gas composition and cleaning efficiency [89].
The main ways to lower the temperature of dielectric passivated films deposition within
the pyrolitic method are the following:
(i) using reactions with a low activation force and, obviously, reactive components
under relatively low temperatures;
43
(ii) preliminary thermal activation of molecules beyond a deposition zone;

(iii) non-thermal activation (chemical one using the catalyst addition and physical one
under the effect of ionic and electric beams, electric field, light, namely UV or
infrared-radiation).
When it is activated with UV radiation, the film formation process starts under lower
temperatures than it usually occurs with pyrolitic decomposition, with the reaction volume
including active gases like oxygen [90].
Figure 14. n-type SiC MOS high-frequency voltage-capacitance characteristic for the three types of
capacitors (WN2OG under wet N2O oxidation, DN2OG under dry N2O oxidation and DWN2OG under
both dry and wet N2O oxidation) [61].
Figure 15. p-type SiC MOS high-frequency voltage-capacitance characteristic for the three types of
capacitors (WN2OG under wet N2O oxidation, DN2OG under dry N2O oxidation and DWN2OG under
both dry and wet N2O oxidation) [61].
44
V. V. Polyakov
In most cases SiH4, Si2H6 or SiCl2H2 are used as silicon forming component. It is wellknown, however [87, 91], that during thermal chemical deposition, some of the silicon
organic compounds (for example, Tetraethoxysilane (TEOS - Si(OC2H5)4) can provide SiO2
layers, demonstrating electrical and physical properties with high conformability and
uniformity.
But, since high temperature of this process limits its applicability in various technologies,
interest arises to the photochemical deposition of silicon dioxide from TEOS under low
temperatures. TEOS is a nonpoisonous liquid with the boiling temperature as high as 440 K.
High gas pressure of the TEOS provides enough gaseous substance to deposit SiO2 films
under room temperature, however activation energy for its decomposition reaction is high in
value (1.9 eV) [87].
Let us consider the silicon dioxide photochemical deposition from the gas phase of the
Tetraethoxysilane/oxygen (TEOS/2) composition. At the early stage the UV radiation
affects the oxygen and TEOS causing them to undergo photo-excitation and subsequent
dissociation. The TEOS molecule geometrical form (C25)4 Si is a regular tetrahedron with
four ethyl radicals of C2H5 at each of the tops, and the central atom of silicon in the middle
(C25)4. The bond between Si atom and each of radicals is performed by one of four atoms
of oxygen. The (C2H5O)4 molecule structure Si can be represented by projection onto a plane
as follows:
The dissociation of molecules composed and structured in this way is predominantly

radical, and can pass either by means of Si-O bonds, or CO bonds. The rupture of C-C and
S-N bonds leading to ethyl radicals decomposition and formation of the dissociation byproducts, is insignificant for obtaining the final products. By considering that the dissociated
final products are non-saturated silicon oxides or silicon itself, their formation reaction can be
illustrated by the following equation versions:
(C2H5O)4Si 4C2H5+SiO4, [C-O]4;
(15)
(C2H5O)4Si4C2H5O+Si, [SiO]4
(16)
(C2H5O)4SiC2H5+3C2H5O+SiO, [C-O]1[SiO]3
(17)
(C2H5O)4Si2C2H5+2C2H5O+ SiO2, [C-O]2[SiO]2
(18)
(C2H5O)4Si2C2H5O+3C2H5+SiO3, [C-O]3[SiO]1
(19)
Here, after each reaction equation, the type and number of broken bonds are showed.
Total energy value of broken bonds, considered as the activation energy of tetraethoxysilane
45
(TEOS) dissociation in an unexcited state E0 for each of the dissociation mechanisms

considered, is 4290, 3182, 3459, 4013 and 3737 kJ/mol, respectively.
Let us consider the possible mechanisms of tetraethoxysilane (TEOS) dissociation on the
silicon wafer by forming the SiO2 films under UV radiation. We shall start with the following
theses. Energy impact of UV radiation on the TEOS molecule is carried out twice: directly in
the gas phase as a result of radiation energy absorption by molecules (and their excitation)
and, indirectly, on the silicon surface as a result of radiation energy absorption by surface
active centers and transmission of absorbed excitation energy to the molecules adsorbed on
them. Since the average activation energy of TEOS molecule dissociation in the normal level
is large enough (E0 3500 kJ/mol), unlikely molecular decomposition in the gas phase has
not been considered. Dissociation was examined with the substrate participation, only.
As a criterion for activation energy value of probable dissociation mechanism, it was
chosen in the environment the catalytic effect of the activated surface on the excited
molecule. The calculation of the dissociation activation energy was conducted by the method
described in [92], with changes in UV radiation energy effect.
The dissociation mechanism of tetraethoxysilane molecule can be represented as a
sequence of three kinetic stages. In the first stage, one of the four C-O bonds, the closest to
the surface of silicon, breaks. This bond break is possible due to the mechanical interaction of
the excited TEOS molecule with the active centre of activated surface. In the second
dissociation stage, two following C-O bonds break as a result of adsorptive interaction of
TEOS molecule fragment with active centers of the surface in their thermal fluctuation
environment. Finally, at the third stage, the last bond (fourth bond of C-O) breaks, the
excitement of which occurred at the first stage.
The total energy of the TEOS molecule before the interaction with the active center of the
Si surface is defined as the sum of the kinetic energy of molecule thermal motion and the
excitation energy as a result of UV radiation energy absorption by the molecule. The second
component of the total energy includes the kinetic energy of rotational molecule motion and
the kinetic energy of the vibratory motion of atom nuclei along lines of the chemical bonds,
and is stated (by Eyring rule) equal to a quarter of the C-O bond energy. Thus,
TEOS = kT + excited = 4.5461012 gcm2/s2.
The excited impulse of the surface Si atom is
PSi (2 ASi m0 ESi* b)1 / 2 (2 28 1.6 10 24 408 1.66 10 14 )1 / 2 2.46 10 17 gcm/s,

where ASi is the relative atomic mass of Si, m0 is the atomic mass unit, b is the conversion
factor kJ/mol into gcm2/s2. TEOS molecule impulse is calculated by the same formula as for
the impulse of surface Si atom, and is equal to TEOS = 5.51017 gcm/s.
As a result of the TEOS molecule interaction with the active center of Si surface, its
speed in accordance with the law of the momentum conservation is equal to
= (PSi + PTEOS)/(mSi + mTEOS) = 2.1105 gcm/s,

and the energy equals to *TEOS = 0.5mTEOS2/ = 445.15 kJ/mol.
46
V. V. Polyakov
Taking into account that the TEOS molecule contains four C-O bonds, energy of the
atoms forming each of the bonds is increased by the amount of ()*TEOS = 111.28 kJ/mol.
Thus, the activation energy of the C-O bond dissociation (break), being the nearest to the
active center, decreases by the amount of E*TEOS/4 and becomes equal to Ea1 = 268.12
111.28 = 156.83 kJ/mol.
The first component is the activation energy of the C-O bond dissociation in the absence
of excitation.
After the first C-O bond break, the remaining TEOS molecule is adsorbed on two
adjacent active centers, which due to thermal fluctuations can be displaced relatively to each
other at the distance of 2x (x is the Si atom displacement from its equilibrium position due
to thermal fluctuations). The value of x is calculated as x = x0(I + T), where =
0 is the temperature increment in the process, = 2.410-6 deg-1 is the temperature increment
in the process, I is the coefficient of linear expansion, x0 = 5.981010 cm is the Si atom
displacement from its equilibrium position at 0 = 298 .
TEOS molecule fragments, rather rigidly bounded with surface active centers by
adsorption forces, will move away from each other by the same amount (assuming
predominance of the C and O atoms adsorption energy over the thermal fluctuations energy of
these atoms). To break each of the two C-O bonds, lying in the plane of the active centers of
substrate surface, it is necessary to have the distance between the C and O atoms in the TEOS
molecule increased to the value of x = x0 2x, where x0 Ecb / 0 is the distance between the
C and O atoms sufficient to break the C-O bond in the non-adsorbed state (Ecb is the C-O
bond energy, 0 is the force constant equal to 3.96105 dyne/cm).
The activation energy value of each of the C-O bond break in this case is determined as
a2 = Ea1(x/x0)2 = 105.07 kJ/mol.
The activation energy of the fourth and last C-O bond is calculated by considering the
*
energy of its excitation at the first stage of molecule dissociation as a3 = Ecb Eteos
/4 =
963.21 kJ/mol.
Thus, the activation energy of all four C-O bonds in the TEOS molecule will be equal to
a = a1 + 2a2 + Ea3 = 1328.192 kJ/mol.
Similarly, values of activation energy of the TEOS molecule dissociation have been
calculated by other possible mechanisms (16) (19). The calculation results are summarized
in Table 3.
Analyzing the presented data in the table, it is possible to note that irrespective of the
reactions alternate (15) (19), the activation energy of TEOS dissociation under UV
irradiation has been decreased by a factor of about 3 in comparison with non-activated state.
Therefore, if to use thermal effect as the energy equivalent of UV radiation, in this case, the
use of UV radiation as the dissociation activator is adequate to 200-600 degrees reduction in
the background temperature of pyrolytic TEOS decomposition.
The calculation data behavior indicates low dependence of dissociation activation energy
on the radiation wavelength, which in fact confirms the assumption on preferential radiation
energy being absorbed by active centers of the silicon surface. For the selected temperature
values, the greatest decrease of the dissociation activation energy is observed for the shortwave part of the investigated radiation spectrum.
47
Table 3. Activation energy of the TEOS dissociation (kJ/mol) at different

wavelengths of radiation
, microns
T, K
Without UV activation
0.650
300
700
0.577
300
700
0.311
300
700
0.248
300
700
0.198
300
700
Calculation by Equation
(15)
(16)
(17) (18) (19)
4290 3182 3459 4013 3737
1345 961.8 1041 1326 1087
1341 957.6 1036 1322 1083
1345 961.4 1040 1325 1086
1340 956.9 1035 1321 1082
1340 957.5 1036 1322 1083
1329 947.7 1026 1312 1072
1339 956.5 1035 1320 1081
1327 945.3 1024 1309 1070
1339 956.2 1035 1320 1081
1326 944.3 1022 1308 1069
As it can be seen from comparison of the obtained values of the dissociation activation
energy, the dissociation mechanism is the least likely (15). At the same time, the dissociation
according to this mechanism, with the SiO4 radical being the final product is the most
favorable for the subsequent nucleation of silicon dioxide film, structural elements of which
are randomly oriented silicon-oxygen tetrahedron SiO4. The most likely is the dissociation
mechanism (16), in which the growth process of the silicon films is the most probable.
3. EXPERIMENTAL SYSTEMS USED FOR PHOTON STIMULATED

OXIDATION OF SEMICONDUCTORS
Today, for the microelectronic purposes a number of rapid thermal processing systems
have been developed that allow us to implement various processes [1, 3, 4, 8, 93 96]. For
photon stimulated oxidation, the ranges of wavelengths in the visible and ultraviolet (UV)
parts of the radiation spectrum, corresponding to the energy of the covalent bond of many
chemical compounds, are of the greatest interest. UV light area is divided into dipped
(proximal, downward beam) (300 400 nm), the far (distal) (200 300 nm) and vacuum
(120 200 nm) ultraviolet. Selective light absorption by chemical compounds is determined
by their electronic structure. In the wavelength range 200 750 nm a radiation excites the
valence electrons. At wavelength is lesser than 200 nm the radiation interaction with the
molecule may be accompanied by ionization or excitation of the molecule. The
photochemical process consists of multiple stages, namely from excitement and formation of
the molecule and radicals to formation of the final stable compounds. Therefore, when
choosing a source of UV radiation the condition should be followed under which radiation
energy should be sufficient to perform the excitation and break of covalent bonds of the
chemical compounds.
48
V. V. Polyakov
Figure 16. Experimental system for photon-stimulated silicon oxidation: 1 power supply, 2 gates of
pumps, 3 internal electrode, 4 grounded external electrode, 5 radiation with 172 nm wavelength, 6
pressure valve, 7 substrate, 8 heater, 9 oxygen intake [69].
The UV radiation impact on the oxidation process is complex. It causes excitation and
ionization of oxygen in the gas environment, it sparks off the excess electrons in the dielectric
film, and it leads in the semiconductor to the emerging of the internal electric field of about
104 107 V/cm in the subsurface region, which in fact may influence the processes of ions
and electrons migrations in the semiconductor, modifying the electronic structure of the
surface and causing a bend of the energy zones in the subsurface region [1, 96].
In the oxidation of semiconductor hydrogen plasma, excited by high-frequency (HF)
field, the excimer laser, excimer beams, UV lamps are used as the radiation source. The first
three of above-mentioned UV radiation sources allow obtaining the vacuum ultraviolet, with
high energy photons and therefore highly efficient. It enables doubling the oxidation rate in
contrast to the conventional thermal oxidation. Figure 16 shows a diagram of the
experimental system using an excimer lamp as a radiation source [69]. In this system, the
radiation source is isolated from the processing chamber by means of the optical window.
For the photon-stimulating the SiC oxidation, the rapid thermal system, as well as
diffusion equipment, with an additional UV stimulation by a node have been used [70, 95, 97,
98].
The usage of the RTA systems in the processing technology of integrated circuits allows
controlling the heating rate and uniformity of the temperature distribution along the wafer
diameter.
Therefore, the main feature of the created systems is microprocessor control, allowing
precise control of temperature rise rate and its exposure (endurance), taking into account the
nonlinear optical and thermal characteristics of semiconductor structures.
The developed systems based on the block structure allow increasing or decreasing the
emitter capacitance, which are based on quartz halogen lamps QH-220-1500 (QH-220-2000)
or QH-220-1000 (RTA-10MV). The microprocessor makes the control over processing
49
modes more flexible, and the micro-computers, based on it, displays information about the
temperature on the monitor, thus providing the operator with a visual presentation of the
actual temperature process. Figure 17 provides a graphical illustration of the system
construction. The basis of the system is a reaction chamber made of stainless steel. The
camera has a water cooling system, vacuum pumping system and gas supply. Microprocessor
controller allows controlling precisely the heating process, the temperature exposure
(endurance) and cooling. Temperature measurement is carried out with a thermocouple sensor
with low inertia. A distinctive feature of the system is a low gas flow, because the volume of
the chamber is only 2 liters. Holders are made in the form of needles and allow wafer-scale
processing up to 100 mm in size, as well as processing separate samples of silicon carbide for
cost reasons when working out technological modes.
The RTA-18V, PRTA-18 apparatuses with the plates, arranged vertically for thermal
treatment, were designed in addition to the apparatus with a horizontal reactor. It helped to
avoid plate deformation at high-temperature heating of large-diameter supports. The specific
feature of PRTA-18 is bi-lateral irradiation. The coast side is heated with halogen-filled
lamps, and a working face of the plate is treated with UV light. The apparatus is equipped
with two power sources and irradiation control of infrared and ultraviolet radiation.
Figure 17. SiC oxidant with infrared stimulation: 1 water-cooled vacuum reaction cell, 2 infrared
lamps, 3 SiC sample, 4 gas flow regulator, 5 oxygen supply valve, 6 thermocouple amplifier, 7
analog-to-digital converter, 8 lamp control unit, 9 digital-to-analog converter, 10
microprocessor, 11 monitoring panel, 12 display unit [98].
Figure 18. Oxidant with ultraviolet radiation: 1 heating device, 2 quartz tube, 3 UV lamp, 4
feeding unit for the UV lamp, 5 silica boat filled with SiC samples, 6 gas flow regulator, 7
oxygen supply valve [70].
50
V. V. Polyakov
The diffusion of furnace-based oxidant occurs at high rate of gas flow, but provides
collective plate processing in the flow of oxidant gases supplied by an ozonator (Figure 18).
A specially designed ozonizing device was connected to the diffusion furnace to
introduce UV stimulation. The above device consists of quartz tube with embedded
ultraviolet lamp. The oxygen passes through the ozonizing device supplied to the diffusion
furnace.
4. EXPERIMENTAL RESULTS
4.1. Characteristics of Nanostructured SiO2 Films on SiC Obtained by
Thermal Oxidation
One of the most significant elements of SiC technology is formation of oxide layers, their
properties are not certainly defined and depend upon numerous factors, their fabrication
process, in particular [37, 46].
To perform a comparative analysis of SiO2 films obtained by rapid and regular thermal
oxidation, some samples were prepared by rapid thermal dry oxidation at 1273 for 60 and
180 s and by regular thermal steam oxidation at 1373 during 30 and 180 min. The surface
morphology for all the samples was tested by a Nano Scope IIIa (DJ) atomic force
microscope; the transmittance and photoluminescence spectra were measured. Absorption and
photoluminescence spectra were registered by SDL-2 apparatus at room temperature. SIRSh200 spectroscopic lamp was used as a continuous spectrum source during transmittance
spectrum studies, nitrogen laser radiation of = 337 nm was used to excite
photoluminescence spectrum. All optical sensing was performed at room temperature within
the range of wavelength of 400 800 nm. Oxide film thickness was measured using
multibeam monochromatic ellipsometry by a LEF-3-Nd laser ellipsometer with =
632.8 nm in the range of grazing angles at 50 80 C.
The SiO2 film parameters for SiC, calculated according to the ellipsometry data and
obtained by using various methods of thermal oxidation, are illustrated in Table 4. The table
shows the obtained for SiC the refractive index, nSiC, being in good agreement with expected
average (excluding anisotropy) value [74, 75], and absorbance, kSiC, is rather low.
Thermal oxide film SiOx for SiC has nSiOx 1.41 1.51, thus it can be argued that film
composition is related to SiO2. The interdependence of () and () on polarization angles
shows that the thick SiOx layer equals to 100 nm. Such thick layer of an oxide film was
received on the back side of the same sample No 3. Such difference between oxide films is
caused by SiC polar sides and requires a follow-up study. It should be noted that the
absorption spectrum within of 400 800 nm of SiO2/SiC structure is a kind of system integral
characteristic, namely, the resulting spectrum is based on the absorption in SiC volume, as
well as the absorption in the oxide film and at SiO2 SiC interface. The main contribution to
the total absorption spectrum of such complex system is given by an element with the most
forceful absorption in the given spectral range. In the present case, SiC appears to be the
above element.
51
Table 4. Parameters of SiO2 films for SiC obtained using various methods of rapid
and regular thermal oxidation
Rapid thermal dry oxidation at
1273
Oxidation period, s
60
180
30
Parameter
Side
Side Si
Side C
No. 1
Regular thermal steam

oxidation at 1373
Oxidation period, min
120
120
180
Side
Side
Side Si
Si
C
No.
No.
No. 4
3
3b
1.456 1.469
1.407
nSiO2
1.519
1.41
1.412
kSiO2
0.07
0.06
0.0
0.0
0.0
0.0
d SiO2 , nm
8.503
7.892
52.47
22.64
102.6
14.256
nSiC
kSiC
2.63
0.08
2.575
0.0
7.5
50
2.578
0.0
-
2.66
0.0
d SiO2 , nm, Auger
2.627
0.05
-
75
2.61
0.0
-
spectrometry data
G, nm
92
85
83
108
89
-4
-4
-4
-4
2.1110-4
'
SiC
1.2410
1.0710
0.9510
1.3610
where n is the refractive index of SiO2 (SiC), k is the absorbability of SiO2 (SiC), x is the
'
thickness of SiO2 film, k SiC
is the absorbability calculated according to absorption spectrum
for = 630 nm, G is the half-width of the absorption band.
The special feature of spectrum is a wide band of 630 nm connected with a ground state
of donor centers conditional upon the existence of nitrogen impurity in SiC crystals [40, 99,
100], as stated in the literature.
The data for a G half-width of optical absorption band with maximum of 630 nm of
'
samples, as well as k SiC
non-dimensional absorption index calculated with transmittance
spectrum for = 630 nm are given in Table 4.
Table 4 presents an excellent correlation for SiC dimensionless absorption index defined
by optical transmission spectrum and using a multi-beam monochromatic ellipsometry.
It follows from Table 4 that SiO2 thicknesses calculated using ellipsometric measuring
operations and Auger spectrometric measurements coincide one with others as for the
samples, where SiO2 films were processed by using the regular thermal steam oxidation
(samples 1 and 3), as well as for sample obtained by rapid thermal oxidation.
Figure 19 (sample No 3) and Figure 19b (sample No 1), illustrating distribution profiles
of elements in SiO2-SiC structure demonstrate the interface between SiO2 and SiC being
vague. Stoichiometric structure of the oxide film (sample No 1, Figure 19b), x 1.7
corresponds to the data obtained by ellipsometric measurements. There is also carbon
segregation at SiO2 surface layer specified by the specific of binary system oxidation. It
52
V. V. Polyakov
appears that this phase (carbon) is connected with the formation of wave-like (modulated)
oxide structure with keeping its structure. On top of the samples, the observed oxides
structure may arise from the density variability of oxide phase during its growth. The
stoichiometric structure given in Figure 19 remains.
Figure 19. Distribution profiles of elements indicated in atom percents in SiO 2-SiCstructures: ()
regular thermal oxidation = 1373 , oxidation time is 30 min; (b) regular thermal oxidation = 1373
, oxidation time is 120 min; (c) the oxidation using rapid thermal oxidation at = 1273 , oxidation
time is 180 s.
53
By analyzing the Auger spectrometry results, it may be concluded that for various
oxidation methods the content of elements in atom percents is the same as in all the discussed
cases. But dielectric is obtained during lesser time period using the rapid thermal oxidation in
comparison with the case of using thermal steam oxidation. Reasoning from this fact consists
in that the rapid thermal oxidation reduces the time period for this production process.
In addition to structure determination, the electrophysical characteristics of Si CMOS
structures based on the above SiO2 films were also measured in [69]. Their flashes over
voltage and capacity-voltage characteristics were measured. The flashes over voltage of such
MOS structures were 36 40 V. With the area of metal contact equal to 4 106 cm2, electric
strength of MOS structures was 9.2 mV/cm.
The analysis of MOS capacity-voltage characteristics establishes that there are anionic
states in the oxide, and their charge in absolute magnitude is higher than a positive charge in
the oxide. As under the depletion, a surface state charge in absolute magnitude lowers
aspiring to a flat-band point, it can be believed that the above states correspond to acceptor.
It is found that the surface state density when growing SiO2 by the rapid thermal
oxidation was Nss = (2 8) 1011 cm2, the structure charge was Qss = (1.3 3.2) 108
C/cm2. In the case of using the thermal oxidation Nss = 1.5 1012 cm2, Qss = 2.4 107
C/cm2.
4.2. Characteristics of Nanostructurized SiO2 Films Formed Using

Tetraethoxysilane Decomposition at Exposure on Infrared and UV Light
The research works and experimental studies were performed on polished silicon slabs,
doped B or silicon, with diameter of 76 mm and orientation [100]. All slabs experienced the
regular processing procedure using ACS reagents and de-ionized water before deposition. To
receive comprehensive information upon the influence of processing modes on deposition
process kinetics and film properties under formation, experimental methods to control
electrophysical structure parameters and film composition were implemented. Four-probe
technique and diagnostic MOS-structures in the film thickness within 0.1 and 0.2 m, with
aluminum contacts in thickness of 0.5 1 m and with an area within 3 and 4 mm2 were used
to control electric parameters of Si SiO2. The film thickness was found with color Newton's
rings. Fixed charge density and surface state density were calculated according to the
technique described in [101] based on the processing of capacity-voltage characteristics.
Experimental studies on SiO2 film deposition were hold using the engineering apparatus
(see Section 3). The deposition process was hold at the support temperature within 300 400
C. During 20 min the film thickness was from 0.1 to 0.2 m. Radiation energy density is
prominent in the film deposition. If the ultraviolet source was off, the reaction did not
proceed. The major parameter was the oxide thickness depended on the process time,
temperature and the delivery rate of gas reactants and the density of UV light within the
reaction zone. Figure 20 illustrates the dependence of oxide thickness on the deposition time
period for two values of support temperature. The figure shows that the slope of a curve
decreases as the support temperature reduces. By approximating curves for various support
temperatures, the relationship between the film growth rate and the support temperature was
built. The results are shown in Figure 21. It shows that two areas of deposition rate changes
54
V. V. Polyakov
corresponding to growth and saturation process can be marked on the curves. The transition
to the saturation area is observed above 400 . The best film values were obtained at 350
400 .
It should be also stated that the growth rate is influenced by the change of the
tetraethoxysilane-oxygen gas mixture consumption. Different SiO2 film deposition rates can
be obtained by changing the delivery mixture rate; it is confirmed by Figure 22. The decrease
of deposition rate under the high gas flow is explained by the following circumstances: gas
molecules cannot dissociate in the operating area, and for low gas flow the deposition rate is
rather low in default of gas molecules in the reaction site. The number of switched UV lamps
was constantly increased to determine the influence of UV light energy density in the reaction
site upon the film deposition rate in gradual mode. Based on the data obtained, the
dependence given in Figure 23 was constructed. These data indicate that the deposition rate
increases as the radiation energy density grows.
Figure 20. Dependence of oxide thickness on time period of the photochemical deposition from
TEOS/2. The digits show the cases: 1 at = 300 and delivery rate TEOS/2 is 20 l/h;
2 at = 400 and delivery rate TEOS/2 is 20 l/h.
Figure 21. Dependence of SiO2 film growth rate on the support temperature. The digits show the cases:
1 delivery rate TEOS/2 is 5 l/h; 2 - delivery rate TEOS/2 is 20 l/h.
55
Figure 22. Dependence of SiO2 growth rate on TEOS/2 delivery rate. The digits show the cases: 1 at
deposition temperature of 300 ; 2 - at deposition temperature of 400 .
Figure 23. Effect of UV light density on SiO2 deposition rate at the delivery rate of TEOS/2 equal to
20 l/h.
Figure 24. Dependence of Nss and Qss on SiO2 deposition temperature.
The electrophysical characteristics, namely, flash over voltage, surface state charge and
density at Si Si02 interface for deposited SiO2 films were studied. The flash over voltage
56
V. V. Polyakov
was measured using curve-tracing oscilloscope and was into range of (3 6) 106 V/cm for
different samples, conforming the data for films obtained by tetraethoxysilane pyrolytic
decomposition.
The surface state charge and density (Qss and Nss) were measured after the processed
oxide had flashed with aluminum contacts according to capacity-voltage characteristics of
obtained MOS structures. The results are given in Figure 24. The diagrams show that the
surface state density (Nss) and charge (Qss) highly depend on the support temperature during
film deposition process. The number of defects grows strongly, in its near layer, in particular,
at the temperature reduction. Thus, the electrophysical characteristics of SiO2 films obtained
by using Tetraethoxysilane re-solution are caused by the support temperature, gas delivery
rate, pressure and surface density of UV radiation energy. The obtained values of
electrophysical film characteristics are compared with similar parameters of the films
deposited at standard Tetraethoxysilane temperature pyrolysis reaction.
The major disadvantage at the photochemical decomposition is uneven thickness of SiO2
on the support diameter. The elimination of this disadvantage is connected with the solution
of complex gas dynamic problem to deliver the reactants in the reaction zone and to the
surface. For example, the sample rotation with the speed of 1-2 rev/min during the
photochemical decomposition increases SiO2 thickness uniformity from 60-65 up
to 75-80 .
ACKNOWLEDGMENTS
The author expresses his gratitude to Dr. Svetlichny A. M. for useful discussions and
comments provided during the preparation of this paper.
This work was executed in the Centre of Collective Use of Equipment of the Research
and Education Centre "Nanotechnology" of the Southern Federal University.
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ISBN: 978-1-63321-239-8
Chapter 3
METHODS TO STUDY MODIFIED

ALUMINUM SILICATES
V. A. Yavna*, A. S. Kasprzhitskiy and G. I. Lazorenko
Chair of Physics, Rostov State Transport University, Rostov-on-Don, Russia
ABSTRACT
The modification of aluminum silicates with various nanoscale additives leads to
formation of new layered periodic structures showing unique physical and chemical
properties. They have a wide application in the development of new efficient materials
for water conditioning and sewage purification, sorbents in pharmacology, in creating the
antimigration and antifiltration barriers for long-term storage of hazardous wastes, etc.
This work is aimed at the determination of interaction mechanisms between layered
aluminum silicates and nanoscale additives and the explanation of the nature of certain
physical properties of these objects. The solution of the problem formulated demands the
application of mathematical simulation, numerical methods, quantum-chemical software
systems and modern experimental spectroscopic methods for the study of electronic
structure of these objects.
1. INTRODUCTION
The prevailing rock-forming minerals of the outer crust of earth are clay minerals. Their
content, according to various estimates, is 40 50% of the total rock composition [1, 2]. Clay
minerals, hydrated layered and layer-ribbon aluminum silicates differ from other layered
silicates in high dispersion ability and hydrophilic behavior; this determines their specific
physical and chemical properties, namely sorption and ion exchange [38].
Corresponding author: Email: vay@rgups.ru.
62
V. A. Yavna, A. S. Kasprzhitskiy and G. I. Lazorenko
The study of the structure and the properties of layered alumosilicate minerals is
considered to be an important scientific problem focusing on discovering factors that
determine the possibility of creating new multifunctional materials on their basis [9 14].
Such possibility is determined by specific physical and chemical properties of these layered
minerals: developed specific surface area, active centers of different nature, ion-exchange and
adsorption capacity. The properties of layered aluminum silicates open the way for their wide
application, for example, in creating new efficient materials for water conditioning and
sewage purification, sorbents in pharmacology, for creating the antimigration and
antifiltration barriers for a long-term storage of hazardous wastes etc.
Designing of new layer-periodic structures with unique physical and chemical properties
[12, 14 21] is based on modification of minerals by various nanoscale additives. A wide
application of these materials for solving relevant technological problems is restrained by the
fact that the influence of modification on their structure, sorption and other physical
properties is presently studied insufficiently. In spite of intense interest in the study of layered
aluminum silicates there is number of open questions dealing with the description of variation
of their properties in presence of various reagents. For this reason, it is necessary to study the
processes that take place on the phase boundary of nanoadditives [22, 23] and atomic layers
of the layered minerals, as well as to predict their physical properties.
To solve such problems, the modern experimental and theoretical research methods are
used. As experimental methods one could be mentioned X-ray diffraction and spectroscopy,
nuclear magnetic resonance method, infrared and Raman spectroscopy, electron microscopy,
chemical and thermal analysis etc. [13, 2426]. These methods provide useful information
on the structure of layered minerals, the location of different inclusions in the pores, the
presence of defects, and physical properties. However, all these methods have a number of
significant restrictions. It is particularly a rather complicated task to determine the location
and condition of the modifiers, the water molecules and the hydroxyl groups, and to specify
energy characteristics of interactions between certain particles. At the same time the
information obtained by experimental methods becomes less defined when the disorder
increases due to crystal lattice defects, and combination of different sequences of individual
mineral packets.
There are also a number of problems in studying of layered minerals modified by
nanoadditives. Primarily it is connected with the fact that the interaction between
nanoadditives and layered minerals leads to the modification of properties of interacting
components of a system. As a result, an object gets radically new properties as compared with
those of the components it consists of. By that, the existing methods do not allow reliable
describing of the complicated structure formed, particularly the absorption layers that appear.
To solve the problems discussed, in addition to experimental methods, it is necessary to
use theoretical methods based on computer simulation of complicated periodic structures and
nanosystems. These methods are based on quantum-chemical conceptions that must take into
account the structure of object under study, and accurately describe the interaction of
molecules, functional groups and active centers with the atomic groups of layered aluminum
silicate structure.
The approaches we suggest in this work, based on the application of numerical simulation
by methods of quantum chemistry and combined with experimental spectral methods, must
63
clarify the mechanisms of the interaction between different kinds of nanoscale additives and
layered aluminum silicates, and specify the correlation between electronic properties of
polyatomic systems and their physical macro-characteristics.
2. EXPERIMENTAL METHODS IN THE STUDY OF LAYERED

ALUMINUM SILICATES
The objects of study in the present work are clay minerals that belong to the class of
layered alumosilicates. The base of clay mineral crystal structure is formed by two basic
structural elements: silicon-oxygen tetrahedrons and octahedrons consisting of oxygen atoms
or hydroxyl group where the atoms of aluminum, magnesium or iron [1, 3] are located in
octahedral coordination. Joined together through common oxygen vertices, these structural
elements form two-dimensional hexagonal, tetrahedron, and octahedron grids. Tetrahedral
and octahedral grid combination forms two- or three-level packages with grid relation of 1:1
or 1:2. Clay minerals demonstrate a wide variety of groups and variations; this fact being due
to their ability to isomorphic heterovalent substitution of some Si4- or Al3+ ions with smallervalence ions (usually Al3+, Fe3+, Mg+, Zn2+ etc.). The most common minerals of this class are
montmorillonite and kaolinite studied in this work. The samples of montmorillonite were
taken from the bentonite clays of Millerovo field (Rostov Region, Russia), the samples of
kaolinite were taken from the clays of Glukhovtsy field (Vinnitsa Region, Ukraine).
Kaolinite belongs to double layer silicates marked as 1:1. Their crystal lattice consists of
double-layered packets, with one octahedron grid per one silicon-oxygen tetrahedron grid
(Figure 1).
Tetrahedron and octahedron grids are combined via common oxygen ion vertices in such
a way that the ions of Si do not lie immediately above or below the ions of Al. This
compensates the repulsive forces between similarly charged polyvalence cations. The
incomplete correspondence of tetrahedron and octahedron grid sizes leads to certain distortion
in tetrahedrons location. As a result, the voids between tetrahedrons lose their perfect
hexagonal form and become ditrigonal. Kaolinites are dioctahedral, two thirds of their
octahedral positions are occupied by Al, and one third remains vacant. The octahedrons
occupied by the aluminum ions and the empty ones form continuous series parallel to x-axis.
The crystal-chemical formula of kaolinite has the form Al4(OH)8[Si4O10]. At the same time
the isomorphism is not typical of kaolinites, though in some cases a small quantity of Al ions
in octahedrons can be substituted by Fe3+ or Mg. The hydrogen bonds between the hydroxyl
groups of the octahedron grid in one package and oxygen ions of the tetrahedron grid in
another packet ensure such a strong interaction in kaolinite that penetration of water
molecules, cations or any other components into the inter-packet spaces turns out to be
difficult [1].
Upon moistening, the size of the inter-package space practically does not change, that is
why these minerals are characterized by low swelling and water penetration capacity. At the
same time, the kaolinite crystals do swell if one inserts some organic polar liquids into their
inter-packet space and they form specific organic kaolinite complexes due to strengthening of
the hydrogen bonds, and the inter-packet distance increases up to 10 14 [1].
64
Figure 1. Structure of the crystal lattice of kaolinite. Image of the crystal lattice: a side view (A) and
plan view (B), a multilayer structure, a side view (C).
Montmorillonite belongs to the group of three-layer silicates marked as 2:1. Their crystal
lattice has 2 tetrahedron grids with vertices facing each other and an octahedron layer
between them. The tetrahedron and octahedron grids are combined via common tetrahedron
and octahedron oxygen vertices, therefore the inter-packet binding in this layered mineral is
significantly weaker than in kaolinite (Figure 2). The generalized crystal-chemical formula of
dioctahedron montmorillonite has the following form: (Ca, Mg,)(Al, Fe3+, Mg)2(OH)2[(Si,
Al)4O10] nH2O. The cations, situated in the inter-package space of montmorillonite, neutralize
the negative charge of the three-layer package that appears due to heterovalent isomorphism
in tetrahedral and (or) octahedral positions. The concentration of different inter-package
cations can vary according to the composition of the surrounding solution. In addition, the
cations can be contained in octahedrons.
Irrespective of the crystallographic location of the charge, all minerals of the
montmorillonite group are characterized by specific and important common property, a small
charge quantity caused by low isomorphism of ion substitutions in tetrahedral or octahedral
positions. The charge quantity varies from 0.2 to 0.6 of units per one elementary cell. The
small charge leads to weak electrostatic interaction between negatively charged three-layer
packages and inter-packet cations. By that, the charge of the layer is located in the
octahedrons grid situated farther from inter-packet cations than the tetrahedrons grid. As a
result of weak electrostatic bond between packets, the crystal lattice of the most
65
montmorillonite minerals represents a simple disordered overlapping of three-layer packets

with hydrated cations between them.
Capability to intracrystalline swelling and ultra-high dispersiveness result in high
physical and chemical activity of these aluminum silicates; it regularly decreases with the
increase of the portion of non-swelling inter-packet in their structure. Moreover, this feature
of this aluminum silicate enables intensive fluid penetrating into its inter-package space and,
as a result, the layers move apart and the inter-packet bond can be completely destroyed.
Additionally, the existence of inner surface and high dispersivity of montmorillonites is
characterized by a developed specific surface of 600 800 m/g, and cation exchange capacity
varying within range of 800 1500 mmoleq/kg.
The increase of practical interest in disperse materials significantly stimulated the study
of their structure. One can obtain a lot of information mainly from the methods of high
resolution electron microscopy, electron diffractions, and various spectroscopic methods.
Nowadays, one of the most informative instrumental research methods is the X-ray
diffraction method. It enables one to analyze minerals, to determine their quantitative content
and to obtain information on changes in mineral crystal lattice structure appearing as a result
of weathering and soil-forming. The advantage of this method is quickness and
reproducibility of the results. Rich information provided and a wide range of problems which
can be solved permit to use it as a basic research method in the present work.
Figure 2. Structure of the montmorillonite crystal lattice. Image of the crystal lattice: a side view (A)
and plan view (B), a multilayer structure, a side view (C).
66
Since the clay minerals are usually finely dispersed, the standard practice of X-ray
research means fractionation lesser than 1 m [25]. As the literature review shows [27 29],
there is no unified method nowadays that could allow total peptization of soil mass and at the
same time wouldnt cause the splitting of clay particles on the cleavage face. A method for
separating particles < 1 m is known where soil peptization is produced by its saturation with
univalent cations, usually natrium (a sample is sometimes treated with natrium
hexametaphosphate) [24]. Another method for separating fine grain-size particles from soil
without preliminary destruction of the organic matter and without use of chemical dispersion
reagents is centrifugation [30]. In this method the ultrasound is used as dispersing agent. The
disadvantage of the method is the necessity to tune the insonation regime depending on
mechanical and mineralogical composition of soils.
Nowadays, the procedure of sample preparation and separation of particles with size
lesser than 1 m [31], which has been used in this work, is notable for the procedure wide
application in mineralogical studies. To separate the clay fraction, a clay soil sample was
sifted through a 1 mm hole size sieve and cleared from carbonate and gypsum impurities, and
then decanted by washing with distilled water. Then thus obtained soil sample was placed
into vegetative pots with soil/distilled water ratio of 1:40. The suspension had been
thoroughly shaken in the pot until it had become homogenous and then left standing
motionless. Then, after regular time intervals determined according to [31] the upper 7 cm
suspension layers were poured off; all the solid state phase was then represented by the
particles < 1 m. Fractional precipitation went on until the suspension had become
completely clear.
The suspension obtained in such a manner was coagulated by adding the saturated
solution of 12. The excess of calcium chloride was eliminated by dialysis.
Figure 3. Grain size distribution of the isolated clay fraction.
67
The separated clay fraction was controlled by using the highly dispersed particle analyzer
CPSDC24000 in the range of 0.04 3.0 m via centrifugal fluid sedimentation [32]. Figure 3
represents the spectrum of sample granulometric composition. The results of measurements
show that 95% of montmorillonite clay fraction is represented by mineral particles of 0.04
0.07 m. Separated clay fraction of the kaolinite sample falls in the range of 0.2 0.8 m.
These data confirm the suitability of the samples thus obtained for further mineralogical
studies.
The X-ray analysis of the kaolinite clay fraction is carried out with the diffractometer
Rigaku at the Institute of Geology of Ore Deposits, Petrography, Mineralogy and
Geochemistry of the Russian Academy of Sciences in Moscow by Krupskaya V. V. The
measurements were taken under standard conditions in Bragg-Brentano geometry using
CuK-radiation and graphite monochromator. The intensities were recorded within the angle
interval 3 < 2 < 65 with scanning pitch of 0.02 and exposure time = 2 s. The samples of
montmorrilonite clay fraction were analyzed with the X-ray diffractometer DRON-7.0. The
experiment is carried out under standard conditions with CuK-radiation. The intensities were
recorded within the angle interval 2 < 2 < 40 with scanning pitch of 0.05 and exposure
time = 1 s by using natural samples. The results of experimental study are represented in
Figure 4.
The diffraction spectra were analyzed by their simulation. The calculation of diffracted
X-ray radiation is the interference pattern from overlapping of the waves scattered by
elementary-cell atoms and has the following form:
I hkl ( ) A f j ( H hkl ) j exp( i 2 (hxi ky j lz j ))
(1)
where h, k and l are the integers determining possible reflections of X-ray radiation for the
given crystal lattice, A() is the instrumental function, is the reflection angle, j is the number
of the atoms in the elementary cell, (xj, yj, zj) are relative coordinates of atoms in the
elementary cell, fj(Hhkl) is the atomic scattering factor (form-factor) of j-th atom radiation in
the direction along the reciprocal lattice vector Hhkl, j is Debye-Waller factor.
The value of the form-factor in (1) depends on the number and the distribution of atomic
electrons, as well as on the wave length and the scattering angle of radiation. In this work, it
is calculated according to [33] in the following form:
f j ( H hkl ) j r
0
sin H hkl r 2
r dr ,
H hkl r
(2)
where (r ) is the electron density of the j-th atom.

By simulating the diffraction spectra, we included the atomic thermal oscillations effect
by introducing the Debye-Waller factor which in isotropic approximation was defined by the
following expression:
68
Figure 4. Diffraction patterns of natural samples of the studied aluminosilicates.
j exp( B j sin ) ,
2
(3)
where B j is the temperature factor proportional to mean square root deviation of atoms from
their equilibrium positions.
By simulating diffraction spectra, it is important to select the instrument function
describing the profile of diffraction reflection. Normally, either Lorentz or Gaussian functions
are used; their parameters are tuned so as to fit the individual line profiles. In this work we
employed one of the most popular methods for simulation of the diffraction lines using the
pseudo-Voigt function, i.e. linear combination of Lorentz and Gaussian contributions with
respective weights determined by a variable parameter as
2
A( ) A0
H k
2
2
2 20
2 20 ,
2 ln 2
1

1 4
exp 4 ln 2
Hk
H k
H k
(4)
where A0 is the peak intensity, Hk is the variable parameter, 20 is the diffraction line center
angle, and 2 is the angle between incident and diffracted beams. The use of the Voigt
function is justified by the fact that the peak tails coming from the small size of the crystallite
have reverse quadratic terms (like in the Lorentzian function), whereas the peak profiles
caused by its microdeformations are usually close to the Gaussian function.
69
To determine the crystal structure of the aluminum silicates, we used an efficient

algorithm consisting of three stages: (i) indexing of diffraction spectra (determination of the
unit-cell syngony and its dimensions (translations and axial angles)), (ii) determination of the
structure basis (kind of particles and their coordinates in the unit-cell), (iii) detailing the
structure basis by the Rietveld method.
At the first stage we indexed the diffraction spectra of kaolinite and montmorillonite, i.e.
determined the interference indices hkl for all main lines of the diffraction spectrum. It is
known that the positions of the diffraction peaks are connected with crystal unit-cell
parameters while the intensity of the peaks gives the information on crystal space group and
atoms positions within the unit-cell. The most known methods of indexing the diffraction
spectra are represented in References [34 37]. Generally (for triclinic system that is typical
for the samples under study), the dependence between interplanar space for hkl plane set and
reverse cell parameters is expressed by the formula:
Qhkl
where
Qnkl
2
,
1 dnkl
h2 A k 2 B l 2C hkD klE lhF .
A a2 ,
B b2 ,
C c2 ,
D 2ab cos ,
(5)
E 2bc cos ,
F 2ca cos , d nkl are the interplanar distances defined by the Bragg-Wulff equation:
2d sin n , a, b, c, , , are parameters of the unit-cell.

