CHINESE JOURNAL OF PHYSICS VOL. 50, NO.

4 August 2012

A First Principles Calculation of the Structural and Optical Properties of

PbTiO3 in the Paraelectric Phase

S. J. Mousavi1, ∗ and A. Pourhabib-yekta2

1
Department of Physics, Rasht Branch, Islamic Azad University, Rasht, Iran
2
Department of Mathematics, Islamic Azad University, Sowmesara, Iran
(Received June 18, 2010; Revised June 24, 2011)
We have performed a first-principles study of the structural, electronic, and optical prop-
erties of the cubic state of PbTiO3 by means of the density functional theory full potential
linearized augmented plane wave (FP-LAPW) method with the generalized gradient approxi-
mation (GGA), Engle-Vosco approximation (EVA), and the local spin density approximation
with the Hubbard parameter U (LSDA+U). The calculated electronic structure and charge
density yield a band gap of 3.3 eV at the X point in the Brillouin zone. The theoretical
optical properties and electron energy loss spectrum yield a static refractive index of 2.83
and plasmon energy of 24 eV for the cubic phase of PbTiO3 .

PACS numbers: 71.15.Mb

I. INTRODUCTION

Theoretical computational studies based on ab initio calculations can yield important

information regarding the electronic and structural properties of solids. The ferroelectric
materials with perovskite throughout structure are of considerable interest for application
in electronics, such as non-volatile memories, IR sensors, and dielectric properties. PbTiO3
(PT) is one of the more interesting and more studied perovskites possessing a ferroelectric
phase under ambient conditions [1]. In addition, PT has a large electro-optic coefficient
and high photorefractive sensitivity, so it can be used as an optical sensor. The strong
interest in this compound is caused by its high spontaneous polarization and the wide tem-
perature stability of the ferroelectric phase. The ferroelectric-paraelectric phase transition
temperature 763 K is the highest in the family of ferroelectric perovskites. Above 763 K,
PbTiO3 has a cubic phase (space group Pm3m) and a paraelectric state, while at room
conditions it shows a tetragonal phase (space group P4mm) and is ferroelectric [2]. There
have been some efforts towards determining the electronic and optical properties of the
cubic state of PbTiO3 from either first principles calculations or by experiment [3–9]. The
experimental value for the band gap of the paraelectric phase of PbTiO3 is 3–3.5 eV, but
the best calculated band gap that has been reported is 1.7 eV [3].
In the present work we have calculated the electronic and optical properties of the
cubic state of PbTiO3 . The results, in comparison with the previous theoretical data, are
in better agreement with the experimental results.

∗
Electronic address: [email protected]

http://PSROC.phys.ntu.edu.tw/cjp 628 c 2012 THE PHYSICAL SOCIETY

OF THE REPUBLIC OF CHINA
VOL. 50 S. J. MOUSAVI AND A. POURHABIB-YEKTA 629

II. METHOD OF CALCULATION

The calculation of the structural, electrical, and optical properties of PbTiO3 was
carried out by a self-consistent scheme by solving the Kohn-Sham equations. Using a FP-
LAPW method in the framework of the density functional theory (DFT) along with the
generalized gradient approximation (GGA), Engle-Vosco approximation (EVA), and local
spin density approximation with the aim of the Hubbard parameter U, (LSDA+U) [10–14]
using the Wien2k codes [15]. The calculation was performed with 300 k-points and Rkmax =
7 (R is the smallest muffin-tin radius and kmax is the cut-off wave vector of the plane-wave
basis set) for the convergence parameter for which the calculation stabilizes and convergence
in terms of the energy is achieved. The values of the other parameters are Gmax = 14 a−1 o
(Gmax is the magnitude of largest vector in the charge density Fourier expansion or the plane
wave cutoff and ao is the Bohr radius), RMT (Pb)= 1.6 au, RMT (Ti)= 1.6 au, RMT (O)= 1.7
au (muffin-tin radius), and U = 0.8 eV (Coulomb interaction parameter). The iteration
was halted when the difference charge density was less than 0.0001e a−3 o between steps as
a convergence criterion. The core cut off energy, which defines the separation of core and
valence states, was chosen as −8 Ry.
The imaginary part of the dielectric tensor can be computed from the knowledge of
the electronic band structure of a solid. In the limit of linear optics, in the non-spinpolarized
case, and within the frame of the random phase approximation, we can use the following
well-known relations [16]:
4πe2 X ∞
Z D   E
Imεαβ (ω) = 2 2 dk hck |P α | vk i vk P β  ck δ (εck − εvk − ω) , (1)
 
m ω c,y 0

∞
2 ω ′ Imεαβ (ω ′ ) ′
Z
Reεαβ (ω) = δαβ + dω . (2)
π 0 ̟′2 − ω 2
The optical conductivity is given by
ω
Reσαβ (ω) = Imεαβ (ω) , (3)
4π
where |ck i and |vk i are the electron states in the conduction and valance bands, respectively,
with the wave vector k, and P is the Kooshy integral section. Here, εαβ (ω) = Reεαβ +
iImεαβ = ε1 + iε2 is the complex dielectric tensor.
Knowing the complex dielectric tensor, one can calculate various optical constants
from the following relations, which describe the system response with respect to the prop-
agation of the electromagnetic wave through the material. The refractive index, n(ω), and
the extinction coefficient, k(ω), are given by
r
|ε (ω)| + Reε (ω)
n (ω) = , (4)
2
and
r
|ε (ω)| + Reε (ω)
k (ω) = . (5)
2
630 FIRST PRINCIPLE CALCULATION . . . VOL. 50

