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A Thesis
Presented to
In Partial Fulfillment
Master of Science
Yuan Zhou
August, 2007
MODELING AND SIMULATIONS OF DIELECTRIC MATERIALS
Yuan Zhou
Thesis
Approved: Accepted:
__________________________ __________________________
Advisor Department Chair
Dr. Alper Buldum Dr. Robert R. Mallik
__________________________ ___________________________
Co- Advisor Dean of the College
Dr. Ang Chen Dr. Ronald F. Levant
___________________________ ___________________________
Committee Member Dean of the Graduate School
Dr. Jutta Luettmer-Strathmann Dr. George R. Newkome
__________________________
Date
ii
ABSTRACT
The perovskites ABO3 are the most important class of dielectric materials. The
perovskite SrTiO3 and the perovskite-related material CaCu3Ti4O12 are studied in this
work.
In the first part of this work, we find the structural temperature of SrTiO3 by
nature between Ti and O is found. This is responsible for the TiO6 octahedron behavior
materials of different Ca, Cu ratios. This is the first time to perform ab initio calculations
to study Ca1+xCu3-xTi4O12. We find that with the increase of with increase of Ca in the
material, the optimized lattice constant and band gap increase, and insulator character
becomes much more pronounced in the material. This is in good agreement with the
experimental results.
iii
ACKNOWLEDGEMENTS
Many thanks to my advisors; to Dr. Alper Buldum, for offering valuable advice and
guidance in my research; to Dr. Ang Chen, for his patience, direction and help not only in
my research but also in my life. I will never forget the days working with them.
Akron, for their excellent lectures and generous assistance through these past few years. I
Many thanks to my colleagues and friends in Akron, for their help and assistance.
Many thanks to everyone I met in Akron, for their warmness and hospitality which
iv
TABLE OF CONTENTS
Page
LIST OF TABLES………………………………………………………………….…...viii
LIST OF FIGURES……………………………………………………………………....ix
CHAPTER
І INTRODUCTION ........................................................................................................ 1
v
3.3 Dynamics simulations ................................................................................................ 26
vi
6.6 Summary of the work on Ca1+xCu3-xTi4O12 ........................................................ 51
REFERENCES ................................................................................................................ 53
vii
LIST OF TABLES
Table Page
viii
LIST OF FIGURES
Figure Page
1.3 The MEM charge density distribution of STO at room temperature (a) (001)
(b) (002) and (c) (110) plane................................................................................. 7
1.4 The MEM charge density distribution map of STO at 70 K (a) (001) (b) (002)
and (c) (110) plane ................................................................................................ 8
ix
4.4 Charge densities of SrTiO3 (a) Sr-O plane (b) Ti-O plane .................................. 31
x
CHAPTER І
INTRODUCTION
Many experimental and theoretical methods are performed to study the structural
perovskites. The purpose of this work is to find the structural temperature of SrTiO3 by
molecular dynamics simulations and to examine the ground state properties of SrTiO3
using ab initio calculations in order to understand the chemical bonding nature of SrTiO3,
which is very important to explain the TiO6 octahedron behavior throughout the phase
transition.
Another perovskite-related material, CaCu3Ti4O12 has drawn much interest due to its
unusual dielectric behavior. Another part of this work is to examine the ground state
properties of this material using ab initio calculations. We also investigate the electronic
structures of Ca1+xCu3-xTi4O12 (x=-1, 1, 2, 3). This is the first time to study these
The perovskites ABO3 are the most important class of ferroelectric materials. At
high temperatures, they all share the simple cubic structure, with monovalent or divalent
cation A at the cube corners, penta- or tetravalent metal B at the body centers, and O
atoms at the cube face centers (see Figure 1.1). This structure can also be thought of as a
1
set of oxygen octahedra arranged in a simple cubic pattern and connected together by
shared O atoms, with the A atoms occupying the spaces in between. The latter picture of
octahedra.
The most interesting aspect of the cubic perovskite structure is that as the
diffractometry on single-crystal STO over a large temperature range, from 4.2 K to 300 K.
2
The lattice parameters were determined as a function of temperature. The data was
summarized to show that as the temperature goes down, STO changes to lower symmetry
were performed to find and explain the structural phase transitions in STO. Pytte and
[9]
Feder studied phase transitions in perovskites with the help of a model Hamiltonian.
They found that three degrees of freedom (15 degrees of freedom per unit cell in the
perovskite structure) are directly connected with the structural phase transitions. For STO,
the phase transition from the cubic to the tetragonal phase involves the rotation of the
octahedron about a cube axis. The predictions of their Hamiltonian model qualitatively
agree well with the experimental results except for the magnitude of the angular
distortion. This disagreement suggests that additional anharmonic interactions are needed
[10]
to be taken into account. One year later, Feder and Pytte included the interaction
between soft-mode coordinates and the strains into their Hamiltonian model. Good
3
agreement was obtained with all the experimental results this time.