To identify the parameters of the unit-cell, we selected six independent diffraction lines
with known indices. Then, in order to avoid the uncertainties in selecting the equations, we
made a transformation of m conditional equations to n normal ones by least-square
minimizing of deviations (residuals) of conditional equations. The system of normal
equations thus obtained gives a single solution which is the most probable. In such a manner
we obtain the following system of equations for m measured diffraction lines:
Ah12 Bk 12 Cl12 Dh1 k1 Ek 1l1 Fh1l1 Q1 1
2
2
2
Ah2 Bk 21 Cl 2 Dh2 k 2 Ek 2 l 2 Fh2 l 2 Q2 2
.........
Ah 2 Bk 2 Cl 2 Dh k Ek l Fh l Q
m
m
m m
m m
m m
m
m
m
(6)
where A, B, C, D, E, F are parameters of indicating; Qm 1 d m2 ; m are the residuals for each

value of 1 d m2 .
This system of equations is solved by standard methods of linear algebra. As fidelity
criterion of diffraction spectrum indexing for the minerals studied, we used the Smith-Snyder
criterion FN. In the process of indexing, various syngony types (cubic, hexagonal,
rombohedral and triclinic) are analyzed for a given diffraction spectrum. The indexing makes
it possible to separate a number of possible space groups to one of which the crystal structure
of the layered mineral may belong.
At the second stage of the study, the structure basis was sorted out. Basing on the results
of indexing from American Mineralogist Crystal Structure Database [38], we selected layered
70
aluminum silicates with structure close to the experimental one (for kaolinite [39 41], and
for montmorillonite [42, 43]). After that, for the strong lines of experimental diffraction
spectrum, the intensities were calculated for each selected structure with the formula (1). By
that, the agreement test for the comparison of calculation and experiment was the R-factor
determined by the formula:
R 100
I
nkl
T
nkl
E
I nkl
E
I nkl
(7)
nkl
where I
T
nkl
is the intensity calculated, and I
E
nkl
is that of experimental diffraction spectrum.
At the final stage, the basis and the parameters of the instrumental function (4) were
additionally finely tuned by the Rietveld method [44] for the selected smallest-R structure of
layered aluminum silicate. The Rietveld method is nowadays the principal method for the
refinement of structures from powder diffraction data. It can be successfully used for
nanocrystal objects up to 5 nm, when it is still possible to record the diffraction peaks, even
with low resolution.
By using this method, we optimized coordinates of the atoms in the unit-cell. As the
optimization criterion the R-factor (7) was applied. The results of determination of the
minerals crystal structure are presented in Figure 5 and in Table 1.
Figure 5. Unit cells of the studied aluminosilicates based on the results of diffractograms modeling.
71

Table 1. Lattice parameters and interatomic bond lengths for unit cell of kaolinite
and montmorillonite
Length()
b
c
kaolinite
Test [39]
5.148 8.920
Test [40]
5.155 8.945
Test [41]
5.153 8.942
This work 5.215 9.011
montmorillonite
Test [42]
5.18
8.98
Test [43]
5.191 8.976
This work 5.185 8.985
Distance()
Bond
kaolinite
O(1)-H(1)
1.006
O(2)-H(2)
1.065
O(3)-H(3)
1.102
O(4)-H(4)
1.127
O(5)-H(5)
0.970
O(6)-H(6)
0.900
O(7)-H(7)
1.075
Al(1)-O(1)
1.931
Al(1)-O(3)
1.871
Al(1)-O(9)
1.956
Al(2)-O(1)
2.035
Al(2)-O(3)
1.771
Al(2)-O(4)
1.661
Al(2)-O(5)
1.739
Al(2)-O(8)
2.060
14.535
7.405
7.391
7.460
15.00
11.32
9.9
Bond
Al(3)-O(5)
Al(3)-O(6)
Al(3)-O(7)
Al(3)-O(8)
Al(3)-O(10)
Al(4)-O(7)
Al(4)-O(10)
Si(1)-O(9)
Si(1)-O(12)
Si(1)-O(13)
Si(2)-O(11)
Si(3)-O(3)
Si(3)-O(11)
Si(4)-O(10)
Si(4)-O(14)
Angle ()
90
91.700
91.926
91.910
100.2
104.862
105.046
104.655
90
89.822
89.797
89.885
656.901
329.893
328.708
338.919
90
90
90
100.56
90
90
Distance()
kaolinite
1.912
1.975
1.798
2.054
1.970
1.857
2.072
1.747
1.725
1.588
1.448
1.461
1.677
1.559
1.663
90
90
90
697.746
518.516
461.214
Distance()
montmorillonite
1.597
1.631
1.619
1.633
1.924
1.929
1.953
Volume (3)
Bond
Si-O(1)
Si-O(2)
Si-O(3)
Si-O(6)
Al-O(1)
Al-O(4)
Al-O(5)
The elemental composition of the clay fraction was analyzed with multifunctional SPECS
microprobe using the X-ray photoelectron spectroscopy at the Rostov State Transport
University by Sidashov A. V. The natural surface of a 1 mm thick powder sample was
studied. The X-ray photoelectron spectra were recorded with the fixed analyzer energy at the
pressure of 5107 Pa. The X-ray tube operating mode was the following: anode voltage Ua =
10 kV, anode current Ia = 15 mA.
The energy analyzer is the 180 spherical deflector with median trajectory radius r0 = 50
mm. The absolute resolvable energy interval with inclusion of the AlK line-width made
1.2eV. This value was chosen as a compromise settlement as it makes possible both the study
of the inner levels of the X-ray photoelectron spectra fine structure and the elemental
composition of the surface.
72
In the X-ray photoelectron experiment, the review spectrum, and then the spectra of inner
levels were recorded. The results are given in Figure 6.
It follows from the experiment that the surface of the particles of studied material has
predominantly aluminum-silicate chemical composition. At the same time, one notes a small
content of C and K atoms in the montmorrilonite samples.
The next stage of experimental research was devoted to modification of selected samples
of the layered aluminum silicates with the ions of light metals Na, Ca, Mg, Li and estimates
of hygroscopicity of the modified samples.
The aluminum silicates were modified via the chemical method consisting of saturating
previously acid activated samples by various reagents. The acid treatment is a widespread
method to affect material structure. According to the results of [45, 46] the strongest reagent
is sulfuric acid. It is believed that the following effects are the most probable:
(i) displacement of alkaline and alkaline-earth metals, iron and aluminum off the
mineral, formation of unsaturated valence bonds and increase of the surface as the
salts of the mentioned metals pass into solution,
(ii) increase of free silicic acid SiO2 (by 15 20 %) and aluminum oxide (aluminum
sulphate hydrolysis product),
(iii) substitution of the alkaline metals in groups [14/2]+ by + or 3+, which can
interact in their turn with one of the four lO bonds in aluminum-oxygen
tetrahedrons and break it with the formation of the hydroxide group,
(iv) retention of the structure of the source material to a considerable degree.
To be modified, the mineral samples were dried during two hours at the temperature of
130 . The dried material was mixed with sulfuric acid of the concentration lesser than 2.33
mol/l (20 % of mass) in mass relation 1:3 and was activated for an hour by continuous stirring
and heating in water bath. The obtained pulp was filtered by vacuum pump through a
synthetic fiber filter up to pH = 4.
Then the sediment after activation was washed by distilled water up to = 4, then it
was flooded with 0.1 reagent solution in relation 1:22 (volume) and placed into electric
mixer ( = 2 hours, = 55 C). After that it was filtered and washed until the HCl traces
appeared (they were controlled by adding the silver nitrate solution until light dregs appeared)
and placed into the drying box for two hours at 100 150 . As reagent solutions, MgCl2,
NaCl, CaCl2, LiOH were used.
The influence of the modification on surface properties of aluminum silicates was
evaluated according to values of water vapor adsorption. For the measurements, we used
510 g samples dried to their constant mass (approx. 8 hours) at the temperature 105 2 C.
They were kept open during 24 hours at fixed temperature and air humidity.
The study has shown that the modification of kaolinite by the ions of Na, Ca, Mg leads to
the increase of adsorption (Figure 7). Since the penetration of ions into the inter-packet space
is handicapped, such behavior of the adsorption can be explained by the modification of
mineral particle surfaces. On the contrary, the modification of kaolinite with the ions of Li
leads to the decrease of adsorption of the mineral as compared with other modified forms of
this mineral. The results of experimental study of adsorption properties of the modified forms
of kaolinite compare well with the results of theoretical studies presented in Section 3. One
73
can see direct correlation between the equilibrium inter-packet distance determined in theory
and the adsorption value of modified kaolinite forms we have studied.
The analysis of the data in Figure 7 for the adsorption values of modified montmorillonite
forms shows that the greatest effect on this material arises from lithium. One can see in this
case that the adsorption values decrease as compared with all studied forms of
montmorillonite. Note that the largest value of adsorption is seen for montmorillonite
modified by the Mg ions.
Figure 6. X-ray photoelectron spectra of the studied aluminosilicates samples.
74
Figure 7. Hygroscopic moisture of the studied aluminosilicates.
3. SIMULATION OF ELECTRONIC STRUCTURE AND

LAYERED ALUMINOSILICATE PROPERTIES
The mathematical methods are widely used to calculate parameters of crystal structure,
clusters and molecules, as well physical properties and reactivity of different chemical
compounds. These methods along with traditional methods of physical and chemical
experiments are currently considered to be one of the main instruments of scientists engaged
in research work and development of new materials of wide application spectrum. These
methods rest on computational methods of quantum chemistry, where the structure and the
properties of chemical compounds, their interaction and transformations in chemical reactions
are analyzed based on the ideas and methods of quantum mechanics [47, 48].
Modern methods of quantum chemistry make it possible to describe various physical and
chemical properties of molecular systems: molecules and periodic structures. Electronic and
spatial structures of molecular systems within the accuracy are compared with data of
experimental methods. When using quantum-mechanical computational methods one cannot
only calculate the most important properties of molecular systems but also get information on
such characteristics that sometimes are inaccessible or difficult to assess in experimental
research.
To describe properties and behavior of many-electron systems as atoms, molecules and
crystals, according to the principles of quantum mechanics, we use the Schrdinger equation
having the following general form:
H x1 ,..., x N ,..., R1 ,..., RN Ex1 ,..., x N ,..., R1 ,..., RN ,
(8)
75
where x1 is the coordinate of i-th electron and Ri is the coordinate of i-th atom of a manyelectron system.
In (8), H is the Hamiltonian operator of the system which has the following form if
external electric and magnetic fields are absent:
1 N
1 M 1 2 N ,M Z j N , M Z i Z j
H i2
j
.
2 i 1
2 j 1 M j
i j 1 rij
i j 1 Rij
(9)
The wave function of i-th state i x1,..., xN , R1,..., RN depends on 3N spatial and N
spin electron coordinates, and 3M coordinates of nuclei. It meets the normalization condition:
x ,..., x
1
, R1,..., RN dV 1 .
2
(10)
Because of great mathematical difficulties, Equation (8) has no exact solution for a manyelectron system. It is then substituted by the approximations that can be divided into three
classes: non-empirical, semi-empirical, and density functional method [49].
In non-empirical calculation methods (ab initio starting from the beginning) one
does not use the parameters extracted from experimental data. In semi-empirical methods one
introduces in the equations the parameters that are directly taken from the experiment or
chosen in such a way that the calculation of a certain set of reference compounds reproduce
the experimental data on the properties of those compounds best of all. The density functional
method takes the intermediate position, because it uses a number of parameters
approximating the results of theoretical calculations of electron gas properties.
When analyzing complicated polyatomic system such as crystals of layered aluminum
silicates and nanoparticles, the most suitable calculation theoretical approach to study their
properties is one of several realizations of density functional theory (Density Functional
Theory, DFT) [50, 51]. It is caused by the presence of effective exchange-correlation
functions, the use of plane waves in calculation model, and rather low resource and computer
requirements which allows performing calculations on rather large periodic structures.
The DFT method, even when using local density approximation (Local Density
Approximation, LDA [52]) yields in certain cases satisfactory results comparing well with
experimental data. At the same time, the calculation resource requirements are not high as
compared with other approaches to solution of multiparticle problem in quantum mechanics;
this allows using it for the calculations of crystal structures under study. The progress in
describing the exchange and correlation interactions made the DFT method one of the main
methods for solving the condensed state physics problems.
This approach is based on the construction of electron density (r) of electron system
using the spin-orbitals i obtained by solving the equation of the following kind:
1 2
2 Veff (r ) i i i ,
(11)
76
with the local effective potential:
Veff (r ) Vext (r ) VH (r ) V XC (r ) ,
where VH (r )
r r d
(12)
r is the Coulomb (Hartree) potential, Vext (r ) is the external
potential and V XC (r ) is the exchange-correlation potential.

As the methods of quantum chemistry and computational algorithms were advanced and
the computer technology spread, a great number of software packages for simulation of
molecules, clusters and periodic structure were developed in the past few decades.
All quantum-chemical computer codes are characterized by their own operational
functionality and peculiarities. The difference between them consists in mathematical
methods being used for the realization of principal algorithms, computing platforms
(operating system type, computer type, parallel computing capability etc.), means of the result
interpretation, interfaces. At the same time all quantum-chemical codes use the same
approach to obtaining the wave function of many-electron system.
Nowadays, there is a number of software packages used for quantum-chemical
calculations. Below we give a brief review of the most popular quantum-chemical software
packages.
GAMESS (General Atomic and Molecular Electronic Structure System) is a software
package to compute energy, geometry and molecular structures, as well as a variety of
molecular properties in gas phase and solution, in ground and excited states. For this purpose
the program contains a lot of algorithms for various computational methods of quantum
chemistry showing different accuracy grade and computing load, beginning with the simplest
and fastest semi-empirical methods AM1 and PM3, and ending with the most precise but
computer-resources-consuming MCQDPT and MP4-SPTQ. The main features of the package
are: calculation of electron correlation energy based on the perturbation theory, configuration
interaction, coupled cluster, and density functional; automatic geometry optimization, search
of transition states using analytical gradients; calculation of molecular properties such as
dipole moments, electrostatic potential, electronic and spin density. GAMESS software
modules support parallel calculation regimes, both on multi-processor computers and on
clusters of workstations. GAMESS is available almost for all known hardware. There are
several versions of this software product. The American version of the code GAMESS (US)
[53] is free (noncommercial) software and is maintained by the Ames Laboratory group. The
English variant GAMESS (UK) Ames Laboratory [54] is maintained by Daresbury
Laboratory group.
PC GAMESS/Firefly [55] is a software package for theoretical study of molecular system
properties. It is based on the codes of the GAMESS (US) software package, but differs in
platform-specific parts (parallel running, memory allocation, etc.), in mathematical functions
(for example, matrix operations), in quantum chemical methods (Hartree-Fock, MllerPlesset theory, and density functional theory). The advantage of this package is a large-scale
coverage of principal quantum chemical computing algorithms and availability for a large
number of processor architectures and parallel calculation media. Since 2008 the project is
dissociated from GAMESS (US) and renamed into Firefly.
77
Another widely known product in the field of molecular system computer simulation is
the software package Gaussian [56], created by Gaussian Inc. This software product is
distinguished by a wide range of quantum chemical calculation methods, high efficiency, and
user friendly interface. The Gaussian software package allows computing molecular
structures and their energies, electron, Raman and vibrational spectra, potential energy
surfaces, a variety of molecular properties in the gas phase and solution in ground and excited
states etc. In this software product the methods for taking correlation energy into account are
available: energy calculation and analytic gradient optimization for perturbation theory,
coupled clusters, configuration interaction, density functional, multiconfiguration selfconsistent-field methods are possible. The Gaussian software package allows using highperformance computing clusters. The latest versions of the software permit to simulate very
large-scale molecular systems due to a molecule partition procedure ONIOM. As the
disadvantages of the Gaussian software package, one can mention a relatively slow operation
speed and high hardware requirements. The software is available on a commercial basis.
The software program PRIRODA [57], developed by D. N. Laikov and Yu. A. Ustynyuk
from Moscow State University is an example of an original approach to solve the resourceintensive problems of molecular simulation. Using the density functional method PBE
combined with triple-zeta basis set this software product can decrease calculation expenses
when calculating Coulomb integrals to N instead of N4. Along with DFT, the perturbation
theory and coupled-cluster methods are available. It is possible to use Dunnings correlation
consistent basis sets and pseudopotential basis sets taking relativistic corrections into account.
PRIRODA program suite was developed for parallel computing on multiprocessor systems
with shared or distributed memory, driven by Unix-like operation systems. The initial code is
written in C language using a standard message passing interface MPI. The program can
easily be adapted for calculations on single-processor workstations and personal computers
working under various operation systems. As disadvantages of this program suite, we can
mention a limited number of calculation methods, for example, it is impossible to include
diffuse shells or additional polarization functions in the basis set.
Among the software products aimed to simulation of nanosystems we can mark out the
software package Materials Studio [58]. Materials Studio package contains more than 30
modules with various functional capabilities. It is distinguished by its user friendly interface
and one makes it possible to exchange the models under study between different calculation
modules that can calculate molecular structure properties within the framework of quantum
mechanical, semi-empirical, parametrized empirical and classical representations. This
software kit was developed and is distributed by the American company Accelrys Software
Inc. This software is used in advanced theoretical research in chemistry, material science,
nanophysics. Materials Studio provides the instruments to construct, modify, and compute
molecules and periodic structures, using DFT, QM/MM and semi-empirical methods. An
important part of this software package is the possibility to simulate periodic systems and
surfaces. The Gaussian program suite interface is available. This software is a commercial
product.
ABINIT software package [59] is one of the most popular and easily available
instruments to calculate electron spectrum, space structure and macroscopic properties of
various systems including large organic molecules and nanoparticles with high computational
complexity. Besides the integrated MPI, based on support of parallel calculations, ABINIT
enables parallel running of executed tasks. The ABINIT program suite allows solving the
78
following theoretical problems: calculation of total energy, charge density, electron structure
of atomic systems (molecules and periodic structures), and other physical and chemical
properties. These problems are solved via the use of local density approximation with
pseudopotentials and various bases, i.e. plane waves, augmented plane waves. In addition,
with ABINIT one can make molecular and crystal structure optimizations, solve molecular
dynamics problems, and calculate various macroscopic properties of the objects under study:
dynamic, dielectric, mechanical, magnetic, thermodynamic and other characteristics. The
ABINIT software package is a non-commercial product.
CRYSTAL [60] is one of the packages using the DFT method. The constrained and
unrestricted Hartree-Fock methods and hybrid methods are also available. The program suite
is developed at the University of Torino and distributed on commercial basis. The software is
aimed to the calculation of properties and wave functions of periodic systems, vibration and
phonon spectra, dielectric permittivity, optical and other properties of crystals.
HyperChem [61] is a commercial software product for quantum chemical simulation of
atomic structures. The HyperChem program suite is popular enough among novice scientific
chemists especially due to its intuitive graphic user interface. It incorporates the methods of
molecular mechanics, quantum chemistry and molecular dynamics. The force fields that can
be used in HyperChem are MM+ (based on MM2), Amber, OPLS and BIO+ (based on
CHARMM). Semi-empirical methods are available: extended Hckel method, CNDO, INDO,
MINDO/3, MNDO, AM1, PM3, ZINDO/1, ZINDO/S. Ab initio methods and density
functional methods are also available. The program suite has excellent visual representation
facilities that could be used both in preparing the input information (molecular structures) and
in analyzing the results, for example, calculated characteristics of IR and UV spectra.
HyperChem software package can be used with other quantum chemical software
(Brookhaven PDB, Sybyl MOL2, and MOPAC). The advantage of this program suite is a
large database of molecular fragments for easy making of the input geometry. Since the
HyperChem software package is not fit for computing large molecular structures and may
consume much time and computer resources, it is mainly used in teaching. As disadvantages
of the HyperChem software package, one can mention an inefficient use of computer
resources which results in significant time spending, a narrow choice of basis sets and the
methods to account for electron correlation. The inclusion of symmetry is only possible
through the geometry input in the form of Z-matrix; it reduces significantly the value of
interactive simulation of molecular structure.
Among the fastest and resource-saving quantum chemical software programs for semiempirical calculation is the MOPAC package [62]. It is a free software package used for
computing electron structures of ground and excited states of atoms and molecules. In
MOPAC the semi-empirical methods RM1, MNDO, AM1, PM3, and PM6 are available. The
MOPAC software product is able to perform calculations of molecular orbital energy,
formation heat, derivatives of molecular energy with respect to molecular geometry change.
In this way, it is possible to calculate vibration spectra, thermodynamic parameters, isotopic
substitution effects and dynamic constants for molecules, radicals and ions, as well as
transition state structure on the potential energy surface. The latest versions of the software
package include the MOZYME program for studying the electron structure of
macromolecules and they make it possible to compute large (up to 15,000 atoms) molecular
systems using localized molecular orbitals.
79
Besides the software packages briefly discussed above and being distributed free or on
commercial basis, there are other algorithms of quantum chemical calculations that differ in
their functionality and content (ADF, Quantum ESPRESSO, ORCA, Q-Chem, VASP, DLPOLY, GROMACS, TINKER, SPARTEAN, NWChem, NonoEngineer, COSMOS, Amber,
AMPAC, TURBOMOLE, MPQC, Schrdinger Suite etc.). The choice of a specific software
product is determined by a specific problem and computational capability of available
computers.
One of tools used for solving the problem of studying the properties of modified
aluminum silicate and the processes on those minerals atomic layers inter-phase boundary and
on non-additives boundaries, are the software products ABINIT and NWChem based on the
density functional theory. Below we show the results of this programs package application for
solving the mentioned problems.
By using the DFT in crystal system calculations, it is important which approximation is
chosen for an unknown exchange-correlation functional (local density approximation LDA,
gradient approximation GGA [63 68], multimodal approaches).
On the computational base, the determination of the electron structure in the context of
DFT can be made easier by introducing pseudopotentials in the model. These
pseudopotentials consider the fact that electrons sitting on tightly bonded filled electron shells
of atoms practically do not change their state upon interaction with other atoms (chemical
bond creation and breaking etc.). In such a manner within the model the electrons can be
divided into valence electrons whose Kohn-Sham wave functions are calculated and core
electrons described by effective pseudopotential. When constructing pseudopotentials one
usually demands correspondence between the valence electron wave-functions in complete
all-electron and pseudopotential representations.
To analyze the applicability of existing exchange-correlations potentials when studying
the electron structure of aluminum silicates, we calculated the total energy in local density
approximation (LDA) and in generalized gradient approximation (GGA): PBE, RPBE, PW91,
WC, PBESOL, where nuclear potentials and core electron potentials were calculated with
pre-generated atomic norm-conserving pseudopotentials. Electrons Bloch functions of the
crystal are found as plane-wave basis decomposition with cut-off energy of 350 eV. To
generate the k-points we used the Monkhorst-Pack method [69] with a 3 1 1 grid sizes.
The condition for convergence of self-consistent calculations was invariability of systems
total energy within 105 eV.
The calculation results are represented in Figure 8. The analysis of the potential curves
shows that for both types of studied minerals the systems energy minimum is reached when
the exchange-correlation potential PW91 had been used.
The adequacy of the calculation methods chosen can be verified by calculating vibration
spectra of the studied minerals and comparing them with the results of experimental studies
performed on Fourier-transform IR spectrometer ALPHA by Bruker Optik GmbH, Germany
by frustrated total internal reflection method (Figure 9).
The vibration spectra are calculated in generalized gradient approximation (GGA) with
PW91 potential and electron Bloch function plane-wave basis decomposition with cut-off
energy of 350 eV. To generate the k-points we used the Monkhorst-Pack method with 3 1
1 grid size. The results of the research are shown in Figure 9.
80
Figure 8. Dependence of the minerals total energy (per one unit cell) on the magnitude of inter-package
space.
Figure 9. The IR spectra of the studied aluminosilicates samples.
81
One can see that the calculation agrees well with experiment. The analysis of the
frequency spectrum for kaolinite (Figure 9, 10) shows that the presence of the absorption
bands in the 1000 1200 cm1 region is due to the valence vibration of Si-O bonds and the
deformation vibrations of the - bonds in the gibbsite layer; among them the most intensive
bands are those with frequencies of 1007 and 1029 cm1. The absorption in the 900960 cm1
region is caused by the deformation vibrations of the -groups of aluminum-oxygen
kaolinite octahedrons.
The group of absorption peaks in the interval from 3600 to 3750 cm1 is caused by
valence bonds of O-H gibbsite layer in kaolinite; these include absorption at frequencies of
3618, 3649, 3673, and 3688 cm1.
The analysis of frequency spectrum for montmorillonite (Figure 9, 10) showed that the
observed broad band with the maximum at 1004 cm-1 is due to valence and deformation
vibrations of Si-O bonds.
Figure 10. The calculated lattice vibrations of the studied aluminosilicates.
82
Similar assignment can be performed when studying the effect of modification of the
layered aluminum silicates on their physical properties.
The follow-up theoretical calculations are carried out in the context of the previously
chosen approximation for the exchange-correlation functional using the parameters of
unmodified sample basis set. The ions of Li, Mg, Na and Ca were taken as modifiers. The ion
concentration in the model is set to be 1 ion per mineral elementary cell. The curves of
potential energy and electron state densities have been calculated for studied minerals and
their modified forms.
Figure 11. The total density of electronic states for the unit cell of the aluminosilicates studied and their
modified forms.
83
Figure 12. Curves of the total energies of interaction of the studied aluminosilicates and light
metal ions.
Figure 13. Variation of hygroscopic moisture of the studied aluminosilicates, with their modification of
light metals ions.
84
The calculation of total and partial electron state density for modified forms of kaolinite
(Figure 11) shows that the additional intercalation of ions into the inter-packet space leads to
the band gap width reduction along the Li > Mg > Na > Ca sequence. The results of similar
calculations for montmorillonite (Figure 11) indicate that the band gap width correlation has
the following form: Ca > Mg > Li > Na. In both cases the modification of layered aluminum
silicates leads to band gap width reduction which is caused by the appearance of an additional
impurity levels in the band gap. Such a modification, reached by respective concentration of
metal ions, can increase the electron conductivity of these materials. It is worth noting,
however, that the classical DFT exchange-correlation functionals lead to undervaluation of
band gap width. It is also known [70, 71] that the calculation error is connected with wrong
description of excited state properties and some special features of density functional itself.
For more exact theoretical estimates of band gap width one can use the corrections suggested
for example in the work [72], and the so-called hybrid functionals as well. The most popular
among such functionals is B3LYP [73], containing an exact exchange contribution calculated
within the Hartree-Fock method. The inclusion of Hartree-Fock exchange makes it possible to
include the non-locality of the exchange energy, but computational and time resource
requirements increase significantly.
The calculation results for potential curves given in Figure 12 make it possible to
estimate the inter-packet distances of the objects under study. Figure 13 shows the variation
of water mass fraction absorbed by the modified samples of kaolinite and montmorillonite in
relation to the initial form. Experimental results are obtained according to the data represented
in Figure 7. In the case of montmorillonite one can see correlation between experimental and
theoretical results, and this fact can explain the hygroscopic behavior by inter-packet space
increasing.
In the case of kaolinite the penetration of ions into the inter-packet space turns out to be
difficult [1, 3, 24]. In this context it is possible to compare experiment and theory if the
theoretical results are given in relation not to initial form, but to a certain variable value
accepted to be 4.7 which characterizes the distance between the mineral particles in the
sample.
To conclude, the analysis of theoretically calculated curves of mineral-nanoadditives
interaction total energies makes it possible to evaluate the sorption properties of the objects
and, in the case of montmorillonite, to establish correlation between the inter-packet distance
corresponding to equilibrium state of the crystal system and macroscopic properties of
minerals.
ACKNOWLEDGMENTS
The work was carried out with partial financial support from the Ministry of Education
and Science of Russian (project codes Nos. 16.513.11.3125, 14.132.21.1666).
85
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ISBN: 978-1-63321-239-8
Chapter 4
INVESTIGATIONS OF DEFECT FORMATION

DURING SAPPHIRE CRYSTAL GROWTH
S. P. Malyukov1, Yu. V. Klunnikova1 and I. A. Parinov2
1
Engineering Technological Academy, Southern Federal University, Taganrog, Russia

2
Vorovich Mechanics and Applied Mathematics Research Institute,
Southern Federal University, Rostov-on-Don, Russia
ABSTRACT
Crystal growth processes provide basic materials for many applications. Heat and
mass transfer at all stages of sapphire crystals production were studied. The theoretical
model for the stress and bubbles formation in sapphire crystals is presented. The
mathematical simulations and calculations allow us to estimate the large number of
factors influencing the crystals growth and quality and to determine the main cause of the
defect structures formation in the solid phase. Finally, by means of various experimental
methods the preliminary results of study of different defects in sapphire polished and nonpolished samples were obtained.
1. INTRODUCTION
The big size crystals growth with improved structural characteristics became a priority of
modern science and equipment. In the last decades the Czochralskys method, Kiropouloss
method, the horizontal directed crystallization (HDC) method and Stepanovs method were
applied for big size monocrystals growth. These crystals were widely used in electronic
technique [1].
The sapphire crystal quality can be characterized by the orientation, density and the
nature of point defects distribution, density of single dislocations, extention of block borders
and their disorientation, the value of residual tension, chemical purity and impurity
heterogeneity [2 13].
E-mail: malyukov@fep.tti.sfedu.ru
90
S. P. Malyukov, Yu. V. Klunnikova and I. A. Parinov
The impurity atoms placed in nodes and lattice interstices belong to the point defects. The
position of the impurity atoms is defined by the energy of their implantation. The impurity
atoms try to occupy the nodes of closest to them on the chemical nature of atoms. As a rule,
the small-size atoms are located at the lattice interstices. The implantation of the big-size
atoms can be possible only in the case of defects like dislocations and block borders.
There are some mechanisms of dislocation formation during crystals growth from the
melt [14]: (i) growing dislocations from the fuse crystal, and also the growing dislocations
during crystal growth; (ii) plastic deformation caused by the thermoelastic tension; (iii)
impurity capture by the growing crystal (the impurity mechanism); (iv) disk-shaped vacancies
accumulation and subsequent formation by them of dislocation loops (the vacancy
mechanism); (v) incoherent accretion in the conditions of incomplete compliance of germs,
growth layers, dendrites branches. The critical dislocations density on the plane (0001) for the
sapphire grown by the HDC method is (2 3)104 cm2.
The point of view about temperature stresses in the growing crystal as the main source of
dislocations was already strongly approved. The theory of their formation during crystal
growth was developed by V. L. Indenbom [15, 16]. The formation of dislocations occurs
under influence of the internal stresses caused by nonlinearity of temperature distribution in
the growing crystal. If the value of the thermal stresses exceeds the critical magnitude (2950
MPa) then the conditions for formation of the structural defects will be created in the material
volume.
The micro- and macroblocks are ones of the most important defects in crystals. The
analysis of blocks in various crystals allowed one to reveal the following mechanisms of their
formation: vacancy, impurity, inheritance of fuse crystal borders, polygonization, incoherent
accretion of layers [17].
The common condition of pore formation (from sub-micronic scale up to 3 5 mm) is the
saturation of melt by the dissolved gases, the main source of the gas saturation is the melt
dissociation and also melt interaction with impurities in powder, container, and medium. At
high concentration of such defects (more than 105 cm3), the material becomes unsuitable for
optical application. The bubble with the size, which to be lesser than the critical one, is
pushed off by the crystallization front. At weak liquid mixture the concentration consolidation
[17] and increase in the sizes of bubbles lead to their contact with the front of crystallization
and their keeping by forces of superficial tension. As the crystal growth over the bubble is
complicated, the pore is formed in the solid phase.
It is difficult to avoid an overheating of separate zones of the container, and, therefore,
the melt during sapphire growth with the use of the container. The moving front can take the
colder micro-volumes of melt. In this case, the voids are formed during crystallization of
these micro-volumes because of the difference between densities of crystal and melt. The
melt dissociation is not only source of melt gas saturation. Such elements of technological
process (the initial raw materials, crucible, atmosphere, constructional materials of growth
equipment) have serious impact on the formation mechanism and the gas structure of voids.
Thus, the determination of functional dependences of the real crystal parameters on
conditions of its growth remains to be the paramount task, because the solution of the
problem of growth sapphire crystal with definite and preliminary given properties depends on
it. The detailed analysis of processes and the environment structure from which monocrystals
Investigations of Defect Formation during Sapphire Crystal Growth
91
grow up allow us to change or improve growth conditions for processing high-qualitative

crystals.
2. HEAT PHYSICAL PROCCESES INFLUENCE ON FORMATION

OF BUBBLES DURING GROWTH OF CRYSTALS
The formation of bubbles in the melt and their capture by the crystallization front are one
of the problems during sapphire crystal growth by the HDC method. It is shown in the
photographs of the crystals taken at lighting, and presented in Figure 1.
(a)
(b)
Figure 1. Inclusions in sapphire crystals: (a) at the distance of 60 mm from the fuse, b) at the distance of
250 mm from the fuse.
Figure 2. Scheme of position of the crystallization front and bubbles congestion at various stages of
growth (the arrow shows the direction of crucible movement).
It is noticed [18, 19] that at the different stages of growth the position and form of
congestions of the bubbles are various. The largest problem for removal of the bubble
congestions is to locate the bubbles in the benthonic zone beginning approximately at the
distance of 250 mm from the fuse in the case of the container length of 320 mm. It is shown
schematically in Figure 2.
At capture, the bubble positions are defined by the movement speed of crystallization
front and its form [7]. It is actual the problem to define position and the crystallization front
form during sapphire growth and to reveal the factors influencing on growth kinetics at
various stages of crystal growth. In the case of HDC, the projection of Archimedean velocity
on the direction of front movement is zero, and the direction of the temperature gradient in
the melt T coincides with the direction of growth front velocity.
92

Let consider the thermocapillary force in the stationary mode [14, 20]:
Fk 2r 2
T ,
T
(1)
where T is the direction of the temperature gradient in the melt, r is the radius of gas
bubble, is the surface tension between gas and liquid boundary must be equal to the force
of the medium viscous resistance [21]:
Fc 6rvk .
(2)
The rate vk of the bubble thermocapillary movement relatively to the liquid can be
determined by the formula:
vk
r
T ,
3 T
(3)
where is the dynamic viscosity of liquid. It is also considered that for the majority of liquids
the derivative T 0 . At the rate va 0 , the velocity vp of the bubble relatively the
growth front (vf is the front velocity) is defined as
vp
r
T v f .
3 T
(4)
As we can see from (4) in the ensemble of bubbles in the melt, there are bubbles of
critical size r * , at which the bubble motion direction relatively the crystal growth surface is
changed. Gas bubbles with the size
r r
3 v f
T T
(5)
will move in the direction from the front, and smaller bubbles r r will move in the
opposite direction.
Bubbles with the radius r r , appeared at surface of phase transformation during
crystallization will be captured by the growing front. So they create system of steady defects
into material volume.
It is necessary to calculate the temperature distribution in equipment for the sapphire
crystal growth by the HDC method for defect diagnostics. The temperature distribution
determination in the crystal-melt-crystal powder system is defined by solution of the heat
conductivity equations [22]:

Ti ( x, y, z, )
T ( x, y, z , )
T ( x, y, z, )
T ( x, y, z, )

ai i
ai i
ai i
z
z
Ti ( x, y, z, )
W
,
x
93
(6)
where i 1,2,3 corresponds to the crystal, melt and crystal powder, respectively, ai is the
heat diffusivity coefficients ( ai
i
, where i is the thermal conductivity coefficient;
i Ci
i is the material density; Ci is the specific heat); W is the container movement speed.
The results of temperature calculation in the crystal-liquid-powder system are present
in Figure 3. The temperature fields in the crystal-liquid-powder system are shown in Figure
3, a. The temperature fields in vertical crystal cross-section are present in Figure 3, b.
(a)
(b)
Figure 3. Temperature distribution in crystal-liquid-powder system.
The results showed that the melt width enlarged with heat temperature increase on 300 K
and, as a result, the crystallization front location changed. So, we can conclude that we have
possibility to control the crystallization front location by heat temperature increase and it can
lead to redistribution of the defects.
The temperature gradients allow us to estimate the sizes of forming vapor bubbles. At
bubble capture, the ratio of rates of the crystal growth to bubble defines a final form of the
inclusion. The received dependences of average size of the bubbles on the growth speed can
be explained. At the set of crystallization speed, the bubbles with certain radius can be
characterized by the greatest probability of capture. The increase in growth rate will lead to
increase the probability of bubble capture of the larger size.
So, it is known that the crystal growth rate influences on the capture of impurity and
foreign inclusions by the front of crystallization. The dependence of segregation effective
coefficient on the interface of phases on growth rate can be determined in the form [1, 18]:
K eff
K0
,
K 0 1 K 0 exp( v / D)
(7)
94
where 0 is the equilibrium segregation coefficient, is the depth of the area with raised or
lowered concentration of impurity at the crystallization front, D is the diffusion coefficient of
impurity in melt, v is the crystal growth rate. At the intensive interfusion 0 or at the
small crystallization speed v 0, Keff 0, the impurities and bubbles are taking away in
melt. When the growth speed v >> D/, i.e. exp(v / D) 0, and = 1, it means that all
eff
bubbles and impurity are taken by crystal.

The growth rate depends on position of the container relatively the heater and increases
throughout the process of sapphire crystal growth in the conditions of large temperature
gradients [18]. The effective coefficient dependence at the various stages of growth is shown
in Figure 4.
Figure 4. Effective coefficient of segregation depending on the crucible position: 1 the gradient in
melt is 1000 K/m, 2 the gradient in melt is 500 K/m.
From Figure 4, it is visible that only at the initial stage (x = 0.1 m) the effective
coefficient of the segregation is close to equilibrium value. It is defined by small growth rate.
Thus the crystal grows without foreign inclusions. As you can see from the figure the
effective coefficient of segregation does not depend on temperature gradient in melt,
practically.
2. RESEARCH OF INTERNAL STRESSES IN THE CRYSTAL

BY POLARIZING AND OPTICAL METHOD
The role of thermal tension as one of the factors defining structural perfection, and,
therefore, the final quality of sapphire, is now recognized conventional. The analysis of real
processes of sapphire crystal growth shows that sub-structural zones as different sources of
95
tension are formed practically always in volume of crystals. The sectors of the faced growth,
the strip of growth and solid-phase inclusions are the main ones from them.
The sapphire crystal observations in parallel polarized light allow us to view the internal
stress distributions in them. The polarizing and optical method of internal stress definition
consists of the double refraction measurement [1, 18]. It is known, that by viewing the basis
plane along the optical axis, the observable double refraction is defined by internal stresses
since in this direction own crystal double refraction is absent. In this case the double
refraction is proportional to the difference of the main stresses 1, 2, acting into plane,
which is perpendicular to the direction of observation:
= ij(1 2),
(8)
where ij = 2.13105 kPa1.