III. RESULTS AND DISCUSSION

III-1. Electronic structure and bulk modulus

Many aspects of the crystalline behavior can be understood when the total energy
of the system is known, or more often, when the energy difference between two or more
electronic or nuclear configurations are known as a function of some parameters. The
calculations were first carried out applying the experimental data for lattice constants,
then by minimizing the ratio of the total energy of the crystal to its volume (volume
optimization) the theoretical lattice constants were obtained. From the literature, we know
that the bulk elastic properties of a material determine how much it will compress under
a given amount of external pressure. The ratio of the change in pressure to the fractional
volume compression is called the bulk modulus (B) of the material and it can be written
as follows:
∂P
B = −V . (6)
∂V
In term of energy, the bulk modules is also defined by the equation of state (EOS)
and evaluated at the minimum:
∂2E
B=V . (7)
∂V 2
The position of the minimum of the EOS defines the equilibrium lattice parameter
and unit cell volume at zero pressure. In this calculation, from a series of strained lattices
the static lattice potential corresponding to the total energy was calculated. From such
results the equilibrium volume, bulk modulus, and its pressure derivative were derived. A
series of total energy calculations as a function of volume can be fitted to an equation of
state according to Murnaghan [17]:
" ′
#
B0 V ( V0 /V )B0
E (V ) = + 1 C. (8)
B0′ B0′

Here B0 is an equilibrium bulk modulus that efficiently measures the curvature of the
energy versus volume curve about the relaxed volume V0 , and B0′ is the derivative of the
bulk modulus.
The calculation were first carried out applying the experimental data for lattice con-
stants, then by minimizing the ratio of the total energy of the crystal to its volume (volume
optimization) the theoretical lattice constants were obtained.
Figure 1 shows the total energy with respect to volume of the unit cell after opti-
mization for the cubic state of PbTiO3 .
The band structures for PbTiO3 have been calculated with the FP-LAPW-GGA,
FP-LAPW-LDA, and FP-LAPW-EV and FPLAPW-LSDA+U methods, and we have been
reporting the FPLAPW-LSDA+U method results. The calculated band structures for
PbTiO3 along the high-symmetry lines of the Brillouin-zone (BZ) by the FP-LAPW-
LSDA+U method are better than other methods and are shown in Fig. 2.
VOL. 50 S. J. MOUSAVI AND A. POURHABIB-YEKTA 631

FIG. 1: Variation of energy with volume for PbTiO3 .

Fig. 2. Band structure of PbTiO along the high symmetry point

FIG. 2: Band structure of PbTiO33 along the high symmetry point.

For PbTiO3 there is a band gap which separates the valence and conduction bands
with 3.3 eV at the point. The experimental value for the direct band gap of PbTiO3 is
3–3.5 eV. Our calculated value for the band gap is very close to the experimental value and
is very much better than the other theoretically calculated values that have been reported.
(For comparison please see Table I). Our calculations with the DFT are fundamentally
 632 FIRST PRINCIPLE CALCULATION . . . VOL. 50

ground-state calculations and, therefore, tend to underestimate the band gap energy, since
this energy corresponds to a transition to a higher-energy exited state of the solid [18].

TABLE I: Unit cell volume, lattice constants ratio, and bulk modulus for PbTiO3 .
PbTiO3 V(a.u)3 a(Ao ) B(GPa)
FPLAPW-GGA 422.67 3.97 171
FPLAPW-LDA 403.79 3.91 182
FPLAPW-EV 435.58 4.01 158
FPLAPW-LSDA+U 413.02 3.94 177
Expt. [1] 416.32 3.95 —

The total density of state (DOS) that describes the electron distribution in an energy
spectrum is shown in Fig. 3. The electronic state is separated into three regions, the lower
valence band (LVB), upper valence band, and conduction band (CB). The LVB density of
the state peak is about −15 eV and has a 1.5 eV width that is separated by a large gap of
about 7 eV from the UVB states which have a width of about 8 eV.
eparated by a large gap of about 7 eV from UVB states which have a width of about 8 eV.

FIG. 3.FIG.
Total density
3: Total density ofof state
state of PbTiO
of PbTiO 3.

The total DOS of PbTiO3 for Pb, Ti, and oxygen atoms are shown in Fig. 4. The
electronic states below the fermi level are dominated by oxygen and Pb states. The lower
valence bands (LVB) are composed of the O-2s and Pb-5d orbitals, and the upper valence
bands (UVB) consist mostly of the O-2p and Pb-6s orbitals. The Ti-3d and Pb-6s states
contribute mainly to the conduction band (CB) DOS.
 VOL. 50 S. J. MOUSAVI AND A. POURHABIB-YEKTA 633

b-6s orbital. Ti-3d and Pb-6s states contribute mainly to the conduction band (CB) DOS.