[11]
Zhong and Vanderbilt claimed that the previous phenomenological model
[9, 10]
Hamiltonian approach had been limited by oversimplification and ambiguities in
perovskite compounds. Monte Carlo (MC) simulations were performed on the STO cubic
lattice with periodic boundary conditions. The system was found to adopt the cubic
They also found that increased pressure enhances the AFD instability while suppressing
the FE one.
the materials. However, it is important to see whether one can understand such features as
applied to STO to find that the AFD phase transition temperature decreases from 130 K
[11]
to 110 K, in excellent agreement with the experimental result of 105 K. They also
found that the quantum fluctuations completely suppress the FE phase transition, i.e. the
FE phases disappear. This implies that quantum effects on the FE instability are much
stronger than on the AFD instability in STO. Since the structural differences and energy
4
barriers between the cubic structure and the distorted structures are very small, a rough
ΔE ≥ h 2 /(8mΔq 2 ) (1.1)
Where,
which may prevent the occurrence of the distorted phase if it is larger than the classical
free-energy reduction. It is known that the AFD instability involves only the motion of
oxygen atoms, while the FE instability involves mainly Ti atoms. The structural change
involved in the FE distortion (0.1 a.u. for Ti in SrTiO3) is much smaller than for the AFD
distortion (0.3 a.u. for O). Therefore, mΔq2 turns out to be three times larger for the AFD
case, even though Ti atoms are three times heavier than the oxygen atoms. According to
Equation (1.1), the effect of the quantum fluctuations will be more significant for the FE
case.
The structural phase transition of STO at ~110 K is represented by the rotation of the
TiO6 octahedron. [13] The tetragonal structure of STO at low temperature is shown in
Figure 1.2. The oxygen atoms are all equivalent in the cubic phase, while they can be
distinguished as two kinds O(1) and O(2) in the tetragonal phase. It should be noted that
O(2) atoms are no longer located at the face centers. The mechanism of the phase
transition is understood by both neutron [15] and X-ray [16] diffraction, however why the
5
Figure 1.2 Low temperature phase of SrTiO3 (tetragonal) [14]
[14]
Therefore Ikeda et al. applied the Maximum Entropy Method (MEM) to X-ray
diffraction data to understand the chemical bonding nature of STO in both phases and to
reveal the structural changes at the electron level which occur throughout the phase
transition. MEM charge density maps of STO at room temperature are shown in Figure
1.3.
6
Figure 1.3 The MEM charge density distribution of STO at room temperature
(a) (001) (b) (002) and (c) (110) plane.
Contour lines are drawn from 0.4 at 0.2 eÅ3 intervals.
Four unit cells are shown. [14]
From Figure 1.3, both Sr and O atoms are found to be isotropic and no covalence
electrons are found between them. A rather strong covalent bond is found to exist
between the Ti and O atoms. MEM charge density maps of STO at 70 K are shown in
7
Figure 1.4 The MEM charge density distribution map of STO at 70 K.
(a) (001) (b) (002) and (c) (110) plane. Contour lines are the same as Figure 1.3.
Two tetragonal cells are shown. [14]
From Figure 1.4 (a), both the Sr and O(1) atoms are fairly isotropic and no
covalence electrons are found between Sr and O(1). From Figure 1.4 (b), there is a strong
covalent bond between Ti and O(2). The charge density distribution around the oxygen
atoms is not symmetrical with respect to the Ti-Ti lines. There is a little positional shift of
8
the O(2) atom in the direction of the arrow. In Figure 1.4 (c), the covalent bond between
Ti and O(1) is observed to be similar to that in Figure 1.3 (c). Therefore, it shows that
there is no significant change of chemical bonding through the phase transition. The
phase transition of STO at 110 K is purely due to the TiO6 octahedron, which seems to be
CaCu3Ti4O12 (CCTO) has drawn much recent interest due to its unusual dielectric
properties. Subramanian et al. [17] first observed the unusually high dielectric constant of
CCTO. This compound possesses a large dielectric constant about 12,000 at 1 kHz, which
is nearly constant over the temperature range 100-380 K. [18] It is also found that the
frequency. One curious result is that the dielectric constant drops as low as 100 when
The structure of CCTO was first determined from neutron powder diffraction
data. [19] The crystal structure is shown in Figure 1.5. The structure of CCTO can be
viewed as a perovskite-related structure, in which four ATiO3 units comprise the primitive
cell (where A is either Ca or Cu). Because there are 5 atoms in an ATiO3 unit cell, the
structure in Figure 1.5 contains 40 atoms. This is a doubled conventional cell, which is
also the primitive cell of the spin structure. The CuO4 plaquettes are nearly square,
because the bonds between Cu and O are all the same length, while the angles between
bonds differ slightly from 90 degrees. In a similar way, the distances between Ti and its
six neighbors are the same, but the angles deviate slightly from 90 degrees. Every oxygen
9
atom belongs to a single planar CuO4 plaquette and to the two connected tilted TiO6
octahedra.
ferroelectric, but empirical evidence tends to exclude CCTO from either category.