By measuring the difference between courses of beams (the fluctuation direction of one
of them disposes along the geometrical axis of the crystal, the other direction is perpendicular
to it), it is possible to calculate the average value of axial pressure along the direction of
observation. With this purpose, the measured difference of course G (also frequently named
the value of abnormal double refraction) in the given crystal area is necessary to divide on
crystal thickness h and the photoelastic constant is defined as
= G/(hij).
(9)
The stresses in sapphire samples are defined on the polariscope-polarimeter PKS-125 or

konimeter IPL-51. By means of these devices the difference of courses of the beams G = 3
where is the measured rotation angle of analyzer. By substituting the relation G = 3 in the
formula (9), the average value of tension in crystal is defined. The error in measurement of
the double refraction value by the polarizing and optical method is equal to about 3% of the
measured size. The method disadvantage is the measurement of the main stresses difference
only along the crystal optical axis.
The given method allows us to define not only the average value of stresses in grown
crystal, but also the influence of grinding on the residual stresses. For the solution of this task
the samples are prepared by the following way. The cubes with the sizes of 5 5 5 mm3 or
10 10 10 mm3 are cut out. Their two planes have orientation (0001). These planes are
polished and further do not machine any more as size is measured along the direction (0001)
and polarized light passes through these two planes. At the definition of contribution of the
machining certain type in the internal tension, the value of 0 is measured in the sample before
processing the lateral surfaces, then the four planes which are perpendicular to the basis
planes are processed and the size is measured again. The contribution of this type of
processing is estimated by the relative change of tension in the sample.
3. MODEL OF RELAXATION OF STRESSES IN SAPPHIRE CRYSTALS

The research technique of stress relaxation in sapphire structures [23] has certain
limitations. The reason is the fragmentariness of its description complicating reproduction.
96
The authors suggested one of the variant for model of the stress relaxation. The introduction
of temporal distributions of structural and stress relaxations depending on temperature was
proposed.
The studies of the stress relaxation were carried out by using the polarimeter PKS-125.
The sapphire sample was stabilized at some temperature T during time. This time is enough
for the structural relaxation completion (i.e. the state at which equality of the actual and
structural temperatures T = Tf was reached).
The mathematical calculation of the numerical results was conducted by using an
algorithm having much in common with algorithms of the work [24]. In the assumption of
thermorheological simplicity the calculation of stress relaxation in these algorithms was
carried out by using the following equation:
t
(t ) n
g i exp ,
(0) i 1
i
(10)
where g i is the weight coefficient (specific contribution) for i-th process and
gi 1 ,
t is
i 1
the time, i is relaxation time, connected with the viscosity factor and constant K i ,
independent on temperature and equal to the viscosity value at i = 1 in the ratio. Thus,
distribution of relaxation times, completely described by sets of values ( g i , K i ), remained the
same at any temperature.
The refusal of the thermorheological simplicity assumption demanded entering changes
in algorithms [24]. In new algorithm, the coefficients g i in (10) did not depend on
temperature, and values of i were determined by Fulchera-Tammans equation used for the
description of temperature dependence of viscosity in the wide interval of temperatures:
lgi = A + Bi/(T T0)
(11)
lgi = Ai + Bi/(T T0),
(12)
or
where A and T0 are the constants which are general for all n terms of the series, Ai and Bi are
the constants which are characteristic only for i-th term of this series. Thus, in equation (11)
at the tendency of return temperature to zero, the values of all i aspired to the same value of
0 that provided continuous shorting of the relaxation times range with temperature growth.
This change of the range is well agreed not only with data [25], but also with large
volume of ultrasonic studies of melts in the wide interval of temperatures [26]. However, if
the application of equation (11) does not allow one to describe available experiment with the
demanded accuracy, it is necessary to enter correction of the dependences of relaxation times
on temperature for the separate relaxation processes, using the equation (12), where
i = / Ki.
97
(13)
The other change of calculation algorithm concerns of dependences of the relaxation

times on temperature in the conditions of the "frozen" structure (at Tf = const). Such
dependences are described by Arrheniuss equation:
lg = lg0 + Bg/T,
(14)
where 0 and Bg are the constants. Since according to the relaxation theory the values of are
the function of structure temperature, one of constants in (10) sould depend on Tf. In
algorithms [24], it was proposed that 0 = f(Tf) and Bg did not depend on Tf. In work [27] the
opposite principle for calculation of stress relaxation times was accepted for the first time. So,
0 does not change with Tf and Bg = f(Tf). For calculation of the structure relaxation times this
principle was found in [21].
The simplest variant of this approach used is the assumption on equality 0i for all n
relaxation processes, i.e.
01 = 02 = 03 ... = 0n,
(15)
but this assumption is not stringent one, and in case of need (the problem of minimization
of calculation deviations from the experiment demands it) each constant of 0i can be
prescribed by its own value.
So, the algorithm applied here with the specified changes can be written as follows:
t
dt'' dT (t ' ) ''
T fi T exp
dt ,
' (t '' ) dt'
0
t i
i 1
i 1
T f gi T fi , where gi 1 ,
Tf
Tf
lg i A
lg 0
1 ,
T f To T
T
Bi T f
lg 0 f 1 ,
lg i Ai
T Toi T
T
i 1
n
dt '
,
where
g i 1 .
'
i 1
i (t )
(t ) (0) g i exp
(16)
(17)
(18)
(19)
(20)
Here variables with the index characterize the values describing stress relaxation, and
the other variables belong to the structure relaxation. As we can see from the equations (19)
and (20) at calculation of stresses relaxation, it was assumed that at the set of structural
conditions of matter the values of structure temperature for relaxation times both structures
and stresses coincided.
98
Figure 5. The schematic description of temperature dependence of structural relaxation times.
The optimum values of the constants, used at calculation of stress relaxation in sapphire,
were present in [1, 18]. In Figure 5, the compliance between calculating (lines) and
experimental (points) dependences characterizing the relaxation of stresses in studied
sapphires is shown. Apparently, the compliance is quite satisfactory, despite very wide
intervals of structural and experimental temperatures within which measurements were
carried out. Thus, it is possible to conclude that the suggested model describes adequately
processes of the stress relaxation in sapphire and can be used for the solution of various
scientific and practical tasks.
4. STUDY OF SAPPHIRE SAMPLE DEFECTS BY DIFFERENT METHODS

The different methods such as the method of surface acoustic waves (SAW),
vibrodiagnostics method, optical and thermal methods are used for determination of sapphire
sample damage (the size and location of defects, for example microcracks, pores, etc. with
aim to state the corresponding function of damage distribution).
4.1. Method of Surface Acoustic Waves (SAW)

Below we present a sequence of stages of non-destructive control of the defects by using
the SAW method (see Figure 6). Figure 7 show frequency dependences of modulus of the
reflection factor S11 for various distances from defect and Fourier transform of the measured
frequency dependence (see Figure 8).
99
Figure 6. Excitation of SAW by using wedge (digital designations are present into text).
Figure 7. Typical frequency dependencies of the modulus of reflection factor S11.
The gauge of complex factors of transmission (MCFT) 1 generates periodically long

electric-magnetic pulses with linear frequency of modulation 2 to converter of SAW 3,
disposed on the treated surface 4, on which exist defects 5, from which SAW could be
reflected.
The SAW converter could be made in the form of wedge-shaped transducer for lowfrequency measurements and in the form of piezoelectric substrate, on which surface the onedirected interdigital transducer (IDT) is disposed. The piezoelectric substrate is joined to the
studied polished sapphire surface through liquid layer (distilled water, alcohol) with a
thickness no more than 1 2 m.
At the definite length of the transition layer, SAW can be totally translated from one
surface to other. The piezoelectric substrate edges are rounded and on the substrate faces
there is a thin layer of acoustic absorber in order to decrease a reflection from the
piezoelectric substrate edges (see, Figure 9).
The control method of defects in sapphire (standard disc specimen is shown in Figure 10
includes the next procedures. At the generation from MCFT 1 to SAW converter 3 of long
electric-magnetic pulses with linear frequency of modulation 2 with definite period, it begins
to radiate SAW with successively different frequencies. These waves, propagating along the
sapphire surface, are reflected from defects 5 and again return to the converter 3. Here they
transform into electric-magnetic signal and reach MCFT 1, which conducts measurement of
the reflection parameter S11.
100
Figure 8. Fourier transform of the typical frequency dependence; distance s from defect is calculated as
s = vSAW/2, where is the delaying time of reflected SAW, vSAW is the SAW velocity: (a) and (b) SAW
reflection from the sample edge at the distance between edge and wedge equals to 10 cm and 65 cm,
respectively (the normalized factor 0.38326 is found on maximal amplitude of SAW reflected from the
sample edge).
Figure 9. SAW excitation in sapphire crystal by using one-directed IDT.
The transformed electric-magnetic signal begins to make interference with the electricmagnetic signal, which is reflected directly from electric input (output) of the SAW
transducer leading to occurring of numerous maxima and minima of the parameter S11 in
dependence on frequency (Figure 7). The frequency limits are given by the frequency band of
pulse with linear frequency modulation. The distance between maximum and minimum of S
depends on amplitude of reflected SAW (the greater reflection of SAW of defect define the
101
greater value of S). The distance between adjacent minima and maxima f depends on
distance between defect from which the SAW are reflected and the SAW transducer (Figure
7): the greater distance defines lesser f. The discreteness of the frequency reconstruction in 1
Hz allows us to define the distance between nearest maxima and minima f with discreteness
in 1 Hz increasing the measurement accuracy.
Figure 10. The studied sample and SAW activation by the wedge.
Fourier transform of the measured frequency dependence is shown in Figure 8. From this
figure, it follows that presence of the piece-shaped frequency dependence leads to occurring
the reflection peaks, whose size and location depend on value of the SAW reflection of
defects and distance to them. In this measurement method, the value of the parameter S11 is
defined at each frequency point during some time range, for which SAW pass a distance
which is longer than double distance between transducer and defect. This leads to increasing
the measurement accuracy due to the amplitude of the reflected signal is measured at the
definite frequency more than one time and also because the phases of hindrance signals have
accidental character weakening one of other during the measurement time. Moreover, due to
periodicity of generating the frequency-modulated pulses, the measurement at each frequency
point is conducted several times. These measurements could be summarized leading to
decreasing influence of the hindrances on measurement results and increasing the
measurement accuracy.
Preliminary studies of the sapphire disc (Figure 10) were conducted by means of the
device MCFT "Obzor-103" which measures the parameter S11 of the wedge-shaped converter
of SAW, consisting of the triangular prism from plexiglass and the piezoceramic disc with 1
mm thick and 1 cm diameter which radiates volume waves in plexiglass.
The parameter S11 frequency dependence is shown in Figure 11. It is visible that the
transducer radiates SAW around 2 MHz, effectively. In the figure, the rutted amplitudefrequency characteristic (AFC) is presented because of SAW reflections from the disc edge.
Fourier transformation of this AFC allows us to see the reflected pulse in the time (see
Figure 12). It is visible that the reflected pulse locates rather close from the reversing impulse.
Therefore, it is impossible to tell that there are no reflections from defects in the crystal
because these impulses cannot be visible due to the reversing impulse proximity. Moreover,
here the SAW length is equal about 2 mm that does not allow one to find small defects (with
size is lesser than 1 mm).
102
Figure 11. The parameter S11 frequency dependence.
Figure 12. Pulse response: the relative units are on the vertical axis; t=0.2 ti are on the horizontal axis.
Therefore, it is necessary to increase considerably the SAW frequency. It is possible to

make by using the SAW transducer representing itself the piezo-substrate from YX/1280 cut of
lithium niobate, on which polished surface the unidirectional interdigital transducer is
disposed. By means of such transducer it will be possible to excite and accept SAW in the
sapphire substrate with the polished surface. It allows one to make it without SAW damping
on the roughness because SAW is excited with the frequency of 93 MHz and SAW length of
50 m. In this case, the SAW excitement is conducted through the thin layer of liquid
between the piezo-substrate and sapphire substrate surface.
4.2. Vibrodiagnostics Method

The low-frequency vibroacoustic method is one of interesting methods of defect study.
The low-frequency vibroacoustic methods of diagnostics use relation between eigenfrequencies of oscillations of sample and its physic-mechanical characteristics [28].
103
The resonant frequency of disc radial fluctuations can be determined by the well-known
formula:
2
E
,
2r (1 )
(21)
where r is the disk radius, is the material density, is the Poissons coefficient, E is the
Youngs modulus, which defines the sample material elastic properties and density of
scattered defects, is the coefficient determined by the value of Poissons coefficient () and
equal approximately 2.05.
Figure 13. Measurement device for testing vibroacoustic method: 1 radiator, 2 preliminary elastic
contraction, 3 receiver of acoustic signals.
However the task becomes complicated because there are some eigen-frequencies of
oscillations for any solid body. The set of these frequencies form the frequency range and it is
necessary to make a choice of necessary mode of oscillations. For sample with the simple
shape, it is possible to solve the problem of selection of the certain type of oscillations for
specific arrangement of supports and reception-radiating system.
In order to test the vibrodiagnostics method by using the sapphire disc, it was used the
device shown in Figure 13. As a result of the conducted testing this method of nondestructive control on the sapphire disc, it has been preliminary concluded on practical
possibility to use the vibroacoustics method in experimental investigations of sapphire since
at the loading of the disc by the load of 1 g, we observed AFC changing.
Figure 14. Structural scheme of vibroacoustic method realization.
104
It allows to exam the change of structure morphology and as a result to consider the
dynamics of defect change in sapphire structure. The structural scheme of vibroacoustic
method realization is shown in Figure 14. It consists of object 1, radiator 2, sensor of acoustic
oscillations 3, the measurer of amplitude-frequency oscillations 4 and the recorder combined
with computer 5.
4.3. Optic Method of Registration of the Optical Transmission

through Sample
The registration method of optical transmission through sample was tested on disc nonpolished and rectangular polished (see Figure 15) sapphire specimens.
Figure 15. Rectangular polished sapphire sample used for testing the registration method of the optical
transmission.
Figure 16. Photos of fragments of the sapphire disc surface: (a) the top part of the characteristic
sapphire surface, (b) the boundary defect like chip, (c) scaling shown by using human hair.
105
Figures 16, 17 show corresponding photos of the sapphire samples obtained by using the
microscope with the two-hundred times multiplication. The sapphire non-polished disc was
illuminated on the light (see Figure 16). The results of sapphire polished surface study are
shown in Figure 17.
(a)
(b)
Figure 17. Photos of fragments of the sapphire rectangular plate with polished surface.
4.4. Other Experimental Methods

The picture of defects can be determined also by the thermal method (with the use of
thermal imager). Some preliminary results of study of the round sapphire disc by using this
method are present in Figure 18. The method of acoustic emission can be also used at various
technological stages of sample production, at phase and structural transformations, initiation
and growth of defects and damage.
(a)
(b)
Figure 18. Preliminary results of studying the defects in sapphire by using of thermal imager.
CONCLUSION
The obtained results allow making the quantitative estimation of formation of the various
nature defects in sapphire crystals. The disturbance of thermal conditions at the front
106
crystallization leads to capture of gas bubbles into liquid by interphase boundary. These
bubbles can be the cause of emergence pores in crystal being tension concentrators and
additional source of dislocations and, as a result, causing the arising defects in the form of
blocks. The simulation results can help to define defect formation zones and can be used to
make recommendations on crystal quality improvement.
The temperatures gradients allowed us to estimate the sizes of the formed vapor bubbles.
At bubble capture the ratio of crystal growth and bubble rates defined a final form of
inclusion. At the initial stage of sapphire growth (x = 0.1 m) the effective coefficient of
segregation is close to equilibrium one. It is defined by small growth rate. Thus the crystal
grows without foreign inclusions. In this case the effective coefficient of segregation does not
depend on temperature gradient in melt, practically. The polarizing and optical method was
used for internal stresses definition and sapphire block structure study. The developed method
allows us to define not only the average value of stresses in grown crystal, but also the
influence of grinding on the residual stresses.
The suggested model describes adequately processes of stress relaxation in sapphire at
the condition of non-compliance with thermorheological simplicity principle. It can be used
for the solution of various scientific and practical tasks. By means of various experimental
methods (the method of surface acoustic waves, vibroacoustic diagnostics, optical and
thermal methods) the preliminary results of study of different defects in sapphire polished and
non-polished samples were obtained. They allow us to exam the change of structure
morphology and, as a result, to consider the dynamics of defects change in sapphire structure.
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ISBN: 978-1-63321-239-8
Chapter 5
PHYSICS AND DESIGN OF MULTI-FUNCTIONAL

CERAMIC MATERIALS WITH SPECIAL ELECTRICAL
AND MAGNETIC PROPERTIES
L. A. Reznichenko, A. G. Abubakarov, K. P. Andryushin,
I. N. Andryushina, V. A. Alyoshin, N. A. Boldyrev,
I. A. Verbenko, S. I. Dudkina, A. A. Pavelko, A. V. Pavlenko,
H. A. Sadykov, M. V. Talanov, S. V. Titov, V. V. Titov,
A. V. Turik and L. A. Shilkina
Research Institute of Physics, Rostov State University,
ABSTRACT
Physics of functional materials with special electrical and magnetic properties is the
most practically demanded direction of the condensed matter physics. Ceramic materials
are used in large quantities, since they have the advantages in industrial production.
Ceramics on the basis of multi-component systems have better process ability and a wide
variety of properties.
This paper outlines the issues related to the possible consideration of ceramics as
physical objects, whose properties can be described by a statistical approach. The objects
will be macro- and micro-heterogeneous (colloidal) ceramic materials with different
types of micro-heterogeneity (crystal-layer in the ferroelectric ceramics and
antiferromagnetic - ferromagnetic separation in multiferroics). The phenomena of
dielectric relaxation and retardation, electric effect are described. Particular attention will
be paid to the relationship of the crystallographic characteristics of these objects with
their macroscopic responses.
The results of multifractal investigations of ceramic materials were discussed. The
materials studied were: lead-free ferroelectric ceramics, solid solutions of lead zirconatetitanate, multiferroics, different solid solutions of multiple components. The results of
multifractal parameterization performed during the different stages of ceramics
preparation (synthesis, sintering, source components thermodynamic history, phase
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L. A. Reznichenko, A. G. Abubakarov, K. P. Andryushin et al.

states and doping) were analyzed. The perspective approaches and ways of future studies
were ground.
The dielectric and pyroelectric properties of multicomponent PbTiO3 PbZrO3
PbNb2/3Mg1/3O3 solid solutions were investigated. The temperature dependences of
dynamic pyroelectric current revealed additional low-temperature peaks, corresponding
to the rhombohedral-tetragonal phase transition. From the anomalies of pyroelectric and
dielectric properties {x, T}-phase diagram of the system was constructed on isothermal
sections.
1. THE INVAR EFFECT AND THE DEVILS STAIRCASE IN ALKALI

AND ALKALINE EARTH NIOBATES
1.1. Introduction
Our previous investigations [14] of the behavior of the crystal structure of ceramics of
metaniobates of alkali metals: lithium (LiNbO3), sodium (NaNbO3), and silver (AgNbO3);
and pyroniobates of alkaline earth metals: strontium (Sr2Nb2O7) and calcium (Ca2Nb2O7) in a
wide temperature range (up to 970 K) revealed for each noted compound a large number of
ranges of different width (10 40 K) characterized by a constant volume V (Invar effect) of
the perovskite cell and, as a result, zero values of the coefficients of thermal expansion
(CTEs). These temperature ranges correspond to the regions of phase transitions. Similar
phenomena were also revealed by us in single crystals of alkali metal metaniobates grown by
the mass flux method using different salt systems as solvents. For example, the temperature
dependences of the perovskite-cell parameters of NaNbO3 in the range from room
temperature up to ~ 600 K were reported in [5]. The perovskite-cell volume V is constant in
the ranges 300 330 K and 340 380 K (it was not reported in [5]). The continuation of the
study of these single crystals in the temperature range up to ~ 920 K also revealed a number
of other regions of stability of the volume V, which correspond to the phase-transition
regions.
A compromise between two competing processes, thermal expansion of the cell with an
increase in temperature and its compression caused by crystallographic shears, was
considered in [3] as a possible reason for the constancy of the cell volume during heating or
cooling of samples. Crystallographic shears evolve as a self-organizing compensating
mechanism of annihilation of point defects (oxygen vacancies formed both with a change in
the oxidation state of the elements with variable valence (Nb, Ti, W, etc.) [6] and during the
sublimation of alkali metal oxides at temperatures close to 970 K [7]). In complex oxygenoctahedral compounds (including those with perovskite structure), in the first case, the
number of cuboctahedral positions decreases by the number of excluded O positions [8], as a
result of which the structure becomes denser. Such crystallographic shears in niobium oxides
of different composition and Ti-containing compounds (Magneli phases) were described by
us in [9, 10]. Enhanced defect formation in the regions of structural instability [11] activates
crystallographic shear and, as a result, the cell volume decreases. This is the reason for the
correspondence (see [15]) between the temperature ranges with invariable V and the regions
of structural transformation. In studies [1220], devoted to the materials with
incommensurate phases, specific anomalies in the temperature dependences of the linear
111
lattice parameters were found, up to the vanishing of CTEs in certain directions. Such a
specific feature was revealed in proustite Ag3AsS3 [12], tin selenohypodiphosphate Sn2P2Se6
[1315], mixed crystals of the Sn2P2S6Sn2P2Se6 system [16], zinc phosphate ZnP2 [17, 18],
thiourea SC(NH2)2 [19, 20], Cs2ZnI4 crystals [21], and some other compounds [2224]. Since
this unusual behavior of the lattice parameters was observed in the region of
incommensurability, the Invar effect was attributed to the presence of incommensurability. A
crystallographic model for these lattice anomalies was proposed in [21]. This model is based
on the mechanism of compensation of the elongation of interatomic bonds upon heating by
the increase in their slope. This mechanism is possible in incommensurate phases because, in
the modulated state, the static displacements of chemically different atoms, having the same
wavelengths, differ in amplitude.
In this study, we report complete data on the high-temperature behavior of the structural
characteristics of the NaNbO3, KNbO3, AgNbO3, Ca2Nb2O7, and Sr2Nb2O7 compounds,
which make it possible to reveal ranges of the Invar effect for both volume and linear cell
parameters and find a correlation between these ranges and the phase-transition regions. An
explanation for the occurrence of the Invar effect is proposed.
1.2. Objects of Study: Methods of Sample Preparation and Measurement

The objects of the study were sodium, potassium, silver, strontium, and calcium niobates.
The crystallographic characteristics and the room-temperature dielectric properties of these
compounds are listed in Table 1. Table 2 contains the data on their polymorphism [25-28].
Table 1. Crystallographic parameters and the alkali and alkaline earth niobates
at room temperature
In NaNbO3, along with those compounds listed in Table 2, the following phase
transformations are known: (i) transitions to the incommensurate phase (410 440 K) [5], (ii)
transitions within the R phase (R1 R2 at 700 K) [29], and (iii) transitions between the
ferroelectric phases Q, Q1, and Q2, coexisting with the antiferroelectric phases P and R (Q
Q1 at 570 K) and (Q1 Q2 at 700 K) [30]. In addition, there is also a structural instability
near 350 K [5]. We suggested in [5] that the incommensurate phase exists in AgNbO3 in the
same temperature range (~ 350 K) as in NaNbO3. Some other anomalies of the structural
characteristics were established in [3], which are likely to be caused by the presence of a
phase transition (in Figure 1a, the regions of such anomalies are indicated by dashed vertical
lines). In Sr2Nb2O7 and Ca2Nb2O7, along with the phase transition at TC (Table 1),
112
incommensurate phases were revealed, respectively, in the range 490510 K [31] and near
750 K [32] and a number of other structural instabilities were found at 114 135, 630, 660,
760, and 850 K (Sr2Nb2O7) and 350, 450, and 1110 K (Ca2Nb2O7) [33, 34].
Table 2. Polymorphism of the alkali niobates
113
Figure 1. Temperature dependences of the perovskite-cell parameters of the (a) AgNbO3, (b) NaNbO3,
and (c) KNbO3 compounds: (1) bmon, (2) amon = cmon, (3) , (4) atetr, (5) ctetr, (6) apsc, (7) V, (8) |y|, and
(9) .
114
The experimental samples were prepared by the conventional ceramic technology (solidphase synthesis with subsequent sintering without applying pressure). The optimal conditions
for the synthesis and sintering of the objects under study were chosen by varying fine-grain
media, the duration and number of grindings, the molding temperature and pressure, and the
atmosphere and number of firings.
The choice of the optimal conditions was based on the thermogravimetric, X-ray
diffraction, and microstructural analysis and the measurements of the density and electrical
characteristics of the ceramics sintered from the samples synthesized. The conditions for
preparation of the samples of specific compounds are listed in Table 3.
As the main reagents for the synthesis, we used niobium pentaoxide Nb2O5 (NbO-Pt
(technical) grade) carbonates of silver (Ag2CO3, high-purity grade), sodium (Na2CO3,
analytical grade), potassium (K2CO3, reagent grade), strontium (Sr2CO3, analytical grade),
and calcium (CaCO3, analytical grade). To obtain intermediate products for sintering, we used
the technique of powder granulation: two-step grinding of pressed small blocks, first through
a sieve with a cell size of 0.70.9 mm and then, after 4-h storing in a closed vessel, through a
sieve with a cell size of 0.250.3 mm.
This operation made it possible to increase the density of the intermediate products and
the ceramic samples (after sintering). The values of the theoretical density (theor = 1.67 M/V,
where M is the molecular weight and V is the cell volume per formula unit), the experimental
density (exper) (measured by hydrostatic weighing of the samples in octane), and the relative
density (exper/theor) and the relative permittivity /0 (0 is the dielectric constant) of
unpolarized samples of niobate materials are listed in Table 4.
Table 3. Regimes of preparation of the samples of the alkali and earth niobates
Table 4. Densities and relative permittivities of unpolarized samples

of the niobate ceramics
115
X-ray powder diffraction analysis was performed on DRON-3 and ADP diffractometers
(FeK-radiation, Mn filter, FeK-radiation, BraggBrentano focusing scheme). The objects in
the solid state were either ceramic samples in the form of disks 10 1 mm2 in size, with a
polished planar surface, or powders obtained by grinding of the ceramics. The latter technique
made it possible to exclude surface effects, stresses, and textures which arise during the
sample preparation. The powders were pressed into a quartz cell without using a plasticizer to
avoid additional diffuse scattering. The profiles of X-ray lines were obtained by step-by-step
2 scan (with a step of 0.01 in the 2-mode and a pulse-collection time of 10 s at each
point) and by recording on a chart tape with counter velocities of 1/2 and 1/4 deg/min. The
integrated reflection intensity was calculated as the area under the intensity-distribution curve
by the Simpson method. The unit-cell parameters and volumes were calculated
conventionally. The errors in measuring the lattice parameters were as follows: a = b = c
= 6 10-4 and = 0.05 for NaNbO3, KNbO3, and AgNbO3 and a = 6 104, b = 8103,
and c = 1 103 for Ca2Nb2O7 and Sr2Nb2O7. The temperature step of measurements was
varied from 2 to 20 K with an error of 1 K, the time of isothermal exposure was 5 min, and
the rate of temperature variation was not specified. The modulation period near the region
of the incommensurate phase was calculated by the position of the satellite of the 020 line
(indices correspond to the perovskite-cell axes).
1.3. Results and Discussion

Analysis of the experimental results indicates that sufficiently dense pure samples were
obtained (except for AgNbO3) (Table 4). Figures 1 and 2 show the temperature dependences
of the cell parameters of AgNbO3, NaNbO3, KNbO3, Sr2Nb2O7, and Ca2Nb2O7. Table 5
contains the regions of existence of the Invar effect for these samples. Correlation between
the regions of the Invar effect and the phase-transition regions in the compounds under
consideration can be clearly seen.
Let us discuss another possible reason for the effect revealed, in addition to that
considered in [3]. The facts that the Invar effect always manifests itself at phase transitions
and the behavior of the lattice parameters in this case is similar to their behavior in systems of
solid solutions with a variation in temperature (polymorphic phase transitions) [35] or with a
variation in composition (morphotropic phase transitions) [36] suggest that the lattice
anomalies observed have the same nature: The Invar effect occurs at the boundary between
two phases and characterizes the region of their coexistence. In heterogeneous solid-state
media, at relatively low temperatures (typical of the X-ray diffraction experiment), diffusion
processes and the related structural rearrangements are decelerated.
At a sufficiently high heating rate, this circumstance impedes the samples reaching of
the equilibrium state. As a result, there arise regions of coexistence of alternating phases with
limiting values of the cell parameters corresponding to the boundaries of their stability. The
cell parameters in these regions do not change, and the relative number of phases obeys the
lever rule.
The width of these regions depends on the fabrication conditions: the solid state of the
objects (in single crystals, the coexistence regions are narrow or absent at all, whereas in
ceramics they are much wider) and quantitative and qualitative impurity composition of raw
116
reagents used to synthesize the objects [36]. In commensurate phases, the dependence of the
coexistence-region width on the isothermal exposure time was not observed. In
incommensurate phases, this dependence plays an important role (see [5] for details). The
structural similarity of alternating phases in NaNbO3 and AgNbO3 makes it impossible to
distinguish the behavior of the cell parameters in each phase.
As a result, we observe the integrated effect in the form of a plateau near the phase
transition. In KNbO3, the dominance of the monoclinictetragonal transition is responsible for
the significant differences in the cell parameters of the coexisting phases. As a result, the
constancy of the parameters of each phase can be clearly seen near this phase transition. Note
that the regions of existence of the Invar effect in KNbO3 at low temperatures (below 400 K)
are similar to those observed in NaNbO3 and AgNbO3.
These regions may be related to the transition to the incommensurate phase (which
occurs in KNbO3 at lower temperatures (360 400 K) in comparison with NaNbO3 and
AgNbO3) and with the change in the defect subsystem at 320 360 K. Theoretically all cell
parameters in the region of the Invar effect should remain invariable. However, in reality as
well as in the morphotropic region, some parameters may weakly change.
Table 5. Temperature ranges of the Invar effect for the structurel parameters, K
117
Figure 2. Temperature dependences of the unit-cell parameters of the (a) Sr2Nb2O7 and (b) Ca2Nb2O7
compounds: (1) a, (2) c, (3) b, (4) V.
The reason for this phenomenon is that it is difficult to reach thermodynamic equilibrium
in heterogeneous regions because of processing difficulties. In some cases, narrow regions of
existence of the Invar effect can be divided into two or more regions that are separated into
even narrower temperature ranges, in which the cell parameters vary.
In this sense, the behavior of the structural characteristics in the vicinity of the transition
to the incommensurate phase in NaNbO3 is typical.
118
Figure 3. Changes in the modulation wavelength in the region of the incommensurate in NaNbO3.
We performed a more detailed structural investigation at temperatures close to the

transition to the incommensurate phase, thereby showing that the region of
incommensurability in NaNbO3 has a number of specific features:
(i) It is wider than that determined in [5]; specifically, it ranges from 400 to 480 K.
(ii) It has a complex morphology caused by several closely spaced phase transitions, as
was noted in [37] for other compounds.
(iii) It is characterized by different behavior of the modulation period in the peripheral
parts of the region of existence of the incommensurate phase (near 400 and 480 K)
and in its center (420 460 K) (Figure. 3). The change in at the center (three steps,
including the plateau) has the form of an incomplete devils staircase (double
bending with the constancy of the parameters between them, the Invar effect). The
temperature dependence of near the transitions to the commensurate phase (on the
left and right from the center of the incommensurate-phase region) represents a
complete devils staircase.
(iv) It has a nucleus and a shell. On the basis of the definition of the devils staircase
[3739], we can say that the nucleus of the incommensurate phase consists of true
incommensurate states, forming plateaus separated by comparable states (the
analytical mode [40]). This nucleus is surrounded by a shell representing a
sequence of discrete comparable configurations (the stochastic mode [40]), the
transition between which requires overcoming potential barriers [37, 39, 41] (see
Figure 3).
119
(v) It is characterized by very large values of (608 at 400 K and 280 at 480 K),
which decrease with an increase in temperature (see Figure 3). This behavior is
characteristic of a soliton lattice [42 45]. The increase in the intensity of the
satellite peaks below 460 K is likely to be related to the increase in their density. The
decrease in the intensity of these peaks at higher temperatures is caused by the
gradual decay of the soliton lattice.
1.4. Conclusion
Some anomalies of the structural characteristics of metaniobates of alkali metals
(NaNbO3, AgNbO3, and KNbO3) and pyroniobates of alkaline earth metals (Ca2Nb2O7 and
Sr2Nb2O7) are revealed. The constancy of one or several unit-cell parameters and/or volumes
(the Invar effect) in the temperature ranges corresponding to the regions of phase transitions
of different nature are related to the coexistence of alternating phases with limiting
(corresponding to the limits of their stability) unit-cell parameters. The latter remain constant
in these regions. The relative number of phases obeys the lever rule. An additional reason for
the Invar effect for the unit-cell volume can be the compromise between the competing
processes of the thermal expansion of the lattice upon heating and its compression caused by
crystallographic shears, which are enhanced in the regions of structural instabilities. Complex
morphology of the region of incommensurability in NaNbO3, including the portions with
incomplete and complete devils staircases, is established. It is suggested that the
incommensurate phase has a soliton structure.
2. FEATURES OF THE DIELECTRIC SPECTRA OF NIOBATE-BASED

MATERIALS MODIFIED WITH MANGANESE AND COPPER OXIDES
2.1. Introduction
In studies of solid solutions (SSes) based on the (Na, Li)NbO3 system [46], it has been
noted that the temperature dependence of the relative dielectric permittivity (/0) typical of
ferroelectric materials with a pronounced maximum at the Curie temperature (C) has a
number of peculiarities: at the moment of phase transition (PT), C shifts to lower
temperatures with a rising electric field frequency (f); in the paraelectric (PE) region away
from the PT, there is a substantial increase in the dispersion of low-frequency /0, anomalies
in the thermal and frequency dependences of /0, and a dramatic increase in /0 at
temperatures i, which are greater for higher f. The observed effects were linked to an
increase in the reach-through conductivity due to the higher content of defects in SSes as a
result of losing highly volatile compounds of alkaline metals during synthesis, and to the
partial reduction of niobium. This work is a continuation and elaboration of earlier studies
and deals with SSes based on (Na, Li)NbO3 hyperstoichiometrically modified with (12) wt
% of MnO2 or CuO.
120
2.2. Experiment
Specimens were prepared by two-stage solid-phase synthesis at T = 850 870 C lasting
1 = 2 = 6 hours and sintered at Ts = 1160 1200 C (depending on composition) for 1 hour.
X-ray crystallographic investigations were performed on DRON-3 diffractometer. The
dielectric spectra were measured on the YuKOMP 2.0 laboratory workbench using an E7-20
impedance meter in a temperature interval of 25700 C at frequencies of 25 Hz 1 MHz.
2.3. Results and Discussion

X-ray analysis showed that the prepared specimens were high-density ceramics without
impurities of perovskite-type structure.
Figure 4. Relationships /0() for ceramic solid solutions based on the (Na, Li)NbO3 system modified
with (a) 1 wt % of CuO, (b) 1 wt % of MnO2, and (c) 2 wt % of MnO2. The inserts on the right show
enlarged fragments of the spectra.
121
Figure 4 shows the thermal and frequency dependences of /0 for the investigated SSes.
It was found that they exhibit the same attributes as those observed in [46]. Additional
anomalies were observed in the paraelectric (PE) region near TC (the sharp rise in /0
at Ti ~ 355 ). Because this anomaly (Figure 4a) is always present in a PT, we may assume
that the PT causes /0 to grow due to defects arising at the time of restructuring (the breaking
of old chemical bonds and the formation of new bonds).
The function of the latter can be performed by clusters of the emerging phase, regions of
coherent scattering, vacancies, etc. As was noted in [46], anomalies in the temperature
interval of 400 600 are most likely related to changes in the valence band states of
niobium Nb5+ Nb4+ [47] (Figure 4b).
Given the scale of polymorphism in Nb oxide compounds [6, 48, 49] and the complexity
and multistage character of oxidation reduction in the NbO system [48], we may assume that
reversible reduction of niobium can take place in a much wider interval than was reported in
[47] and can be accompanied by several Ti in the high-temperature region as we make our
observations (Figure 4c).
Note the different rate of change in /0 near i and i as it gradually diminishes in
proportion to its distance from the PT. Like the Hedwall effect (the enhanced reaction
capacity of solids during or as the result of polymorphic transformations), the maximum rates
in the vicinity of the PT are apparently due to enhancement of the diffusion processes,
including the propagation of defects stimulated by the high mobility of the lattice components
during restructuring; their decline farther from the PT is evidence of the diminishing role of
restructuring in the processes of defect formation that occur at different stages of the
permanent reduction and oxidation of Nb.
3. PHYSICS OF FERROELECTRIC CERAMICS

3.1. Thermodynamic and Statistical Approach
In contrast to single crystals, the ferroelectric ceramics have complex structure
(chaotically located and oriented crystallites, crystalline interfaces, domains, doping and
casual impurities), i.e. the ferroelectric ceramics is a heterogeneous polycrystalline material.
Two approaches, namely a thermodynamic approach and a statistical one were historically
used to research the ferroelectric ceramics. The first approach is represented inadequate,
because due to complexity of domain structure, the state of the ferroelectric ceramics with the
same polarization can be realized at various domain structures. From two basic types of the
statistical approach (nonself-consistent and self-consistent), the basic for the ferroelectric
ceramics is the self-consistent one.
The statistical approach can be used for the description and research of physical
properties both the micro- and macroheterogeneous (composite) systems. The ferroelectric
ceramics are microheterogeneous systems with various types of microheterogeneity. The
basic types of microheterogeneity arise owing to distinction of properties of the crystallites
and crystalline interfaces and antiferromagnetic ferromagnetic division in multiferroics.
122
3.2. Dielectric Retardation and Relaxation in PbFe1/2Nb1/2O3 Ceramics

Lead ferroniobate PbFe1/2Nb1/2O3 (PFN) is a multiferroic in which the electric and
magnetic orders coexist [50, 51]. For a linear medium, it is accepted to distinguish between
dielectric retardation and dielectric relaxation. This difference is due to the specific features
of the behavior of the complex dielectric permittivity = i under applied step voltage
(retardation) and complex electric modulus M = 1/ under applied step charge (relaxation)
[52, 53]. The relation between the average retardation and relaxation time constants /M =
s/, where s and are the static and high-frequency dielectric permittivity, respectively.
The relation is precisely given only for Debye dielectrics, semiconductors and ferrites.
However for non-Debye materials the relation can appear incorrect and is to be checked.
At the assumption that the electric field E existed infinitely long up until the considered
instant t, it is possible to obtain the electric induction D by means of the superposition
principle [52] as
t
D(t ) E (t ) E (u ) (t u )du .
(1)
We will consider that the function (t), describing decay of the electric induction D or
polarization P with time, has the Debye type (an exponent with the characteristic time
which does not depend on time, but can depend on the temperature):
(t )
s t /
e .
(2)
Differentiation of D with respect to time t allows transforming the integral equation (1) to
the differential one:
d
( D E ) ( D E ) ( s ) E.
dt
(3)
Let us consider now solutions of Equation (3) for the following two cases. For the case in
which E = E0 = const, dE/dt = 0 (retardation) using Equation (3) we obtain
dD
D s E0 , ( D s E0 ) e t / ; ,
dt
(4)
i.e. the charge on the condenser plates exponentially rises with time. For the case in which D
= D0 = const, dD/dt = 0 (relaxation), we have
dE
E D0 / s ; ( D0 / s E ) e t / M ; M
dt
s
(5)
123
where M = 1/, i.e. the voltage on the condenser plates exponentially decreases
with time.
Thus, the relation /M = s/, characterizing delaying the retardation processes in
comparison with the relaxation ones, can be strictly proved only for Debye dielectrics with
one retardation (relaxation) time and exponential function of decaying the electric induction
(or the electric field) with time. For non-Debye dielectrics transition from the integrated
equation (1) to the differential equation (3) and obtaining the relation /M = s/ are
impossible, and for each kind of distribution function of relaxation times a special
consideration is required.
The complex dielectric permittivity of the PFN ceramics * = ' i'' (' and '' are the
real and imaginary parts of *, respectively) was measured at frequencies f = 1 2 106 Hz
using a Novo-control ALPHA High-Resolution Dielectric Analyzer equipped by a system for
high-temperature measurements and LCR-meter HIOKI 3522-50 and Agilent 4285A. The
specific conduction was calculated by the formula * = i* = ' + i'', where a circular
frequency = 2f.
3.3. Retardation
The '()/0, ''()/0 (0 is the permittivity of the free space) and ''/0('/0) (ColeCole
diagrams) measured at temperature of 250 C and frequencies of (5 1.2106) Hz are shown
in Figure 5.
Figure 5. Dependences (a) '()/0, (b) ''()/0, '() (the inset in figure (a)), and (c) ''/0('/0) of the
PFN ceramics measured at temperature of 250 C. The dark symbols indicate the values of ''/0 after
excluding the singular (divergent at 0) terms.
The '()/0 spectra have a plateau at low and high frequencies, whereas the ''()/0
spectra demonstrate a monotonic increase as decreases (bright symbols); this increase is
due to very high dc-conductivity of the PFN ceramics at these temperatures (inset in Figure
6a). To clearly select the relaxation maxima of ''()/0, we exclude, from the imaginary part
of the permittivity ''/0, the singular term /(0) determined by the contribution of the dcconductivity. As a result, the maxima appear in the ''()/0 spectra; the maxima are shifted to
higher frequencies and decrease as temperature increases. In addition the arcs, which were not
observed initially, appear in the ColeCole diagrams at T = 250 C (Figure 5c, dark symbols).
This fact testifies that at the temperature, the relaxation process occurs in the PFN ceramics.
124
The shape of the ''/0 ('/0) dependences indicates that the non-Debye relaxation is observed
in the PFN ceramics.
According to [54], the physical basis for the non-Debye relaxation can be the Maxwell
Wagner polarization [55] and relaxation in an electrically inhomogeneous matrix system with
cells consisting of ceramic grains with approximately the same diameters surrounded with
thin layers (shells) having a small or high conductivity and the dielectric permittivity different
than that of grains. The variation of the permittivities, conductivities, and thicknesses of
grains and shells leads to a wide distribution of the relaxation times and provides high values
of the permittivity and conductivity and the non-Debye relaxation in the PFN ceramics.
3.4. Relaxation
Experimental dependences of M() and M() on the circular frequency are depicted
in Figure 6. Comparison of Figures 5 and 6 shows, that the main difference of the relaxation
from the retardation is very big distinction of their characteristic frequencies: rM 7 106
rad/s >> r 5 104 rad/s. Unlike, ''(), experimental dependence of M''() has welldefined relaxation maximum. Great values of relaxation frequencies provide weak influence
singular members on dielectric spectra. And the Cole-Cole diagram for M''(M) dependence
looks more convincingly, than in ''(') case. From Figure 6 it is visible, that approximation of
experimental data using the model for an insulator with the rectangle distribution function of
relaxation times f() [7 (56)] allows to describe well frequency dependences of M and M.
Figure 6. Dependences (a) M'(), (b) M''() and (c) M''(M') of the PFN ceramics measured at
temperature of 250 C. The solid lines are the results of calculations according [7 (56)] for 1 = 0 s, 2 =
7.5 105 s, s = 42,000, and = 3,000.
3.5. Magnetodielectric Effect in Bi1/2La1/2MnO3 Ceramics

Bismuth-lanthanum manganite Bi1/2La1/2MnO3 (BLM) is a multiferroic with coexisting
electric and magnetic orders [57]. Earlier, when studying the BLM ceramics at the
temperature of 80 K, we detected non-Debye retardation of the complex dielectric constant
= i with mean relaxation frequency fr = (2.5 3) 103 Hz. In this work we study the
magnetodielectric effect of the BLM ceramics.
Magnetodielectric effect (MDE) is manifesting itself as an influence of a magnetic
induction B on dielectric properties and is characteristic for multiferroics. Quantitative
125
measures of the MDE are magnetodielectric coefficient MD and magnetoelectric coefficients

ML of dielectric losses:
MD( B)
" ( B) " (0)

' ( B) ' (0)
,
, ML( B)
" (0)
' (0)
(6)
where = i is the complex dielectric permittivity of the material, (B) and (0) are the
dielectric permittivities measured at alternating electric field with strength and induction D
in presence and in absence of the constant magnetic induction B, respectively, tg = /.
Bi1/2La1/2MnO3 suffers ferromagnetic phase transition at temperature TFM = 120 K [58],
and it is possible to expect strong MDE in the BLM ceramics. According to [55], MDE can
be a combination of magneto-resistance and MaxwellWagner polarization due to differing
resistances of ceramic grains and shells. Dependence of the resistances on a magnetic field
leads to changes owing to MaxwellWagner polarization.
Figure 7. Frequency dependences '()/0 and ''()/0 of the BLM ceramics measured at temperature
of 80 K.
The real and imaginary parts of the complex dielectric permittivity in the absence
(0) and in presence (B) of the constant magnetic field with the induction B = 0.85 T were
measured at mechanically free PFN samples (111 mm2) in the electric field with the
strength E = 1 V/mm at frequencies f in the range from 20 Hz to 2 106 Hz. The results of the
measurements are shown in Figures 7 and 8.
The low and wide maximum of at the frequency of the relaxation fr ~ 3 103 Hz
testifies about non-Debye character of a dielectric spectrum. Magnetodielectric coefficient
MD > 0 and passes through a maximum at increasing frequency of measuring electric field.
Such a behavior can be connected with sharp reduction of close the relaxation frequency. It
126
confirms opinion of authors [59] about dynamic strengthening MDE owing to controlled by
magnetic field dielectric relaxation. More difficult behavior is characteristic for ML: ML < 0
at f < fr and ML > 0 at f fr. The least value |ML| ~ 0 is observed near to a maximum , that
is in a vicinity of the relaxation frequency fr. Thus, dynamic strengthening MDE on the
relaxation frequency fr is accompanied by sharp reduction of magnetoelectric coefficient ML
of dielectric losses.
Figure 8. MD(B) and ML(B) dependences of the BLM ceramics measured at temperature of 80 K.
4. IMPACT OF 2+ MODIFICATION ON THE ELECTRIC FIELD

