Physics Letters A 372 (2008) 2137–2140

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Dielectric response in ferroelectric BaTiO3

Fan Wan a,∗ , Jiaguang Han a,b , Zhiyuan Zhu a
a Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, People’s Republic of China
b School of Electrical and Computer Engineering, Oklahoma State University, Stillwater, OK 74078, USA

Received 29 October 2007; accepted 5 November 2007

Available online 12 November 2007
Communicated by V.M. Agranovich

Abstract
The far-infrared optical and dielectric properties of ferroelectric perovskite titanate powder BaTiO3 are reported. The terahertz time-domain
spectroscopy (THz-TDS) measurement reveals that the low frequency dielectric response of BaTiO3 is closely related to the lowest pair of
transverse optical (TO) and longitudinal optical (LO) modes near at 180 cm−1 , which is verified by Raman spectroscopy. This result provides
a better understanding of the relation of low-frequency dielectric function with the optical phonon mode for ferroelectric materials. Combining
terahertz TDS with Raman spectra, the overall low frequency optical phonon response of BaTiO3 is presented in an extended spectral range
from 6.7 to 1200 cm−1 .
© 2007 Elsevier B.V. All rights reserved.

PACS: 77.84.Dy; 77.22.Ch; 78.20.Ci; 63.22.-m

Keywords: Perovskite; Barium compounds; Optical phonons; Far-infrared; Raman; Spectroscopy

1. Introduction
As ferroelectric material, barium titanate of the perovskite
structure plays a very important role among the ferroelectrics
family, ABO3 compounds. Because of the excellent dielectric
properties and the potential for technological applications in
ferroelectricity, microelectronics and optoelectronics, BaTiO3
have attracted much attention not only for fundamental research
but also for device applications. There has been a great in-
terest to understand the behaviors of dielectric properties of
ferroelectric titanates, particularly to explore the relationship
between the dielectric properties and the optical phonon re-
sponses [1,2]. Being a lead-free ferroelectric ceramic, BaTiO3
is an environmentally friendly material. It seems a good candi-
date for various applications including capacitors, positive tem-
perature coefficient resistors, high-density optical data storage,
ultrasonic transducer, piezoelectric devices and semiconductors
and so on [3,4]. The dielectric and optical properties of BaTiO3
are closely related to its low frequency optical phonon modes.
In the past the dielectric and optical properties of this kind of
titanates have been studied by many methods in various fre-
quencies ranges. But in the THz region there is little research
about BaTiO3 optical characteristics.
In this Letter the low frequency optical properties and com-
plex dielectric function of powder BaTiO3 in the range of
0.2 THz (6.7 cm−1 ) to 1.5 THz (50 cm−1 ) are experimentally
characterized by the optoelectronic technique of terahertz TDS
[5,6]. The experimental results of power absorption coefficient,
refractive index and complex dielectric function were well fit
by the four-parameter semiquantum (FPSQ) model. To verify
the THz-TDS measurements, the optical resonance of BaTiO3
was also characterized by Raman light scatter. Our results re-
vealed that the dielectric response of BaTiO3 in the terahertz
region does not be dominated by only single optical mode, but
by the interaction of two TO and LO phonon modes.
2. Materials and experimental methods

* Corresponding author. Tel.: +86 21 59554533; fax: +86 21 59553021. The BaTiO3 powder sample was purchased from Acros-
E-mail address: wanfan@sinap.ac.cn (F. Wan). Organics that has a purity of higher than 99% without further
0375-9601/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.physleta.2007.11.009
2138 F. Wan et al. / Physics Letters A 372 (2008) 2137–2140

purification. The sample was prepared by milling the mix-
ture of BaTiO3 powder and polyethylene powder carefully, and
then the mixtures were made into pellets with thickness about
1.5 mm with an oil press. All procedures were carried in dry
environment and room temperature. A standard THz-TDS ap-
paratus for far-infrared transmission measurements is employed
in experiments. The setup and corresponding methods of exper-
imental data analysis have been described in previous reports
[7–9]. In brief, the laser is model-locked Ti: sapphire system
that provided 100-fs pulses at a wavelength of 800 nm with av-
erage power of 700 mW. Pulsed THz radiations was produced
by illuminating the GaAs photoconductor antenna and detected
in a ZnTe crystal via electro-optical sampling. The used band-
width of the spectrometer is 0.2–1.5 THz and the spectral res-
olution is better than 40 GHz. The THz beam path was purged
with dry nitrogen in order to minimize the absorption of water
vapor.
The BaTiO3 sample was placed in a mechanical holder while
another identical clear hole was used as a reference. Both the
sample and reference were centered by the THz beam in or-
der to ensure the entire frequency component passing through
the sample and reference. The experiments were performed at
room temperature. The transmitted electric field of terahertz
pulse through the sample and reference were recorded in time
domain and the corresponding frequency data were obtained
by numerical Fourier-transform. Both the amplitude and phase
of the spectrum were all recorded simultaneity by THz-TDS, so
the analyzed data can be extracted without the Kramers–Kronig
relationship. In order to increase the signal-to-noise ratio, every
sample data was the average of five individual measurements.
The complex spectrum of the transmitted sample pulse Es (ω)
can be extrapolated in terms of reference spectrum Er (ω) and
transfer function as [6,10],
Es (ω) −αL
= t12 t21 eiL(k−k0 ) e 2 ,
Er (ω)
where t12 and t21 are the frequency-dependent complex Fres-
nel transmission coefficients, L is the thickness of the sam-
ple, α is the power absorption, k = 2πnr /λ and k0 = 2π/λ
are the propagation wave vectors. Based on this equation, the
frequency-dependent power absorption coefficient α(ω) and re-
fractive index n(ω) of the BaTiO3 can be determined by the
measured data directly and quite accurately.
it is not always clear which EMT model is a better approach for
the composites. For extreme cases, with Q = 0 or Q = 1, all
these models lead to the same result. So experimentally mea-
sured dielectric constants are considered to determine which
model would be used. In our case the simple model is a bet-
ter approach of the mixed samples. According to simple model,
two elements are treated equally and there is no interaction be-
tween them. The simple model gives formula as below [13,15]
ε = Qεm + (1 − Q)εh where the ε, εm and εh are the dielec-
tric constants of the effective medium, the pure inclusion and
the host medium, respectively. Q is the packing density of the
pure inclusion, i.e., the filling factor defined by the ratio of pure
materials. Then the pure material dielectric function can be ex-
tracted as εm = ε−(1−Q)εQ
h
. Here in our experiment, εh is the
dielectric constant of polyethylene.
3.2. THz experimental spectra
The power absorption coefficient α(ω) and refractive index
n(ω) of pure BaTiO3 in the THz-TDS transmission spectra ex-
tracted from experimental composite sample by simple model
are plotted as open-circles in Fig. 1 over range from 0.2 to
1.5 THz. The power absorption is enhanced with increasing
frequency, no prominent absorption peaks are observed be-
low 1.5 THz, and meanwhile the refractive index also shows
no prominent changes. The frequency-dependent complex di-
electric function ε(ω) is determined by the data of the power
absorption and the refractive index through the relationship
ε(ω) = (nr + ini )2 , where the imaginary part of the refrac-
tive index ni is related to the power absorption as ni (ω) =
α(ω)λ/4π . The real and imaginary parts of dielectric constants