[18]
Ramirez et al. excluded ferroelectricity as a cause of the unusual high dielectric
response by X-ray diffraction and thermodynamic data. Instead they explained their
common to relaxor materials, are not observed. Neither superstructure peaks nor strong
Many researchers have presented theoretical insights into intrinsic lattice of CCTO.
10
[20]
He et al. performed first-principles calculations within the local spin-density
approximation (LSDA) on CCTO to study the structural and electronic properties. Their
crystal structure with space group Im3, arguing against the possibility that CCTO is a
He et al. [21] extended their previous work on CCTO by carrying out a parallel study
leave many calculated quantities largely unaltered. This indicates that both CCTO and
CdCTO possess similar intrinsic structural, vibrational and dielectric properties. As for
the lattice contributions to the static dielectric constant, the discrepancy between their
computations and those measured at frequencies below the Debye cutoff range, reinforces
the conclusion that some extrinsic mechanism is likely to be the source of the large
insulating character of CCTO, and show a similar density of states as that presented by
[20]
He et al. They applied the superexchange picture of magnetism to CCTO, and
suggested that extremely long-range interactions are important and perhaps even
11
responsible for the AFM order.
Li et al. [23] applied FLAPW method within the generalized gradient approximation
(GGA) to investigate the basic electronic and magnetic properties of CCTO. Their
calculated indirect band gap of 0.51 eV and direct band gap of 0.58 eV within GGA are
much closer to the experimental optical gap (≥ 1.5 eV) [24] than those in He et al.’s work
[20]
, but still underestimate the experimental data. A metastable state is found to be
calculations is discussed in Chapter II. The molecular dynamics simulations and ab initio
calculations on SrTiO3 are discussed in Chapter III and IV, respectively. The electronic
properties are provided. The strong covalent bonding between Ti and O is found to
explain the TiO6 octahedron behavior throughout the structural phase transition. In
Chapter V and VI, we present the results of ab initio calculations on Ca1+xCu3-xTi4O12, i.e.
in the material, the optimized lattice constant and band gap increase, and insulator
12
CHAPTER ІI
large that it is impossible to find their properties analytically. Molecular dynamics (MD)
simulations, first introduced by Alder and Wainwright in 1950, are a widely used method
such as thin film growth and ion-subplantation. In biology, the MD method can provide
much detailed information on the fluctuations and conformation changes of proteins and
energy and heat capacities, are deduced from microscopic information. [26] Therefore MD
simulations act as a bridge between the macroscopic world and microscopic length and
time scales (shown in Figure 2.1). The connection between macroscopic properties and
macroscopic properties to the distribution and motion of the atoms. MD solves the
r
atom mass, and ai is its acceleration. This is the so-called N-body problem. Since the
r
r r d 2 ri
acceleration a can be expressed as ai = 2 , Newton’s equation is expressed in the
dt
following form,
r r
d 2 ri
Fi = mi 2 (2.1)
dt
r
The force F can be considered as the derivative of the potential energy with
14
r
We need to find the potential energy U to calculate the force Fi from Equation 2.2.
r
If Fi is known, with the help of Equation 2.1, we can compute trajectories. (The
coordinates and velocities of all the particles are called the trajectory of the system.)
lengths, bond angles and torsions, also the non-bonding van der Waals and electrostatic
interactions between atoms. [27] A simple force field functional is shown in Equation 2.3.
r ki k
U (r ) = ∑
bonds 2
(li − lo ) 2 + ∑ i (θ i − θ o ) 2
angles 2
Vn
+ ∑
torsions 2
(1 + cos(nω − γ )) (2.3) [27]
N N ⎛ σ ij σ ij qi q j ⎞
+∑ ∑ ⎜⎜ 4ε [( )12 − ( )6 ] + ⎟
4πε 0 rij ⎟⎠
ij
i =1 j = i +1 ⎝ rij rij
r
U (r ) denotes the potential energy which is a function of the positions of N
particles. The first two terms in Equation 2.3 model the interactions between pairs of
bonded atoms, modeled by a harmonic potential. The third term is a torsional interaction
potential. The last term is the non-bonded term. The non-bonded term is modeled using a
Coulomb potential term for electrostatic interactions and a Lennard-Jones potential for
From a potential energy forcefield, MD can solve the classical equations of motion
for a system of N interacting atoms. Combining Equation 2.1 and 2.2, we can rewrite
Newton’s equation,
r r
d 2 ri
−∇iU = mi 2 (2.4)
dt
Given the initial coordinates and velocities at time t , the positions and velocities at
15
time t + Δ t are calculated. The initial coordinates are determined in the input file or
from a previous operation such as energy minimization, while the initial velocities are
randomly generated at the beginning of each run based on the desired temperature.