INDUCED DIELECTIC AND PIEZOELECTRIC PROPERTIES
OF PMN-PT-BASED MULTICOMPONENT CERAMICS
4.1. Introduction
Materials on the basis of solid solutions of relaxor ferroelectrics Pb(Mg1/3Nb2/3)O3
(PMN) and Pb(Zn1/3Nb2/3)O3 (PZN) and classical ferroelectric PbTiO3 (PT) are of a big
interest for practical application in sonars and actuators. The compositions of these systems
near the morphotropic phase boundary (MPB) which separates rhombohedral (Rh) and
tetragonal phase (T) demonstrate high electromechanical properties [60] induced by electric
field (E). At the same time, stabilization of perovskite structure in the number of highperformance solid solutions based on relaxor ferroelelctrics (for example PZN) is quite
difficult. One way to have such stabilization is to introduce in to A-sublattice 2+ cations that
127
partially substitute Pb2+ [61] and have less electronegativity and polarizing effect in
comparison with Pb2+. As a result, covalence of - bonds reduces and relative dielectric
permittivity increases together with ferroelectric softness of objects [62]. Besides, the
preference of 2+ to octahedral site in oxides decreases the tendency of Zn2+ ions to enter a
four-coordinated state which is no typical for perovskite structure [63]. That is why
introduction of 2+ should favor perovskite structure stabilization. In addition, it is well
known that 2+ cations stimulate changes in microstructure of some ferroelectrics [64] and
lead to diffusion of () maximum as well as intensification of relaxor properties [65].
Recently, aiming to find new materials with optimal combination of properties, a
significant interest has been paid to multicomponent systems including relaxor ferroelectrics
and defined by MPB presence. Earlier there was a study of ceramics and monocrystals of
ternary systems such as: Pb(Mg1/3Ta2/3)O3 (PMT)-PT-PbZrO3 (PZ) [66], Pb(In1/2Nb1/2)O3
(PIN)-PMN-PT [67], PZN-Pb(Ni1/3Nb2/3)O3 (PNN)-PT [68], PbSnO3 (PSn)-PMN-PT [69]
and some others. However 2+modification impact on piezoelectric and dielectric properties
of solid solutions of multicomponent systems based on relaxor ferroelectrics, close to MPB,
remains poorly explored. The main purpose of this research paper is the definition of 2+
modification role in formation of structure, microstructure, dielectric and piezoelectric
properties of ceramics of multicomponent system PMN PNN PZN .
4.2. Objects and Methods of Research

Objects of this research were represented by high-density ceramics of the following
composition: Pb(1-z)Baz(Mg1/3Nb2/3)m(Zn1/3Nb2/3)y(Ni1/3Nb2/3)nTixO3 (z = 0 and 0.05, m =
0.4541, y = 0.0982, n = 0.1477, x = 0.3) close to MPB of the system [70]. These compositions
were prepared by standard ceramic technology with the use of columbite precursor method
[71]. Synthesis of columbite-like compositions MgNb2O6, NiNb2O6, ZnNb2O6 from oxides
MgO, NiO, ZnO and Nb2O5 included two stages: for ZnNb2O6 and MgNb2O6 it was burning
at temperatures 1 = 1000 , 2 = 1100 during 6 and 4 hours, respectively, for NiNb2O6
T1 = 1000 C, 2 = 1240 burning during 6 and 2 hours, respectively. Solid solutions of a
final composition were produced by a single-phase synthesis of columbite combinations that
were obtained earlier and also by the synthesis of PbO, TiO2 and BaCO3 (in case of modified
samples) at = 950 during 4 hours. A preliminary optimization of sintering temperature
(sint.) was carried out on the series of samples in order to increase the density of the ceramics.
For non-modified ceramics, an optimal sint. came to 1220 C. For the modified ones it
reached 1180 C. As far as an increase of sint up to 1220 C in modified ceramics leads to
decrease of density for 0.5 % only, sintering of both modified and non-modified ceramic
samples is possible at one and the same temperature (which is convenient in terms of
technology). In our case the needed temperature is sint = 1220 C during 3 hours [70]. Nonpolarized samples were represented by discs with the 10 mm diameter and 1 mm thickness
with silver-bearing electrodes applied (by double firing) to the flat butt end surfaces.
X-ray diffraction (XRD) analysis was carried out using DRON 3.0 device (Cu-K
radiation, focusing arrangement of Bregg-Brentano).
Microstructure of ceramics was studied by scanning electronic microscope TescanVEGA
II LMU (Common use center of South Federal University Research Center of Mineral Raw
128
Materials and Environmental Conditions). Research of microstructure was done on the

ceramics fracture.
The ()-dependences were obtained with the help of measuring test bench including
LCR-meter Agilent E4980A at the frequencies of measuring electric field 0.1 1,000 kHz
and temperature range 25 600 . Study of electric-field-induced properties was carried out
at room temperature. Measurement of () dependences was done at the magnitude and
frequency of the measuring electric field 1 V and 1 kHz, respectively, on the testing bench
which includes LCR-meter Agilent 4263. DC voltage of shifting electric field was changing
reversely in the range (25 +25) kV/m. The (PE) hysteresis loops were obtained using
modified scheme of SawyerTower at 50 Hz frequency of electric field. Measurement of
longitudinal deformation 3 was done in quasi-static conditions in the range = 12 kV/m.
The value of piezoelectric coefficient d33 was defined upon the following formula: d33 = 3/E.
4.3. Experimental Results and Discussion

Experimental density of both solid solutions samples is 95 % from the theoretical one
which is considered to be almost a limiting result for a standard ceramic technology [72].
Figure 9 (a) shows the XRD patterns of modified and non-modified samples. On the
XRD patterns of modified 5 mol. % Ba2+ sample pyrochlore phase is not observed while on
the XRD patterns of unmodified sample (222) and (400) pyrochlore phase reflections are
seen, the relative intensity of which does not exceed 3 %. Non-modified sample (Figure 9 b,
cdiffraction reflections (002)C and (222)C) has diffraction pattern that is typical for solid
solutions near MPB: overlapped picks, splitting of which corresponds to combination of
tetragonal and rhombohedral phase and diffuse scattering in the area of lines edges. XRD
patterns of the sample modified by 2+ which is characterized by lower diffuse scattering
shows distinct multiplet 002 and 200. It corresponds to tetragonal distortion of a cubic cell.
Parameters of a lattice cell of the non-modified solid solution are as follows: a = 4.010 , c
= 4.037 , c/a = 1.007, V = 64.90 3, aRh = 4.020 , = 89.88, VRh = 64.95 3. Parameters
of the modified one are: a = 4.014 , c = 4.034 , c/a =1.005, V = 64.99 3. An increase
of cell volume in the latter case is natural as ionic radius of 2+ is greater than ionic radius of
Pb2+ (1.545 and 1.411 with coordination number 12, respectively). Therefore 2+
stoichiometric modification of the solid solution under the investigation shifts it into
tetragonal area of the phase diagram. Similar effect occurred with the addition of Sr2+
(electronic analogue of 2+) to ceramics based on PbZr1-xTixO3 (PZT) (compositions that are
close to MPB) [73].
Figure 10 shows the microstructures of non-modified (Figure 10a) and modified (Figure
10b) samples of ceramics under the investigation. It can be seen, that during the process of
modification by 2+ an average size of grain decreases from (3 4) m to (2 3) m while
heterogeneity of microstructure increases. Such peculiarities of microstructures being
modified by 2+ were observed in ceramics of the following composition:
(Pb0.97xLa0.02Bax)(Zr0.75Sn0.12Ti0.13)O3 [64]. The fracture of the non-modified sample goes
mainly in the boundaries of grains while the fracture of the modified one goes both in the
boundaries and trans-granularly. Meanwhile only big crystallites (> 3 m) are subject to the
trans-granular spall, as a rule. Intergranular fracture of the non-modified sample can be linked
129
with presence of pyrochlore phase. This phase can be concentrated on the borders of
crystallites (can be seen as an inclusion on the surfaces of grains see Figure 10a, in the
upper left corner) [74] and, as a consequence, can lead to the intergranular fracture.
Figure 9. XRD patterns (a) and the spitting of (200)c (b) and (222)c reflections of non-modified (top)
and modified (bottom) samples.
Figure 10. SEM images of non-modified (a) and modified (b) samples.
Figure 11 shows the dependency of real () and imaginary () parts of complex

dielectric permittivity (* = i) of modified and non-modified samples on the
temperatures measured at different frequencies of measuring electric field. It is seen that
maximums, linked with phase transition into paraelectric state, are shifted to the higher
temperatures with an increase of measuring field frequency (with an increase of f from 1 kHz
to 1 MHz Tm = 11 degrees for the modified sample and 5 degrees for the non-modified one)
which is typical for relaxor ferroelectrics. In this case, modification by barium leads to the
temperature decrease of maximum for almost 50 degrees (Tm = 81 C in modified sample
and 130 C in the non-modified one at f = 1 kHz). This can be explained by the decrease of
covalence degree of chemical - bonds while 2+ introducing in -sublattice. Moreover,
the samples modified by barium are characterized by greater diffusion of maximum than
non-modified ones. Quantitative estimation of phase transition diffusion size was done upon
130
the formula [75]: 1/ 1/m = (T Tm)/C, where is Curie constant and is the diffusion
level of ferroelectric phase transition that varies in the range from 1 for normal ferroelectric to
2 for ideal relaxor ferroelectrics. For both samples there is dependence which is close to the
linear one (1/ 1/m) from log (T Tm) at f = 1 kHz (Figure 11b). Meanwhile, for the
modified sample = 1.85 versus 1.58 for the non-modified. Great increase of and Tm at
modification by barium allows us to suppose intensification of relaxor properties and change
of domain structure.
Figure 11. Dielectric properties of the modified (+Ba) and non-modified samples of the studied
ceramics: (a) the dependence of the real ' (closed symbols) and imaginary '' (open symbols) parts of
the complex dielectric permittivity *; (b) the dependence of log (1/ 1/m) on log (T Tm) at f = 1
kHz (the figure shows the values of for the two samples); (c) d'/dT (T)-dependence; inset shows the
curves of '(T) obtained during heating (closed symbols) and cooling (open symbols).
131
The d/dT dependences, of the modified and non-modified samples, on temperature and
temperature hysteresis of (T)-dependence (insert) are given in Figure 11 in order to provide
an additional information about the possible changes of ferroelectric phase transition
character. The shape of d/dT (T)-dependence curve of non-modified sample is characterized
by the sudden inflection close to Tm, which is typical for first-type phase transition. At the
same time, d/dT (T)-dependence of the sample modified by barium is characterized by a
more diffused out line. It may be an indirect evidence of both: the first-order phase transition
diffusion and also the tendency to shift the type of phase transition with the further increase of
2+ content. The following fact may also be given in the favor of the last statement: the
temperature hysteresis of (T)-dependence (insert), typical for the first-order transition phase
while modification by barium, decreases from T 12 degrees to T 4 degrees close to Tm.
Figure 12 shows the dependences of polarization P(E) (Figure 12a), dielectric constant (E)
(Figure 12b), piezoelectric coefficient d33(E) (Figure 12c) and longitudinal strain 3(E)
(Figure 12c, inset) obtained in different modes of electric field application. Figure 12a shows
PE hysteresis loops of modified and non-modified samples obtained at = 5 kV/m and 10
kV/m. At = 10 kV/m in both cases there were saturated loops of hysteresis with the close
values of coercive electric fields () and remanent polarizations (Pr): 5.0 kV/m, 16 C/m2
for non-modified sample and 4.6 kV/m, 14 C/m2 for the modified one.
An in significant decrease of Pr at substitution by 2+ can be explained by the lower
polarizability of 2+ in comparison with Pb2+. However at = 5 kV/m a big differences can
be seen: P-E hysteresis loop of modified sample is characterized by the greater value of Pr (10
C/m2) than non-modified one (6 C/m2) with close values of . Similar regularity is also
seen while comparing () curves of modified and non-modified samples. For example, at
= 0, of modified sample is more than two times higher than of non-modified one (9,100
and 4,300, respectively). Further increase of electric field leads to the decrease of , which is
much more dramatic in case of modified sample. At > 20 kV/m, () dependences almost
merge into one. Similar results are observed for d33()-dependences obtained from 3()
directly for modified and non-modified samples. Maximum values of d33 are observed at
6 kV/cm both for modified (d33 = 1140 V/m) and non-modified samples (d33 = 970 V/m).
However at > 10 kV/m the curves d33 () merge into one.
Therefore, the most significant differences between piezoelectric and dielectric
properties, induced by electric field of modified and non-modified samples, appear at < 10
kV/m. We associate it with different original states of modified and non-modified samples,
and first of all, with their domain structures. As it was mentioned in [76], in case of
PbSc0.5Ta0.5O3, addition of 2+ can lead to the transfer from ferroelectric to relaxor state.
Due to a big ionic radius of Ba2+, in comparison with the one of Pb2+, octahedra of BO6 close
to barium are disordered along the direction <111> and Pb-O bonds become shorter in the
plane {111}. Thus, local elastic fields appear. These fields suppress long-range ferroelectric
order and lead to the development of relaxor features and, therefore, to the change of domain
structure. In addition, when ceramics under the investigation were modified by 2+, it
resulted in an essential temperature reduction of (T)-dependence maximum and its
broadening (Figure. 11). A similar effect appeared in many other samples of isovalent
replacement of Pb2+cations in A-position [64, 65, 73, 74]. For example, in [73] it is mentioned
that adding Sr2+ to PZT ceramics results in complication of domain structure and big
reduction of domains size. Moreover, due to the differences of Pb2+and 2+, ionic radiuses
132
modification by barium can lead to production of chemical pressure which functions in a

similar way as an external hydrostatic one. Dielectric properties of solid solutions of relaxor
ferroelectrics and lead titanate (PMN-PT and PZN-PT) of compositions close to MPB under
hydrostatic pressure were studied in the number of researches [77 79] which show that
effect of high hydrostatic pressure leads to the diffusion of ferroelectric phase transition,
reduction of Tm and intensification of relaxor properties similar to the ones observed in our
experiment. According to [77] the increase of hydrostatic pressure (more than 5 kbar) in solid
solutions PZN-9.5PT leads to ferroelectric relaxor crossover induced by the pressure. At
the same time it is expected to have an increase of correlation length of polar areas at the
increase of hydrostatic pressure, which in general, is in line with our hypothesis regarding the
change of original domain structure of studied ceramics under the modification by barium.
Figure 12. Electric-field induced properties of non-modified (triangular symbols) and modified (circular
symbols) samples: () PE hysteresis loops at = 5 kV/cm (open symbols), = 13 kV/cm (closed
symbols), (b) () dependences, (c) d33(E) dependences on 3(E) (inset).
133
Crossover from the ralaxor to normal ferroelectric state accompanied by the formation of
microscopic domain structure can occur under the influence of electric field. Moreover, as
mentioned in [80] for the ceramics with similar composition, the transition from hetero-phase
state (T + Rh) to mono-phase one (T) is possible at ~ 5 kV/m. The last-mentioned one
explains disappearance of 3()-dependence hysteresis of non-modified sample at E > 6
kV/cm (Figure 11). Hereby at quite high values of the difference between phase states and
domain structures of modified and non-modified samples becomes minimal, which leads to
microscopic properties that are close by value.
4.4. Conclusion
This research was concerned with the impact of stoichiometry modification of solid
solutions of the following system: mPb(Mg1/3Nb2/3) yPb(Zn1/3Nb2/3) nPb(Ni1/3Nb2/3)
xPbTiO3 (m = 0.4541, y = 0.0982, n = 0.1477, x = 0.3) by 5 mol. % 2+ on structure,
microstructure and E induced piezoelectric and dielectric properties. Modification by
2+shows that:
(i) (i)it allows to obtain ceramics of the system under the investigation without the
pyrochlore phase;
(ii) it shifts solid solution from morphotropic to the tetragonal area of phase diagram;
(iii) it leads to the decrease of average grain size from (3 4) m to (2 3) m and
change of fracture mode: from transgranular to combined (trans- and intergranular);
(iv) it causes a decrease of Tm (from 130 to 81 at f = 1 kHz), intensification of
relaxor properties (increase of from 1.58 to 1.85 and Tm from 5 degrees to 11
degrees), decrease of temperature hysteresis (T from 11 degrees to 4 degrees),
typical for the first-order phase transition;
(v) it facilitates significant increase of polarization (from 6 C/m2 to 10 C/m2 at = 5
kV/m) of dielectric (, from 4,300 to 9,100 at = 0) and piezoelectric (d33, from 970
V/m to d33 = 1140 V/m at 6 kV/cm) properties. In addition significant differences
between values of microscopic properties disappear under the effect of electric field.
The above mentioned features of materials indicate the increase of their ferroelectric
softness while their modifying and explain changes in the initial state of crystalline, domain
and grain structures. Results of work can be used for creation of actuators and low-frequency
receivers based on ceramics under investigation.
5. THE DETECTION OF INHOMOGENEITIES IN GRAIN PATTERN

OF (1X)BIFEO3XPBFE0.5NB0.5O3 CERAMICS BY
MULTIFRACTAL SCANNING
The aspiration to versatility and price reduction of different electronic devices requires
the combination of different functional properties in one material. It leads to developing the
materials based on complex multicomponent systems. The objects of the current study were
134
(1x)BiFeO3xPbFe0.5Nb0.5O3 multiferroic solid solutions ceramics where 0 < x < 1. At the

same time, the unique combination of ferroelectric, piezoelectric and magnetic properties of
named ceramics adjoins with its extreme sensitivity to the compounds purity and conditions
of manufacturing. The small x leads to domination of BiFeO3, with critical dependence of its
structure from the conditions of synthesis, increasing electric conductivity and instability of
dielectric properties on temperature. Increasing of x leads to the stability of named properties
and higher resistivity.
The phase diagram becomes more complicated. Inhomogeneity of composition is
increasing caused by concurrence between different cations during placing in A- and Bposition of perovskite cell (including cations with different valence).
Figure 13. Scheme, showing the microstructure separation into two fields with low and high fractal
dimension D0 in 0.5BiFeO3 0.5PbFe0.5Nb0.5O3 solid solutions ceramics. The areas with high (black
continuous outline), mean and low (white interrupted outline) relative values of parameter are shown.
The multifractal parameters of grains pattern (microstructure) are sensitive indicators of

changes in crystalline structure of solid solution and its mesostructural ordering, what have
influence on macroscopic response. To reveal the spatial arrangement and distribution of the
inhomogeneities in the ceramics microstructure the new method was elaborated and used.
This method is based on multifractal scanning of the surface. The results are represented as
colored schemes. It works as follows. The snapshot of big areas (containing 2000 or more
grains) of sample surface is made with low magnification ( 200) and high resolution. The
image is divided into equals adjoining square regions Rij with the size of 100 100 pixels.
Multifractal analysis is performed by the method described in [81], multifractal parameters
(dimensions D0 D40, parameter of homogeneity f and parameter of ordering ) are
135
calculated according [1 (81)]. Minimal and maximal values of multifractal parameters of site
are determined.
The values of multifractal parameters of sites are compared with extremal values and
divided into three groups, for example, for dimensions D0 and = (D0min D0max)/3: D0min <
D0ij < D0min + , D0min + < D0ij < D0max , D0max < D0ij < D0max. The groups founded are
made by colors. When we show this distribution of parameter the area Rij, colored by
corresponding color, the outlines show the area boundaries (Figure 13). The method is able to
operatively reveal tendencies of formation of structures and optimize the technology of
ceramics production. In the system under study we distinguish the compositions having
ferroelectric and antiferromagnetic ordering simultaneously and characterizing by stable
piezoelectric state. It is very interesting for possible practical application. By our opinion,
multifractal scanning is perspective method for identifying the spatial distribution of
structural inhomogeneities, detecting the areas with high concentration of defects not only in
ceramics but also in metals and alloys.
6. PHASE DIAGRAMS AND FERROELECTRIC PROPERTIES OF SOLID

SOLUTIONS OF THE TERNARY SYSTEMS (NA, LI, CD0.5)NB3
AND (NA, LI, SR0.5)NBO3
6.1. Introduction
The present section is a continuation and a refinement of the works [82, 83]. Based on
some additional structural studies, more precise phase diagrams of the systems (Na, Li,
Cd0.5)NbO3 and (Na, Li, Sr0.5)NbO3 were constructed that allowed a more detailed
interpretation of their physical properties. As in [82, 83], the systems were studied by means
of z-sections that corresponded to 5 20 mol. % Cd0.5NbO3 and 2 50 mol. % Sr0.5NbO3 as
well as y-sections with the LiNbO3 content from 1 2 mol.% up to 15 mol.%. The regimes of
synthesis and sintering of the samples are given in [82, 83].
6.2. Solid Solutions of the (Na, Li, Cd0.5)NbO3 System

Figure 14 shows a portion of the phase diagram adjacent to NaNbO3. The thin lines show
y- and z-sections and the thicker ones indicate the boundary lines of the regions of different
symmetry (one-, two- and three- phase ones). The phase diagram of the ternary system agrees
with the diagrams of the binary systems limiting it [84 86], and, accordingly, we see wide
regions of crystallization of the NaNbO3-based SS of orthorhombic structure with
quadruplication (phase M4) and reduplication (phase M2) along the b-axis, the tetragonal
structure (phase T4) and the narrow regions of rhombohedral (Rh) and orthorhombic (M2)
structures together with the regions of their coexistence.
As is well-known [87 89], the electrophysical parameters of ferroelectric SS of
different systems containing morphotropic regions (MR) have extreme values in the vicinity
of MR which correlate with the values of structural parameters, in particular, with the
homogeneous deformation parameter 8 [90].
136
Figure 14. Phase diagram of the ternary system (Na, Li, Cd 0,5)NbO3.
Figure 15. Dependences of structural and electrophysical characteristics of SS of the (Na, Li,
Cd0.5)NbO3 system on the LiNbO3 content for the section z = 5 mol. % Cd0.5NbO3.
137
Let us consider the best studied sections of the system which, in addition, pass through
the largest number of phases and MR. Among the z-sections, satisfying these conditions is the
section z = 5 mol. % which passes through three phases M4, M2, Rh and three MR (a narrow
two-phase MRj (M4 + M2), a wide three-phase MR2 (M2 + T4 + Rh) and a very narrow twophase MR3 (Rh + M2)) (Figure 15a, b). Figure 15a shows the concentration dependences of
the parameter 5, the dielectric permittivities /0 and T33/0 and the piezoelectric parameters
Kp, d31, g31.
Figure 15b presents the dielectric loss tangent tan , the mechanical quality factor Qm, the
sound speed VR and Young's modulus YE11. It may be seen from Figure 15a that both the
dielectric permittivities of SS and the parameters Kp and d31 have two maxima: the larger
maxima are placed near the center of the three-phase MR2 and the smaller ones are at the
right-hand boundary of the narrow MRj. In addition, all these parameters pass through the
minima inside the phase M2.
As for the piezoelectric parameter g31 which is known to be proportional to the remanent
polarization Pr, its maxima are shifted to the left from both MRj and MR2 to the side of the
phases M2 and M4 (in the phase M4 this maximum is not fully examined because of the
absence of corresponding samples). Such positions of the maxima of g31 are observed usually
in ferroelectric systems [87, 88]. The considered dependences of the electrophysical
parameters may be related to the behavior of the parameter , which is minimum inside both
MRs and passes through the maximum in the phase M2. (The extreme narrowness of MO3
makes it difficult to take into account its influence on the concentration dependences of the
parameters).
Of special interest is the fact that in Figure 15a the larger maximum of 33/0 is located
not outside the right-hand boundary of the wide MR2 [87, 88] but inside MR2. The same
situation was observed in some sections of the (Na, Li, Pb0.5)NbO3 system [89] and this was
explained, in particular, by coexistence of two phases (M and Rh) leading to a considerable
increase in the number of possible directions of the spontaneous polarization vector: N =
8(Rh) + 12(M) = 20 as compared with the pure phases. (In PZT-based systems [87, 88] this
number is much smaller: N = 8(Rh) + 6(T) = 14 and does not, practically, affect the position
of the 33/0 maximum). In the case under consideration, in the three-phase MR2, N is much
larger: N = 8(Rh) + 12(M) + 6(T) = 26 which leads to a remarkable increase of the orientation
part of dielectric permittivity inside MR and determines the corresponding position of
maxima of both /0 and T33/0. This, in turn, has an influence on the positions of the Kp and
d31 maxima, which are only slightly affected by the magnitude of g31 which anyway is small
in this system.
A similar situation is observed in the narrow MR, where N = 12(M2) + 12(M4) = 24 and
the T33/0 maximum has a larger effect on the Kp and d31 values than the g31 maximum
concentration dependences of the parameters tan , Qm, VR and YE11 shown in Figure 15b can
be explained in terms of influences [87].
As shown in [87], with the enhancement of ferrostiffness, the parameters , Qm. VR, YE11
increase while T33/0 and tan decrease.
This leads to the closeness of positions of the T33/0 and tan maxima and minima (see
Figure 15b), whereas the positions of the Qm, VR and YE11 maxima are close to the position of
the T33/0 minimum (and vice versa). The parameters of some compositions of the (Na, Li,
Cd0.5)NbO3 system are present in Table 6.
138
Among the y-sections the most clear-cut regularities in variations of the parameters can
be observed at y = 4 mol. %. This section passes through the regions of the phases M2 and T4
and the two MRs: a wide MRj (T4 + M2) and a narrow MR2 (M4 + M2) (see Figure 14). The
regularities in the variation of electrophysical parameters are similar to those observed in
most ferroelectric systems [87, 88] and correlate with the behavior of .
Table 6. Parameters of some compositions of the (Na, Li, Cd0.5)NbO3 system
6.3. Solid Solutions of the (Na, Li, Sr0.5)NbO3 System

As in the majority of the niobate systems, compositions of the system under consideration
admit a high sound speed and have a low density and also a high Curie temperature TC (> 400
C) as well as a wide spectrum of dielectric permittivity values (from 160 to 1000 1200) at
the acceptable piezoelectric parameters, this enables one to use them in high-temperature
transducers operating in high- and middle-frequency ranges.
Figure 16 shows a portion of the phase diagram adjacent to NaNbO3. Thin lines show the
y- and z-sections and the thicker lines delineate the boundary lines of regions of different
symmetry (one- and two-phase regions). It should be noted that the phase diagram of the
system under study is of lesser complicated character than that described above. In the (Na,
Li, Sr0.5)NbO3 system one can distinguish a wide MRj (M2 + Rh) and a narrow MR2 (Rh + M2)
in the vicinity of which one should expect the appearance of extreme values of
electrophysical and structural parameters.
Let us consider the z-section which is the most typical section of the system under
consideration. Figure 17a, b shows the concentration dependences of parameters for z = 15
mol. %; dashed lines delineate a wide MR1 and a narrow MR2. Figure 17a presents , T 33 /0,
/0, Kp, d 31 , g 31 and Figure 17b shows tan , Qm, VR, YE11. It is seen that the dielectric
parameters and the parameter g31 pass through the maxima at the opposite boundaries of MRj
which is typical of the ferroelectric systems. The positions of the Kp, d31 and T33/0 maxima
coincide. Corresponding to them are the minimum values inside MR1.
As to other parameters (Figure 17b), the behavior of some of them correlates with the
change in the degree of ferrostiffness of SS, namely: the parameters VR and YE11 vary in the
direction opposite to the change of T33/0. However, the changes of tan and Qm cannot be
explained from this point of view. It should be noted that their dependences exhibit kinks at
the boundary between MR 1 and the Rh phase.
139
Figure 16. Phase diagram of the ternary system (Na, Li, Sr 0.5)NbO3.
Figure 17. Dependences of structural and electrophysical characteristics of SS of the (Na, Li, Sr0.5)NbO3
system on the LiNbO3 content for the section z = 15 mol. % Sr0.5NbO3.
140
Unlike the z-section, in other sections of this type one can observe considerably broken
characteristics and this may be related not only to the MR position. Approximately in the
same range of the LiNbO3 concentrations, where one can observe the maxima of T33/0, Kp,
d31, g31, subsystems with a different degree of compositional ordering of various ions in Asublattices were revealed.
To elucidate the effect of the degree of ordering of these ions on electrophysical
parameters of SS under study we have analyzed the data of [90] on the origin of high values
of the dielectric permittivity in complex oxides A(B'1/2B'1/2)O3 with a disordered structure. In
[90], it was concluded that in an ordered structure the small ions being in a regular
surrounding by the larger ions have a considerably smaller free space for displacements than
in a disordered structure. Therefore, on applying an electric field, the small ions shift much
easier in the disordered structure without destruction of the oxygen framework than in the
ordered one. This leads to a larger polarization per a unit of the electric field and, hence, to
larger dielectric permittivity values. The same mechanism of the increase of the dielectric
permittivity and the dependent electrophysical parameters may, in our judgement, account for
the observed extremums on the boundaries of the above-mentioned systems with a different
degree of ordering. One of the most interesting properties of individual SS of the system
under consideration is the combination of rather low values of the dielectric permittivity
(T33/0 = 105 125) with a quite high electromechanical coupling factor (Kp = 0.2 0.3),
which leads to high values of the coefficient g31 characterizing sensibility to mechanical
stresses. As known [87, 88], such materials may be effectively used in accelerometers,
defectoscopes and diagnostic medical equipment. The low dielectric permittivity is favorable
for these materials to be utilized in high-frequency transducers. Table 7 summarizes a number
of compositions with such properties.
Table 7. Parameters of some compositions of the (Na,Li,Sr0,5)NbO3 system
6.4. Conclusion
The precision of X-ray studies of SS of the ternary systems (Na, Li, Cd0.5)NbO3 and (Na,
Li, Sr0.5)NbO3 enabled us to determine more accurately the symmetry of crystallizing phases,
structural transitions and the morphology of morphotropic regions.
The dependences of electrophysical parameters of SS of the above-mentioned systems
were studied in a wide range of concentrations, and their relation with structural parameters,
in particular, with the homogeneous deformation parameter was established.
Compositions were obtained with unique combinations of electrophysical parameters
(low values of density, high values of sound speed and piezoelectric parameters for a broad
141
spectrum of dielectric permittivity values) useful for various applications (HF- transducers,
defectoscopes, accelerometers, diagnostic medical equipment).
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ISBN: 978-1-63321-239-8
Chapter 6
NEW MODEL FOR PIEZOELECTRIC MEDIUM WITH

VOIDS FOR APPLICATION TO ANALYSIS OF
ULTRASONIC PIEZOELECTRIC TRANSDUCERS AND
POROUS PIEZOCOMPOSITES
G. Iovane*1 and A. V. Nasedkin2
1
D.I.E.M, University of Salerno, Fisciano (SA), Italy

Department of Mathematics, Mechanics and Computer Sciences,
Southern Federal University, Rostov-on-Don, Russia
ABSTRACT
In this chapter, for modeling piezoelectric porous materials and transducers, the new
mathematical model, which generalize the model of the piezoelectric medium with
damping properties, and the Cowin-Nunziato model of the elastic medium with voids are
proposed. Using these models for piezoelectric bodies with voids or pores, the effective
moduli of porous piezocomposite ceramics could be defined more precisely.
In new generalized Cowin-Nunziato model, the field functions of mechanical
displacements, electric potential and function of the porosity change are considered. On
the base of this model, we have obtained the formulations of the generalized continual
statements for piezoelectric bodies with voids or porous and finite element approximation
in the expanded and reduced forms. We have also investigated the mathematical
properties of the natural frequencies and eigenvectors for piezoelectric bodies with voids
for different types of the boundary conditions, including the boundary conditions of
mechanical and electric contact types. We have established some theorems on changes of
the resonant frequencies with changes of the boundary conditions and material properties.
For numerical analysis, we have obtained the finite element approximations of the
problems for piezoelectric bodies with voids.
By using the new model for piezoelectric bodies with voids, the effective moduli of
porous piezoceramics for some piezoelectric materials are defined more precisely. The
*
iovane@diima.unisa.it, D.I.E.M., University of Salerno, Via Ponte don Melillo, 84084, Fisciano (SA), Italy
nasedkin@math.rsu.ru, Department of Mathematics, Mechanics and Computer Sciences, Southern Federal
University, 8a, Milchakova Street, 344090 Rostov-on-Don, Russia
146

efficiency of the proposed model and finite element approximations is verified by the
analysis of a focusing spherical device, made from porous piezoceramics and emitting
ultrasonic waves in surrounding acoustic medium. Modal, harmonic and transient
analysis for single piezoelectric emitter and full transducers, loaded on the acoustic
medium, is carried out. The focal zone in acoustic medium is determined for resonant
frequencies and transient problem.
1. INTRODUCTION
As it is well known, porous piezoceramic materials have received considerable attention
due to their application in ultrasonic transducers, hydrophones, pressure sensors and other
piezoelectric devices. The piezocomposites in the form of porous lead zirconate titanate
(PZT) materials show considerably improved transducer characteristics. Porous
piezocomposites have great potential for low acoustic impedance and higher efficiency
compared to conventional dense PZT piezoceramic materials.
The microstructural characterization, analysis and classification of piezoelectric
composites have been initiated by Newnham's connectivity theory [1]. In compliance with
this theory, the porous piezoceramic could be classified as two-phase composite. However, at
that porous composite piezoceramic having pores, lesser than 100 m may be accepted as a
quasi-homogeneous medium with some effective moduli for most applications. There are
many publications, in which the effective properties of porous piezocomposite media have
been analyzed using different theoretical models [2 4, etc.]. For example, the use of
Marutake's and Bruggeman's approximations for calculation of effective moduli of
piezocomposites was offered in [4]. The dilute, self-consistent, Mori-Tanaka and differential
micromechanics theories were extended in [2] to consider the effective characteristics of
piezocomposite materials. The application of each theory was based on three-dimensional
static solution of an ellipsoidal inclusion in an infinite piezoelectric media. Theoretical
models, including optimization techniques and homogenization methods, have also been
proposed for piezocomposite in [3].
For further applications, in nearly all investigations the porous piezocomposite was
considered as a homogeneous material with the re-counted effective moduli. Thus, the
influence of porosity at such approaches is taken into account only through effective moduli.
It is necessary to note also, that the usual dense piezoceramics, obtained in a result of
sintering of ceramic powders, is actually a weakly porous material, and its density differs
from the density of a continuous piezoceramic material approximately in 2 %. For elastic
materials with voids, a special theory has been offered by Nunziato and Cowin in [5, 6].
Development of this theory on the case of a piezoelectric material has been given in [7] for
general case and in [8 11] for cases of modal, harmonic and transient problems.
In this paper, we use FEM for analyzing different problems for piezoelectric media with
voids with some damping effects. We consider non-classical mechanical boundary conditions
with rigid stamps and non-classical electric boundary conditions for the system of opencircuited and short-circuited electrodes. Note that the boundary conditions for covered
electrodes surfaces are the required boundary conditions for the real piezoelectric devices.
The similar setting for the corresponding electroelasticity modal problem has been considered
in [12, 13], but only for pure piezoelectric body without taking into account mass
New Model for Piezoelectric Medium with Voids for Application to Analysis
147
characteristics of punches, and also in [14, 15] for elastic body with voids without taking into
account the piezoelectric properties of material.
The chapter is organized as follows. In Section 2, the classical formulation of dynamic
problems for piezoelectric media with voids is present; whereas the generalized or week
formulation for dynamic problems there is in Section 3. In Section 4, we give the week
formulation for harmonic and modal problems and we demonstrate the way for generation of
the reduced formulation. The mathematical properties of the natural frequencies and
eigenvectors are described in Section 5. Also in Section 5, we formulate some theorems on
changes of the resonant frequencies with changes of the boundary conditions and material
properties. Section 6 is devoted to the finite element approximations of the generalized
formulation for transient, harmonic and modal problems. In Section 7, the numerical
examples are considered. Conclusion and remarks are present in Sect. 8.
2. CLASSICAL FORMULATIONS OF TRANSIENT PROBLEMS FOR

PIEZOELECTRIC MEDIA WITH VOIDS
Let R be a region occupied by a piezoelectric material with voids or with very
small porosity; is the boundary of the region; n(x) is the vector of the external unit
3
normal to . We will assume that the region and its boundary are subjected to the
following conditions: is the sum of a finite number of sets, star-shaped with respect to any
spheres contained in them, while is a Lipschitz boundary of class C . These ( , )
usual mathematical conditions for elastic problems are detailed in [16].
We consider linear piezoelectric material with voids where the porosity is simulated by
the Cowin-Nunziato model with memory effect for the intrinsic equilibrated body force
[5 7].
1
Let ui ui (x, t ) denote the components of the displacement vector; (x, t ) is the
electric potential; (x, t ) is the porosity change function (the change in the volume
fraction from the reference configuration); x {x1 , x2 , x3 } {x, y, z} ; t is the time. By the
first two functions, one can determine the components of the strain tensor ij and the
components of the electric fields vector Ei
1
2
ij (ui , j u j ,i ) ; Ei ,i .
(1)
In the context of the linear theory, we assume the constitutive equations for piezoelectric
bodies similarly to [7] omitting some terms and complementing elastic, electric and porosity
change by the damping effects as
E
ij cijkl
( kl d kl ) e kij Ek Bij ,
(2)
148
Di d D i e ikl ( kl d kl ) ikS Ek gi Gik, k ,
(3)
h i Gik Ek Aik, k , g Bkl ( kl d kl ) g k Ek ,
(4)
where ij are the components of the stress tensor; D i are the components of dielectric
displacement vector; h i are the components of the equilibrated stress vector; g is the
E
intrinsic equilibrated body force; cijkl are the components of the fourth rank tensor of elastic
moduli, measured for a constant electric field; e ikl are the components of the third rank
tensor of piezoelectric moduli; ik are the components of the second rank tensor of
S
permittivity moduli for a constant mechanical strain; Aik , Bij , g i , Gik and are the
constitutive constants characterizing the properties of porosity changes;
d , d and d are
non-negative damping coefficients. Note that in comparison with [7], we use some different
definitions and neglect dependencies from the temperature. We also omitted some terms so
that when considering materials without piezoelectric connectivity we could get the
relationships adopted in [7] for the case of pure elastic materials with voids.
In the case of the transient problem for a piezoelectric medium with voids, structural,
electric and porosity-dependent damping and without inertia effect, caused by porosity, we
have the following system of the field equations:
ij , j fi ui d ui ,
(5)
Dj, j ,
(6)
h j , j g l d l 0 ,
(7)
where is the density of the material; f i are the components of the mass forces vector;
is the additional non-negative damping coefficient;
is the volumetric density of free
electric charges (usually, 0 ); l is the extrinsic equilibrated body force.

In model (1) (7) for the piezoelectric material with voids, we accept a generalized
Rayleigh method of damping evaluation similarly to [12, 13], which is suitable for many
practical applications.
For the case of a pure elastic material with voids ( e ikl 0 , gi 0 , Gik 0 ), system
(1) (7) is reduced to the form from [12, 13]. When in (3)
d 0 , then for the piezoelectric
media without voids ( Bij 0 , gi 0 , Gik 0 ) we have usual model with the mechanical
attenuation which is adopted in several well-known finite element packages. It is true that, by
149
virtue of the coupled state of mechanical and electric fields, the damping effects will be also
extended into the electric fields, when
d 0 . More complicated model (2) (4) extends the
Kelvin's model for electric fields to the case of piezoelectric media with voids.
We suppose that the density function (x) is piecewise-continuous, and 0 0 :
(x) 0 . The other moduli in (2) (4) are piecewise uninterrupted together with its first
derivatives
E
ijkl
E
jikl
with
E
ijlk
respect
to
(x)
and
have
the
usual
symmetry
properties:
c , e ikl e ilk , , Aik Aki , B ik B ki , G ik G ki . In

E
klij
S
kl
S
lk
addition to this for the positive definiteness of the intrinsic energy for the piezoelectric
medium with voids the following inequalities must be satisfied ( ij ji , Ei , , bi ):
W0 0
E
cijkl
ij kl 2 2Bij ij Aijbib j ijS Ei E j W0 ( ij ij 2 b jb j E j E j ) .
(8)
The boundary and the initial conditions should be added to the system (1) (7) with (1)
(4). The boundary conditions are of three types: mechanical, electric and "porous".
To formulate the mechanical boundary conditions we will assume that the boundary
can be divided into two subsets: and u ( u ). We suggest that on the
boundary the mechanical stress vector p p (x, t ) is defined, i.e.
ij n j pi ; x .
(9)
Suppose that u i u i ; i 0, 1, 2, ..., L ; u 0 , u i do not border one another;

while among u i there are L 1 l surfaces with given functions of displacement u u
( i J r {0, l 1, l 2,..., L} ) and l plane regions ( i J p {1, 2, ..., l} ), in friction-free
contact with rigid massive punches (stamps). We will connect with region u i , i J p the
1(i ) (2i ) (3i ) so that the axis (3i ) coincides in direction with the
(i )
local coordinate system O
(i )
direction of external normal n at the point O ; and the axes
1(i ) and (2i ) will be the main
axes of inertia for the punch with number i (Figure 1). Then, we can assume the following
boundary conditions for u i :
2
ui ni iku (ki ) , ( (0i ) 1 ), x u i , i J p ,

k 0
(10)
150
u i
(pi ) kl nk nl d (ipu dipu )M p(i ) Pi p , p 0,1, 2 , i J p ,
(11)
ik nk ( k mnk nm ) ni 0 , x u i , i J p ,
(12)
u u i , x u i , u 0 , i J r ,
(13)
where in (10), (11) the summation by repeating index i and p is missing; i0 is the normal
u
displacement of the punch with number i ;

angles about axes
iu1 (2i ) , iu2 1(i ) are the punch rotation
(2i ) and 1(i ) , respectively; M (0i ) is the mass of punch; M 1(i ) J
(i ) (i )
2 2
M (2i ) J ( i ) ( i ) are the inertia moments of punch; Pi p are the force (with p 0 ) and the
1
moments (with p 1, 2 ), acting on the punch with number i ; u i ui (x, t ) are the
components of determined functions of displacements on u i , i J r .
Figure 1. Mechanical contact type boundaries with plane punches.
Let us pass to a formulation of electric boundary conditions. We assume that the

boundary is also subdivided into the parts D and ( D ).
The surface D is assumed free of electrodes, and the following condition is satisfied
n j D j D ; x D ,
where
(14)
D is the surface density of electric charge (usually, D 0 ).
The subset itself is subdivided into M 1 sub-domains j ( j J e o J e s ),
J eo {1, 2, ..., m} , J es {0, m 1, m 2,..., M } , 0 , which are not adjacent to one

another, and are coated by infinitely thin electrodes. We will specify the following boundary
conditions on these areas:
j (t ) ; x j , j J e o ,
151
(15)
nk Dk d Q j , Q j I j , j J eo ,
(16)
V j (t ) , x j , 0 , j J es ,
(17)
where the variables j , Q j , V j depend only on time t ; Q j is the overall electric charge on
electrode j , and the sign " " in (16) is chosen in accordance with the accepted direction
of the current I
in the electric circuit.
By (15), (16) there are
m electrodes on which the electric potentials j are initially
unknown, but the overall electric charges Q j or currents I
on each electrode are defined.
The remaining M 1 m electrodes are the electrodes with the known electrical voltages
Vj .
Let us note that j in (15) and V j in (17) are independent from the space coordinates
x , and therefore, the electrodes are equipotential surfaces. Integral condition (16) is similar
(i )
to the mechanical contact condition for rigid massless punches ( M p 0 ). But the
distinguishing feature of the piezoelectric elements is that the boundary conditions (15) (17)
are necessary for them, since they determine the outer electric influence between the electric
potentials and the charges or circuits.
Note that for homogeneous boundary conditions on the electrodes j with Q j 0 in
(16) and V j 0 in (17), these surfaces are called the open-circuited electrodes and the shortcircuited electrodes, respectively.
To specify the "porous" boundary condition we suppose that the boundary is also
divided into two parts: 0 and n ( 0 n ). We take the homogeneous Dirichlet
condition on the surface 0 :
0 ; x 0 ,
(18)
and we accept the homogeneous Neumann condition on n :
hk nk 0 ; x n ,
(19)
where in real situations the boundary condition (18) is usually absent.