Fig. 4. Total
FIG. 4:density of ofstate
Total density state for Pb,
for Pb, Ti, Ti
and and
oxygenOxygen
atoms. atoms
The electronic charge density for the (100) and (110) planes, in two and three dimen-
sion, are shown in Figures 5 and 6. From the contours of the charge density it appears that
the bond between Pb and O is typically ionic whereas Ti and O have a covalent character.

(a) (b)
. 5. Charge density in two dimension for PbTiO3 in cubic phase related to (a) (110) and (b) (100) pl
FIG. 5: Charge density in two dimension for PbTiO3 in the cubic phase related to the (a) (110)
and (b) (100) plane.
634 FIRST PRINCIPLE CALCULATION . . . VOL. 50

Pb Pb
Pb Pb
Pb Ti Pb
O Pb

O
O Pb

(a) (b)

FIG. 6: Charge density in three dimension for PbTiO3 in the cubic phase related to the (a) (110)
and (b) (100) plane.

IV. OPTICAL PROPERTIES

The dielectric tensor for the orthorhombic PbTiO3 is diagonal and has the following
form:
  ț
Imεxx 0 0
Imε =  ª 0 H Imεyy 0  º (9)
 

H «0 «
0 H Imεzz . »
»
H »¼1 (ω), and imaginary, ε2 (ω), parts of the dielectric
Fig. 7(a) «¬and 6(b) show the real, ε
functions calculated for PbTiO3 as a function of the incident photonp energy. √ The value of
the static refractive indexİ along
Ȧ the a-axis obtainedİ Ȧis na (0) = Reε(0) = 8.1 = 2.83
which is close to the experimental value 2.94.
Our calculated results for the imaginary part of epsilon shows two main peaks at
H
around 4 and 7 eV and other peaks are around 13.5 and 17 eV. These points are related
to interband transitions from the valance to conduction band states. The origin of the
different peaks in dielectric functions is from interband transitions. In terms of selection
rules, only transitions that imply a change ∆ι = ±1 in angular momentum are allowed.
The peak at 4 eV for ε2 (ω) is related to the transition from the Pb-6s to Pb-6p states.
From the real part of the dielectric function, Fig. 7(a), the static dielectric function ε1 (ω)
is deduced, and its value is 8.1.
The optical reflectivity of PbTiO3 in terms of energy was calculated and is shown in
Fig. 8. The main peak around 23 eV was calculated. As we know from the literature, an
exciton is a bound electron-hole pair, usually free to move together through the crystal.
These excitons are produced when a photon of energy greater than the energy gap 3.3
eV for PbTiO3 is absorbed in a crystal. These excitons may move through the crystal
transporting exciton energy but not charge. Because of its charge neutrality it does not
contribute directly to the electrical conductivity. If an insulator contains bound electron-

ǻȚ
 «¬ H »¼

İ Ȧ İ Ȧ

H
VOL. 50 S. J. MOUSAVI AND A. POURHABIB-YEKTA 635

FIG. 7, (a)FIG.
real7: (b) imaginary and part of dielectric function of PbTiO
(a) real (b) imaginary and part of the dielectric function of PbTiO3 .

hole pairs it is called an excitonic insulator. However, in the case of PbTiO3 , from the
optical reflectivity we can see such excitonic features at 4.5, 10, 23, and 37 eV.

ǻȚ
İ Ȧ
İ

FIG. 8: Optical reflectivity of PbTiO3 .

FIG. 8, Optical reflectivity of PbTiO
The EELS function can be deduced from the following relation [16]:
ε2
−Im (ε)−1 = 2 . (10)
ε1 + ε2 2
EELS is a valuable tool for investigating various aspects of materials. It has the
H
H
advantage of covering the complete energy range including non-scattered and elastically

H H

!Z
 H
 H 

H H

636 FIRST PRINCIPLE CALCULATION . . . VOL. 50

scattered electrons (Zero Loss), electrons which excite the atoms’ electrons of the outer
!Z9 the energy loss function
shell (Valence Loss), or valence interband transitions. In Figure
is plotted for PbTiO3 . The energy of the main maximum is assigned to the energy of the
volume plasmon, h̄ωp , and is equal to 24 eV.

FIG. 9,FIG.
Electron energy
9: Electron lossspectrum
energy loss spectrum of 3PbTiO
of PbTiO . 3

V. CONCLUSION

We have calculated the structural, electronic, and optical properties of PbTiO3 using
the full potential linearized augmented plane wave (FP-LAPW) method with generalized
gradient approximation (GGA) in the framework of density functional theory. The crystal
structure has been optimized, the lattice constant, and its equilibrium atomic position were
calculated. The calculated electronic structure and charge density yield a band gap of 3.3
eV at the point in the Brillouin zone. The total density of state calculation shows that
below the Fermi level the Pb-5d and O-2s state are dominate. The calculations show a
static dielectric function along the a-axis 8.1, an electron energy loss spectrum of 24 eV,
and a refractive index of 2.83 along the a-axis.
ɏ

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