Therefore, dynamics runs can not be repeated exactly except if the same speed is used for
Numerous numerical algorithms have been developed for integrating the equations
of motion (Equation 2.4), such as the the Verlet algorithm, the Leapfrog algorithm, the
Verlet velocity algorithm and Beeman’s algorithm. Verlet algorithm is used to our MD
simulations. All the integration algorithms assume the positions, velocities and
1
r (t + δ t ) = r (t ) + v(t )δ t + a (t )δ t 2 + K ,
2
1
v(t + δ t ) = v(t ) + a(t )δ t + b(t )δ t 2 + K , (2.5)
2
a(t + δ t ) = a(t ) + b(t )δ t + K ,
When choosing which algorithm to use, we should consider whether the algorithm
efficient and whether it permits the use of a relatively long time step for integration.
The MD simulation acts not only as a bridge between macroscopic and microscopic
as I mentioned above, but also as a bridge between theory and experiment. Sometimes we
can conduct a simulation and compare the theoretical results with experimental results to
test a theory or a model. A better advantage of MD simulation is that we can carry out
simulations on the computer that are difficult or impossible to conduct in the laboratory.
16
2.2 Ab initio (First-principles) calculations
simply interactions between electrons. These interactions can be described by the laws of
quantum physics. This means that all material properties (chemical, mechanical, electrical,
magnetic, optical, thermal…) can, in principle, be predicted from the atomic number and
mass of the atomic species involved, with the aid of quantum physics. This is precisely
An ab initio calculation is performed from first principle. The Latin term ab initio
means “from the beginning”. It implies that the calculation starts directly at the level of
established laws of physics and does not depend on empirically derived parameters.
Density functional theory (DFT), for which Prof. Walter Kohn was awarded the
molecular electronic structure. The fundamental idea of DFT is that any property of a
system of many interacting particles can be viewed as a functional of the ground state
charge density. DFT, which maps the original many-electron problem into an equivalent
The Kohn-Sham method, the most common implementation of DFT, has provided a
way to make useful approximate ground state functions for real systems of electrons. The
17
Figure 2.2 Kohn-Sham approach
The Kohn-Sham method assumes that the ground state density of the original
nks (r ) = n( r ) (2.6)
EKS (n) = TKS (n) + EHartree (n) + Eext (n) + Exc (n)
where
1 n
TKS (n) = − ∑
2 i =1
ψ i ∇2 ψ i (2.7)
the time-independent Schrödinger’s equation, except that the potential experienced by the
1
[− ∇ 2 + VHartree ( nGS ; r ) + Vext (nGS ; r ) + Vxc ( nGS ; r )]ψ i ( r ) = ε iψ i ( r ) (2.8)
2
potential, which describes the effects of the Pauli principle and the Coulomb potential
energy functional is the local density approximation (LDA) which assumes that the
Figure 2.3), and the exchange-correlation energy at each point in the system is the same
Exc ( n( r )) = ∫ n( r )ε xc ( n( r )) dr (2.9)
∂Exc (n(r ))
Vxc (n(r )) = (2.10)
∂n(r )
The LDA functional within the Kohn-Sham approach has been proved to be an
There are two methods to deal with the external potential Vext , which is complicated
in real circumstances. One is called the all-electron calculation method, the other is the
pseudo-wavefunctions are normalized and the total pseudocharge inside the core matches
that of the all-electron wave function. This method provides a way to construct
basis-set size is needed to satisfy the norm-conserving condition. This leads to more
[28]
calculations than those in other cases. Therefore, Vanderbilt developed ultrasoft
fewer plane-waves for calculations of the same accuracy. This method is always used in
20
CHAPTER III
Molecular dynamics simulations were carried out using Cerius2 Version 4.10.
Cerius2 provides a wealth of tools for applications in life and materials science modeling
and simulation. It offers capabilities for modeling materials structure, properties, and
3.1 Structure
Both cubic and tetragonal structures were built. The cubic structure was used to get
energy minimization and the tetragonal structure was used in dynamics simulations.
3.1.1 Cubic
The space group of STO is pm3m. The Wyckoff positions are Sr (0, 0, 0), Ti (0.5,
0.5, 0.5) and O (0.5, 0.5, 0). The charges are fixed to be +2, +2.2, -1.4 for Sr, Ti and O,
respectively, due to the bond covalency— the Ti-O bond in real crystals has both ionic
and covalent character. [29] The crystal structure is shown in Figure 3.1.
21
Figure 3.1 Cubic structure of SrTiO3
3.1.2 Tetragonal
The space group is p4. The Wyckoff positions and charges are shown in Table 3.1.
Table 3.1 Coordinates and charges for SrTiO3 in the tetragonal phase
Coordinate Charge
Sr (0, 0, 0) 2.0
below 110 K but the unit-cell volume remains unchanged through the transition. At 300 K,
a=3.905 Å. The volume is a3= 59.54744 Å3. In the tetragonal phase, the volume is
22
a2*c=59.54744 Å3.