We also assume that all domains , u i , D , j , 0 and n have Lipshitz
1
boundaries of class C [16].
152
For transient problems, it is also necessary to state the initial conditions, which can be
written as
ui (x,0) u*i (x) , ui (x,0) v*i (x) ; x ,
(20)
where u*i are the components of initial displacement vector and v*i is the components of
initial velocity vector of the bodys points x .
Formulae (1) (20) represent a classical formulation of the linear problems of
piezoelectricity with voids and with the generalized Rayleigh damping.
3. GENERALIZED AND VARIATIONAL FORMULATIONS

To formulate the weak or generalized solution of dynamic problem for piezoelectric solid
with voids in the beginning we will introduce the space of functions , and the vector
functions u {u1 , u2 , u3} , defined in , which we will need later.
We will denote by H the space of vector functions u L 2 with the scalar product:
0
( v, u)H 0 vk uk d .
(21)
On the set of vector functions u C which satisfy homogenous boundary conditions

1
u
(13) on u i , i J r , and (10) for arbitrary ik on u i , i J p , we will introduce the scalar
product:
( v, u)H1 vi , k ui , k d .
ul
The closure of this set of vector functions
(22)
u in the norm generated by scalar product (22)
1
ul
will be denoted by H , where l is the number of boundary conditions (10) (12) for rigid
punches.
C1 which satisfy homogenous boundary conditions (17) on

j , j J es , and (15) for arbitrary j on j , j J eo , we will introduce the scalar
On the set of functions
product:
( , )H1 , k, k d .
m
(23)
153
The closure of this set of functions in the norm generated by scalar product (23) will
1
be denoted by H m , where
m is the number of boundary conditions (15), (16).
We will introduce the scalar product on the set of functions
C1 , which satisfy (18):
( , )H1 , k, k d .
(24)
The closure of this set of functions in the norm generated by scalar product (24) will
1
be denoted by H .
Finally we will introduce the spaces Qu l , Q m and Q as
1
1
Qu l L2 (0, T; H1u l ) , Q m L2 (0, T; H m ) , Q L2 (0, T; H ) ,
(25)
where for Banach space X with norm || . || X , the space L2 (0, T; X ) is the space of (class)
functions t f (t ) from [0, T] into X which satisfies the condition:
1/ 2
T || f (t ) || 2 d t
X
0
|| f || L 2 (0,T; X ) .
We present the solution {u, , } of the transient problem (1) (20) for piezoelectric
medium with voids in the form:
u j u 0 j ub j , 0 b ,
(26)
where u 0 i , 0 satisfy homogeneous boundary mechanical and electric conditions and u b j ,

b satisfy the inhomogeneous boundary conditions, i.e.
2
k 0
k 0
u 0 j n j iuk0 (ki ) , u bjn j iubk (ki ) , iuk0 iukb iuk , x u i , i J p ,
(27)
u 0 j 0 , ub ui , x u i , u 0 , i J r ,
(28)
0 0 j , b bj , 0 j bj j , x j , j J eo ,
(29)
0 0 , b V j , x j , 0 , j J es ,
(30)
and therefore,
154
u0 Qu l , 0 Q m , b Q M .
(31)
To formulate the weak or generalized solution of dynamic problem for piezoelectric solid
with voids we scalar multiply Equation (5) by some arbitrary vector function v(x) Hu l ,
1
Equation (6) by some arbitrary function

function
(x) H1 m and Equation (7) by some arbitrary
(x) H1 . By integrating the obtained equalities over domain and using
integration by parts, taking into account the formulated boundary conditions, we obtain the
weak formulation of dynamic problem for piezoelectric solid with voids.
Definition: The functions {u, , } in the form (26) with (27) (31) ( u0 Qu l ,
0 Q m , Q ) are the weak solution of dynamic problem of the piezoelectric media

with voids, if the following integral relations are satisfied:
0 ) d ( v, u 0 ) c( v, u0 ) e(0 , v) b( v, ) L u ( v)
~( v, u
e( , u0 d u 0 ) ( , ) g ( , ) L ( ) d
b(u0 d u 0 , ) g (0 , ) a( , ) L ( ) d
~
L ( ) ,
t
~
L ( ) ,
t
(32)
(33)
(34)
H1 m , H1 , and the initial conditions (20) are also hold.
1
for t [0, T ] ; v Hu l ,
Here we introduce the bilinear forms and functions:

l
~( v, u) ( v, u) ivk iuk M (ki ) , ( v, u) ( v, u) H ,
(35)
E
c( v, u) cijkl
ij ( v) kl (u) d , e( , v) eikl kl ( v),i d ,
(36)
b( v, ) Bij ij ( v) d , ( , ) ijS ,i , j d ,
(37)
g ( , ) (Gij ,i, j gi ,i ) d , a( , ) ( Aij,i, j ) d ,
(38)
d ( v, u) d ~( v, u) d c( v, u) ,
(39)
Lu ( v) L fp ( v) ~( v, ub ) d ( v, ub ) c( v, ub ) e( b, v) ,
(40)
i 1 k 0
l
155
L fp ( v) vi fi d vi pi d ivk Pi k ,
(41)
~
L ( ) L ( ) e( , ub d u b ) ( , b ) ,
(42)
i 1 k 0
m
~
L ( ) d D d X j Q j ,
(43)
j 1
~
~
L ( ) L ( ) b(ub d u b , ) g ( b , ) , L ( ) l d ,
(44)
where
ivk are the values from (10) for vector-function v H1u l and X j are the values
from (15) for function
H1 m .
From this weak formulation of transient problem, we can easily obtain the weak
formulation of static problem, modal problem and harmonic problem for piezoelectric solid
with voids.
4. HARMONIC AND MODAL PROBLEMS

When all external influences, specifying boundary pressures, forces, charges,
displacements and potentials, vary as the same harmonic law, exp[ jt ] , we have the
~ exp[ jt ] , ~ exp[ jt ] , exp[ jt ] .

behavior of steady-state oscillations: u u
In this case, as it is obvious from (32) (34), we have the system of integral relations for the
amplitude functions and values:
2 ~( v, u0 ) j d ( v, u0 ) c( v, u0 ) e( 0, v) b( v, ) L u ( v)
(45)
~
e( , u0 j d u0 ) ( , 0) g ( , ) L ( ) j d L ( ) ,
(46)
~
b(u0 d u 0 , ) g ( 0, ) a( , ) L ( ) j d L ( ) ,
(47)
~ H1 , ~ H1 ,
where the symbol {~ } for amplitude functions and values is absent, u
0
m
0
ul
~
H1 .
The resonance frequencies f k k /( 2 ) for piezoelectric solid with voids can be
found from the solution of the generalized eigenvalue problem or modal problem, obtained
from (45) (47) with d ( v, u0 ) 0 , L u ( v) 0 , L ( ) 0 , L ( ) 0 , L ( ) 0 ,
~
L ( ) 0 , i.e. without all external inhomogeneous influences and without damping effect
( d d d d 0 ):
156
2 ~( v, u) c( v, u) e( , v) b( v, ) 0 ,
(48)
e( , u) ( , ) g ( , ) 0 ,
(49)
b(u, ) g ( , ) a( , ) 0 ,
(50)
where u u 0 ,
0 , since ub 0 , b 0 for homogeneous boundary conditions.
Problem (48) (50) is an eigenvalue problem and consists of finding the eigenvalues
2 and eigenfunctions u , and , which give non-trivial solutions of the

homogeneous boundary problem.
We can transform the system (32) (34), (45) (47), (48) (50) by consecutive
elimination of the functions and . For example, for modal problem (48) (50), we can
realize the following operations [9].
~
Note that by virtue of the properties assumed earlier, the forms ( v, u) , c( v, u) ,
( , ) and a( , ) are symmetrical, bilinear and positive defined in L 2 , H1u l , H1 m and

H1 , respectively, while e( , v) , b( v, ) and g ( , ) are only bilinear forms.
Since for fixed u Hu l ,
1
H1 m and H1 the forms b(u, ) , g ( , ) and
a( , ) are linear-bounded functions in H1 , by Riesz theorem the elements bu , g ,
a H1 exist and are unique so for that for H1 we have

b(u, ) (bu, )H1 , g ( , ) ( g , )H1 ,
(51)
a( , ) ( , a )H1 .
(52)
1
It is obvious that bu , g and a are linear operators acting from H u l into H , from
1
H1 m into H1 and from H1 into H1 , respectively, and an inverse exists for the operator
a .
From (50), (51) and (52) we obtain that
1
a bu g , Bu G , B a 1b , G a g ,
(53)
1
1
where the operators B and G act from H u l into H and from H m into H ,
respectively, and are linear and bounded.

Using (51) (53) we can represent the system (48) (50) in the reduced form:
157
c~( v, u) e~( , v) 2 ~( v, u) ,
(54)
e~( , u) ~( , ) 0 ,
(55)
where
c~( v, u) c( v, u) a( B v, Bu) ,
(56)
e~( , v) e( , v) a( B v, G ) , ~( , ) ( , ) a(G , G ) .
(57)
Note that for transformation of the system (48) (50) we used the transform:
b( v, ) (b v, )H1 (a a 1b v, )H1 a( B v, ) ,
and similar chains of equalities.

By excluding the porosity change function , we obtain the system (54), (55), which
describe the natural vibrations for porous piezoelectric medium with modified piezoelectric
~( v, u)
properties. By virtue of positive defined potential energy of material (8), the forms c
1
~
and ( , ) are positive defined in H u l and H m , respectively. Therefore we can proceed
1
with reduction of system (54), (55) by eliminating the function of electric potential .
H1 m , the forms e~( , u) and ~( , )

1
~ ~
, by Riesz theorem the elements e u , H
exist
Analogously, since for fixed u Hu l and

1
are linear-bounded functions in H m

and are unique, so that for
H m we have
1
e~( , u) ( , e~u)H1 , ~( , ) ( , ~ )H1 .

m
m
(58)
1
1
~
~
It is obvious that e u and are linear operators acting from H u l into H m and from
H1 m into H1 m , respectively, and an inverse exists for the operator ~ .

From (55) and (58) we obtain that
~ e~u , A l m u , A l m ~ 1e~ ,
(59)
1
1
where the operator A l m acting from H u l into H m , is linear and bounded and the
subscripts l , m indicate the problem with l rigid punches and m open-circuited electrodes.
By using (58), (59), we can represent system (54), (55) in the final form:
158
c~l m ( v, u) 2 ~( v, u) ,
(60)
where
c~l m ( v, u) c~( v, u) ~( A l m v, A l mu) .
(61)
Definition: We will call the set of quantities ( , u Hu l ,

2
H1 m , H1 ), which
satisfies (60) for arbitrary vector function v Hu l or which is equivalent (54), (55) for
1
arbitrary v Hu l ,
1
H1 m or (48) (50) for arbitrary v H1u l , H1 m , H1 , a
generalized solution of eigenvalue problem for piezoelectric body with voids.

Analogously, we can obtain the reduced formulation for the transient problem (32) (34)
and harmonic problem (45) (47).
5. MODAL PROBLEM. MATHEMATICAL PROPERTIES

AND SOME THEOREMS ABOUT EIGENFREQUENCIES
1
By repeating the topics presented in [16], we can show that the space H c , which is the
closure of the set of vector function u C , satisfying (10) and homogeneous boundary
1
condition (13) in the norm generated by the scalar product (61), is the equivalent to H u l , and
the next two theorems follow from the complete continuity of the embedding operator from
H1u l
into
H 0 ,
as
also
in
the
general
situation
[17].
Here
the
form
c( v, v) ( , ) a( , ) 2b( v, ) should be positive defined, that is provided by

conditions (8).
Theorem 1: The operator equation (60) has a discrete spectrum 0 1 ... k ... ;
2
2k as k , and the corresponding eigenfunctions u (k ) form a system that is

0
1
orthogonal and complete in the spaces H and H c .
Theorem 2: (The Courant Fisher minimax principle).

max
min
Rl m ( v) ,
v 0 , vH1u l
w 1 , w 2 ,...,w k 1 H1u l
~ ( v , w j ) 0; j 1,2 ,...,k-1
2
k
where R l m(v) is the Rayleigh quotient
159
R l m( v) c~l m ( v, v) / ~( v, v) .
Proofs of these two theorems completely repeat well-known proofs of corresponding
theorems for the conventional elastic media with replacement of the forms c and by c~l m
~
and [17].
We observe that the orthogonality conditions in Theorem 1 can be present in the forms:
(u(i ) , u( j ) ) H 0 0 , (u(i ) , u( j ) ) H 1 0 , i j .
Then, we will observe the change of the natural or resonance frequencies of the problem
(48) (50) or (60) when some of its parameters change. These changes will be indicated
explicitly in the formulations of the following theorems, and all the quantities referring to the
modified problems will be indicated by subscripts l m or by an asterisk. For the initial and
modified problems are no specified in formulations of theorems the determining parameters
are assumed to be identical.
We will also call problem (48) (50) or (60) the l m -problem, emphasizing by this the
presence of l areas of u i ; i 0, 1, 2, ..., l , in contact with rigid plane punches and m
open-circuited electrodes j , j 0, 1, 2, ..., m .
We will consider two similar l m - and p m -problems, which solely differ in the number
l and p of contacting surfaces of u i in (10) (12). All the remaining input data from (1)
(19) in the l m - and p m -problems are assumed to be the same.
Theorem 3: If 0 l p L , for any k , the k -th natural frequency l m k of l m problem is no lesser than k -th natural frequency p m k of p m -problem, i.e.
l2m k p2 m k
.
We note that in conditions of Theorem 3, we do not change the boundary u . When
passing from l m -problem to p m -problem we only change conditions of fixed boundary by
the conditions of contact with punches on the parts of u i .
We will now consider two similar l m - and l n -problems, which solely differ in the
number m and n of open-circuited electrodes of j in (15) (17).
Theorem 4: If 0 m n M , for any k , the k -th natural frequency l m k of l m problem is no greater than k -th natural frequency l n k of l n -problem, i.e.
l2m k l2n k .
Theorem 5: If the rigid clamped and contacting with punch parts of boundaries of two
problems are such that u *u , u i *u i , i 0, 1, 2, ..., L , we have
2k *2k for
k.
Theorem 6: If the elastic moduli, piezomoduli, the constitutive constants characterizing
the properties of porosity changes, the densities and the masses and the inertia moments of the
160
~ ( v, v) c~ ( v, v) , ~( v, v) ~ ( v, v) for
punches of two problems are such that c
*
lm
l m*
v H1u l , then 2k *2k for k .
Theorem 7: If the electrode boundaries of two problems are such that * ,
j * j , j 0, 1, 2, ..., M , we have 2k *2k for k .

Theorem 8: If the permittivities of two problems are such that
( , ) * ( , )
H1 m , then 2k *2k for k .

Theorem 9: If the "porous" Dirichlet boundaries of two problems are such that
0 * 0 , we have 2k *2k for k .

Theorem 10: If the diffusion coefficients for porosity change of two problems are such
that a( , ) a* ( , ) for H , then
1
2k *2k for k .
Note that the proofs of these theorems are present in [9]. Now we will summarize the
results of Theorems 3 10.
If on certain areas of u i we replace the boundary conditions of rigid clamping (13) by
the contact boundary conditions (10) (12), then by Theorem 3 the natural frequencies can
only decrease.
On the contrary, if on certain areas of j we replace the boundary conditions for the
electric potential to be zero (17) by the electric boundary conditions of contact type (15), (16)
for open-circuited electrodes, then by Theorem 4 the natural frequencies can only increase.
Note that the natural frequencies in the problem with all the short-circuited electrodes are
usually called by the electric resonance frequencies, while the natural frequencies in the
problem with some open-circuited electrodes are the electric antiresonance frequencies.
Therefore, Theorem 4 also asserts that the electric antiresonance frequencies are no lesser
than the electric resonance frequencies with the same order numbers.
By Theorems 5 and 6, a reduction in the boundaries u i of rigid clamped or contacting
with rigid punches or a specific reduction in the elastic moduli and an increase in the density
or in the massive characteristics of punches can lead only to a reduction in the natural
frequencies.
Conversely, by Theorems 7 and 8, a reduction in the electrode boundary or a specific
reduction in the permittivity moduli can lead only to increase in the natural frequencies.
Comparing the effects reflected in Theorems 3, 5, 6 and 4, 7, 8 we can conclude that a
similar change in the mechanical and electric boundary conditions or in elastic and
permittivity moduli leads to opposite change in the natural frequencies.
Meanwhile, by Theorems 9 and 10 a reduction in the boundary 0 or a specific
reduction in the diffusion coefficients for porosity change can lead only to a decrease in the
natural frequencies. Comparing the effects reflected in Theorems 5, 6 and 9, 10, we can
conclude that similar changes in the elastic and porous boundary conditions or in the elastic
moduli and in the constitutive constants characterizing the properties of porosity lead to
uniform changes in the natural frequencies.
161
It could be noted, that the changes in mechanical conditions lead to the known changes in
natural frequencies [17], which have clear physical explanations. Thus, for the more rigidly
fixed body its mechanic vibrations become more constrained, therefore eigenvalues can only
increase. If the changes in moduli and physical properties are such that the potential energy
increases and kinetic energy decreases then the natural frequencies also increase.
As it can be seen, the piezoelectric effect shows up so that the same effects are caused by
the change of electric conditions that seems to be opposite in comparison to the change in
mechanical conditions. On the contrary, the changes in the properties and boundary
conditions related with porosity lead to the similar changes for eigenvalues as analogous
changes of mechanical properties and boundary conditions.
6. FINITE ELEMENT APPROXIMATIONS

For solving problems (32) (34), (45) (47), (48) (50) in the weak forms, we will use
the classical finite element approximation techniques [18, 19]. Let h be a region of the
ek
ek
corresponding finite element mesh: h , h k , where is the separate
finite element with number k . On the boundary h h we can introduce the boundaries
h , h u , h u i etc., which will be the approximations of the corresponding boundaries

, u , u i etc. Then, for h with the suitable boundaries we can define the functional spaces
1
1
H1h u l , H h m , H h and Qh u l , Qh m , Q h similarly to the functional spaces from Section
3.
On the finite element mesh h k
ek
we will find the approximation to the weak
solution { u h 0 u0 , h 0 0 , h } for the transient problem (32) (34) in the form:
uh 0 (x, t ) N*u U(t ) , h 0 (x, t ) N (t ) , h (x, t ) N V(t ) ,

*
(62)
*
where N u is the matrix of the shape functions for the displacements, N is the row vector
of the shape functions for the electric potential, N is the row vector of the shape functions
for the porosity changes, U(t ) , (t ) , V(t ) are the global vectors of the nodal
displacements, the electric potential and the porosity changes, respectively. All shape
functions form the basis in the corresponding finite-dimensional spaces: Vh u l Qh u l ,
t
Vht m Qh m and Vht Qh , for transient problem or in the finite-dimensional spaces:

1
1
Vh u l H1h u l , Vh m Hh m and Vh H h , for harmonic and modal problems. Then,
for transient problem: u h 0 Vh u l ,

t
h 0 Vht m , h Vht .
Here, in (62) for harmonic and modal problems, U , and V are constant vectors.
162
v , and in finite-dimensional spaces Vh u l ,
We represent the projecting functions
Vh m and Vh , respectively, by the formulae:

v(x) N*u U , (x) N* , (x) N* V .
(63)
In accordance with conventional finite element technique, we approximate the continual

weak formulation (32) (34) by the problem in finite-dimensional spaces. Substituting (62),
(63) into the problem (32) (34) with (35) (44) for h , we obtain:
~
~
C
Muu U
uu U K uu U K u K u V Fu ,
(64)
U) K K V Ft F ,
K*u ( d U
(65)
U) K* K V Ft F ,
K*u ( d U
(66)
with the initial conditions:
(0) V ,
U(0) U* , U
*
(67)
which are derived from the corresponding continual conditions (20).
Here, Muu Muu M p , Cuu Cuu d M p , M p is the matrix of punch mass and
inertia characteristics, Muu
M
a
ek
uu
, Cuu
C
a
ek
uu
, K uu
K
a
ek
uu
, K u
K,
a
ek
u
K u K uek etc. are the global matrices, obtained from the corresponding element
a
matrices ensemble (
), and the element matrices are in the forms:
ek
Muu
ek
ek
ek
Nue Nue* d , Cuu
d Muu
d K uu
,
(68)
ek
K uu
S ue* c E S ue d , K uek
S ue* e* Se d ,
(69)
K uek
ek
Sue* B Ne* d , K
Se* S Se d ,
(70)
ek
K
[Se* G Se Se* g Ne* ]d ,
ek
ek
ek
ek
ek
ek
(71)
ek
K
ek
[Se* A Se Ne Ne* ]d ,
163
(72)
Sue L() Nue* , Se Ne* , Se Ne* ,
(73)
1 0
L () 0 2
0 0
(74)
e*
3 2
3 2
0 1 ,
1 0
e*
e*
where N u , N , N are the matrices and the row vectors of approximate shape functions,
respectively, defined on separate finite elements.

In (69) (72), we use vector-matrix forms for the moduli: c
moduli, c c
E
(ij ) ,
E
ijkl
; , 1,,6 ; i, j, k , l 1, 2, 3
is the 6x6 matrix of elastic
with the correspondence law
(kl) ,
1 (11) , 2 (22) , 3 (33) , 4 (23) (32) ,

5 (13) (31) , 6 (12) (21) ; e is the 3 6 matrix of piezoelectric moduli (
ei eikl ); B {B11, B22, B33, B23, B13, B12} .

ek
ek
Note that here the global, local mass and stiffness matrices M uu , M uu , K uu , K uu are
ek
ek
formed similarly, as in the case of pure elasticity, and the matrices K u , K u , K , K

t
are usual finite element matrices for a piezoelectric body. The vectors Fu , F , F , F , F
in (64) (66) are obtained from the boundary conditions, the corresponding right parts of the
week statements, and the finite element approximations.
For determining the matrix properties of this problem the following energy inequality
obtained from (8), (64) (66) is essential
Wh 0 , U, , V : U* K uu U 2U* K u V
V* K V * K Wh (U* U V* V * ) .
(75)
Note that we can use the Newmark method for integrating Cauchy problem (64) (67) in
a formulation of which the velocities and accelerations in the time layers are not explicitly
given, similarly to [13, 15].
We can also represent the system (64) (66) in different reduced forms by eliminating
the vectors and V . The results are more compact, if
d d d .
For the case of the homogeneous principal boundary conditions with
d d d , we
can apply the mode superposition method for solving harmonic and transient problems. The
given fact is one of the primary preference for the selected method for damping account and
164
the supplement of the terms with
d , d and d in constitutive equations (2) (4) and field
equation (7).
Note that similarly to [13], we can use an effective algorithm with symmetric matrices for
solving FEM Equations (64) (66) for transient, harmonic, modal problems and for the
problems of interaction between porous piezoelectric bodies and acoustic medium [11]. All
the procedures that we need in FEM manipulations (the degree of freedom rotations,
mechanical and electric boundary condition settings, etc.), we can also provide in a symmetric
form.
7. NUMERICAL EXAMPLES
For practical applications among piezoelectric materials with voids, the porous ceramics,
which can be processed by using special technologies, are of great interest. Note, that the
original concept of microstructure designing the porous polymer-free polycrystalline
composite materials was suggested in [20]. This concept consists in the controllable
substitution of separate crystallites, which form a polycrystal with pores, by the crystallites of
different composition, structure or amorphous substances, depending on the results of
preliminary finite element modeling of this structure and its properties.
Piezoceramic, polarized along the axis z x3 , is a material of crystallographic class
6mm and its moduli have the following structure:
c11E
E
c12
c13E
E
c
0
0
c12E
c13E
E
11
E
13
E
13
E
33
E
c44
E
44
0
0
0
0
0 * 0
, e
0
0
e15
0
E
c66
0
0
0
0
e15
0
0
e31
B1
B
e31
1
B3
e33
, B ,
0
0
0
0

0
0
11S 0
Q11 0
0
0
0
S
S
0 11 0 , g 0 , Q 0 Q11 0 ,
S
0
0
g 3
0 33
0 Q33
(76)
(77)
E
E
E
where c66 (c11 c12 ) / 2 , Q denotes the matrix A or G . Thus, the effective moduli of
the porous piezoceramics have the similar structure.

By the proposed generalized Cowin-Nunziato model, the more precise technique for the
effective moduli calculation for the composite porous piezoceramics includes the following
stages [10]:
165
determination of the porous piezoelectric material characteristics by the effective

moduli method from the finite element solutions of five special static piezoelectric
problems for the representative volume of a 3-3 connectivity structure;
ii comparison of the basic characteristics determined from the calculated effective
moduli with the corresponding values obtained from the experiments and the
practical design formulas;
iii fitting of the values of the material properties responsible for the porosity change
properties, minimizing the differences of the selected characteristic parameters of the
porous piezoceramics, obtained by the effective moduli method and as a result of the
experimental data evaluation.
As an example, we will consider a spherical ultrasonic piezoelectric emitter (transducer)
with a cylindrical hole in the center. The meridian section of this piezoelectric device is
shown in Figure 2. The transducer (area S1 in Figure 2) is made of the porous piezoceramics,
polarized along directions, perpendicular to the spherical surface faces. Working on the first
thickness modes, the emitter generates the waves in the surrounding acoustic medium (areas
S2, S3 in Figure 2, which are focused in the focal point 0f, which is the center of the emitter
spherical surfaces. This type of device is designed for medical applications for creating
sufficiently powerful ultrasonic fields in a focal zone [10, 11].
Figure 2. Spherical piezoelectric transducer with a hole submerged in acoustic medium, the meridian
section and geometry.
The geometrical transducer characteristics are as follows: R = 54 mm is the internal

radius, h = 7 mm is the thickness of emitter, d = 8.5 mm is the radius of the hole, D = 60.5
mm is the greatest diameter of the spherical segment with respect to the central axis z. Face
surfaces rf = R and rf = R + h of the emitter are covered by indefinitely thin electrodes used for
the piezoceramics polarization and further functioning of the device. Thus, the piezoceramics
of the emitter is polarized along radius rf in direction to the point 0f. In this case, the structure
166
of the physical constants matrices (76), (77) belongs to the spherical coordinate system
connected to the focal center 0f.
The acoustic region S2 have the height and the width equal to 80 (mm), and the height of
the region S3 is equal to 50 mm. We assume the dimensions of the acoustic regions to satisfy
the requirement that focal zone is entirely located in this region and the impedance boundary
conditions do not produce the reflected waves essential for focal zone.
For a transducer material, we will choose the piezoceramics PZT-5 with porosity of 20
%. We take the following mechanical, dielectric and piezoelectric constants for the dense
piezoceramics PZT-5:
7.75 103 kg/m3, c11E 12.1 1010 , c12E 7.54 1010 ,
E
E
E
2.11 1010 N/m2, e31 5.4 , e33 15.8 ,
c13
7.52 1010 , c33
11.1 1010 , c44
S
e15 12.3 C/m2, 11S 916 0 , 33
830 0 , 0 8.85 1012 F/m. Starting from these
data by the technique [21] for the representative volume with porosity of 20 %, it is possible
to calculate the effective moduli [11]:
c12E 4.08 1010 ,
E
c13
3.97 1010 ,
6.2 103 kg/m3, c11E 7.51 1010 ,
E
c33
6.61 1010 ,
E
c44
1.87 1010
N/m2,
S
e31 3.0 , e33 12.3 , e15 9.5 C/m2, 11S 733 0 , 33
639 0 .
For the considered case of the piezoceramics PZT-5 with porosity of 20 % the
calculations gave the following "optimal", values of the porosity constants: b 1 0.09 ,
b 3 0.1 , g 1 1011 (in International system SI). These values together with the
previously calculated theoretical values of the porous piezoceramics PZT-5 with porosity of
20 % were used for further finite element calculations.
For an acoustic medium, the paraffin oil has been taken for calculation with the following
constants: the density a 0.835 10 kg/m3, the sound velocity ca 1.42 10 m/s.
3
For numerical analysis of piezoelectric transducer, we will construct a regular finite

element mesh of tetragonal finite elements with bilinear approximation of the fields. The
piezoelectric finite elements, having uniform normals along radial direction rf = R in the
middle points, have identical element coordinate systems and consequently provide identical
radial polarizations.
In order to verify the efficiency of the considered device we solve the finite element
harmonic problems for a single piezoelectric transducer and for a piezoelectric transducer,
loaded on the working acoustic medium. Constructed as a result of the finite element
calculations, the graph of the electric admittance Y I / V ( I is the current) with
submission of the voltage V V0 exp[ jt ] on the electrodes 0 , r f R ; V ,
V0 20 V, r f R h and with the quality factor Q 100 is shown in Figure 3. The

damping constants
d , d (with d d 0 ) were calculated from the quality factor Q
on the interval ( f bd , f ed ), fbd 200 kHz, f ed 300 kHz. Indeed, supposing that Q factor is quasi constant in the frequency interval ( f bd , f ed ) we find the damping coefficients
167
d and d similarly to the case of a pure elastic body [18]: d 2 fbd fed /( f sd Q) ,
d 1/ (2 f sd Q) , f sd fbd f ed .
As is well known, the amplitude of the electric admittance Y has maximal values on the
electric resonant frequencies. In Figure 3, the solid curve depicts the plot of the electric
admittance for a single transducer and the dotted curve, depicting the plot of the electric
admittance for a transducer, loaded on the working acoustic medium, is also shown. As we
can see from Figure 3, the account of an acoustic loading shifts the resonant frequencies and
increases the damping properties of the system and the bandwidth frequencies. Here, for the
single transducer the working frequency f
t
r
of the thickness electric resonance is equal to
237.6 kHz and for the transducer with surrounding acoustic medium the working frequency
is equal to 240.4 kHz.
Figure 3. Real part of electric admittance depending on frequency.
Figure 4. Acoustic pressure intensity
Ia
along axis
z.
168

Characteristics of a focal acoustic zone are illustrated in Figure 4, where the plot of the
dependence of the acoustic pressure intensity I a on the distance z along the symmetry axis
Oz is shown for the frequency f tr 240.4 kHz. Here the acoustic pressure intensity I a
was determined by the finite element calculation results of the acoustic pressure p and the
T
acoustic velocity
v : I a (1/ T )0 Re p Re v dt , T 2 / 1/ f .
From Figure 4, it is clear, that the maximum of the acoustic pressure intensity I a is
achieved in the focus point z O f 80 mm, and the acoustic pressure intensity strongly
grows when approaching the focal zone that proves the high efficiency of the piezoelectric
device considered.
We also solve the transient problem for the considered piezoelectric transducer when the
function of input voltage V (t )
is the impulse function, V0 ( H (t ) H (t t* )) ,
t* 1/( 2 f tr ) s, f tr 240.4 kHz, and we obtain the focal zone around a focal point [11].
Note that the dependence of acoustic pressure p on the distance z along the symmetry axis
Oz for the time, when the leading edge of acoustic wave passes the focal point [11], is
similar to the dependence for the real part of pressure along the axis Oz for the harmonic
problem.
CONCLUSION
In continuation of the investigations [8 11], the present chapter has considered the
transient, harmonic and eigenvalue problems for piezoelectric bodies with voids described by
Cowin-Nunziato model. Statements of classical and generalized settings of transient,
harmonic and modal problems have been obtained in extended and reduced forms. By using
the classical finite element approximations we have received the generalized finite element
system of motion. Some theorems on changes of the resonant frequencies with changes of the
boundary conditions and material properties have been established.
The efficiency of proposed model and finite element approximations is illustrated by the
example of the analysis of a focusing spherical emitter from porous piezoceramics. Using the
Cowin-Nunziato model, we have determined more exactly the effective moduli of the porous
piezoelectric material by the criterion of closeness between the basic theoretical and
experimental characteristics of the porous piezocomposite. As a result, for the working
frequencies of the thickness resonance, we have obtained a very good agreement with
experiment. We have carried out modal, harmonic and transient analysis for both single
piezoelectric emitter and transducers, loaded on the acoustic medium.
It is possible to draw a conclusion that the application of the theory for piezoelectric
bodies with voids together with the finite element techniques will allow us to develop
adequate modeling of the porous, polycrystalline and others piezocomposite materials and the
devices made on their basis.
169
ACKNOWLEDGEMENT
This work is partially supported by grants of the Russian Foundation of Basic
Researches.
REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
Newnham, R. E.; Skinner, D. P.; Cross, L. E. Vater. Res. Bull. 1978, vol. 13, 525-536.
Dunn, H.; Taya, M. J. Am. Ceram. Soc. 1993, vol. 76, 1697-1706.
Silva, E. C. N.; Fonseca, J. S. O.; Kikuchi, N. Comput. Meth. Appl. Mech. Eng. 1998,
vol. 159, 49-77.
Wersing, W.; Lubitz, K.; Moliaupt, J. Ferroelectrics. 1986, vol. 68, 77-97.
Nunziato, J. W.; Cowin, S. C. Arch. Rational Mech. Anal., 1979, vol. 72, 175-201.
Cowin, S. C.; Nunziato, J. W. J. Elasticity. 1983, vol. 13, 125-147.
Ciarletta, M.; Scarpetta, E. Mech. Res. Commun. 1996, vol. 23, 1-10.
Nasedkin, A. V. Proc. 7 EUROMECH, Solid Mech. Conf. (ESMC2009). Sept. 7-11,
2009, Instituto Superior Tcnico, Lisbon, Portugal. J. Ambrosio et. al. (Eds.) CD. Paper
ID: 0820_GS-CP.
Iovane, G.; Nasedkin, A. V. Applied Mathematical Modelling, 2010, vol. 34(1), 60-71.
Iovane, G.; Nasedkin, A. V. Applied Mathematical Modelling, 2010, vol. 34(1), 47-59.
Iovane, G.; Nasedkin, A. V. J. Coupled Systems and Multiscale Dynamics, 2013, vol.1,
393-403.
Belokon, A. V.; Nasedkin, A. V. J. Appl. Math. Mech. (PMM), 1996, vol. 60, 145-152.
Nasedkin, A. V. In: Piezoceramic Materials and Devices. I. A. Parinov (Ed.); NOVA
Publishers: N.-Y., 2010, pp. 177-218.
Iovane, G.; Nasedkin, A. V. Computers and Math. with Applications, 2007, vol. 53,
789-802.
Iovane, G.; Nasedkin, A. V. Computers and Structures, 2009, vol. 87, 981-989.
Belokon, A. V.; Vorovich, I. I. Some Mathematical Problems of the Theory of
Electroelastic Solids, In: Current Problems in the Mechanics of Deformable Media, Izv.
Dnepropetr. Gos. Univ., Dnepropetrovsk, 1979. (in Russian)
Mikhlin, S. G. Variational Methods in Mathematical Physics, Pergamon Press, Oxford,
1964.
Bathe, K. J.; Wilson, E. L. Numerical Methods in Finite Elements Analysis, PrenticeHall, Englewood Clifs, New Jersey, 1976.
Zienkewicz, O. C.; Morgan K. Finite Elements and Approximation, N. Y., J. Wiley and
Sons, 1983.
Rybianets, A. N.; Nasedkin, A. V.; Turik, A. V. Integrated Ferroelectrics, 2004, vol.
63, 179-182.
Nasedkin, A. V.; Shevtsova, M. S. In: Ferroelectrics and Superconductors: Properties
and Applications. I. A. Parinov (Ed.); NOVA Publishers: N.-Y., 2011, pp. 231-254.

ISBN: 978-1-63321-239-8
Chapter 7
COMPARATIVE STUDY OF PARAMETRIC METHODS

FOR ONLINE ESTIMATING THE FREQUENCY AND
AMPLITUDE OF QUARTZ OSCILLATORS
Department of Radiophysics, Volgograd State University,
Volgograd, Russia
ABSTRACT
One of the actual applications of piezoelectric materials is precision of quartz
oscillators, which are the basis of navigation and orientation systems GPS/GLONASS.
Properties of these materials determine the potentially achievable accuracy of the
positioning. Therefore, a comprehensive property control of the piezoelectric material has
to be done by determining the instability characteristics of quartz oscillators based on its.
When analyzing short-term instability characteristics of quartz oscillators, it is
necessary to measure the frequency and amplitude of the quasi-harmonic oscillations in
the observation range comparable with the period of oscillations of the analyzed
generator.
There are several parametric methods among the known digital methods of
estimating the frequency and amplitude in a short observation range. They require a small
fixed number of operations regardless of the measurement range size and the number of
the signal measurements in it.
This chapter contains a description of the methods of online estimating the frequency
and amplitude and some features of their implementation. The comparative analysis of
their accuracy and statistical characteristics as well as guidance for the application of
these methods for study of properties of the quartz oscillators, are present.
100, Universitetsky Ave., 400062 Volgograd, Russia.
172
1. INTRODUCTION
Electric resonators use the piezoelectric effect, characterized by a high quality factor and
stability of their parameters, due to they are widely applied in modern electronic technique.
They used to generate stable oscillations in communication systems, instrumentation and
consumer equipment, computers, for narrowband signal filtering, and they are the base of
highly sensitive diverse physical sensors.
An important area of application is the communication systems where the quartz
oscillators and resonators are important parts in ensuring the reliability and stability of the
communication. The quartz oscillators are important in navigation systems, because its stable
work designates the accuracy of positioning objects. It may be highlight some main
parameters, the most important for each quartz oscillators application.
Minimum dimensions and a wide range of oscillation frequencies in combination with
low cost are important for microprocessor technique. Requirements to communication
technique are more significant. There becomes much more important frequency stability with
temperature changes or other parameters such as the age of the crystal and voltage ripple.
Therefore the temperature compensated oscillators or voltage controlled oscillators are
frequently used. Short-term instability is quite relevant characteristic of quartz oscillator for
digital communication systems.
However, the most requirements produced to the quartz generators, operated in satellite
navigation systems (SNS). The main point in the SNS is the measuring the distance from the
satellite to object and calculation of coordinates of the object by measuring the time of signal
propagation from several satellites and comparing the obtained values. A very high stability
crystal oscillator used to solve this problem. The navigator controller compares the intervals
between pulses of own generator and pulses from satellites for coordinate data acquisition. So
far as the reference carrier signal from the SNS passes with a speed close to the speed of light,
and the diameter of the satellite orbits amounts to several tens of thousands kilometers, it
becomes to be obvious that slight deviation in the oscillation frequency impacts fatally on the
SNS work.
Evidently, the requirements of the resonating components are sufficiently stringent, and
consistency with these requirements allows one to create advanced devices. In particular,
control of the properties of piezoelectric materials, used in SNS, should be made with a
special attention to the short-term instability of crystal oscillators based on them. Short-term
instability of any digital communication system is mainly determined by the crystal oscillator;
all other signal processing only worse the short-term instability.
Increased stability of the oscillator output frequency achieved by using vacuum
resonators with thickness-shear waves. Quartz crystal resonators fabricated from thermostable
cuts, for example, AT-cut or SC-cut, whose frequency of the oscillation is weakly dependent
on the ambient temperature. Additional stability achieved by increasing the temperature using
the so-called temperature compensation. At the same frequency, a control performed by using
reactive element such as varicap on a certain algorithm of data derived from the temperature
sensor [1]. As the temperature sensor can be used thermometers, resistors or semiconductor
sensors. However, these analog correction circuits of temperature shifts of the frequency
largely diminish the long-term stability of the oscillator. If we use crystal resonator with
increased temperature sensitivity, or alias of the oscillation modes that exist in some types of
173
resonators (for example, SC-cut) as a temperature sensor, we can achieve a higher stability of
the oscillator [2]. There are other schemes stabilizing oscillator frequencies, which typically
characterized by its phase noise.
Usually, short-term instability of the quartz oscillator is about 10% of the total system
jitter. Frequency instability of the quartz oscillator is the random modulation signal. Random
modulation is a consequence of the generators noise, buffer stages noise, quartz noise and
noise of power supplies. Clock frequency changed within a width of the resonance region of
the quartz resonator in the oscillator. Width of the resonance region of the quartz resonator is
extremely narrow; however, the generation frequency of crystal oscillator has some
instability. Short-term frequency instability measured and expressed in different ways. In the
frequency domain near the reference frequency, tuning out defined as short-term instability of
the phase noise. In the time domain, it defined as the output frequency to the nominal
frequency over a certain measurement time (Allan variance) [3].
A frequency comparator is used to determine the frequency and phase instability of signal
sources, based on a comparison of the measured frequency with another source. The reference
signal used to compare its accuracy should be at least in an order of magnitude higher than
the accuracy of the controlled source. The quantum frequency standard can be used like a
reference source. Actual level of stability of the precision quartz oscillators is about 1011
109, at the same time the level of stability of quantum frequency standards reaches 10 18 [4].
Comparator measures the frequency difference of two periodic signals and by using it we can
adjust the source frequency quite quickly and accurately. Using the model signal in
measurements allows achieving the high accuracy at a relatively short duration of the
measurement interval.
In this chapter, we consider the application of a source model for estimating the
frequency and amplitude of the quartz resonator signal in the range comparable to the period
of the signal. For example, when we measure with high accuracy and efficiency the
instantaneous frequency and amplitude of the signal coming from satellites in navigation
equipment, it is possible to take into account the frequency deviation of the satellite signal
due to the signal path in the online mode. Thus, it leads to increasing the accuracy of
positioning.
2. ONLINE ESTIMATING FREQUENCY AND AMPLITUDE

2.1. General Definitions
Piezoelectric resonator is included in the electrical circuit, which is equivalent to series
oscillatory circuits with the same high quality factor, which characterizes the resonance
properties of elastic vibrations. An oscillator output signal described as [5]
xt u0 u t cos0t (t ) ,
(1)
where 0 is the nominal angular frequency of the oscillator, u0 is the nominal amplitude of the
oscillator, u(t) is the small, slowly time-varying amplitude of fluctuations and (t ) is the
174
slowly time-varying phase. If the oscillator is qualified as a precision oscillator, it is required

that
u t
1,
u0
(t )
1.
(2)
Signal (1) wrote differently by selecting initial phase 0 as
xt u t cos (t ' )dt ' 0 ut cos t ,