Using the relation c/a=1.00056, we can find a=3.90427 Å and c=3.90646 Å. Therefore,
Universal Force field 1.02 [29] was used. Sr6+2, Ti3+4 and O_2 were set as the types
for Sr, Ti and O, respectively. A five-character mnemonic label is used to describe the
atom types. The first two characters correspond to the chemical symbol; an underscore
appears in the second column if the symbol has one letter. The third column describes the
square planar, 5 = trigonal bipyramidal, 6 = octahedral. The forth and fifth columns are
[29]
used as indicators of alternate parameters such as formal oxidation state. Thus Sr6+2
indicates an octahedral Sr in the +2 oxidation state. The atomic data are shown in Table
3.2.
23
3.2 Energy minimization
Two different methods were used to determine the energy minimum. (1) In the first
method, the minimization algorithm of cerius2 searches the lattice constant and atomic
positions for the local minimum energy. (2) In the second method, the lattice constants
were changed systematically and the total potential energy for each lattice constant was
calculated. Thus we obtain a potential energy vs lattice constant curve. This allows us to
find the lattice constant from the condition that the energy is at a minimum.
Initially, the cubic structure which is shown in Figure 3.1 was used. Keeping the
fractional coordinates (relative distance and orientation) fixed, the current energy is
calculated for every given lattice constant. (see Figure 3.2) From the graph, we find that
when a = 3.619 Å, the energy is the minimum. The first minimization method also
0.00
3.40 3.50 3.60 3.70 3.80 3.90 4.00 4.10
-500.00
Energy/ cal
-1000.00
-1500.00
-2000.00
-2500.00
Lattice constant/ Å
3.9055 Å. The difference between our result and their result may due to the different
24
simulation temperatures. Their calculation was fixed at 300 K, while our energy
minimization program is based on 0 K. Our result is also 7.3 % less than the experimental
The superlattice was created from one unit cell. After creation of the superlattice, the
symmetry changes to p1. In the first minimization method, we allow all atoms to move
while keeping the fractional coordinates fixed. Not only the lattice constant a, b, and c,
but also the angle α, β and γ will change after minimization. The final structure gives that
a = b = c = 3.618 Å
α = β = γ =90.01o
Sr atoms are still located at the vertex of the cubic cell, Ti atoms are located at the
body center as before, but O atoms are no longer at the face center positions.
The same procedure as in 3.2.1 was performed except the 5*5*5 cell was used for
the calculation. The simulation cell contains 625 particles. It turns out that the
Another superlattice was built based on the 5*5*5 cell. The final lattice constant
from the first minimization method is 18.094 Å, which should be divided by 5 to get the
lattice constant for one unit cell. It gives that a = b = c = 3.619 Å, α = β = γ =90o.
To confirm the result, the second minimization method was performed. The
energy-lattice constant graph is shown in Figure 3.3. This gives the same lattice constant
3.619 Å.
25
Figure 3.3 Total potential energy vs lattice constant for 5*5*5 superlattice
The tetragonal structure was used as the initial structure. The simulation was based
on the 5*5*5 supercell. The initial lattice constants are chosen to be a = b = 3.904 Å and
c = 3.906 Å. (see section 3.1.2) The temperature ranges from 60 K to 300 K. Constant
NVT was chosen at 60 K, and then constant NPT were chosen for the other temperatures.
The temperature was fixed for every run, while the structure was allowed to change to
reach the equilibrium at that temperature. T_Damping Thermostat was chosen to keep the
temperature constant. The relaxation time is 0.1 ps and the dynamics time step is 0.001 ps.
Number of steps was chosen large enough to make the system reach equilibrium.
The transition temperature is found to be around 130 K. The average value is 122.5
26
CHAPTER IV
The space group of STO is pm3m. The Wyckoff positions are Sr (0, 0, 0), Ti (0.5,
0.5, 0.5) and O (0.5, 0.5, 0). The charges are chosen to be +2, +4, -2 for Sr, Ti and O,
respectively. The charges are used differently from those in molecular dynamics
simulation. Normal charges are always used in the ab initio calculations. The crystal
27
4.2 Cambridge Sequential Total Energy Package
The Cambridge Sequential Total Energy Package (CASTEP) [31] is a program that
employs DFT to simulate the properties of solids, interfaces, and surfaces for a wide
CASTEP takes the number and types of atoms in a system and predicts properties
density of states, charge densities and wave functions, and optical properties.
The crystal structure of STO shown in Figure 4.1 is loaded. Computations are
performed via the LDA with ultra-soft pseudopotentials. The initial lattice constant is
at a plane-wave cutoff energy of 340 eV, with a 1×1×1 Monkhorst-Pack k-point mesh.
[34]
The relaxations are performed using the BFGS algorithm while the fractional
The optimized lattice constant is 3.867 Å, slightly less than the value of 3.905 Å by
The calculated band structure of STO is shown in Figure 4.2. The G point in Figure
4.2 represents the Gamma point, Γ. Our band structure is similar to that in Samantaray et
al.’s work.[32]
28
Figure 4.2 The calculated energy band structure of SrTiO3
The valence band maximum is located at the R point, i.e., at the corner of the cubic
Brillouin zone. The lowest conduction band state is located at the zone center Γ, which
introduces an indirect band gap. There is a second local valence band maximum at Γ,
which gives rise to a direct band edge at Γ. The calculated direct band gap at the Γ point is
[32]
1.92 eV in Samantaray et al.’s work. From Figure 4.2, our direct band gap at the Γ
[35]
point is 2.3 eV, which is closer to the experimental value of 3.2 eV. But both
theoretical band gaps are smaller than experimental result. As is well known, the LDA
The band structure of STO has energetically separated low lying bands, which are
derived from the O 2s states. These bands are separated from a group of relatively narrow
bands arising from the Sr 4p states. Near the Fermi level in the valence band region, there
is a manifold of several bands, nominally derived from the O 2p states. The conduction
29
bands near the Fermi level have a strong Ti 3d character.
The total density of states of STO is shown in Figure 4.3. We have obtained a similar
picture for the total density of states of STO as in Samantaray et al.’s work.[32]
The lowest bands are located around -18 eV with double peaks and belong to O 2s
states. O 2s band states are -17.5 eV and Sr 4p band state is -15 eV. The Sr 4p state is
very close to O 2s states, which is in good agreement with the XPS measurement. [36, 37]
The upper valence band is made up predominately of the O 2p components. The width of
the O 2p valence band is 5.5 eV, close to 5 eV in Zollner et al.’s work. [38] The peak
nearest to the valence band maximum originates from the O 2p nonbonding components,
30
The Ti 3d contribution is zero at the valence band maximum but rises strongly with
increasing binding energy, while the O 2p contribution rises from zero at the conduction
band minimum with increasing energy. These reflect the Ti 3d to O 2p covalency, i.e. the
(a) (b)
Figure 4.4 Charge densities of SrTiO3 (atoms are colored as in Figure 4.1)
(a) Sr-O plane (b) Ti-O plane
Figure 4.4 (a) and (b) display the calculated charge densities of STO on the Sr-O and
Ti-O planes. The high charge density region is around the nuclear sites and is nearly
spherically symmetric. There is very weak chemical bonding between Sr and O atoms,
which reflects the presence of an ionic bond between Sr and O atoms. From the density
of states of STO, it has been shown that there exists a significant hybridization of Ti 3d
31
with O 2p states. This means that the bonding in Ti-O system cannot be purely ionic but
must exhibit a large covalent part. Figure 4.4 (b) presents a clearer picture about the
nature of chemical bonding between Ti and O atoms. It confirms that the Ti-O bond has a
strong covalent character. This is apparent from the noticeable overlapping charge
distribution at the middle of the Ti-O bond. However there is not much bonding charge to
link the Sr and O atoms, it indicates that the bonding between Sr and O atoms is mainly
ionic.
The optical properties can be derived from the complex dielectric function
ε (ω ) = ε1 (ω ) + iε 2 (ω ) , where ε1 (ω ) and ε 2 (ω ) are the real part and the imaginary part
of the dielectric constant, respectively. The refractive n(ω ) and extinction coefficient
1
n(ω ) = ( )[ ε1 (ω ) 2 + ε 2 (ω ) 2 + ε1 (ω )]1/ 2 (4.1)
2
1
k (ω ) = ( )[ ε1 (ω ) 2 + ε 2 (ω ) 2 − ε1 (ω )]1/ 2 (4.2)
2
Figure 4.5 shows the calculated optical properties of STO. Comparing our result
with Samantaray et al.’s work [32], we find that we have obtained similar results.
32
Figure 4.5 Refractive index and extinction coefficient of SrTiO3
The optimized lattice constant a=3.619 Å and a=3.867 Å from molecular dynamics
simulations and ab initio calculations, respectively. The result from ab initio calculations
is in good agreement with the experimental value of 3.905 Å, based on the consideration
that underestimation is the typical limitation is LDA calculations. The difference between
the result from molecular dynamics simulations and the experimental value is due to the
The transition temperature is found to be 122.5 K, which is 16.7 % higher than the
experimental value of 105 K. Molecular dynamics simulations are not sufficient to find
33
The calculated electronic properties show that there is a strong covalent bonding
between Ti and O, which explains why TiO6 octahedron behaves as a rigid body
34
CHAPTER V
Accelrys MS Modeling 4.0 is applied to build the structure. The space group of
CCTO is Im3. The Wyckoff positions are shown in Table 5.1. The charges are chosen to
be +2, +2, +4, -2 for Ca, Cu, Ti and O, respectively. The crystal structure of CCTO is
Atom Position
Ca (0, 0, 0)
Cu (1/2, 0, 0)
*The structural parameters for the O atom are those of Ref [20]
35
Figure 5.1 The structure of CaCu3Ti4O12 built by MS Modeling
This structure can be obtained from the ideal structure of CaTiO3 by replacing three
out of every four Ca site ions with a Cu ion, which quadruples the cell to CaCu3Ti4O12,
and then performing a correlated rotation of the four octahedron until the Cu ion is
and O are all the same length, though the angles between bonds deviate slightly from 90
degrees. All the following calculations are performed using this 40-atom cell in Figure
5.1.