0
(3)
where u(t) is the slowly time-varying amplitude, (t) is the total phase. The time-rate
(t ) is slowly timedependence of the phase instantaneous angular frequency (t )

varying, too. In this notation, the condition (2) wrote as
1 u t
1,
(t ) u (t )
(t )
1.
2 (t )
(4)
Full conditions which must be imposed on the frequency and the amplitude are given in
[6]. No matter what is the source instability, we assume that this instability is shown in the
range comparable or more of quasi-period oscillations of the generator. The magnitude of this
instability must satisfy the conditions (4) in the range of instability.
We consider the estimation of digital techniques, and therefore discrete values of the
signal processing apparatus. If advanced analog-to-digital converters have a high enough
resolution, the accuracy of the discrete values of limited equidistant sample signal values is
high. Relatively high level of equidistance we achieved by highly stable generator, which
uses a quantum standard signal. We will use the signal samples x(t) with time-step at time
instants tk = k, the values in these points are denoted as x[k] = x(k) = x(tk), and L is the
number of samples on the measurement interval.
To estimate the frequency, in recent years, several different methods proposed, which
divided into the following categories:
(i) slow methods, which are characterized by block processing data with a fixed number
of signal samples L at the measurement interval, require O(L log L) or more floatingpoint operations;
(ii) fast methods in which data blocks are processed the same, but the number of
operations of the order O(L);
(iii) online estimating methods, which use recursion formulae that allow for a small
number of operations floating point calculations.
175
Third group of the methods is suitable for measuring short-term instability. There are the
third group methods, which have also acceptable accuracy but they are poorly present in
literature.
One of such methods is considered in [7] with the frequency estimate calculated as
x[i 2m]x[i m] x[i 3m]x[i ]

1 L
,
arccos
2
Lm i 1
2 x [i 2m] x[i 3m]x[i m]
where m
max
(5)
, min and max define the range of possible frequency values.

min
In addition to this estimate, we discuss some other estimates, obtained using the original
parametric approach, which has been developed by us in several papers [6, 8, 9]. This
approach uses the slow varying signal parameters (4) on some time range of measurement T0
to decompose slowly varying signal parameters in a Taylor series. We will take few values of
the signal with a time step in this range. The range T0 will contain an integer number of
intervals . Method names will mean the number of intervals in the interval T0 (3, 4 or 5point method). Then we will expand the derived relations using the method of least squares
(LSM) to a larger interval T. Interval T will contain an integer number of intervals T0, which
satisfy conditions (4). Thus, we take into account even large changes of parameters of the
studied signal because slow change does not mean small change.
2.2. 3-Point Method

In this section, we consider the method for estimating the frequency, which requires a
minimum of three equally spaced values of the signal and input in various ways. In [10], it is
introduced, as a method for estimating, the frequency of a noisy sinusoidal signal using
narrow-band filters; in [8], it is used the modified second order Prony method. In this chapter,
the method based on the signal model (3) is used.
Consider the signal (3) of the mixed normal white noise (t) with zero mean at time
points t, (t ) and (t 2) and expand it into a series of the full phase and amplitude near the
central point (t ):
2
xt u u cos 0 t ,
2
xt u cos t ,
xt 2 u u cos
2
Here u = u(t ),
(6)
2 t 2 .

t , values
u ut , = (t ), t t ,
of 0 and 2 include all the higher order of magnitude terms of the expansion into a series.
176
Concretize the condition (4) in the range under consideration: we assume that the
frequency and amplitude change slowly at each time interval [t 2, t] as
2 1,
u
1 .
u
(7)
These conditions allow us to ignore the values of 0 and 2 in (6). Consider the sum
2
2
2u cos sin sin

xt xt 2 2u cos cos cos
2
2
2
2
2u sin cos sin
t t 2.
2u sin sin cos
2
2
Using the conditions (7), as well as the smallness of the noise variance 2 << u2, we
expand into series the previous relation:
2 cos sin
xt xt 2 2u cos cos u
2u sin sin t t 2.
Assuming that x(t ) 0 (or /2), consider the variable:
xt xt 2
1
arccos

2 xt
u
t t 2 2t cos

ctg tg
,
u
2u sin cos
2
(8)
where
u
t t 2 2t cos
ctg tg
.
u
2u sin cos
2
is an estimate of the frequency of the signal (3) in the interval [t

Thus, the variable
2, t], is the frequency deviation generated as the slow changes of frequency and
amplitude, and the presence of additive noise. Averaging this deviation and its square, we
obtain systematic and random error in determining the frequency:
ctg tg ,
u
2
(9)
1 2 cos 2
2 .
2u 2 2 sin 2 cos 2
177
(10)
The resulting estimate of the variance of frequency deviation has been described [8].
The formula (8) for estimating the frequency imposes a condition in the range similar to
the condition of sampling theorem [11]:
(11)
For independent verification of relations (9) and (10), the conducted numerical
simulations fully confirmed their validity. Expression (9) tested on the model of the signal
with a linear frequency and amplitude changes:
xn 1 n 1 cos 2f 0 1 n n 0 , n 0,,2
2
for different values of , , 0 and f0. Verification of the expression (10) conducted by using
the pattern signal with constant amplitude and frequency and additive white noise (t):
xn cos2f 0 n 0 n, n 0,,2 .
The simulation was performed for different values of f0 and 0 (with = 2f0 + 0).
Figure 1 shows analytic dependencies (10) of the normalized frequency f0 for different
values of the initial phase 0. Points in the plot show the values obtained by numerical
simulation, at averaging over 100 realizations of the additive random noise and standard
deviation = 0.01. Clearly, the results of numerical simulation are in good agreement with
the analytic dependence (10).
Figure 1. Analytic dependence (10) and the results of numerical simulation, when 0 = 0.5 and 0 = 2.3.
178
If there is a noise in the signal, the three measurement points are insufficient to achieve
acceptable accuracy. Moreover, there is an uncertainty in the expression (8), when x(t ) = 0
and x(t) = x(t 2); this is clearly seen in the graphs (see Figure 1). To increase the accuracy
of estimating the instantaneous frequency, it is necessary to use a greater number of values of
the signal.
We make the sampling signal x(t) with a step , assuming that = Q (Q = 1, 2, 3).
Consider sliding window k [n L +1, n], where L = 2Q + M, and M > 1 is the number of
averages. Then we find the argument of the cosine in equation (8) by LMS:
n
an
x[k 2Q] x[k ]x[k Q]
k n M 1
x [k Q]
(12)
k n M 1
The requirements (8) lead to the following inequalities:
L2 2 1,
u
L 1 ,
u
(13)
and the frequency estimate corresponding to the middle of the sliding window is determined
by the relation:
S n
L 1 1
a 1
n
arccos n
arccos 1

2 Q
2
S
n
2 Q
(14)
and it will be within the range [0, /(Q)]. Note that the use of at least one additional signal
sample eliminates the problem of the uncertainty in the expression (8) at /2.
Search the statistical and systematic errors of this method performed separately. Consider
the signal with a constant frequency and amplitude. Mix this signal with normal white noise
with zero mean. The samples of the noise denoted as [n] = (n):
xk u0 cos0 k 0 k , k n L 1, , n ,
(15)
for computational convenience. Then we introduce the index m = k (n M + 1), leading to a

change in the initial phase 0:
xm u0 cos0 m 0 m, m 0, , L 1
and intermediate value am:
179
M 1
aL
x[m] x[m 2Q]x[m Q]

m 0
M 1
x [m Q]
2
m 0
Then the frequency estimate (14) takes the form:
L 1 1
a
n
arccos L

2 Q
2
and its deviation from the true value is:
1
M 1
m m 2Q cos 0 m Q 0
2Qu0 sin 0 Q DM ,Q m 0
M 1
2 cos 0 Q m Qcos 0 m Q 0 ,
m 0
where
M 1
DM ,Q cos 2 0 m 0Q 0
m 0
M sin 0 M
cos 0 2Q M 1 2 0
2 2 sin 0
The averaged deviation is obviously gives a zero, that is, no biased estimate. The
averaged square deviation allows one to find the variance of the estimation error of frequency
02 G1 , 1 M Q,
2 02 G1 G2 , Q M 2Q,
2
0 G1 G2 G3 , 2Q M ,
where
(16)
180
02
2Q 2u 2 2 DM2 ,Q sin 2 0 Q
G1 DM ,Q 1 2 cos 2 0 Q ,
G2 2M Q 1 cos0Q 2 DM Q ,3Q 2 cos0 Q ,
G3 2 DM 2Q , 2Q M 2Q 1 cos 2 0 Q .
When M >> 1 and M >> Q, in the center of the range 0 [0, /(Q)], the series DM,Q
M/2, so the simple approximation is valid:
2 2
.
Qu 2 M 2 2 sin 2 0 Q
(17)
Verification of this expression carried out by using the signal model with constant
frequency and amplitude:
xn u0 cos2f 0 n 0 n, n 0,, L 1 .
(18)
The simulation was performed for u0 = 1 and different values of f0, 0 and 2 (variance of
white Gaussian noise with zero mean). Figure 2 shows results of numerical simulation and
analytic dependencies (16) and (17) obtained by using 100 realizations with 0 = 0.33 and =
0.01 for different values of Q and M. The first and second plots show the variance reduction
of frequency deviation at increasing the number of averages M that is almost obvious thing.
The second and third plots show the importance of proper selection of decimation ratio
Q. For example, signal processing with frequency f0 = 0.05 at Q = 1 gives the value of f/
0.013, and at Q = 3 gives the four times lesser value (f/ 0.003). The measurement
interval L in both cases the same and the number of averages M in the second case is even
smaller than in the first.
Dependencies (16) and (17) suggest that the optimal value of the decimation ratio Q, in
which the normalized frequency f0 misses is approximately the mid-range [0, 1/(2Q)]. The
frequency changes can continually adjust Q to the optimal value and thus always be close to
the middle of this range. Naturally, the sampling step must be sufficiently small, i.e. f0 << 1.
Take samples of the signal with slowly varying frequency and amplitude of the interval L
= 2Q + M to determine the accuracy of the frequency estimate. For definiteness, assuming M
and L to be odd (M = 2K + 1), we obtain
xk uk cosk k 0 , k n L 1,, n ,
181
Figure 2. Dependencies (16) (thin line) and (17) (solid line) and numerical results (dots) for different
values of Q and M.
It is more convenient to go to the index m = k (n (L 1)/2) = k n + Q + K, i.e. move

the reference point to the middle of the sliding window length L. Expand the signal samples
without noise into a series around the central point of the window, using conditions (13):
xm u um cos m m 2 2 , m Q K , , Q K .
2
We used the following notations: = 0 + ((n Q K)), u = u((n Q K)),

n Q K .
u un Q K , = ((n Q K)) and
In these notations, the frequency estimate takes the form:
182
x[m Q] x[m Q]x[m]
L 1
1
.
n
arccos m K

K
2
Q
2 x 2 [m]
m K
, we obtain approximate
By restricting to the first order of smallness in u u and
expressions for the numerator and denominator of the arccosine:
K
m K
m K
xm Q xm Qxm 2u 2 cosQ C1 1 , x 2 m u 2C1 2 ,
1 uu4 cos Q C2 Q sin Q C3
1
u 2 2 cos Q C4 Q 2C3 2Q sin Q C2 ,
1
u 2 2 C4 ,
2 2uuC2
2
where
C1
C2
C3
C4
M 1
sin M
cos m 2 2 cos2 sin ,
K
m K
sin 2M cos M sin sin M cos

,
m cos m
4 sin
K
m K
K
sin 2 2m sin 2
m K
K
m K
sin 2 2m
sin M
,
sin
sin 2
M cosM sin 2
4 sin 3
M 2 1 sin 2 2 cos 2 sin M .
By using the smallness of the quantities 1 and 2, we obtain an approximate expression

for estimating the frequency:
2u 2 cosQ C1 1
L 1
1
n
arccos

,
2 Q
2u 2C1 22
where
(19)
2 cosQ 2 1
2u 2Q sin Q C1
183
C3
4Q sin Q C2 Q 2C3 C4 cosQ
.
2uC1
4Q sin Q C1
As an example, Figure 3 shows the numerical simulation for signal processing of the
linear frequency and amplitude modulation type:
L 1
xn 1 n
cos 2f 0 1 n L 1 n 0 ,
2
n 0,, L 1.
(20)
The figure shows error f as a function of f0, calculated by using formula (19) and the
resulting numerical simulation with 0 = 0.76, Q = 1, M = 13, L = 15.
In dependence on the modulation parameters and the initial phase of the signal, the error
f shifted to positive or negative area. However, it becomes clear that the change in frequency
has stronger effect on accuracy than the change of amplitude. Plots fully confirm the validity
of expression (19).
Figure 3. Frequency error estimation (19) (line) and numerical results (dots) with linear frequency and
amplitude modulation.
184
One of the main advantages of the 3-point method is that, it can be implemented as a
recursive structure, that requires a fixed number of floating-point operations regardless of the
sliding window length L = 2Q + M, i.e., regardless of the degree of frequency estimates
averaging. Really, consider the series in the expression (10) as follows:
n
an
x[k 2Q]x[k Q] x[k ]x[k Q]
k n M 1
k n M 1
x [ k Q]
2
S1n S1n Q
S 2 n Q
k n M 1
The entered variables
S1n
xk xk Q,
k nM 1
S2 n
x k
2
k nM 1
can be calculated using the recurrence relations:
S1 n S1 n 1 x[n M ]x[n M Q] x[n]x[n Q],

S 2 n S 2 n 1 x 2 [n M ] x 2 [n].
(21)
The calculation of these variables requires 4 multiplicative and 4 additive floating-point

operations, an array of L cells for storing the signal samples x[n] and two arrays of Q cells to
store previous values of S1[n] and S2[n]. Calculation of frequency by using formula (14) still
requires 3 multiplications and computing the function of arccos (it may also be implemented
using an array of values). The structure of the digital recursive systems for calculating the
values of S1[n] and S2[n] (21) is shown in Figure 4.
Figure 4. The structure of the digital recursive systems for calculating S1[n] and S2[n] (21).
185
2.3. 4-Point Method

Rudiment of this method proposed in [12], where signal represented as an exponentially
decaying cosine that was consistent with a second order Pronys model [13]. In the used
model, an additional fourth parameter is the damping coefficient:
xt vt exp t cost ut cost .
(22)
Thus, the partial or complete change of the signal amplitude took into account for the
observation range. Consider the signal (22) in the range T0 = [t 3, t] at four points in time
and expand it into a series of the full phase and amplitude near the central point t 3/2
similarly to the previous method:
3
3
9 2
0 ,
xt u u cos
2
2
8
1
1
1 2
1 ,
xt u u cos
2
2
8
1
1
1 2
2 ,
xt 2 u u cos
2
2
8
3
3
9 2
3 .
xt 3 u u cos
2
2
8
u ut 3 2 , u ut 3 2 ,

t 3 2 . Values of 0, 1, 2
t 3 2 , t 3 2 t 3 2 ,
Here
the
following
notations
are
used:
and 3 include all the higher order of magnitude terms of the expansion into a series and
below they will be not taken into account. We consider several combinations of the signal
values:
2
1
1
1 2

c1 t x t xt 2xt u u cos 2
2
2
8
1
3
1
1 2
3
9 2
cos
,
u u u u cos
2
2
2
8
2
8
1
1
1 2

c2 t x t 2 xt 3xt u u cos 2
2
2
8
3
1
3
9 2
1
1 2
cos
,
u u u u cos
2
2
2
8
2
8
186
1
9
c3 t xt 3 xt xt 2 xt u 2 u 2 2
2
4
9
1
1
cos 3 cos 2 2 u 2 u 2 2 cos cos 2 2 .

4
4
4
2 (if expanded
These expressions include the squares of u and a large powers of
2 ), therefore, the conditions (7) allow some simplification of the

into a series of cos
obtained expressions:
1
1 2
2 sin 2 sin
,
c1 t u 2 uu sin 2 sin 2 sin
2
2
1
1 2
2 sin 2 sin
,
c2 t u 2 uu sin 2 sin 2 sin
2
2
2 .
c3 t u 2 2 cossin 2 sin2sin
The relationships of these combinations give the following expressions:
d1 t

c3 t
v
2 cos exp 1 2
,
c2 t
v
2
d 2 t
c1 t
v
exp 21 2 2
sin 2 ,
c2 t
v
where
v vt 3 2 , v vt 3 2 . From these expressions, it quite easily to get
d1 t
cos .
2 d 2 t
(23)
Restriction on -interval is the same as in the previous method, and satisfies condition
(11). Thus, under conditions (7) the frequency estimate in the interval [t 3, t] obtained as
follows:
3
1
d t
t arccos 1
.
2
2 d 2 t
(24)
187
If necessary, it is also possible to determine the exponential model (22):
1
3
t lnd 2 t .
2
2
(25)
We add white Gaussian noise (t) with dispersion 2 to the signal (22) in points (t i)
and assume that the parameters of the signal in the range [t 3, t] are constant:
3
xt i u u exp t i cos i t i ,
2
i 0,,3,
where , , and u are the values of corresponding fluctuations. By solving the system of
equations, we find frequency fluctuation and averaging its square, we obtain an expression
for the variance of the frequency:
2
2 2
4u exp 6 sin 4 ()
2
2
exp 6 sin
exp( 4) sin
2 sin

2
2
2
(26)
2
exp 22 sin
sin
sin
.
2
2
2
Verification of this expression carried out by using the signal model with constant
frequency and damping coefficient:
xn exp 0 n cos2f 0 n 0 n, n 0, ,3 .
The simulation was performed for different values of f0 and 0 (with = 2f0 + 0).
Figure 5 shows analytic dependencies (26) of the normalized frequency f0 for two values of
the initial phase 0. Points in the plot show the values obtained by using numerical
simulation, by averaging over 100 realizations the additive random noise and standard
deviation = 0.01. Clearly, the results of numerical simulation are in good agreement with
the analytic dependence (26).
188
Figure 5. Analytic dependence (26) and the results of numerical simulation for 0 = 0.5 and 0 = 2.3.
We make the sampling signal x(t) in time range T = [t (L 1), t], where
L = 2Q + M + 1 > 4, and find d1[n], d2[n] by LMS as
d1 n
S 2 n QS3 n S 2 nS1n 2Q
,
S1 n Q S1 n 2Q S 22 n Q
(27)
S nS 2 n Q S1n Q S3 n
d2 2
,
S1 n Q S1 n 2Q S 22 n Q
where
S1 n
x [i],
2
i n M
S2 n
x[i]xi Q,
i n M
S3 n
x[i]xi 2Q .
i n M
Now, in accordance with the expression (24), the frequency estimate, corresponding to
the middle of the sliding window (n (L 1)/2), has the form:
L 1 1
d n
n
arccos 1
.
2
2 d 2 n
(28)
The simulation performed by using the 4-point method at different values of the
decimation ratio Q, thinning and number of averages M. Study the stability of this method.
Figure 6 shows the results of numerical simulation of signal modeling (18), namely the
relative standard deviation estimates of the frequency function f/ of the normalized
frequency f0, obtained by using 100 realizations with 0 = 0.33 and = 0.01 for different
values of Q and M. The comparison of these dependence plots with plots in Figure 2 allows
one to state that statistical characteristics of the 3-point and 4-point methods are almost
identical.
189
Figure 6. Numerical simulation of frequency estimation (28).
Figure 7 shows the numerical simulation for signal processing of the linear frequency and
amplitude modulation type (20), namely the frequency estimation error f as a function of f0
with the same parameters as in Figure 3 (0 = 0.76, Q = 1, M = 13, L = 16, = 0.0013 and
= 0.0084). By comparing these graphs with the plots in Figure 3, we concluded that the
amplitude change affects almost equally. The frequency change within a sliding window by
using the 4-point method is lesser almost an order of magnitude.
190
Figure 7. Frequency estimation error by using the 4-point method with linear frequency and amplitude
modulation.
Figure 8. The structure of the recursive system for calculating S1[n], S2[n], S3[n] (29).
191
This method applied to measure the dynamics of frequency of the weakly nonlinear or
non-stationary systems response to impulse action when the oscillation amplitude decreased
slowly.
Sequence Si[n] in the expression (27) can be recurrent calculated:
S1 n S1 n 1 x 2 n x 2 n M 1,
S 2 n S 2 n 1 xnxn Q xn M 1xn M Q 1,
(29)
S3 n S3 n 1 xnxn 2Q xn M 1xn L,
and values with negative indices should be assumed equal to zero. Corresponding recursive
structure illustrated in Figure 8.
2.4. 5-Point Method

This method based on a comparison of signal samples of two time series with slowly
varying terms, one-to-one associated with the samples of the amplitude and instantaneous
frequency. First basic grounds of this method proposed in [6]. Consider the signal (3) in the
range [t 4, t] at five points in time and expand it into a series of the full phase and the
amplitude near the central point (t 2):
2
2
k ,
x(t k) u 2 k ucos 2 k 2 k
2
k 0,,4.
(30)
We use the following notations: u(t 2) = u, (t 2) = , (t 2) = and
t 2
. The values of k (2 = 0) include all the higher order of magnitude terms of
the expansion into a series and below they will be not taken into account. We construct two
functions:
c1 t x 2 (t 2) x(t 4) x(t ),
(31)
c2 t x 2 (t 2) x(t 3) x(t ) 0,
and substituting them in the expansion (30), we retain only the terms with first order of
smallness:
2 cos 2 2
2 ,
c1 t u 2 cos 2 u 2 u 2 4 2 cos 2 2
c2 t u 2 cos 2
2
2
cos
.
u 2 2 cos
2
2
192
These expressions include the squares of u , therefore, the conditions (7) allow some
simplification of the obtained expressions:
2 cos2sin 2 2
2 ,
c1 t u 2 sin 2 2 sin 2sin 4
2
2
1
2 cos2sin 2
.
c2 t u sin 2 sin 2sin
2
2
(32)
The first condition in (7) allows one to state that second and third terms in these
expressions are significantly smaller than the first one, so
c1 t
4 cos 2 t 2 0 .
c2 t
This expression restricts the range of similar to condition (11) but by more strict
condition:
.
2
(33)
The final expression for the estimation of frequency gave as
1 c1 t
1
t 2 arccos
2 c t .
(34)
We write the expressions (31) for the discrete time with = Q, taking into account
conditions (7) and (33), as
c1 n x 2 n 2Q xn 4Qxn,
c2 n x 2 n 2Q xn 3Qxn Q.
(35)
Then the frequency estimate in accordance with (34) gave as
n 2Q
1 c1n
1
.
arccos
Q
2
c
n
2
(36)
This expression allows one to calculate quickly the frequency estimate. However,
experience shows that these estimates are unstable to noise because they use only five signal
values. To meet the correctness conditions, it is necessary to consider the sequence (35) on
193
some range L > 4Q, within which the conditions (7) and (33) are carried out. In this case
we obtain the overdetermined system of linear equations for c1[n] and c2[n].
It makes sense to apply the LMS as the simplest method of regularizing for the
implementation of this method in the form of real-time algorithm and find relationship
c1[n]/c2[n] by using LMS. Rewrite expression (35), to obtain single value of sliding window
with length L = 4Q + M. Here M is the number of 5-point averaging intervals length 4Q,
shifted relative to each other on value of . In accordance with the LMS, we obtain
S1n
c1mc2 m, S2 n
m n M 1
c m,
2
2
m n M 1
Figure 9. Numerical simulation of frequency estimation (38).
(37)
194
The frequency estimation in the middle of the sliding window found in accordance with
(36) as
1 S1 n
L 1 1
n
arccos

, n L 1,, N 1.
2 Q
2 S 2 n
(38)
The numerical simulation allows one to state that variation of the amplitude of the signal,
which affects the frequency estimate (38), is lesser than the estimates (14) and (27). Figure 9
shows the results of numerical simulation of signal modeling (18), namely the relative
standard deviation estimates of the frequency function f/ of the normalized frequency f0,
obtained by using 100 realizations with 0 = 0.33 and = 0.01 for different values of Q and
M.
The comparison of these dependence plots with plots in Figure 2 and Figure 6 allows one
to state that the range of values f0 with minimum variance of the frequency in the 3-point
and 4-point methods is much wider. Minimum values of the dispersion in all methods are
approximately the same. Ripple on the chart of the 5-point method are small in comparison
with other methods, but it could not be considered as major advantage of the 5-point method.
Figure 10 shows the numerical simulation for signal processing of the linear frequency
and amplitude modulation type (20), namely the frequency estimation error f as a function of
f0 with the same parameters as in Figure 3 (0 = 0.76, Q = 1, M = 13, L = 15, = 0.0013 and
= 0.0084). It is seen that the effect of changes of amplitude and frequency within the sliding
window is much lesser than (more than on order of magnitude) for other methods in the range
f0 from 0 up to 0.22.
Figure 10. Error of frequency estimation by using the 5-point method with linear frequency and
amplitude modulation.
195
Figure 11. The structure of the recursive system for calculating S1[n], S2[n] and S3[n] (39).
Thus, the 5-point method yields the 3-point and 4-point methods on the statistical
characteristics, but exceeds them in terms of accuracy in determining the frequency of slow
changes in the frequency and amplitude within the observation period.
Sequences S1[n] and S2[n] (36) can be represented as recursions:
S1 n S1 n 1 c1 n M 1c2 n M 1 c1 nc2 n,
S 2 n S 2 n 1 c22 n M 1 c22 n,
(39)
It significantly reduces the amount of computations and facilitates the implementation of

this algorithm in the devices based on the signal processor. Figure 11 shows the structure of
an apparatus for obtaining digital sequences S1[n] and S2[n].
2.5. Operational Method for Estimating the Amplitude

The estimate of the signal amplitude could be found by LMS, solving the overdetermined system of equations (18), after finding the frequency estimates. It could be taken
into account if the frequency estimate is obtained by 4-point method and found by the
damping factor . However, this approach requires a very large number of floating-point
operations that depend on the length of the sliding window.
In this section, we present an expanded operational method of estimating the amplitude.
This method allows the calculation within the sliding window with a fixed number of
floating-point operations, which does not depend on the length of the window.
196

Suppose there are three samples of signal (6) satisfying (7). Rewrite second function (31):
c2 t x 2 (t ) x(t 2) x(t )
and use the second expression (32):
c2 t u 2 sin 2 c .
The error determined by the second expression (32). Now we can write the estimation
of the amplitude as
u 2 sin 2 c
c2 t
.

sin
sin
(40)
can be any of the previously described one, is the

Here, as the frequency estimator
frequency deviation from the real value.
Turning to step sampling = /Q and averaging the estimate (40) within the sliding
window [n L + 1, n], L = 2Q + M, we obtain
S n
c2 m
mnM 1
x m Q xm 2Qxm,
n
mn M 1
and estimate of the amplitude takes the form:
L 1
u n

2
S n
.
Q
M sin
(41)
The value S[n] calculated according to the formula:
S n S n 1 x 2 n M Q xn M 2Qxn M x 2 n Q xn 2Qxn
with a minimum of computational operations.
Figure 12 shows the results of numerical simulation of signal modeling (18), namely the
relative standard deviation estimates of the frequency function f/ of the normalized
frequency f0, obtained by using 100 realizations with 0 = 0.33 and = 0.01 for different
values of Q and M. In these simulations, the frequency estimated by 3-point method, i.e. by
using the formula (14). By using the 4-point or 5-point method for the frequency estimation,
we obtained almost the same results. As it follows in the range of f0 from 0.05 up to 0.45,
variance of the amplitude is almost constant. Therefore, the choice of decimation ratio Q is
determined completely by the frequency estimation method.
197
Figure 12. Numerical simulation of amplitude estimation (41).
3. COMPARISON OF NUMERICAL SIMULATION METHODS

For all methods, numerical simulation carried out and compared their performance and
robustness. In the simulation method for estimating the frequency (5) it was also calculated
by recurrence relations. For this method, the window length is L = 3Q + M 4. The
estimation of the frequency in the new notation has the form:
[i]
i
1
c [ n]
arccos 1
, i L 1,, N 1 ,
MQ niM 1
2c2 [n]
(42)
c1[n] x[n Q]x[n 2Q] x[n]x[n 3Q] , c2[n] x2[n Q] x[n]x[n 2Q] .
198

The recurrence relation for this method wrote as
i
i 1
1
c [ n]
c [ n L]
arccos 1
.
arccos 1
Lm
2c2[n]
2c2 [n L]
After these changes, the number of floating-point operations at the calculation of

estimates of the instantaneous frequency is minimal and independent of the number of
samples in the range L. We call this method by L-point method.
Then, we discuss the results of numerical simulations with different variation of the
amplitude and instantaneous frequency with an arbitrary level of additive noise. In numerical
simulations, the following estimates of the frequency: (i) L-point method (42), (ii) 3-point
method (14), (iii) 4-point method (28), and (iv) 5-point method (38) were obtained. The
amplitude calculated using the relation (41).
Figure 13 shows the deviations of the frequency and envelope estimates (f and a) and
the corresponding standard deviations (f and a), obtained by using 100 realizations of the
signal
x[n] 1 0.19 sin0.09nsin0.126 sin2 0.0017n 2 0.079n n,

n 0,,511,
(43)
averaged over the window length L for several values of standard deviation of white
Gaussian noise with zero mean and Q = 2, M = 19. Figure 14 shows the same dependence
obtained by processing the signal model:
xn exp 0.0013nsin 2 0.179 1 0.0001n 2 / 2 1.29 n,

n 0, ,511.
(44)
The curves were obtained by using 100 realizations for the following parameters: Q = 1,
M = 27.
As it follows from the plots, the deviation estimates do not differ significantly with signal
(43) in contrast with the signal (44). Best results obtained by 5-point method. This is due to
averaging the values in other methods. Since the frequency in signal (43) changes
harmonically, the averaging is lesser noticeable in contrast to signal (44).
About performance techniques, it could be said the following. In each of these methods
due to high speed of computing recurrence relations, the amount of computation at each step
almost equally and we can say that in speed almost all the methods are the same. Also in all
of four methods, there is a function of arccos, calculation of which cannot call operational. In
the L-point method, it is necessary to calculate this function M times per sample (and twice by
using recurrence relations), unlike other methods, in which one is calculated only once per
sample. Thus, the accuracy of calculation does not affected, as shown by numerical
simulations.
199
Figure 13. Signal model (43) for = 0.1 (a), the mean and standard deviation estimates of the
frequency deviation (b, c) and amplitude (d, e) ( L-point method, 3-point method, 4-point
method, 5-point method).
200
Figure 14. Signal model (44) for = 0,1 (a), the mean and standard deviation estimates the frequency
deviation (b, c) and amplitude (d, e) ( L-point method, 3-point method, 4-point method,
5-point method).
4. FREQUENCY MEASUREMENT OF LABORATORY GENERATOR

Experiments carried out by measuring the frequency of the laboratory generator. The
digital measuring system, used for this, based on the signal processor (Figure 15) and 5-point
method.
201
Figure 15. Block diagram of the digital measuring system.
As a basic unit of signal processing block selected the digital signal processor (DSP)
TMS320VC5509A (manufactured Texas Instruments). As analog-to-digital converter (ADC)
circuit used 16-bit chip ADS1602 (manufactured Texas Instruments). As a clock generator
(CLK) was used Rubidium Frequency Standard CH1-1013 [14], being the source of a highly
harmonic signal frequency of 10 MHz and frequency instability around 1012.
Series of experiments we conducted by measuring the frequency of harmonic signals, the
source of which was the low-frequency precision generator G3-122 [15]. The measurements
of signals carried out at the frequencies of 1 kHz, 10 kHz and 100 kHz with sampling
frequency at 625 kHz. This sampling frequency obtained for the system ADC clocking signal
with frequency of 10 MHz from reference generator.
As it is indicated in the technical description of the generator G3-122, maximum
permissible basic error for the frequency of this oscillator is 5107f within 12 months after
the frequency setting. For signal with frequency of 100 kHz, several measurements we
conducted, which gave the same results of the estimation error. Figure 16 shows the
estimation of the signal frequency of 100 kHz with M = 675. As it follows, the frequency
estimation error does not exceed 0.005%.
Figure 17 shows the result of measuring frequency signal of 10 kHz. As followed from
the theory, assessment turned greatly biased, because the sampling frequency was on the
order of magnitude greater than frequency signal. In this case, we must apply decimation ratio
according to the expressions (37) and (38). Minimum error of the estimation turned out at Q =
10 and M = 513, for the measured frequency is shown in Figure 18.
It was also applied the decimation ratio for a signal frequency of 1 kHz. Figure 19 shows
the measured frequency of the signal at Q = 103 and M = 513. In all cases, the estimation
error rate does not exceed 0.01%.
Fluctuations in frequency estimates presented on the plots cannot explain by the presence
of other harmonics of the signal as shown by numerical simulation. In addition, the measured
signal previously passed through a digital band-pass finite impulse-response filter with linear
phase, i.e. the obtained frequency deviation largely caused by internal instability of the
generator itself.
202
Processing the data obtained show that the relative frequency instability of the generator
G3-122 is about 5105, whereas, as declared in [15] only 5107. However, measuring the
oscillator frequencies and frequency standards always performed using the integral indicators
in the time or spectral domain [5], that is, the used time intervals contain a very large number
of signal periods.
Figure 16. Measured frequency of signal of the generator G3-122 at 100 kHz (a) and its fragment (b).
Figure 17. Measured frequency of signal of the generator G3-122 at 10 kHz, obtained without
decimation ratio (Q = 1, M = 1, L = 5).
CONCLUSION
The measurement of the frequency and amplitude can be performed at relatively short
time intervals, which may be lesser than quasi-periods of investigated signals in the proposed
methods. Measurement results will not be the average frequency in this range, but some
dependence repeating its dynamics. The methods do not require significant computational
203
power and allow the implementation based on modern signal processors, due to the
recurrence relations.
Figure 18. Measured frequency of signal of the generator G3-122 at 10 kHz, obtained with decimation
ratio (Q = 10, M = 513, L = 553) (a) and its fragment (b).
Figure 19. Measured frequency of signal of the generator G3-122 at 1 kHz, obtained with decimation
ratio (Q = 103, M = 513, L = 925).
The proposed methods are optimal for the realization of measurements in real time. They
allow us to realize a digital measuring system with frequency range up to hundreds of
megahertz. They could be recommended for rapid estimation of the instantaneous frequency
and amplitude broadband signals with low noise levels. Undoubted advantage of these
methods is the independence of the number of floating-point operations on number of signal
samples for the measurement interval.
204
The reference signals allow the frequency synchronization of crystal oscillators as

defining the frequency; therefore, we can take into account changes in the resulting
calculations. This gives us the opportunity to create a new type of frequency standards, which
are continuously adaptively adjusted frequency references. In this case, it is possible to reduce
significantly the instability and the frequency error of their output signals.
REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
Stofanik, V.; Balaz, I. Radioengineering. 2004, vol. 13(2), 17-19.

Vig, J. R.; Filler, R. L.; Kosinski, J. A. Proc. 36th Annual Symp. Freq. Contr. 1982, pp.
181-186.
Barnes, J. A.; et. al. IEEE Trans. Instrum. Meas. 1971, vol. IM-20(2), 105-120.
Bloom, B. J.; et. al. Nature. 2014, vol. 506, 71-75.
Riley, W. J. Handbook of Frequency Stability Analysis; SP 1065; NIST: Washington,
DC, 2008; pp. 1-136.
Ignatjev, V. K.; Nikitin, A. V.; Yushanov, S. V. Radiophys. and Quant. Electr. 2010,
vol. 53(2), 132-145 (in Russian).
Labutin, S. A.; Pugin, M. V. Meas. Tech. 1998, vol. 41(9), 837-841 (in Russian).
Nikitin, A. V.; Yushanov, S. V. Meas. Tech. 2008, vol. 51(2), 188-194 (in Russian).
Ignatiev, V. K.; Nikitin, A. V.; Khoruzhii, D. N.; Yushanov, S. V. Meas. Tech. 2011,
vol. 54(1), 46-52 (in Russian).
Savaresi, S. M.; Bittanti, S.; So, H. C. IEEE Trans. on Autom. Contr. 2003, vol. 48(7),
pp. 1285-1292.
Crochiere, R. E.; Rabiner, L. R. Multirate Digital Signal Processing; Prentice Hall:
Englewood Cliffs, NJ, 1983; pp. 1-410.
Nikitin, A. V.; Yushanov, S. V. Phys. of Wave Proc. and Radio Syst. 2006, vol. 9(2),
57-63 (in Russian).
Marple, S. L. Digital Spectral Analysis: With Applications; Prentice Hall: Englewood
Cliffs, NJ, 1987; pp. 1-492.
CH1-1013 Rubidium Frequency Standard Specification. [E-text type]
http://www.ruknar.com/prod/img/CH1_1013.pdf
Technical data G3-122. [E-text type] http://www.priborelektro.ru/download/to/G3122%20PDF%20Teh.dannie.pdf

ISBN: 978-1-63321-239-8
Chapter 8
THE LIMITS OF MEASUREMENTS ACCURACY

PARAMETERS OF ELECTROMAGNETIC
OSCILLATIONS IN PIEZOELECTRIC MATERIALS
V. K. Ignatjev, A. A. Orlov and D. A. Stankevich
Department of Radiophysics, Volgograd State University, Volgograd, Russia
ABSTRACT
Many methods of advanced piezoelectric materials of a microelectronic component
base are now being studied extensively. One of the most important directions in these
investigations is the development of composite piezoelectric resonators and filters. This
technique shows high accuracy and high long term-stability of frequency characteristic in
microwave band.
This chapter is about a fundamental restriction on quality of piezoelectric devices.
These restrictions are the standard quantum limits of measurement errors of
electromagnetic oscillations in piezoelectric devices. We explore methods of advancing
phase and frequency stability for oscillations in piezoelectric resonators. We obtain the
low limit for estimation error of signal parameters in resonators and filters by modern
methods of digital processing signals based on Rao-Kramer inequality, as the result of the
exhaustive study.
1. INTRODUCTION
One of the key challenges in creating multiple devices is the problem of signals
synchronization, time scales and ensuring the stability of the frequency. Quartz resonators
have found wide application in the last century. The majority of clock generators include
quartz oscillators [1]. Very many papers have been devoted to the study of characteristics,
technology, creation, and processing of natural and synthetic quartz [2]. There are many
research directions connected to the finding of new piezoelectric materials, such as gallium
orthophosphate, langasite etc. They are considered to be better than quartz in some frequency
bands [3, 4]. Generators, based on piezoelectric products, may have relatively long-term
206
stability at the order of 1011 with short-term stability no less than 1012 over 1 second,
now [5].
Modern quantum standards have to oust piezoelectric devices. However, their key
drawback is high phase noise at small values of the frequency detuning [6]. Time and
frequency standards, produced by JSC Nizhny Novgorod "Vremia-Che" (VCH-1008, Ch11007, etc.) are the world advanced ones by the characteristics of long-term frequency stability
and phase noise. This company has been carrying out researches of methods to optimize the
time-base characteristics [7].
Applying a group of quartz crystals having been connected in a special scheme allows
one to construct quartz filters having tens of thousands quality and high temperature stability
parameters. Those characteristics are otherwise unattainable for filters making on discrete
capacitances, inductances, and resistors. The increased precision of manufacturing allows
creating volume microwave oscillations resonators. Using of this resonators open the path to
creation microwave systems without PLL frequency multiplication [8]. That reduces the
phase noise of generators and improves characteristics of the devices based thereon.
The improved stability and noise reduction of piezoelectric devices involves the
establishment of functional connection between the technology of manufacturing an element
and its metrological characteristics. That process is the identification of a dynamic system.
We solve the problem by the methods of digital signal processing. It allows find the
parameters of non-stationary systems through the measurement of slowly varying frequency,
phase, and amplitude of the quasi-harmonic oscillations. Applying parametric signal
processing techniques allows improving accuracy of radio-physical measurements. It allows
improving dramatically the efficiency and the speed of the characteristics optimization for
piezoelectric materials with a minimal cost. Data-measurement system includes not only
identification of the object with slowly varying parameters, the quasi-harmonic oscillation
that carries information about its parameters. Nevertheless, the system includes quantum
reading system, dequantizer, analog-to-digital converter, and adaptive algorithms for
nonlinear parametric signal analysis. The application of the quantum statistic methods for that
data-measurement system will develop efficient algorithms for real time parameter
estimations approaching to the standard quantum limit (SQL) errors.
The result, on one hand, will prevent attempts to overcome fundamental limitations by
technical means. On the other hand, the standard quantum limit depends on the measurement
procedures in contrast to the Heisenberg uncertainty relations. Therefore, the results will
optimize this procedure or develop a new one. Achieving dispersion limits for parameters
estimate deviation from the real value, that sets inequality Rao Cramer seems to prove the
optimality of the proposed methods of radio-physical measurement. It would eliminate
"blind" search of best practices that pose with considerable overhead cost time and money.
2. THEORY OF LIMITS IN PARAMETRIC ESTIMATION

2.1. Phase Noise and Jitter
Spectrum of the phase noise and jitter are quality characteristics of signals and
generators. These values characterize the stability of the instantaneous frequency of the signal
The Limits of Measurements Accuracy Parameters
207
at different times of observation. One of the important characteristics of harmonic signals of

the generators is instantaneous frequency instability. They describe quasi-harmonic signal by
model
x(t) = a(t)cos[(t)] = [a0 + e(t)]cos[t + 0 + (t)].
(1)
Here a0 is the constant component of the signal amplitude, e(t) is the amplitude of noise
signal, which at any given time is significantly lesser than a0, is the instantaneous
frequency, 0 is the initial phase of the signal, (t) is the phase noise corresponding to the
condition:
dt
,
dt
where we introduce the instantaneous frequency noise, (t). The spectral power density of
the phase noise and frequency noise are found by using a Fourier transform of the
autocorrelation function of the noise and they are denoted by S(f) and S(f), respectively:
S f 2 R exp 2if d ;
0
(2)
S f 2 R exp 2if d ,
0
where
1 T
R lim
t t dt ;
T 2T T
1 T
R lim
t t dt
T 2T T
are the noise autocorrelation functions of the instantaneous frequency and phase, respectively.
Here, the value of f denotes the detuning from the central frequency of the signal. Noise
spectral density functions of phase and frequency are meaningful relationships of the standard
deviations on the bandwidth measurement 1 Hz.
In practice, to characterize the quality of the spectral purity of signals we can apply the
normalized spectral density L(f) as the ratio of the spectral density of the single-sideband
signal into a 1 Hz bandwidth near the frequency f to the total signal power. Obviously,
normalization relations are of the form:
L f df 1 .
(3)
208
The normalized spectral density can be expressed through S(f) in the form of
approximate estimate for small deviations from the central frequency [8]:
L (f) S(f)/2.
(4)
Measuring the phase noise perform by many different techniques. The simplest way is to
calculate the phase noise from the signal spectrum. However, in practice, this technique is the
subject of considerable error. At present the more promising technique is the scheme used in
the phase noise analyzers Agilent E5052B (Figure 1) [9]. It consists of two identical signal
generators, trapped in the Phase Locked Loop (PLL) from the input signal. Correlated part of
voltage from control inputs of voltage control oscillators is a signal of phase noise source
being under investigation.
It is worth to note that the relationship between the correlated part of the voltage
controlled oscillator (VCO), and a phase noise spectrum [9] is artificial assumption. The
accurate estimation without non-physical basis can be obtained through the methods of
correlation analysis of the dynamics of the instantaneous frequency fluctuation (t) in
accordance with (2). However, this method requires a high accuracy of instantaneous
frequency dynamics measurement of quasi-harmonic signal with form (1).
Modern measurement equipment intended for working with pure harmonic signal. The
measurement accuracy of amplitude, instantaneous frequency, and phase of quasi-harmonic
signal is much worse. It significantly restricts the using of the frequency method for
measurement of physical quantities that change over time, such as phase noise spectrum. We
can use the proposed technique based on the existing architecture of the correlation dynamics.
We should replace the PLL generator (Figure 1) on the instantaneous frequency parametric
meters. We connect the instantaneous frequency signals at the same time to the correlator.
Thus, we replace the voltage signal of the VCO in the PLL blocks.
Figure 1. Diagram of a two-channel correlation analyzer based on phase noise correlation signal PLL
[9].
209
International standards of telecommunications gives the definition of jitter and its

measurement scheme are given in the [10, 11]. Jitter is the term denoting the short-term
variations of significant temporary fronts from the ideal position in time. Its frequency of
change is higher than 10 Hz. The similar changes with the frequency below 10 Hz have name
wandering or drift.
The expression for the square of jitter , obtained on the basis of the power spectral
density of the phase noise is given as [12]
f0
2
S f sin f / f df .
2
(5)
Here f0 is the central frequency of the test signal. The inverse transformation from jitter to
phase noise, see from formula (5), is impossible without supplying the additional information
on the nature of the form of the distribution. However, we obtain such relationship in some
cases, for example, by assuming the proximity to white noise distribution [13].
For generator on equivalent LC-circuit we can estimate expression for phase noise (4),
expressed through the loop parameters [14] such as
2kT f 0
L f
Psig 2Qf
(6)
Here Psig is the full signal strength, Q is the quality factor of the loaded circuit, k is
Boltzmann constant, T is the temperature of active elements of the circuit. The proposed
formula includes the assumption of a white thermal noise in generator elements, and it
predicts quadratic decline phase noise at an offset from the carrier frequency. In practice, the
Leossons formula is used [15]:
f f
2kT
L f
1 0 0
Psig
f 2Qf
f
1 0 .
f
(7)
They offer new terms in this equation. Independent of frequency, the term of detuning
manifests itself at large detuning. The term proportional to f-1 is responsible for flicker. A
noise of circuit parameters adds the term proportional to f3.
The need for an analytical description of jitters and phase noise signals arises from the
requirement to provide high relative frequency stability or the propagation of a signal on a
long distance. Solving of such tasks encountered in radar systems [6], or due to the necessity
of synchronizing multiple receivers of signals distributed in space [16]. The use of various
cuts of quartz plates in the design of resonators allows us to get different characteristics of the
phase noise [17].
Telecommunication standards attach grate importance of short-term stability of the
reference oscillators.
210
There are special protocols and methods for testing the presence of phase noise and the
possibility of using such channels at different data transfer rates [18].
Methods of checking and measuring parameters of quartz crystal resonators adopted for
industrial applications are present in [19]. They allow each manufactured device to get the
quality factor Q, included in formulae (6) and (7). Such measurements allow us to select
quartz resonators for installing resonators with high Q-factor in the device where the
principled small phase noise arises at small offsets of the carrier frequency.
New piezoelectric resonators allowed one to carry out experiments in order to create
connected piezo-mechanical electrical systems and demonstrate with their help the
possibility of cooling modes of vibration [20]. This should reduce the phase noise of the
oscillator by changing the parameter T in equations (7) and (8).
Creation of group time-base standards is the next path to development and improvement
of the characteristics of piezoelectric resonators. They combine high short-term volatility of
piezoelectric sources and high long-term stability of quantum frequency reference. We need
in description of these devices in one language, to create such time bases, which obviously
must be the quantum statistics.
At present, we have deep enough understanding of the fundamental limits for harmonic
signals parameter meters [21]. At the same time, such a theory is virtually nonexistent for
measurement of slowly varying parameters of quasi-harmonic signals. The new techniques of
measuring the frequency, phase, and amplitude are suitable only for narrow-band signals. The
width of their spectra determines the instantaneous frequency error. Wide spectrum of
vibrations in a piezoelectric resonator can be much more than the jitter in the presence of drift
or wander.
Therefore, the accuracy of existing methods of measurement, the radio-physics is
insufficient for optimizing the performance of the piezoelectric material and it requires
special analysis.
2.2. The Uniqueness of the Quasi-harmonic Representation with Slowly

Varying Amplitude and Phase
Let us consider the following quasi-harmonic process:
x(t) = X(t)cos[(t)],
(8)
satisfying the physically based assumptions about the continuity, positivity, limitation and
slow variation of the amplitude and the instantaneous frequency (SVAF):
0 m t
d t
M ,
dt
0 X m X t X M ,
d t
t m
dt
(9)
d n X t
X t Xn , X m ,
dt n
(10)
in the form of oscillations with slowly varying amplitude and phase (SVAP).
211
Split the full phase (t) into fast (t) and slow (t) components so that at any time and
anywhere the conditions [22] are satisfied:
dX
d
cos t X t sin t , t t t ,
dt
dt
d
0.
dt
(11)
Under conditions (11), the expression for the derivative of oscillation (8) is of the form:
~t sin t ,
~t t .
xt X t
(12)
We shall show that if the signal (8) has the quasi-harmonic representation satisfying
conditions (9) (11), then one is unique. Lets introduce the dimensionless variable = Xt,
then condition (10) implies the boundedness in the totality of all the derivatives of function
X():
d n X
XM .
d n
(13)
Therefore, the function X() could be represented by the converged in the whole real axis
Taylor series:
1 d n X 0
X t cn ; cn
.
n! d n
n 0
Thus the function X() is analytic one. Taking into account inequality (13) for order of
this function, we obtain
lim n n!cn lim n X M 1 .

n
Then, by using the Paley-Wiener-Schwarz theorem [23], the function X() can be
represented by a Fourier integral:
X
( ) exp(i )d ,
( )
1
2
X exp( i )d ,
and, therefore, the function X(t) has a finite spectrum whose support lies in the interval [X,
X]:
X t
( p) exp(ipt )dp .
(14)
212
Assume that the oscillation's quasi-harmonic representation (8), satisfying conditions (9)
and (11), is non-unique. It means that in addition to the functions X(t) and (t) there are
functions X1(t) and 1(t) such that x(t) = X1(t)cos[1(t)], and that both functions X(t) and X1(t)
satisfy conditions (9) and (11), but X(t) is not identical to 1(t).
We select a time moment sequence tn, such that x (t n ) 0 . The conditions (8), (12) imply
that
(tn ) 1 (tn ) n ; X (tn ) X 1 (tn ) x(tn ).
(15)
The interpolation problem (15) has always a solution in the class of entire analytic
functions [24]. This solution is not unique. Assume that the entire functions X(z) and X1(z),
where z = t + iu, are the solutions of the interpolation problem (15). It follows from the
condition of the instantaneous frequency positivity (9) that at the points t = tn the function
sin[(z)] has simple zeros. Then the function B(z) = [X(z) X1(z)]/sin[(z)] is also entire
analytic one, since the zeros of the denominator coincide with the zeros of the numerator.
Therefore, the general solution of the interpolation problem (15) in the class of entire
functions has the form:
X1(t) = X(t) + B(t)sin[(t)],
(16)
where B(z) is the arbitrary entire function.

If the function B(t) is not identically zero, then spectrum of the function X1(t) in the form
(16) is bounded above by a frequency no lesser than m, which contradicts the condition (14),
that the spectrum amplitude is limited by the frequency X < m. Consequently, B(t) 0 and
X1(t) X(t), that proves the uniqueness of solution of the interpolation problem (15) in the
class of entire functions with finite spectrum of the slowly varying amplitude.
Note that for specified functions x(t) and X(t), conditions (15) and (16) uniquely
determines the function (t) up to an inessential constant multiplier of 2, and condition (11)
~ t t .
determines the (t) up to a constant, which in turn uniquely defines the function
Consider the derivative of the phase (t) in the interval tn t tn+1, which corresponds to
a total phase variation within the range: n (n +1). We choose a point in time t such
that (t) = (n + 1/2), and denote = t t. In the interval under consideration, taking into
account conditions (9), it expresses t n t , t 2 . Then from condition (11),
it follows that
X t
ctg t d k X t k 1
ctg t
.
X t
X t k 2 dt k
k!
Taking into account inequalities (10), we obtain
ctg t X t
X t
k 2
k!
ctg t X2
X t
X t
k 0
213
k!
k 2!
k 0
X 2 t k
X2
2 t exp .
y ctg y
t
k
!
k 0
There we denote = X/m < 1, y = n, |y| /2 and assume that in this interval the
condition |yctg(y)| 1 is satisfied.
Since this estimate is valid for any of the adjacent intervals tn t tn+1, with << 1 at
any time, the condition of slow phase variation is satisfied:
t 2t t .
(17)
2.3. Oscillator Phase Operator in the Quasi-harmonic Approximation

In the analysis of parameter measurement error of dynamic systems, one should take into
account that the measurement accuracy is restricted not only by technical capabilities of the
used instruments, but also by quantum-mechanical properties of the devices and objects. The
quantum measurement theory describes equally both the macroscopic and microscopic
objects. However, methods of measurement can be different. For example, the difference is
that in the macroscopic experiments, the ensemble of identical objects is strongly restricted,
and we can extract the necessary statistical information from a plurality of repeated
measurements [25]. The quantum limits of physical quantities measurement are due to the
reaction of the measuring device on the system. The reversibly interacting with the quantum
system block of the device has name quantum readout system (QRS). The following blocks
must be classical instruments and must irreversibly interact with the QRS, that is, the
dequantization of the signal occurs [26].
The quantum non-perturbative measurement of the physical quantity is the measurement,
which does not affect the results of the first and subsequent measurements of this quantity.
The operator of the observable quantity must commute with itself at any time [26]. A
necessary criterion for the precise measurement is obviously the absence of the noncommuting with the measured quantity terms in the Hamiltonian of the system and instrument
interaction. Now, it is not possible to establish phase measurement design in which the
Hamiltonian of the interaction would not depend on the amplitude of the signal, not
commuting with its phase. The direct techniques of phase measuring are not yet available in
the classical theory. Only the indirect determination by the oscillator coordinates measuring is
possible [28].
In the passing from classical to quantum description of the system, it is required to
associate the dynamic variables with the corresponding linear Hermitian operators. As a rule,
the harmonic oscillator phase operator is introduced by using the exponential expansion of the
214
i
creation and annihilation operators: a e n , a n e . Moreover, the commutation
relation n, i is held. Therefore, we can obtain the indeterminacy relation [29]:
n 1 2 .
(18)
However, the introduced operator is not Hermitian one [30] and consequently, the
theoretically accurate phase measurement is not still possible. We can find violation terms for
the indeterminacy relation in the form (18), when n 0 , in [28]. The phase intervals limits
are [0, 2).
From the standpoint of radio-physics, the phase monotonically depends on the time and
the phase limitation is associated with the periodicity of harmonic functions. We introduce the
Hermitian operators S , C corresponding to these functions in this context. It also raises a
number of difficulties: firstly, these operators do not commute with each other, therefore, the
phase is determined uniquely, and secondly, the sum of the squares of the sine and cosine
operators is not equal to the identity operator [31].
A fundamental cause of the difficulties may be the fact that the phase is associated with
the non-Hermitian annihilation operator, which does not correspond to any measurable
physical quantity.
However, one must measure the phase shift angle between oscillations in the generator
oscillator and receiver oscillator is required to solve the dynamic system identification
problems.
In this case, the phase is associated with the Hermitian operator of the oscillatorgeneralized coordinate. Receiver oscillator is QRS for electrical oscillations in the form (8),
which is excited by the generator. One can consider the oscillator to be a RLC-circuit with
variable parameters, including a source of quasi-harmonic signal u(t) = U(t)cos[(t)] in the
form (8), satisfying conditions (9), (10) and (11). The equation for fluctuations in this
circuit is
q (t )q 02 (t )q P(t ) cos (t ) ,
(19)
where
1
L (t ) R(t )
, (t )
,
L(t )
L(t )C (t )
P(t )
U (t )
.
L(t )
Asymptotic methods allow analyzing the oscillating circuit reaction to the signal with
slowly varying amplitude and instantaneous frequency [32, 33]. Under natural assumptions
for radio-measurement systems such as
dL
L(t )0 (t ),
dt
dC
C (t )0 (t ),
dt
dR
d
R(t )
R(t )0 (t ),
0 (t )
dt
dt
L(t )
(20)
215
The forced oscillations in the circuit will be a quasi-harmonic SVAF process in the
form (8):
q(t ) A(t ) cos (t ).
(21)
The full phase of SAVP oscillation (21) includes clearly divided rapidly and slowly
varying components (t ) (t ) (t ) , so that conditions (16) and (17) are satisfied. Then
by condition (12) the generalized momentum p(t ) L(t )q (t ) describing the oscillator (21)
will have the form:
~(t ) A(t ) sin (t ) .

p(t ) L(t )
(22)
Since for quasi-harmonic SVAF process (21) for specified functions u(t), L(t), C(t) and
~(t ) (t ) (t ) is uniquely determined. We can consider the

R(t), the function
functions A(t) and (t) to be dynamic variables, uniquely connected with variables q(t) and
p(t) by the relations following from (21) and (22):
A(t ) q(t ) 2
.
p(t ) 2
p(t )
, (t ) arctg
2 ~2
~
L(t ) (t )
L(t ) (t )q(t )
(23)
We can associate these functions with operators A and . Classical analogy technique
allows finding the commutation relations for these operators when the commutator of two
operators is assigned with Poisson bracket, regarded as an operator:
A , iA, i Ap q Aq p Li(t )A~(t ) .

1
(24)
2.4. Quantum Uncertainty of Quasi-harmonic Signal Parameters

Measurement
The commutator (24) allows one to obtain the quasi-harmonic oscillator phase operator in
the Q-representation in the explicit form:
i
1

~
L(t ) (t ) A A 2 A
and the corresponding uncertainty relation:
(25)
216
1
2
A ,
2L
1
.
A2
(26)
Note that from the oscillator energy expression W = n = L2A2, where n is the number
of quantum in the oscillator, it follows that for n >> 1 we can put
A n
1
1
L
n
A
A and 2 2
. Then the uncertainty relation (26)
A
n
Ln
n
A
takes the form n 1 2 coinciding with (18).

It follows from (26) that infinite oscillation amplitude is required for precise phase
measurements. That is physically impossible. From the physical standpoint, we should
identify the oscillator phase uncertainty in the state with a given average number of quanta
n 1 . The minimum of the phase uncertainty in this case have form:
1.376 1.376
.
n
L A2
(27)
Uncertainty relation for this optimal value n 0.615... has name the Heisenberg
uncertainty phase limit [34].
The relationships (21) and (22) allow us to introduce the following dynamic variables for
quasi-harmonic oscillator:
C t cos t
qt
pt
, S t sin t
.
At
Lt t At
It is clearly seen that {C, S} = 0, i.e. the sine and cosine operators of quasi-harmonic
oscillator phase commute in contrast to the similar operators for the annihilation operator
phase and they seem to be the measurable observable quantities. Therefore, the trigonometric
quasi-harmonic oscillator phase functions are measurable observables, and the phase itself
can be determined indirectly through measurement of these observables.
Equation (21) describes the oscillations in a system with the explicitly time-dependent
Hamilton function of the form:
t
q2
t
p2
H q, p, t exp t dt
exp t dt
u t q .
2
C
t
2
L
t
0
We perform the canonical transformation [35]:
t t
xt exp
dt qt X t cos t
0 2
217
with generating function
t t
q, y, t exp
dt qy ,
0 2
t t
dt At is the slowly varying amplitude, satisfying conditions
0 2
where X t exp
(10), when |(t)| << 1. Then
1 t
exp t dt y .
q
2 0
The Hamilton function H(x, y, t) takes the form:
t t
x2
y2
t
H H
xy exp
dt ut x H 0 t V t ,
t 2C t 2 Lt 2
0 2
where, according to the relations (8) and (12)
~ 2 t X 2
Lt
~
y Lt xt Lt X t t sin t , H 0 t
,
2
~ 2 t x 2
1t

t
V t
xy exp t dt u t x 1 2
.
2
2
2
C
t
t
0
The corresponding Hamiltonians in the Schrdinger representation exist in the forms:
~ 2 t X 2
Lt
H t H 0 t V t , H 0 t
,
2
~ 2 t x 2
t t

t
xy yx exp
V t
dt ut x 1 2
.
4
0 t 2C t
0 2
From the relations (24) and (25), it follows that we can choose an inductance modulation
law:
~t ,
Lt Z 0
(28)
218
in order the Schrdinger representations of both phase operator and its commutator
with amplitude operator X are independent explicitly on time. Taking into account
~
commutation relation (24), the phase operator dynamics t U 1 U has the form of the
following equation in the interaction representation [29]:
~
d
~ ~
i
, H 0 U 1U , U 1 H 0U U 1 , H 0 U
dt
Lt ~ 2 t U 1 Lt ~ 2 t U 1
iX 1
, XX U
XX X X
~ t U
2
2
L
t
(29)
i~ t Lt ~ 2 t U 1
, X XU i~t .
2
2
i t
There U t exp H 0 t dt is the unitary evolution operator and the wave

0
function in the interaction representation, satisfying the Schrdinger equation, at the time t =
0 is assumed to coincide with the wave function in the Schrdinger representation:
~ 1 ~
U t V t U t .
t
From Equation (29) and the normalization condition, it follows that
~
d
~
~
t x, t
x, t ~t ~x, t ~x, t t t .
dt
t
Thus, the measurement of the variable instantaneous frequency has fundamental error,
which by virtue of (17) depends on the rate of oscillation amplitude change. It is might be
worth noting that the constant instantaneous frequency of exponentially decaying free
oscillations in the oscillator with constant parameters is determined precisely. Indeed, for
such oscillations if (t) = = const, we have
At exp t 2A0 ,
X t exp t 2At A0 const.
~ t const .
t 0,
Accordingly, 0,
219
2.5. The Standard Quantum Limit of Parametric Estimation Phase in the

Quasi-harmonic Approximation
Modern metrology allows us to use the term phase for no strictly periodic phase
processes [36]. The verification schemes based on the representation of signals by harmonic
functions includes techniques of measuring the phase shift. Changing frequencies and
envelopes of the signals result in an error [37].
That substantially restricts the accuracy of measuring phase shift of quasi-harmonic
signal by correlation, compensation methods, and the methods of direct conversion. The
parametric estimation of successive measurements of the generalized oscillator coordinate
ensure the required accuracy of slowly varying phase shift measurement for quasi-harmonic
signals in a short observation range.
Cauchy problem has a unique solution for equation (19). This problem describes the
forced oscillator, which exposes by quasi-harmonic signal:
t t t 0
t
q(t ) qt 0 exp
dt
cos t dt
t 2
t
t0
t t pt 0 Lt 0 t 0 qt 0 2 t
exp
dt
sin t dt
t 2
Lt 0 t 0 t
t0
t
t t t
sin t dt Pt1 cos t dt ,
exp
d
t
1
1
t 2
t
t1
t t0
1
1
where
(t ) 02 t
1 d (t ) 2 (t )
t .
2 dt
4
The coordinate operator at time t + for a given external influence on the oscillator
includes terms of the coordinate and momentum at time t by the arbitrariness of time t0:
p t Lt t q t 2
t q t
q (t ) exp
cos
sin
2 t
Lt t t
t t t
Pt1
exp
dt sin t dt
cos t1 dt1 .
t1
t
2
t1
1
The commutation relation for the operators of coordinates at times t and t + has form:
220
q t , q t
Lt t
sin t .
The uncertainty relation for successive frames of reference oscillator with the condition
(27) [38] has form
t t
where
sin t
,
2 Lt t
2 t qt qt
(30)
is the dispersion uncertainty generalized coordinate of
quasi-harmonic oscillator.
Consider the steady state oscillation circuit. It expose by the sample-and-hold device.
Here the circuit will be in a steady state, and we can assume that (t) (t + ), then
sin t
.
2 Lt t
(31)
We must note that if the measurement is performed twice per a quasi-period, then (t) =
. The state of the oscillator, where n = (t = tn = n) = 0 is theoretically possible. This is the
so-called q-state.
In this state the generalized coordinates of the oscillator uncertainty are zero at the time
moments tn. However, the uncertainty of the generalized coordinates will be infinitely large at
time t = tn + /2.
Therefore, the application of the q-state measurement of the instantaneous frequency and
phase of the quasi-harmonic vibrations requires a priori information about the exact value of
the measured values for providing the necessary synchronization.
This requirement makes little sense for the measurement procedure. In addition, q-state
oscillator is physically impossible, since it corresponds to infinite energy.
If the measurement is performed 4 times per a period, that is (t) = /2, then we obtain
the minimum value of the uncertainty of the generalized coordinate power from (31):
c t
.
2 Lt t
(32)
Uncertainty has form (32) in a coherent state of the oscillator. It is taken into this state by
the classic indirect force P(t). The uncertainty of the coordinate in the coherent state is
independent of the oscillation phase. Thus, we do not need synchronize the measurements
precisely.
221
This method of measurement is practically realizable, if the dequantizer of classical noise

(thermal, shot, etc.) is substantially smaller than the threshold (32).
Finally, if the measurement sample frequency is significantly more than 4 signal
frequency, and we have the condition << 1/, then the uncertainty of generalized oscillator
coordinate may be obtained as
m t
c t .
2 Lt
(33)
This uncertainty we can see in the compressed state of the oscillator. We can translate
system to this state by periodic parametric action. This influence on the oscillation circuit, in
particular, carries itself dequantizer. It includes a sample-and-hold based on an intermittently
connected capacitor to the circuit.
2.6. Cramer-Rao Inequality to Estimate the Parameters

of Quasi-harmonic Signals
Consider the problem of estimating the amplitude, frequency and phase of the quasiharmonic oscillations in the form (8) for a specimen of N successive equidistant samples of
the generalized coordinates q(t), which are taken with an range of << 1/ at time moment t.
Let T = N << m.
Then we can neglect the variation of the amplitude and the instantaneous frequency of the
signal (8), according to conditions (9) and (10), in the observation range [t T/2, t + T/2] and
we can set in this range
q[n] A cosn n .
(34)
Here we denote: q[n] = q(t + n), N / 2 n N / 2, A = A (t), = (t), and (t) is the
function of additive fluctuation describing uncertainty values of q(t), and that includes
quantum uncertainty, too.
We should find the limits of the Cramer-Rao [39] to estimate the parameters of the
harmonic signal in the circuit under the influence of sample-storage devices. We assume that
the fluctuation (t) has a Gaussian distribution and it is independent on values of the
generalized coordinates q(t). Then the expression of its distribution f(q[n]) can be written for
each sample q[n] as
f qn
nt
qn A cosnt 2
exp
.
2 2 nt
2
(35)
The Cramer-Rao inequality gives the lowest possible bound for variance estimation of a
parameter from the known data set, the variance of which is given. We calculate limit with
222
help the amount of information about the system. The known data set allow represents the
Fisher information matrix [39] in this form:
ln P ln P
,
where , are the unknown system parameters to be estimated, and P is the probability
distribution function of N signal samples in the case of uncorrelated noise. We can obtain the
distribution from multiplying the expression (35) for all N samples:
N 1
P f qn
n 0
N 1 qn A cosnt 2
exp

.
N 1
2
N
t
n 0
2 nt
1
(36)
n 0
The Fisher information matrix elements with unknown parameters estimated A, , for
the set of random events, given by the distribution (36), will look as
2
N 1
cos 2 nt
2 2
2 sin nt
,
I
t
A
n
,
2 nt
2 nt
n 0
n 0
N 1
I AA
At N 1 sin 2nt 2
cos 2 nt
I
A
, A
n 2 nt ,
2 n 0
2 nt
n 0
N 1
N 1
I A 2 t n
n 0
(37)
A N 1 sin 2nt 2
sin 2 nt
I
,
2 nt .
A
2 n 0
2 nt
If the dispersion of samples can be considered as the same one in the time range [t T/2,
t + T/2], i.e. (t) = , then expressions (37) can be calculated in series. We can calculate the
series, often encountered for this in the following forms:
2 j 0 e 2 j0 Lt 1
2 j 0 L 1 2 j0 nt
cos
2
Re
e
e
Re
0
0
e
2 j0 t
e
1
n 0
n0
sin 0 Lt
cos 0 L 1t 2 0
,
sin 0 t
L 1
2 j 0 e 2 j0 Lt 1
2 j 0 L 1 2 j0 nt
sin
2
Im
e
e
Im
0
0
e
e 2 j0 t 1
n 0
n 0
sin 0 Lt
sin 0 L 1t 2 0
.
sin 0 t
L 1
(38)
223
We substitute (38) into (37) and obtain
I AA
1
sin Nt
N cos N 1t 2
,
2
sin t
2
A2
2 2
sin Nt
N cos N 1t 2 sin t ,
t 2 A 2 N N 12 N 1 2 N cos2Nt 2 N sin 2 t 1
3
4 2
2 sin 2 t
sin 2Nt 2 1 2 N 2 sin 2 t sin 2
,
2 sin 2 t tgt
(39)
I A
At cos 2 N 1t 2 sin Nt cosNt 2
N
,
sin t
4 2
sin 2 t
A 2 t
sin 2 N 1t 2 sin Nt sin Nt 2
N N 1 N
,
2
sin t
4
sin 2 t
I A
A
2
sin N 1t 2
sin Nt
.
sin t
The estimated lower bound of the Cramer-Rao, which characterizes the system under a
large number of unknown parameters, has the form:
2 B ,
(40)
where B is the inverse matrix to the Fisher`s matrix and is one of the parameters estimated.
Expression (40) is valid for unbiased estimators, which is true for many parametric signalprocessing techniques [40]. They consider the case of the biased in literature, and although
one is more accurate, however in most cases it is excessive for most applications [39].
Estimates of the parameters of signals, produced by ultra-low samples, are particularly
interesting in the analysis of the instantaneous frequency. Therefore, we write the form of the
Fisher matrix elements for N = 3 and N >> 1 as
I AA
I
cos 2 cos 2 t cos 2 2t
2
t 2 A 2
sin t 4 sin 2t ,
2
224
A2
I A
cos cos t cos 2t ,

2
At
sin2t 2 2 sin 4t 2 ,
2 2
A 2 t
I A
(41)
sin t 2 sin 2t ,
A
2 2
sin2t 2 sin 4t 2 .
They propose in [41] construction of analytical evaluation is too cumbersome based on

the matrix (39) or (41), so a similar estimate for N >> 1. After substitution of (33), we obtain
,
Lt N
12
2 2
,
A Lt N N 2 1
2 2 N 1
2 2
,
A Lt N N 1
A2
(42)
Comparison of variance estimates obtained by one of the methods [40] of parametric

analysis with the Cramer-Rao boundary is present in Figures 2 and 3.
We can see in Figure 2, great increasing the variance estimates relationships between the
frequency of the signal and its initial phase. The vanishing of one of the elements of the
matrix increases the dispersion.
The analysis of the results in Figure 3 shows that proposed in [40] parametric estimation
algorithm for short sample length N < 10 reaches the set of limits by the Cramer-Rao
inequality, and in this sense, this method is optimal. For N 1, variance of the amplitude of
the signal obtained by the parametric methods discussed corresponds to the boundary of the
Cramer-Rao. Variance estimates of the instantaneous frequency and the initial phase of an
increasingly exceeds the lower boundary of the Cramer-Rao.
At the same time, the variance of the instantaneous frequency decreases with the
increasing number of reports approximately how N2, i.e. it decreases slower than it follows
from (42). However, the initial phase variance estimate does not depend on data set length.
This is probably because the proposed methods work with short patterns (N = 3, 4, 5),
distributed to an array of the data with a large number of points with the least squares method
[40].
225
ft
100
10-1
10-2
10-3 0
0
0.1
0.2
0.3
0.4
0.5 ft
0.3
0.4
0.5 ft
0.3
0.4
0.5 ft
(a)
q/A
100
10-1
-2
10
10-3 0
0
0.1
0.2
(b)
101
100
-1
10
10-2 0
0
0.1
0.2
(c)
Figure 2. Comparison of the dispersion parameter estimates of the parametric analysis method [40], that
are obtained numerically (pointed by dots) with the Cramer-Rao boundary (pointed by curves)
depending on the signal frequency: (a) the dispersion of the frequency count, (b) the dispersion of the
amplitude, (c) dispersion of the initial phase (N = 3, = 0, /A = 0.001).
226

f /fd
10
-4
10-5
10-6
10
-7
10
-8
10-9
0
500
1000
1500
2000
(a)
q /A
10-4
N
10
-5
500
1000
1500
2000
(b)
10
-3
10-4
N
10
-5
500
1000
1500
2000
(c)
Figure 3. A comparison of the dispersion estimates of the parametric method [40], obtained numerically
(pointed by dots), with the Cramer-Rao boundary (pointed by line), depending on the length of signal
measurements: (a) the dispersion of the frequency count, (b) the dispersion of the amplitude, (c) the
dispersion estimates of the initial phase (/A = 0.001, = 0, t/2 = 0.18)
227
3. TECHNIQUE OF ANALYSE AND EXPERIMENT

3.1. Measurement Technique
The presence of direct and inverse piezoelectric effect is a phenomenon of electrical
oscillation resonance of a circuit equivalent to the quartz crystal. Parameters of that resonator
related with help terms of the physical constants of the crystal and through the electrical
connection between the quartz crystal element and holder [1]. The equivalent circuit diagram
(Figure 4) consists of a quartz resonator resistance R1, capacitance C1 and inductance L1.
They are connected in series. Capacitance C0 is connected parallel to them. Parameters R1,
C1, L1 are basic ones and they are the dynamic parameters of the piezoelectric resonator.
Parameter C0 is a static capacity.
We can find quartz resonator parameters indirectly. Accuracy of their determination
depends on the accuracy of methods for measuring the frequency and phase fluctuations.
Figure 4. Schematic diagram of replacement of the quartz resonator.
Let us find the quantum limit of instantaneous frequency estimation by the method
described in [40]. According to the method of assessment of the frequency
n 1 xn2 , xn1 , xn at time t = (n 1), it is formed by three equidistant signal
measurements q(t) in the range [(n 2), n] as
qt qt 2
.
2qt
t arccos
Here is the sampling step. Estimate of the frequency variation (43) is equal to
n 1 f n2qn2 f n1qn1 f nqn ,

where
(43)
228
f n2
f n1
q n 2
q n 1
1
2
qn qn2
4
q n1
fn ,
q n21
q n q n2
q n21 4
qn qn2 2
q n21
Since the variations of reporting signals at different times are independent, hence the
variance of the frequency is
2 n 12 f n2 2 qn2 2 f n1 2 qn1 2 f n 2 qn 2 .
Here qi qi , and the line over functions implies the averaging in time. Function
arguments fi are consistent signal measurements qn = Acos(n + ). Since the operator of
generalized coordinate does not commute with itself at different times, the relations of
uncertainty have the form (30):
2
qn1 2 qn2 2

,
2 L
qn1 2 qn 2

.
2L
Here it is assumed that the measurements are made 4 ... 6 times per the period of the
signal and sin() 1. This implies that the uncertainty in estimates of frequency:
2 f n1 2 qn1 2
qn1
2L
f f ,
2
n2
wherein at least
2L
f n1 2 f n 2 f n2 2
is achieved, when we have the equality:
q n 1
2 L
f n 2 f n 2 2
.
f n1 2
Calculation of derivatives fk allows one to obtain the following estimates of the frequency
variation:
f n1 2 f n 2 f n2 2
1,L250Q
2
1,250
.
2CU 2
229
(44)
Here U = A/C is the amplitude of the voltage across the capacitor C. We can use form
(44) to estimate the minimum relative uncertainty of the frequency parametric method. It has
the form:
25
n
where n
(45)
CU 2
is the number of quanta in the oscillator.
2
Hence, it follows from (44) that the relative uncertainty of the estimate of frequency (43)
at the time of observation 107 seconds is 105. This result is for the quartz resonator with the
central part of the 5 MHz and equivalent capacity of 1 pF at a sampling frequency of 25 MHz
and amplitude of voltage oscillations 1 V. The characteristic time of oscillation measurements
for high-qualitative resonator is approximately Q-oscillation period where Q is the quality of
the resonator. For typical modern quartz resonators, value of Q is 105 106. We can use it to
analyze the dynamics of the instantaneous frequency of a sliding window with the duration of
about 0.1 seconds. As seen in Figure 3a for estimation (43), uncertainty decreases in
proportion to the duration of the observation interval. We can expect that the relative error of
measurement of the instantaneous oscillation frequency of the quartz resonator, due to
quantum uncertainty. It will be 1011 in the window of 0.1 second.
Figure 3c shows that the error in determining the initial phase of a three-point parametric
method [40] does not decrease with the increasing duration of the observation interval. In this
sense, the parametric algorithm of three-point measurement of the phase waves is no optimal.
This may be due to the uncertainty of the initial phase of the oscillation itself, which depends
on the choice of the initial time. In [46] they describe a method of parametric estimation of
the phase difference 0 between two quasi-harmonic signals with different amplitudes and the
same frequency:
tg 0
A2 n 4 A22 n A12 n
A1 nA3 n 2 A2 nA4 n
where
A1 n q1 n 4q 2 n q1 nq 2 n 4,
A2 n q1 n 3q 2 n 1 q1 n 1q 2 n 3,
A3 n q1 n 3q 2 n 1 q1 n 1q 2 n 3,
A4 n q1 n 1q 2 n 1 q1 n 3q 2 n 3,
(46)
230
and q1[n] = q1(n), q2[n] = q2(n) are the measurements of the first q1(t) and the second q2(t)
signals, respectively. This value does not depend on the choice of the reference signal
measurements, if q1(t) and q2(t) are measured synchronously.
Similarly, for the proof of (44) for the instantaneous frequency we can show that the form
of the phase difference uncertainty of (46) is
0 2 3.20
C
1
1
2 .
2
U1 U 2
(47)
For the same parameters the measurement error of quartz phase difference due to the
quantum uncertainty is about 7 108 rad.
The parameter estimation error of quartz resonators due to quantum uncertainty is
fundamental. We cannot overcome it by hardware or software. The optimization of datameasuring system shall provide hardware measurement error lesser than the quantum
uncertainty. On the other hand, the achievement of a hardware error substantially lesser than
the quantum uncertainty does not lead to the increased accuracy.
Voltage quantum uncertainty of the equivalent capacitance C for the oscillations in a
coherent state has from equation (32) as
c t
C
2 LC 2
.
2C
(48)
This value is 50 nV for the equivalent capacitance of 1 pF and the resonance frequency of
5 MHz. Since the charge on the container can only be changed by an integer electron charge
e, there is the shot noise of the measured charge uniformly distributed in the range [e/2, e/2]
with variance e2 = e2/12.
The corresponding uncertainty voltage e = e/C for the equivalent capacitance of 1 pF is
40 nV. Given to the input noise of presently high preamp does not exceed 1 nV/Hz1/2. When
value of Q of the resonator is 105 and the resonance frequency is 5 MHz, the equivalent
bandwidth reception could reach 100 Hz. The measurement error of preamplifier due to its
noise is 10 nV.
We analyze the contribution of thermal fluctuations of the quartz resonator in
measurement error of parameters of its electrical oscillations in detail. Because the
fluctuation-dissipation theorem is applicable only to the equilibrium state, the coherent state
of the oscillator is far from thermodynamic equilibrium. We can assume that the dissipative
processes in the resonator lead to additive thermal fluctuations of the number of photons in
the resonator with an exponential probability distribution:
PT n
n
exp
kT
kT
231
kT
and dispersion T2
. In the coherent state, the oscillator distribution of the

number of quanta is Poissons one:
Pz n
n!
exp n
with variance 2z n , where n

Then T
kT
CU 2
is the average number of quanta in the oscillator.
2
12
0.1 at T = 300 K, U = 1 B, C = 10 V and f = 5 MHz. Thus, the
U C
uncertainty due to noise preamplifier, shot and thermal noise of the resonator are small to the
quantum uncertainty.
3.2. Hardware-Software Complex Parametric Estimation of Frequency

and Phase of Quasi-harmonic Signal and Its Defining Characteristics
The hardware part of the complex consists of two units: digitization and controller USB
3.0 interface. Figure 5 shows the unit diagram of digitization unit. The digitization unit
contains two 16-bit ADCs DD3, DD4 LTC2203 with a sampling frequency up to 25 MHz
[42]. Timing of the ADC occurs of the generator ZQ1 or an external source. By using a
divider by 2, formed on the circuit element DD2, the clock frequency may be increased up to
50 MHz.
Chips DA2 amplify the analyzed signals 5 times, DA3 of type LTC6406. They are
differential amplifiers with low-noise, low-voltage, and bandwidths up to 800 MHz [43].
Internal reference voltage of the ADC generates common-mode voltage 1.25 V for
differential amplifiers. Supply voltage of 3.3 V power stabilized DA1 digitizing unit is
formed from a battery with a voltage of 5 V. As USB 3.0 interface controller, we use the
developed board CYUSB3KIT-001 [44] with 32-bit microprocessor CYUSB3014. The
microprocessor architecture is ARM-9; it contains 512 kilobytes of internal memory, a
parallel 32-bit input-output port allowing one to transfer the information between the
microprocessor and the digitization block with a frequency up to 100 MHz.
The accuracy of the hardware-software complex was evaluated at different input sources
and timing signals of ADC. In the first series of experiments, we used OCXO MORION
MV89A 10 MHz [45] as the clock. The estimation of the phase shift has been made for 4106
signal measurements at the frequency of 1 MHz by the described method [46], the band of the
FIR filter being 20 kHz. Since, the error of parametric methods increased with the decrease in
the phase shift to processing, one of the signals delayed by one measurement. The
instantaneous frequency was determined for each channel individually. We do it in
accordance with the method of parametric estimation of the frequency and the amplitude [47],
and two signals from the formula described in [46]. These frequency estimates are denoted by
f1, f2 and f0. After an hour warm-up of both inputs, we processed signal from the precision
232
generator G3-122. The averaged estimates of frequency, built in the window L = 10,001 at
RMS f0 = 1.5104 Hz, f1 = 1.5104 Hz and f2 = 1.5104 Hz adopted the following
values <f1> = 999.99929723 kHz, <f2> = 999.99929725 kHz, <f0> = 999.99929732 kHz.
Figure 6 shows the dynamics of the phase difference deviation from the mean, built on the
window L = 100,001. RMS deviation of the phase difference from the average value was
1.3104 rad.
Figure 5. Block diagram of digitization unit.
We have used generator with independent intermediate frequency reference oscillator

MORION MV89A to creating the input signal. In this experiment, the frequencies (L =
10,001) were <f1> = 1000.000000 kHz, <f2> = 1000.000000 kHz, <f0> = 999.9999999 kHz
with RMS f0 = 4104 Hz, f1 = 3104 Hz and f2 = 4104 Hz. The dynamics of the phase
233
difference deviation from the mean value for L = 100,001 is shown in Figure 7, the standard
deviation is 1.7104 rad.
In this case, as both the complex and the intermediate frequency signal generator are
clocked by a crystal oscillator frequency with RMS f0 = 104 Hz, f1 = 104 Hz, f2 = 104
Hz, the phase difference is 3.3105 rad. Figure 8 shows the dynamics of deviation of the
phase difference.
The similar experiment was performed when the reference generator was rubidium
standard 10 MHz FE-5680 [48]. The averaged estimates of frequency in this case amounted
<f1> = 999.99999 kHz, <f2> = 999.99999 kHz and <f0> = 999.99999 kHz at RMS f0 =
5105 Hz, f1 = 4105 Hz and f2 = 5105 Hz. RMS phase-difference estimates for L =
100,001 and 500,001 are respectively = 2105 rad and = 3106 rad. The dynamics
of the phase difference in that case has noise-like character (see Figure 9).
, 10-4 rad
2
-2
0
100
200
300
400 t, ms
Figure 6. Dynamics of deviations from the mean phase difference in an experiment with G3-122 (L =
100,001).
, 10-4 rad
2
0
-2
-4
0
100
200
300
400 t, ms
Figure 7. Dynamics of deviations from the mean phase difference in an experiment with DDS (L =
100,001).
234