The crystal structure of CCTO shown in Figure 5.1 is loaded. Computations are
performed via the LDA with ultra-soft pseudopotentials. The highest occupied p shell
36
electrons, for Ca and Ti, are treated as valence. The potential considers electrons in the 3d
The total energy is computed while the lattice constant and the fractional coordinates
are kept fixed. The lattice constant is changed in steps and each time the energy is
determined. The total energy vs lattice constant is shown in Figure 5.2. Therefore, we
find the equilibrium lattice constant when the total energy is minimum.
-33390
6.3 6.5 6.7 6.9 7.1 7.3 7.5 7.7 7.9 8.1 8.3 8.5
-33400
Total energy/ eV
-33410
-33420
-33430
-33440
-33450
Lattice constant/ Å
The lattice constant ranges from 6.50 Å to 8.10 Å. a = 7.29 Å is found to be the
lattice constant for the minimum energy. It is the same result as in He et al.’s work. [20]
The experimental value is 7.384 Å measured at 35 K [20], which is 1 % more than our
37
5.3 Geometry Optimization of CaCu3Ti4O12
The crystal structure of CCTO shown in Figure 5.1 is loaded. Computations are
performed via the LDA with ultrasoft pseudopotentials. The initial lattice constant is
at a plane-wave cutoff energy of 500 eV which results in convergence of the total energy
performed using the BFGS [34] algorithm. The internal parameters of the structure are
The optimized lattice constant is 7.29 Å, which confirms the result from energy
minimization. The Wyckoff position for O is (0.305, 0.174, 0), which is somewhat
different from that in He et al.’s work. [20] while all the other positions for Ca, Cu and Ti
Figure 5.3 Bond lengths and angles of CaCu3Ti4O12 after Geometry Optimization
(bond lengths are in blue and angles are in black.)
38
Bond lengths and angles after geometry optimization are shown in Figure 5.3. The
Cu cation along with its four nearest neighboring O atoms forms a slightly distorted
square of CuO4 with Cu-O distance of 1.907 Å, 0.68% smaller than 1.92 Å in He et al.’s
work [20] and O-Cu-O angle of 96.498o. The four next nearest neighboring oxygens are
2.785 Å away from Cu, with O-Cu-O angle of 118.153o. The third nearest neighboring
oxygens are 3.252 Å away from Cu, with O-Cu-O angle of 93.808o. These three kinds of
Figure 5.4 shows the calculated band structure of CCTO. The unoccupied
are composed of the Cu 3d-O 2p manifold. The Fermi energy is 0.48 eV. The direct band
39
gap is 0.57 eV, which is greater than 0.27 eV in He et al.’s work [20] and closer to the
experimental optical gap of 1.5 eV as a lower limit.[see ref. 20 in (20)] The underestimation of
the gap is common in LDA calculations and results from the underestimation of
correlation effects.
Our density of states shown in Figure 5.5 is similar to that presented by He et al.[20]
The bands shown in the energy range in Figure 5.4 are mainly O 2p and Cu 3d orbitals.
The bands from -7.25 eV to -0.5 eV consist mainly of Cu 3d orbitals that hybridize
weakly with O 2p orbitals that point toward their Ti neighbors. In the range from -0.5 eV
to 3 eV around the Fermi level, the band structure reflects two narrow bands each of
40
which contains three bands. These six isolated bands consist of antibonding interactions
of Cu 3d orbitals and O 2p orbitals pointing to the Cu from its four near oxygen
The total charge density is symmetric and the spin density is antisymmetric, under
the fractional lattice translation (½, ½, ½), consistent with an AFM state. Spin-up and
spin-down charge densities are shown in Figure 5.6. It indicates antibonding interactions
between Cu 3d and O 2p, which extend over the central cluster composed of a Cu ion and
6.1 Structure
Accelrys MS Modeling 4.0 is applied to build the structure. The structures are
shown in Figure 6.1-6.4. The structures of CuTiO3, Ca3CuTi4O12 and CaTiO3 are built
Ca3CuTi4O12 is shown in Figure 6.3. CaTiO3 is built by substituting Cu by Ca. The crystal
CaCu3Ti4O12, so this structure is built separately from the others. The space group of
Ca2Cu2Ti4O12 is Pm3. The Wyckoff positions are shown in Table 6.1. The charges are
chosen to be +2, +2, +4, -2 for Ca, Cu, Ti and O, respectively. The crystal structure of
42
Figure 6.1 The structure of CuTiO3 Figure 6.2 The structure of Ca2Cu2Ti4O12
Figure 6.3 The structure of Ca3CuTi4O12 Figure 6.4 The structure of CaTiO3
43
Table 6.1 The Wyckoff positions for Ca2Cu2Ti4O12
Atom Position
Computations are performed via the LDA with ultra-soft pseudopotentials. The
initial lattice constant is 7.29 Å which is the equilibrium lattice constant from our former
cutoff energy of 500 eV, with a 2×2×2 Monkhorst-Pack k-point mesh. The relaxations are
performed using the BFGS [34] algorithm and all the atoms are allowed to relax during
For CuTiO3, the optimized lattice constant is found to be 7.25 Å. The optimization
result shows that Cu and Ti atoms are still in the original positions, which agrees well
with the fact that the CuTiO3 structure is perovskite structure. The O atoms move from
their original positions, but the result doesn’t show obvious tendency of moving towards
44
For Ca3CuTi4O12, the optimized lattice constant is found to be 7.55 Å. From the
optimized structure, Ca, Cu and Ti atoms are still in the original positions. The O atoms
move towards the center of each side of the primitive cell, which shows a tendency
For CaTiO3, the optimized lattice constant is found to be 7.57 Å. Wang et al. [39]
pseudopotential method to find that the theoretical lattice constant is 3.88 Å. Since we
use 40-atom cell in our calculations, the lattice constant is 7.57/ 2= 3.785 Å in a 20-atom
cell, which is 2.5 % smaller than the theoretical one in Wang et al.’s work. [39] Compared
with the experimental one of 3.8950 Å [40], our theoretical lattice constant is 2.8 % smaller.