, 10-4 rad
0.4
0
-0.4
-0.8
0
100
200
300
400 t, ms
Figure 8. Dynamics of deviations from the mean phase difference in an experiment with DDS clocked
from a single crystal oscillator (L = 100,001).
In the next experiment, we carry out complex and DDS-generator timing by two
independent rubidium standards. The average frequency estimates being respectively <f1> =
999.9999997 kHz, <f2> = 999.9999998 kHz, <f0> = 999.9999996 kHz at RMS f0 = 5105
Hz, f1 = 4105 Hz and f2 = 4105 Hz. RMS phase difference L = 100,001 and 500,001,
power = 2105 rad and = 6106 rad. The dynamics of the phase difference in this
case has also noisy character (see Figure 10).
We investigate experimentally the signals, obtained with the simulator of the phase shift.
Figure 11 shows the circuit diagram of the simulator. It consists of two RC-chains
C1C2R1R2, which values give the phase difference about /2. In the circuit, the reed SA1 is
also mounted. In addition, at the closure of which the phase difference of amplifier level
simulator can be estimated.
In the experiment, the phase shift of simulator signal was connected to 5 MHz DDS,
which reference oscillator is a rubidium standard and experimental setup clocked 25 MHz
generator AKIP-4113/6 [49]. The average phase difference was <> = 1.59556099 rad,
when averaged over the window length L = 100,001 and 500,001, RMS in this experiment
was = 3104 rad and = 7105 rad, respectively.
, 10-4 rad
0.4
-0.4
-0.8
0
100
200
300
400 t, ms
from a rubidium standard (L = 100,001).
235
, 10-4 rad
0.4
0.2
0
-0.2
-0.4
0
100
200
300
400 t, ms
from different rubidium standards (L = 100,001)
Figure 11. Schematic diagram of the simulator phase shift.
, 10-4 rad
8
4
0
-4
-8
0
100
200
300
400 t, ms
Figure 12. Trend deviation of the phase difference experiment with simulator of the phase shift (L =
100,001).
236
Figure 12 shows the dynamics of phase difference. With the closure of the reed, the
obtained phase difference <> = 0.018959 rad and RMS is = 4104 rad (L = 100,001)
and = 6105 rad (L = 500,001). The increased error in experiments with the simulator of
the phase shift is primarily due to the low stability of the oscillator frequency of AKIP4113/6.
CONCLUSION
The developed data-measuring complex is optimal for studying the properties and
characteristics of piezoelectric materials. It allows one to achieve measurement precision of
electromagnetic oscillations bounded by the quantum uncertainty of the dynamical variables
of the object of study, namely the quartz resonator and the Cramer-Rao inequality. The
estimation of lower boundary Rao-Cramer variance parameter shows that software cannot
improve the accuracy of measurement. At the same time, the SQL of measurement errors
depends on the procedure. In the above data-measuring complex, it has reached the minimum
values of errors for the quantum uncertainty oscillator in a coherent state. We can take the
oscillator to this state by the classic indirect force. This limit is insuperable for measuring
systems based on sample and hold device as a dequantizer. Parametric action, allowing one to
prepare a concise state of the oscillator, provides cooling modes of vibration in it. Variance of
the resonator parameters, increased stability of the phase and the frequency of
electromagnetic waves in them allow the variance to be reduced.
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INDEX
#
3-point method, 184, 196, 198, 199, 200
4-point method, 188, 189, 190, 194, 195, 198, 199,
200
5-point method, 175, 194, 195, 196, 198, 199, 200
A
ABINIT software, 77
absorbed radiation, 20
accelerometers, 140, 141
acid, 72
acoustic absorber, 99
acoustic emission, 105
acoustic pressure, 167, 168
activation energy, 30, 35, 44, 45, 46, 47
active centers, 45, 46, 62
actuality, 13
actuators, 126, 133
adatom, 34
ADC, 201, 231
additives, vii, 24, 42, 61, 62, 63, 79
ADF software, 3
adlayer, 32, 33
ADP, 115
adsorption, 6, 17, 32, 33, 42, 46, 62, 72, 73
age, 172
algorithm, 69, 96, 97, 163, 172, 193, 195, 224, 229
alkali, 110, 111, 112, 114, 119
alkaline earth metals, 110, 119
aluminum oxide, 72
aluminum silicates, vii, 61, 62, 70, 72, 75, 82, 84
ammonium, 40
amplitude, viii, 42, 100, 101, 104, 111, 155, 166,
171, 173, 174, 175, 176, 177, 178, 180, 183, 185,
189, 190, 191, 194, 195, 196, 197, 198, 199, 200,
202, 203, 206, 207, 208, 210, 212, 213, 214, 216,
217, 218, 221, 224, 225, 226, 229, 231
amplitude modulation, 183, 189, 194
analog-to-digital converter (ADC), 201
angstroms, 24
angular frequency, 173, 174
anionic states, 53
anisotropy, 35, 50
annealing, vii, 19, 20, 21, 22, 23, 25, 26, 30, 36, 40,
41, 42
annihilation, 110, 214, 216
antiferromagnetic ferromagnetic division, 121
antiferromagnetic ordering, 135
Archimedean velocity, 91
argon, 22, 41
ARM, 231
arsenic, 42
aspiration, 133
assessment, 201, 227
atmosphere, 22, 23, 24, 26, 29, 42, 90, 114
atmospheric pressure, 40
atomic force, 50
atomic force microscope, 50
atomic interactions, vii, 1, 2, 3, 4
atomic number, 7, 12, 15
atomic scattering factor (form-factor), 67
atomic thermal oscillations effect, 67
atoms, vii, 1, 2, 3, 4, 5, 6, 7, 10, 12, 13, 14, 15, 16,
17, 25, 32, 33, 34, 35, 44, 46, 63, 67, 68, 69, 70,
72, 74, 78, 79, 90, 111
Auger-electron spectroscopy, 7
B
band gap, 25, 26, 39, 84
bandwidth, 166, 207, 230
barium, 129, 131
barriers, 61, 62, 118
240
Index
base, vii, viii, ix, 1, 12, 16, 17, 63, 79, 145, 172, 205,
206, 210
basic research, 65
beams, 43, 48, 68, 95
bending, 118
benthonic zone, 91
Bi1/2La1/2MnO3 (BLM), 124
bias, 39, 41
binding energy, 2, 4, 5, 6, 7, 12, 13, 14, 17
Boltzmann constant, 209
bonding, 25
bonds, 2, 4, 7, 31, 32, 35, 41, 44, 45, 46, 47, 72, 81,
111, 121, 127, 129, 131
boundary surface, vii, 1, 3, 4, 12, 13, 14
by-products, 44
C
Ca2Nb2O7, 110, 111, 115, 117, 119
calcium, 66, 110, 111, 114
carbide(s), 14, 31, 32, 33, 35, 36, 41, 49
carbon, 2, 6, 7, 13, 14, 30, 31, 32, 34, 41, 51, 52
carrier band (CB), 24
catalyst, 43
catalytic effect, 45
cation, 65
Cauchy problem, 163, 219
cell size, 114
centrifugation, 66
ceramic, viii, 109, 114, 115, 120, 121, 122, 124, 125,
126, 127, 128, 133, 146
ceramic materials, viii, 109
challenges, 205
charge density, 53, 78
chemical, vii, 1, 2, 3, 4, 6, 7, 12, 14, 20, 23, 28, 29,
40, 41, 42, 43, 44, 45, 47, 61, 62, 63, 64, 65, 66,
72, 74, 76, 77, 78, 79, 89, 90, 121, 129, 132
chemical bond(s), 2, 4, 6, 7, 20, 45, 79, 121
chemical deposition, 44
chemical interaction(s), 2
chemical properties, 61, 62, 74, 78
chemical reactions, 20, 74
chips technology, 42
classes, 75
classification, 146
clay minerals, 61, 63, 66
cleaning, 42
cleavage, 66
clock generator (CLK), 201
closure, 152, 153, 158, 234, 236
cluster model, 4
clusters, vii, 1, 3, 4, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16,
17, 31, 34, 41, 74, 76, 77, 121
coatings, 1, 16, 17
coefficients of thermal expansion (CTEs), 110
ColeCole diagrams, 123
color, 53, 135
columbite-like compositions, 127
commercial, 77, 78, 79
communication, 172
communication systems, 172
comparative analysis, ix, 50, 171
compatibility, vii, 1, 3, 7
compensation, 111, 172, 219
complexity, 77, 121
compliance, 90, 98, 106, 146
composites, ix, 40, 146
composition, 1, 4, 12, 13, 17, 25, 41, 42, 44, 50, 53,
61, 64, 66, 67, 71, 72, 110, 115, 120, 127, 128,
133, 134, 164
compounds, 3, 13, 14, 15, 31, 47, 74, 75, 110, 111,
113, 114, 115, 117, 118, 119, 121, 134
compression, 34, 110, 119
computation, 13, 198
computer, 62, 75, 76, 77, 78, 104
computer technology, 76
computing, 76, 77, 78, 184, 198
concentration consolidation, 90
conditioning, 61, 62
conduction, 26, 29, 31, 35, 123
conduction band, 26, 29, 31
conductivity, 24, 40, 84, 93, 119, 123, 124
configuration, 33, 34, 76, 77, 147
connectivity, 146, 148, 164
conservation, 45
conserving, 79
consolidation, 90
construction, 49, 75, 224
constructional materials, 90
consumption, 54
convergence, 79
cooling, 41, 42, 49, 110, 130, 210, 236
coordination, 63, 128
copper, 2, 6, 7, 16
correlation(s), viii, 17, 51, 63, 73, 75, 76, 77, 78, 79,
82, 84, 111, 132, 208, 219
correlation analysis, 208
correlation function, 75, 79, 82, 84
cost, 49, 172, 206
Coulomb integrals, 77
covalent bond, 47
Cowin-Nunziato model, viii, 145, 147
Cramer-Rao boundary, 224, 225, 226
Cramer-Rao inequality, 221
crust, 61
CRYSTAL, 78
241
Index
crystal growth, viii, 90, 91, 92, 93, 94, 106
crystal quality, 89, 106
crystal structure, 24, 63, 69, 70, 74, 75, 78, 110
crystalline, 35, 42, 121, 128, 133, 134, 164
crystallization, 89, 90, 91, 92, 93, 94, 106, 135
crystallographic shear, 110, 119
crystals, viii, 51, 63, 74, 75, 78, 89, 90, 91, 95, 105,
110, 111, 206
cuboctahedral position, 110
Curie temperature, 119, 138
cycles, 22
D
damping, viii, 102, 145, 146, 147, 148, 152, 155,
163, 166, 185, 187, 195
data set, 221, 224
data transfer, 210
database, 78
Deal-Grove model, 22, 26, 30
Debye dielectrics, 123
Debye-Waller factor, 67
decay, 119, 122
decimation ratio, 180, 188, 196, 201, 202, 203
decomposition, vii, 19, 42, 43, 44, 45, 46, 56, 79
defect formation, 21, 106, 110, 121
defects, viii, 21, 31, 32, 34, 35, 41, 42, 56, 62, 89,
90, 92, 93, 98, 99, 101, 103, 105, 106, 119, 121,
135
deformation, 34, 49, 81, 128, 135, 140
degradation, 30
delaying time, 100
dendrites, 90
density functional theory (DFT), viii, 2, 75, 76, 79
deposition, 20, 37, 42, 43, 44, 53, 54, 55, 56
deposition rate, 53, 54, 55
depth, 25, 26, 33, 34, 94
derivatives, 78, 149, 211, 228
desorption, 32, 33, 42
destruction, 2, 3, 14, 66, 140
deviation, 68, 172, 173, 176, 177, 179, 180, 196,
198, 199, 200, 201, 206, 232, 233, 235
DFT, 2, 3, 6, 75, 77, 78, 79, 84
dialysis, 66
diamond-like structures, 41
dielectric constant, 34, 114, 124, 131
dielectric loss tangent, 137
dielectric permittivity, 78, 119, 122, 123, 124, 125,
127, 129, 130, 137, 138, 140, 141
dielectric relaxation, viii, 109
dielectric retardation, 122
dielectric stability, 42
dielectric thin films, 30
dielectrics, 20, 122, 123

diffraction, 67, 68, 69, 70, 115, 128
diffraction spectrum, 69, 70
diffusion, 22, 25, 27, 28, 42, 48, 50, 94, 115, 121,
127, 129, 131, 132, 160
diffusion process, 115, 121
diffusivity, 93
diffusivity coefficients, 93
digital communication, 172
digital processing signals, ix, 205
digital recursive system, 184
digital signal processor (DSP), 201
dipole moments, 76
Dirichlet condition, 151
discrete spectrum, 158
discreteness, 101
discs, 127
dislocation, 90
dislocation loops, 90
disorder, 62
dispersion, 61, 66, 119, 187, 194, 206, 220, 222, 224,
225, 226, 231
displacement, 14, 46, 72, 147, 148, 149, 150, 152
dissociation, 23, 24, 25, 26, 27, 28, 29, 44, 45, 46,
47, 90
distilled water, 66, 72, 99
distributed memory, 77
distribution, 21, 26, 41, 48, 51, 66, 67, 86, 89, 90, 92,
93, 96, 98, 115, 123, 124, 134, 135, 209, 221,
222, 231
distribution function, 123, 124
DOI, 85, 238
domain structure, 121, 130, 131, 133
dominance, 116
donar dopant, 35
dopants, 39
doping, viii, 24, 35, 42, 110, 121
double refraction, 95
dry oxidation, 35, 41, 50, 51
drying, 72
durability, 19
dynamic pyroelectric current, viii, 110
dynamic systems, 213
dynamic viscosity, 92
E
effective moduli, 145, 146, 164, 165, 168
elaboration, 119
elastic moduli, 160
electric charge, 148, 150, 151
electric conductivity, 134
242
Index
electric field, 25, 26, 28, 43, 48, 119, 122, 123, 125,
126, 128, 129, 131, 133, 140, 147, 148
electrical properties, viii
electrodes, 42, 127, 146, 150, 151, 157, 159, 160,
165, 166
electromagnetic, ix, 205, 236
electromagnetic waves, 236
electron, vii, 7, 22, 23, 24, 25, 26, 29, 31, 37, 41, 62,
65, 67, 74, 75, 76, 77, 78, 79, 82, 84, 230
electron affinity energy, 24
electron diffraction, 65
electron microscopy, 62, 65
electron paramagnetic resonance, 31
electron state, 31, 82, 84
electron tunneling effect, 22
electronegativity, 35, 127
electronic structure, viii, 47, 48, 61
electrons, 6, 24, 25, 26, 29, 47, 48, 67, 79
ellipsometry, 50
elongation, 111
embedding operator, 158
emission, 23, 24, 105
empirical methods, 78
endurance, 48, 49
energy, vii, 1, 2, 4, 6, 7, 8, 9, 12, 13, 14, 15, 16, 17,
23, 24, 25, 26, 30, 31, 32, 35, 44, 45, 46, 47, 48,
53, 54, 56, 62, 71, 76, 77, 78, 79, 82, 84, 90, 149,
157, 160, 163, 216, 220
energy density, 53, 54
energy zones, 48
engineering, 53
environment, 45, 48, 90
equality, 96, 97, 228
equilibrium, 14, 15, 27, 39, 46, 68, 73, 84, 94, 106,
115, 230
equipment, vii, 19, 26, 48, 89, 90, 92, 140, 141, 172,
173, 208, 236, 237
equivalent circuit diagram, 227
error estimation, 183
etching, 34
evidence, 121, 131
evolution, 218
exchange-correlation functional, 79, 82
excitation, 20, 45, 46, 47, 48, 100
exponential expansion, 213
exposure, 13, 48, 49, 67, 115, 116
external influences, 155
F
fabrication, 21, 22, 25, 50, 115
FEM, 146, 163
ferroelectrics, 126, 127, 129, 132
ferromagnetic, viii, 109, 121, 125

ferrostiffness, 138
fidelity, 69
film formation, 43
film thickness, 20, 25, 32, 34, 50, 53
films, vii, 19, 20, 21, 22, 26, 30, 34, 37, 40, 41, 42,
47, 50, 56
filters, ix, 175, 205, 206
financial, 17, 84
financial support, 17, 84
finite-dimensional space, 161
Fisher information matrix, 222
floating-point operations, 184, 195, 198, 203
fluctuations, 46, 103, 173, 187, 214, 227, 230
fluid, 65, 67
focal zone, 146, 165, 168
forbidden band, 31, 34
force, 12, 13, 17, 42, 46, 78, 92, 147, 148, 150, 220,
236
forecasting, 17
foreign inclusions, 93
formation, vii, viii, 2, 19, 22, 24, 26, 33, 34, 37, 41,
44, 47, 50, 52, 53, 61, 72, 78, 89, 90, 91, 105,
121, 127, 133, 135
formula, 36, 39, 45, 63, 64, 69, 70, 92, 95, 103, 114,
123, 128, 130, 177, 183, 184, 196, 209, 231
Fourier transform, 98, 100, 101, 207
fractal dimension, 134
fragility, 14
fragments, 4, 40, 46, 78, 104, 105, 120
France, 142
freedom, 163
frequency instability, 173, 201, 202
frequency signal generator, 233
frequency stability, ix, 172, 205, 206, 209
frequency synchronization, 204
friction, 14, 149
Fulchera-Tammans equation, 96
G
gallium, 205
GAMESS (General Atomic and Molecular
Electronic Structure System), 76
gas-phase photo-decomposition, vii
Gaussian distribution, 221
Gaussian noise, 180, 187, 198
Gaussian software package, 77
generalized gradient approximation (GGA), 79
geometry, 67, 76, 78, 165
Germany, 79, 107
GPS, 171
graduate students, ix
243
Index
grain boundaries, vii, 1, 2, 3, 13
grain boundary embrittlement, 2, 3
grain size, 133
grants, 168
graph, 166
graphite, 31, 32, 40, 41, 67
grazing, 50
grids, 63, 64
growth, 22, 23, 24, 26, 28, 29, 30, 35, 47, 52, 53, 54,
55, 89, 90, 91, 92, 93, 94, 95, 96, 105, 106
growth dynamics, 23
growth kinetics, 91
growth rate, 22, 23, 24, 26, 28, 29, 30, 53, 54, 55, 93,
94, 106
guidance, ix, 171
H
hair, 104
halogen, 20, 23, 40, 48, 49
Hamilton function, 216, 217
Hamiltonian, 75, 213
hardness, 14
hardware-software complex, 231
harmonic problem, 155, 158, 166, 168
harmonic signal, 201, 207, 208, 214, 219, 221
Hartree-Fock, 76, 78, 84
Hartree-Fock methods, 78
hazardous(s) waste, 61, 62
heat conductivity, 92
heating rate, 48, 115
height, 24, 165
Heisenberg uncertainty phase limit, 216
Henry law, 28
Hermitian operator(s), 213, 214
heterogeneity, 22, 89, 109, 128
heterovalent isomorphism, 64
hindrance signals, 101
history, viii, 24, 109
homogeneity, 134
horizontal directed crystallization (HDC), 89
human, 104
humidity, 36, 72
hybrid, vii, 19, 78, 84
hybrid functionals, 84
hybrid systems, vii, 19
hydrogen, 6, 15, 41, 48, 63
hydrogen bonds, 63
hydrolysis, 72
hydrostatic pressure, 132
hydroxide, 72
hydroxyl, 62, 63
hydroxyl groups, 62, 63
HyperChem software, 78
hypothesis, 2, 132
hysteresis, 39, 128, 131, 132, 133
hysteresis loop, 128, 131, 132
I
ideal, 2, 130, 209
identification, 41, 206, 214
identification problem, 214
identity, 214
image(s), 129, 134
impulses, 101
impurities, 66, 90, 94, 120, 121
impurity capture, 90
impurity centers, 25
incoherent accretion, 90
incommensurate phases, 111, 112
incomplete compliance, 90
independence, 203
indexing, 69
induction, 122, 123, 124, 125
inequality, ix, 163, 205, 206, 211, 221, 224, 236
inertia, 49, 148, 149, 150, 159, 162
information matrix, 222
inheritance, 90
initial state, 133
initiation, 20, 105
insonation regime, 66
integrated circuits, 19, 21, 26, 48
integration, 19, 154
interdependence, 50
interface, 20, 22, 23, 24, 25, 26, 27, 28, 29, 31, 32,
33, 34, 35, 39, 40, 41, 50, 51, 55, 77, 78, 93, 231
interfacial defects, 31, 41
interference, 67, 69, 100
internal stresses, 90, 95, 106
inter-package cations, 64
interphase, 106
interpolation problem, 212
intracrystalline swelling, 65
Invar effect, 111, 115, 116, 117, 119
inversion, 39
ion-exchange, 62
ionization, 24, 29, 47, 48
ions, 28, 48, 63, 72, 73, 78, 82, 83, 84, 127, 140
IR spectra, 80
iron, vii, 1, 2, 3, 4, 6, 7, 10, 12, 13, 14, 15, 16, 17,
63, 72
irradiation, 24, 49
isotope, 34
issues, 109
Italy, ix, 145
244
Index
J
jitter, 206, 209, 210
justification, 22
K
kaolinite, 63, 64, 67, 69, 70, 71, 72, 81, 84
kinetics, 22, 26, 34, 35, 42, 53, 91
kinks, 138
Kohn-Sham wave functions, 79
L
lanthanum, 124
laser radiation, 24, 50
lattice parameters, 111, 115
lead, viii, 14, 16, 31, 84, 90, 93, 109, 127, 129, 131,
146, 160, 178, 230
leakage, 31, 34
leakage currents, 31
light, 13, 16, 20, 29, 39, 41, 42, 43, 47, 72, 83, 95,
105
liquids, 63, 92
lithium, 6, 7, 73, 102, 110
longevity, vii
low temperatures, 22, 24, 42, 44, 115, 116
L-point method, 198
LTC, 231
Luo, 58
lying, 46
M
macromolecules, 78
magnesium, 63
magnetic field, 75, 125, 126
magnetic properties, 109, 134
Magnetodielectric effect (MDE), 124
magnitude, 2, 53, 80, 90, 128, 137, 173, 174, 175,
185, 189, 191, 194, 201
majority, 2, 92, 138, 205
manganese, 6, 7
manufacturing, 134, 206
masking, 42
mass, viii, 45, 66, 72, 84, 89, 110, 146, 148, 150,
162, 163
mass transfer, viii, 89
materials, vii, viii, 1, 2, 12, 16, 17, 35, 61, 62, 65, 74,
84, 86, 89, 109, 110, 114, 119, 122, 127, 133,
140, 145, 146, 148, 163, 168, 171, 172, 205, 206,
236
Materials Studio package, 77
mathematical methods, 74, 76
matrix, 2, 4, 6, 40, 76, 78, 124, 161, 162, 163, 164,
223, 224
matter, 29, 97, 109, 174
MaxwellWagner polarization, 124, 125
mechanical attenuation, 148
mechanical properties, 160, 213
mechanical quality factor, 137
mechanical stress, 16, 21, 22, 140, 149
media, 76, 114, 115, 146, 147, 148, 154, 158
median, 71
medical, 140, 141, 165
melt(s), 90, 91, 92, 93, 94, 96, 106
melt dissociation, 90
memory, 76, 147, 231
Mendeleev, vii, 1, 3, 7, 15
meridian, 164, 165
message passing, 77
metal ion(s), vii, 83, 84
metal oxides, 110
metal-oxide-semiconductor, 30
metals, 2, 7, 14, 16, 17, 40, 72, 83, 110, 119, 135
meter, 120, 123, 128
microelectronics, 60
microfluidic structures, vii, 19
microheterogeneity, viii, 121
microheterogeneous system, 121
microprocessor architecture, 231
microscope, 105
microstructure(s), 127, 128, 133, 134, 164
Ministry of Education, 84
MNDO, 78
modal problem, 146, 155, 156
model system, 6
models, 22, 77, 145, 146
modern science, vii, 89
modules, 76, 77
modulus, 98, 99, 103, 122, 137
moisture, 74, 83
mole, 30
molecular dynamics, viii, 78
molecular oxygen, 23, 24, 25, 26, 27, 28, 29
molecular structure, 76, 77, 78
molecular weight, 29, 114
molecules, 23, 24, 25, 27, 28, 34, 42, 43, 44, 45, 54,
62, 63, 74, 76, 77, 78
molybdenum, 2
momentum, 45, 215, 219
momentum conservation, 45
Monkhorst-Pack method, 79
245
Index
montmorillonite, 63, 64, 65, 67, 70, 73, 81, 84
MOPAC package, 78
morphology, 50, 104, 106, 118, 119, 140
morphotropic phase boundary (MPB), 126
Moscow, 56, 57, 58, 60, 67, 77, 85, 86, 141, 142,
144, 236, 237
MOS-devices, 31
MOZYME program, 78
MPI, 77
multi-component systems, 109
multifractal scanning, 134, 135
multi-layer coats, vii
multiplication, 105, 206
multiplier, 212
N
NaCl, 72
NaNbO3, 110, 111, 113, 115, 116, 117, 118, 119,
135, 138
nanomaterials, ix
nanometer(s), vii, 22
nanoparticles, 75, 77
nanoscale additives, vii, 61, 63
nanosystems, 62, 77
natural frequency, 159
navigation system, 172
Nb2O5, 114, 127
negative effects, 12
neglect, 31, 148, 221
Neumann condition, 151
neutral, 22, 28
Newmark method, 163
nickel, 7, 37
niobate materials, 114
niobium, 40, 110, 114, 119, 121
nitrides, 40
nitrogen, 6, 7, 13, 35, 36, 40, 41, 50, 51
nodes, 90
non-Debye relaxation, 124
non-destructive control, 98, 103
non-polar, 31, 32, 33
nuclear charge, 7, 12
nuclear magnetic resonance, 62
nucleation, 42, 47
nuclei, 45, 75, 118
numerical analysis, viii, 145, 166
O
octane, 114
oil, 166
online estimating, viii, 171, 174

open-circuited electrodes, 151, 159, 160
operating system, 76
operations, 19, 51, 76, 156, 171, 174, 184, 195, 196,
198, 203
optical method, 95, 106
optimization, 70, 76, 77, 127, 146, 206, 230
organic compounds, 44
organic matter, 66
orthogonality, 158
orthogonality conditions, 158
orthorhombic structure, 135
oscillation, 172, 191, 206, 211, 212, 215, 216, 218,
220, 221, 227, 229
oscillator energy, 216
oscillator uncertainty, 220
oscillators, ix, 171, 172, 173, 204, 205, 208, 209
over-barrier injection, 24
oxidant flux, 26, 27
oxidation, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32,
33, 34, 35, 36, 37, 39, 41, 42, 43, 47, 48, 50, 51,
52, 53, 110, 121
oxidation products, 29
oxidation rate, 22, 24, 30, 32, 35, 36, 37, 48
oxidation stage, 23, 31, 32
oxide thickness, 20, 22, 23, 26, 30, 36, 53, 54
oxidizing atmosphere, 29
oxygen, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33,
34, 36, 39, 42, 43, 44, 47, 48, 49, 50, 54, 63, 64,
72, 81, 110, 140
ozone, 22, 23, 24
P
Paley-Wiener-Schwarz theorem, 211
paraelectric (PE) region, 119, 121
parallel, 15, 23, 33, 63, 76, 77, 95, 227, 231
parameter estimates, 225
parameter estimation, 206, 230
partition, 77
passivation, vii, 19
Pb(Mg1/3Nb2/3)O3 (PMN), 126
PbFe1/2Nb1/2O3 (PFN), 122
PbTiO3 PbZrO3 PbNb2/3Mg1/3O3, viii, 110
PbTiO3 (PT), 126
PC GAMESS/Firefly, 76
peptization, 66
periodicity, 101, 214
permit, 65, 77
permittivity, 114, 122, 123, 124, 140, 148, 160
perovskite structure, 126
personal computers, 77
246
Index
pharmacology, 61, 62
phase diagram, 110, 128, 133, 134, 135, 138
phase difference, 229, 230, 232, 233, 234, 235, 236
phase noise, 206, 207, 208, 209, 210
phase shift, 214, 219, 231, 234, 235, 236
phase transformation, 92, 111
phase transition(s), 110, 111, 115, 116, 118, 119,
125, 129, 131, 132, 133
phase uncertainty, 216
phosphate, 111
phosphorus, 2, 7, 13, 42
photochemical deposition, 44, 54
photoelastic constant, 95
photoelectron spectroscopy, 1, 71
photoemission, 24, 31
photo-excitation, 44
photographs, 91
photoluminescence, 34, 50
photons, 23, 26, 48, 230
photo-stimulated oxidation, 26
physical properties, viii, 40, 44, 61, 62, 74, 82, 121,
135, 160
physics, 75, 109, 210, 214
piezoelectric composites, 146
piezoelectric properties, 127, 147, 157
piezoelectric resonators, ix, 205, 210
piezoelectricity, 152
pitch, 67
planar processing, vii, 19
plane waves, 75, 78
plastic deformation, 90
plasticizer, 115
platform, 76
PM3, 76, 78
point defects, 21, 89, 90, 110
polar, 32, 33, 50, 63, 132
polarizability, 131
polarization, 50, 77, 121, 122, 124, 125, 131, 133,
137, 140, 165
polarizing effect, 127
pollution, 42
polyatomic clusters, vii, 1, 16
polymer, 164
polymorphism, 111, 121
porosity, viii, 145, 146, 147, 148, 157, 159, 160, 161,
164, 165, 166
porous materials, 145
porous piezoceramics, viii, 145, 164, 166
Portugal, 169
potassium, 111, 114
precipitation, 66
preparation, viii, 56, 66, 109, 114, 115
principles, 37, 74
PRIRODA, 77
probability, 28, 29, 93, 222, 230
probability distribution, 222, 230
probe, 53
project, 17, 76, 84
propagation, 121, 172, 209
proportionality, 29
protection, 35
pseudopotential, 77, 79
p-type wafer, 24
pulp, 72
pumps, 48
punch rotation, 150
purification, 61, 62
purity, 4, 40, 89, 114, 134, 207
pyrochlore phase, 128
pyroelectric, viii, 110
pyrolitic decomposition, 42
pyrolysis, 56
pyrolysis reaction, 56
PZT-5, 165, 166
Q
quanta, 216, 229, 231
quantitative estimation, 105
quantum chemical calculations, 79
quantum chemistry, 2, 7, 62, 74, 76, 78
quantum mechanics, 74, 75
quantum readout system (QRS), 213
quantum-chemical approach, vii, 1, 3
quantum-chemical calculations, 4, 16, 76
quantum-chemical methods, 2
quantum-chemical software, 61, 76
quartz, vi, ix, 40, 42, 48, 49, 50, 115, 171, 172, 173,
205, 206, 209, 210, 227, 229, 230, 236
quartz filters, 206
quartz resonators, 210, 230
quasi-harmonic SVAF process, 215
R
radar, 209
radiation, 20, 21, 23, 24, 25, 26, 43, 45, 46, 47, 48,
49, 53, 54, 60, 67, 115, 127
radiation sources, 20, 48
radicals, 44, 47, 78
radio, 206, 210, 214
radius, 71, 92, 93, 103, 128, 131, 165
Raman scattering, 31, 41
Raman spectroscopy, 62
Rao-Kramer inequality, ix
247
Index
rapid thermal annealing (RTA), 20
rate of change, 121
raw materials, 90
reactants, 53, 56
reaction rate, 29
reaction zone, 53, 56
reactions, 23, 25, 28, 29, 42, 46
reactivity, 40, 74
reagents, 53, 62, 66, 72, 114, 116
real time, 203, 206
reception, 103, 230
recommendations, 106
reconstruction, 101
recurrence, 184, 197, 198, 203
redistribution, 93
reflection factor, 98, 99
refractive index, 25, 50, 51
relaxation, viii, 21, 22, 23, 95, 96, 97, 98, 106, 109,
122, 123, 124, 125
relaxation frequency, 124, 126
relaxation process(es), 96, 97, 123
relaxation times, 96, 97, 123, 124
relaxor ferroelelctrics, 126
reliability, 19, 172
relief, 14, 15, 16, 17
remanent polarization, 137
reproduction, 95
requirements, 75, 77, 84, 172, 178
residuals, 69
resistance, 1, 2, 6, 7, 12, 13, 14, 17, 21, 39, 40, 92,
125, 227
resolution, 65, 70, 134, 174
resonance frequency, 230
resonator, 172, 173, 210, 227, 229, 230, 231, 236
resources, 76, 78
response, 19, 102, 134, 191, 201
restrictions, ix, 62, 205
restructuring, 121
retardation, viii, 109, 122, 123, 124
rhombohedral phase, 128
Riesz theorem, 156, 157
Rietveld method, 70
rings, 53
room temperature, 33, 34, 39, 41, 42, 44, 50, 110,
111, 128
root, 34, 68
root-mean-square, 34
rotation angle, 95
rotational molecule motion, 45
rotations, 163
roughness, 34, 35, 102
rubidium, 233, 234, 235
rubidium standard, 233, 234
Russia, ix, 1, 19, 61, 63, 89, 109, 141, 145, 171, 205
S
salts, 72
sampling frequency, 201, 229, 231
sapphire, viii, 89, 90, 91, 92, 94, 95, 96, 98, 99, 100,
101, 102, 103, 104, 105, 106
sapphire crystal, viii, 89, 90, 91, 92, 94, 95, 100, 105
satellite orbits, 172
saturation, 54, 66, 90
scaling, 104
scanning electronic microscope, 127
scattering, 31, 41, 67, 115, 121, 128
Schrdinger equation, 74, 218
Schrdinger representation, 217
science, 58, 77
scientific knowledge, vii
sediment, 72
sedimentation, 67, 86
segregation, 2, 3, 4, 6, 10, 17, 51, 93, 94, 106
self-organizing compensating mechanism, 110
semiconductor, 19, 20, 21, 24, 30, 48, 59, 172
semiconductor sensors, 172
semiconductor structure, 19
semiconductors, 35, 122
semi-empirical method(s), 75, 76, 77, 78
sensing, 36, 50
sensitivity, 134, 172
sensors, 146, 172
sewage, 61, 62
shadowing effect, 41
shape, 103, 124, 131, 161, 162
shear, 110, 172
short-circuited electrodes, 160
short-term instability, 171, 172, 173
showing, 61, 76, 118, 134
Si3N4, 41
signals, ix, 101, 103, 173, 201, 202, 203, 204, 205,
206, 207, 208, 209, 210, 219, 223, 228, 229, 230,
231, 234
silica, 49
silicon, vii, 7, 19, 20, 22, 23, 24, 25, 26, 27, 28, 29,
30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 44,
45, 46, 47, 48, 49, 53, 58, 63
silicon carbide structures, 20
silicon dioxide nanostructured films, 20
silicon-oxygen tetrahedron grid, 63
silver, 72, 110, 111, 114, 127
simulation(s), viii, 61, 62, 67, 68, 76, 77, 78, 89, 106,
177, 180, 183, 187, 188, 189, 193, 194, 196, 197,
198, 201
simulator signal, 234
248
Index
single crystals, 110, 115, 121

sintering, viii, 109, 114, 127, 135, 146
SiO2, vii, 19, 20, 21, 22, 23, 24, 25, 26, 28, 29, 30,
31, 32, 34, 35, 39, 41, 44, 45, 50, 51, 52, 53, 54,
55, 56, 72
SiO2 films, 21, 31, 44, 45, 50, 51, 53, 55, 56
SiO2 surface, 51
sliding window, 178, 181, 184, 188, 189, 193, 194,
195, 196, 229
sludge, 31
SNS, 13, 172
sodium, 110, 111, 114
softening elements, 12
software, 3, 61, 76, 77, 78, 79, 230, 231, 236
solid phase, viii, 89, 90
solid solutions, viii, 109, 110, 115, 119, 120, 126,
127, 128, 132, 133, 134
solid state, 66, 115, 237
soliton lattice, 119
solution, 12, 56, 61, 64, 66, 69, 72, 75, 76, 77, 90,
92, 95, 98, 106, 128, 133, 134, 146, 152, 153,
154, 155, 158, 161, 212, 219
solvents, 110
sonars, 126
sorption, viii, 61, 62, 84
sound speed, 137, 138, 140
specific heat, 93
specific surface, 62, 65
spectroscopy, vii, 7, 62
speed of light, 172
spending, 78
spin, 75, 76
Sr2Nb2O7, 111, 117
St. Petersburg, 106, 142
stability, ix, 16, 42, 110, 115, 119, 134, 172, 173,
188, 205, 206, 209, 210, 236
stabilization, 41, 126
standard deviation, 177, 187, 188, 194, 196, 198,
199, 200, 207, 233
standard reaction, 25
state(s), viii, 10, 22, 24, 29, 31, 35, 40, 41, 45, 46,
51, 53, 55, 56, 75, 76, 77, 78, 79, 82, 84, 96, 98,
110, 115, 118, 121, 127, 129, 131, 133, 135, 148,
151, 155, 188, 192, 194, 216, 220, 221, 230, 231,
236
stationary mode, 92
statistic methods, 206
statistical approach, 121
statistical characteristics, ix, 171, 188
statistics, 210
steady state oscillation circuit, 220
steel, vii, 1, 3, 4, 5, 7, 12, 13, 14, 16, 17, 49
stimulation, 20, 23, 48, 49, 50
stoichiometry, 40, 133

storage, 61, 62, 221
stress, viii, 21, 22, 89, 95, 96, 97, 98, 106, 148
stress relaxation, 21, 22, 95, 96, 97, 98, 106
strong interaction, 63
strontium, 110, 111, 114
structural characteristics, 89, 111, 117, 119
structural defects, 90
structural relaxation, 96, 98
structural transformations, 20, 105
structural transitions, 140
structure, viii, 1, 16, 19, 22, 24, 25, 31, 33, 34, 40,
41, 44, 48, 50, 51, 52, 53, 62, 64, 65, 69, 70, 71,
72, 74, 76, 77, 78, 79, 90, 97, 104, 106, 110, 119,
120, 121, 126, 127, 131, 133, 134, 135, 140, 164,
165, 184, 190, 191, 195
structure formation, viii
sublimation, 2, 6, 110
substitution(s), 63, 64, 72, 78, 131, 164, 224
substitution effect, 78
substrate(s), 22, 23, 24, 25, 26, 30, 33, 34, 36, 39, 40,
41, 45, 46, 48, 99, 102
sulfur, 2, 6, 7, 13
sulfuric acid, 72
superposition method, 163
surface acoustic waves (SAW), 98
surface layer, 1, 3, 6, 7, 12, 14, 17, 20, 41
surface passivation, vii, 19
surface properties, 72
surface region, 34
surface state density, 24, 53, 56
surface tension, 92
surface treatment, 35
surplus, 34
swelling, 63, 65
symmetry, 16, 78, 135, 138, 140, 149, 167, 168
synchronization, 204, 205, 220
synchronize, 220
synthesis, viii, 109, 114, 119, 120, 127, 134, 135
synthetic fiber, 72
T
techniques, vii, 35, 146, 161, 168, 174, 198, 206,
208, 210, 213, 219, 223
technology, vii, 14, 19, 20, 21, 22, 26, 40, 42, 48, 50,
60, 114, 127, 128, 135, 205, 206
telecommunications, 209
temperature dependence, viii, 20, 96, 98, 110, 115,
118, 119
temperature gradient, 91, 92, 94, 106
tension, 89, 90, 94, 95, 106
TEOS, 44, 45, 46, 47, 54, 55
249
Index
testing, 14, 103, 104, 128, 210
tetraethoxysilane, 44, 45, 53, 54, 56
tetragonal phase, viii, 110, 126
tetragonal structure, 135
thermal activation, 43
thermal analysis, 62
thermal expansion, 110, 119
thermal fluctuations, 46, 230
thermal method, 105
thermal oxidation, 22, 23, 24, 26, 29, 30, 34, 41, 42,
48, 50, 51, 52, 53
thermal steam oxidation, 50, 51
thermal stresses, 90
thermal treatment, 22, 29, 49
thermocapillary force, 92
thermodynamic equilibrium, 117, 230
thermodynamic parameters, 78
thermorheological simplicity, 96, 106
thin films, 22, 30, 37
thinning, 188
three-point parametric method, 229
time series, 191
tin, 111
titanate, viii, 109, 132, 146
titanium, 16
Tonga, 85
topology, 35
total energy, 45, 78, 79, 80
total internal reflection, 79
trajectory, 14, 71
transducer, 99, 100, 101, 102, 146, 164, 165, 166,
168
transformation(s), vii, 28, 69, 74, 101, 110, 121, 157,
209, 216
transient problem, 148, 153, 158, 161, 168
transition layer, 24
transition metal, 16
transmission, 20, 21, 32, 45, 51, 99, 104
treatment, 21, 57, 72
tungsten, 40
tunneling, 22
tunneling effect, 22
U
Ukraine, 63
ultrasonic waves, viii, 146
ultrasound, 66
uniform, 4, 160, 166
USA, 58
USSR, 106, 141
UV irradiation, 46
UV light, 47, 49, 53, 54, 55

UV radiation, 43, 44, 45, 46, 47, 48, 56
V
vacancies, 90, 110, 121
vacuum, 21, 22, 25, 37, 40, 47, 48, 49, 60, 72, 172
vacuum resonators, 172
valence, 25, 34, 47, 63, 72, 79, 81, 110, 121, 134
valve, 48, 49
vanadium, 6, 16, 40
vapor, 36, 37, 40, 93, 106
variables, 97, 151, 184, 213, 215, 216, 236
variations, 4, 63, 138, 209, 228
vector, 67, 137, 147, 148, 149, 152, 154, 155, 158,
161, 163
velocity, 42, 91, 92, 100, 152, 166, 167
versatility, 133
vibration, 78, 79, 81, 210, 236
vibrodiagnostics method, 103
viscosity, 96
viscosity factor, 96
volatility, 210
voltage controlled oscillator (VCO), 208
W
Washington, 58, 59, 204
water, 26, 30, 36, 38, 39, 41, 49, 53, 61, 62, 63, 66,
72, 84
water vapor, 26, 30, 36, 38, 72
wavelengths, 47, 111
wear, 1, 2, 6, 7, 12, 13, 14, 17
weathering, 65
week formulation, 147
X
xenon, 6, 23
X-ray analysis, 67, 120
X-ray diffraction(XRD), 62, 65, 114, 115, 127, 128,
129
X-ray electron spectroscopy, 7
Z
zinc, 111
ZnO, 127
zone approach, 4

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MATERIALS SCIENCE AND TECHNOLOGIES

ADVANCED NANO- AND

MATERIALS SCIENCE AND TECHNOLOGIES

Additional e-books in this series can be found on Novas website

MATERIALS SCIENCE AND TECHNOLOGIES

ADVANCED NANO- AND

Copyright 2014 by Nova Science Publishers, Inc.

Library of Congress Cataloging-in-Publication Data

Published by Nova Science Publishers, Inc. New York

Methods to Study Modified Aluminum Silicates

Investigations of Defect Formation

Physics and Design of Multi-Functional Ceramic Materials

comparative analysis of their accuracy and statistical characteristics as well as guidance on

Ivan A. Parinov (Ed.)

In: Advanced Nano- and Piezoelectric Materials

COMPATIBILITY OF CHEMICAL ELEMENTS ON

Southern Scientific Centre of Russian Academy of Sciences2,

41, Chekhov Avenue, 344006, Rostov-on-Don, Russia. E-mail: ymigal@mail.ru

Yu. F. Migal, V. I. Kolesnikov and E. S. Novikov

Compatibility of Chemical Elements on Grain Boundaries

Yu. F. Migal, V. I. Kolesnikov and E. S. Novikov

2. CHOICE OF CLUSTER MODEL

Compatibility of Chemical Elements on Grain Boundaries

Yu. F. Migal, V. I. Kolesnikov and E. S. Novikov

3. CALCULATIONS OF BINDING ENERGY OF CLUSTERS CONTAINING

Compatibility of Chemical Elements on Grain Boundaries

Table 1. Binding energy of adsorptive clusters Fe2Fe6X2 (eV)

Table 2. Binding energy of segregative clusters Fe2Fe6X2Fe6Fe2 (eV)

Yu. F. Migal, V. I. Kolesnikov and E. S. Novikov

By comparing the characteristics of atoms in adsorptive and segregative states, it is

Table 3. Energy necessary for dividing segregative clusters Fe2Fe6X2Fe6Fe2 (eV)

Yu. F. Migal, V. I. Kolesnikov and E. S. Novikov

4. CALCULATIONS OF BINDING ENERGY OF CLUSTERS CONTAINING

Compatibility of Chemical Elements on Grain Boundaries

Table 4. Binding energy of segregative clusters containing two types of segregants

Binding energy of clusters, eV

Yu. F. Migal, V. I. Kolesnikov and E. S. Novikov

5. POTENTIAL ENERGY CURVES FOR ADSORBED

Figure 7. Coordinates describing the displacement of atoms on iron surface.

Compatibility of Chemical Elements on Grain Boundaries

Yu. F. Migal, V. I. Kolesnikov and E. S. Novikov

Compatibility of Chemical Elements on Grain Boundaries

2) The comparison of the binding energy of clusters, representing adsorptive and

In: Advanced Nano- and Piezoelectric Materials

DEVELOPMENT AND STUDY OF SILICON DIOXIDE

Corresponding author: Email: vpolyakov@sfedu.ru.

Development and Study of Silicon Dioxide Nanostructured Films

2. CHARACTERISTICS OF SILICON DIOXIDE NANOSTRUCTURED

Development and Study of Silicon Dioxide Nanostructured Films

Development and Study of Silicon Dioxide Nanostructured Films

O +e = O ( Ee > 1.46 eV).

Thus, obtainment of high-quality dielectric by rapid thermal annealing method is

Development and Study of Silicon Dioxide Nanostructured Films

Figure 4. Schematic presentation of oxidation reaction [24].

Thus, the oxidation reaction of silicon is represented by five fluxes:

where D0 is the molecular oxygen diffusion coefficient, 0' is the oxidant

Consequently, the flux system F3 shall be represented as follows

where k1, k2 are the constants of the chemical reaction velocities.

nC 0' D1 and ' (1 n)C0' D2 .

The oxide growth rate will be ascertained by differential equation:

Development and Study of Silicon Dioxide Nanostructured Films

2.2. Processing Dielectric Thin Films SiO2 on SiC by Thermal Oxidation

Development and Study of Silicon Dioxide Nanostructured Films