The optimized structure shows that Ca and Ti atoms are still in the original positions. The
O atoms move towards to the center of each side of the primitive cell CaTiO3. CaTiO3 has
perovskite structure. Therefore, during optimization the structure changes from that of
The summary of optimized lattice constants for different Ca, Cu ratio is shown in
Table 6.2. As the Ca, Cu ratio increases from 0 to ∞, the optimized lattice constant
increases as well except for Ca2Cu2Ti4O12, which shows a divergence. As we know, the
pauling ionic radii of Ca2+ is 99 pauling radius/pm and that of Cu2+ is 96 pauling
radius/pm. Since Ca2+ > Cu2+, the lattice constant should increase if more calcium is
As for the abnormal behavior of Ca2Cu2Ti4O12, one reason may be the simulation
45
structure of Ca2Cu2Ti4O12 is not based on the structure of CCTO, while the structures of
Table 6.2 Summary of optimized lattice constant for different Ca, Cu ratio
Optimized lattice
Material type Ca, Cu ratio
constant
Figure 6.5-6.8.
For CuTiO3, the direct band gap at the Γ point is 0.53 eV. The indirect band gap,
which is between the valence band maximum Γ point and the conduction band minimum
For Ca2Cu2Ti4O12, the direct band gap at the Γ point is 1.22 eV. The indirect band
gap, which is between the valence band maximum Γ point and the conduction band
For Ca3CuTi4O12, the direct band gap at the Γ point is 2.30 eV. The indirect band gap,
which is between the valence band maximum Γ point and the conduction band minimum
which is between the valence band maximum Γ point and the conduction band minimum
Figure 6.5 Band structure of CuTiO3 Figure 6.6 Band structure of Ca2Cu2Ti4O12
Figure 6.7 Band structure of Ca3CuTi4O12 Figure 6.8 Band structure of CaTiO3
47
The direct band gaps are summarized in Table 6.3. With the increase of Ca in the
material, the band gap increases. The increasing band gap indicates the material is more
like an insulator. Therefore, with the increase of Ca in the material, insulator character
becomes much more pronounced. This is in good agreement with the experimental
results.
Table 6.3 Summary of direct band gap for different Ca, Cu ratio
CuTiO3 0.53 eV
CaCu3Ti4O12 0.57 eV
Ca2Cu2Ti4O12 1.22 eV
Ca3CuTi4O12 2.30 eV
CaTiO3 2.20 eV
Figure 6.9-6.12. The dashed line does not indicate the Fermi level in every figure. The
Fermi level is located at 0.32 eV, 0.19 eV, 0.19 eV and 0.27 eV for CuTiO3, Ca2Cu2Ti4O12,
The bands below the valence band maximum are mainly O 2p and Cu 3d in
49
Figure 6.11 Density of states of Ca3CuTi4O12
They show similar results. In this thesis, the charge densities of Ca2Cu2Ti4O12 are shown
as an example. Figure 6.13 (a) and (b) shows the charge densities of Ca2Cu2Ti4O12 on the
50
Ca-Cu-O and Ti-O planes. The high charge density region is around the nuclear sites and
is nearly spherically symmetric. The Ti-O bond has a strong covalent character which
results from the noticeable overlapping charge distribution at the middle of the Ti-O bond.
There is no chemical bonding between any other types of atoms, e.g., Ca-O or Cu-O.
(b)
(a)
Figure 6.13 Charge densities of Ca2Cu2Ti4O12(atoms are colored as in Figure 6.2)
Our calculated ground state properties of CCTO are in good agreement with other
people’s work.[20] The optimized lattice constant is 7.29 Å, which is 1 % less than the
experimental value of 7.384 Å. The density of states and charge densities confirm the
For Ca1+xCu3-xTi4O12, we find that with increase of Ca in the material, the optimized
51
lattice constant and band gap increase, and the insulator character becomes much more
pronounced in the material. This is in good agreement with the experimental results.
52
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