3. Results and discussions

3.1. EMT theories

Since each BaTiO3 sample studied here is a compos-

ite of pure BaTiO3 and polyethylene powder, the measured
frequency-dependent complex dielectric function of experi-
mental samples could be characterized by the effective medium
theories (EMTs), in which electromagnetic interactions be-
tween pure materials and host mediums are taken into ac-
count [11]. The commonly used EMTs include the Maxwell– Fig. 1. The measured data (open-circles) extracted from the simple EMT model
Garnett (MG) model [12], the Bruggeman (BR) model [13] and compared with the FPSQ model calculations (solid line). (a) Power absorption
the simple effective medium model [14]. For a given material, coefficient α(ω); (b) refractive index n(ω).
 F. Wan et al. / Physics Letters A 372 (2008) 2137–2140
Fig. 2. The measured complex dielectric function εm (ω) (open-circles) ex-
tracted from the simple EMT model compared with the FPSQ model calcu-
lations (solid line). (a) Real part εmr (ω); (b) imaginary part εmi (ω).
are determined by the equations εr = n2r − n2i = n2r − (αλ/4π)2
and εi = 2ni nr = αnr λ/2π , respectively. The observed real
and imaginary complex dielectric functions are shown in Fig. 2
as open-circles.
3.3. Theoretical fitting and analyses
In some cases, the complex dielectric function εm can be cal-
culated by the simple classical pseudoharmonic model, where
the interaction of a radiation field with the fundamental lattice
vibration results in absorption of electromagnetic wave due to
the creation or annihilation of lattice vibration. In the frame
of the classical pseudoharmonic model, the complex dielectric
function can be expressed as [16]:
(ε0 − ε∞ )ωTO
2
εm (ω) = ε∞ + , associated with lattice ionicity, as a consequence, each of the
2
ωTO − ω2 − iγTO ω
where ε∞ is high-frequency dielectric constant, ε0 is low-
frequency dielectric constant, ωTO and γTO are the angular
frequency and the damping constant of the transverse optical
phonon mode. However this model assumed γTO = γLO and
thus can apply in only the case of well separated bands.
On the contrary, in the FPSQ model, the complex dielectric
function εm of pure BaTiO3 can be expressed as the product of
each oscillator with four parameters of TO and LO modes, as
shown in below [17]
 ωj2LO − ω2 + iγj LO ω
εm (ω) = ε∞ = εmr (ω) + iεmi (ω),
j
ωj2TO − ω2 + iγj TO ω
where ωj LO and γj LO are the resonance frequency and the
damping constant of the j th LO mode, respectively. This model
2139
assumed γj LO = γj TO and can used for analysis of lattice vibra-
tion of BaTiO3 . In our case the j equal to 1, thus the formula
can be rewrite as
2 ω2 − ω2 ω2 − ω2 ω2 + ω4 )
ε∞ (ωTO LO LO TO
εmr (ω) = 2 − ω2 )2 + γ 2 ω2
,
(ωTO TO
ε∞ (ω3 γTO + ωTO
2 γ ω − ω2 γ ω − ω3 γ )
LO LO TO LO
εmi (ω) = 2 − ω2 )2 + γ 2 ω2
.
(ωTO TO
The solid curves in Fig. 1 and Fig. 2 represent the theoretical
fitting to the measured power absorption coefficient, refractive
index and complex dielectric function with the transverse and
longitudinal optical modes centered at ωTO /2π = 5.35 Hz and
ωLO /2π = 5.4 THz, and with TO and LO damping constants
γTO /2π = 8.2 THz and γLO /2π = 5.2 THz. The dielectric con-
stants used in fitting ε∞ = 5.3 [18,19], and the filling factor
here Q is calculated to be 0.45. According to the two figures,
the theoretical calculations are shown well accuracy fitting on
the experimental data simultaneously. Fig. 1 and Fig. 2 indicate
that the low-frequency terahertz response of BaTiO3 is manly
attributed to the interaction of pair of TO and LO mode near at
180 cm−1 .
Single crystal BaTiO3 undergoes a transition sequence
with decreasing temperature through cubic (405 K), tetrago-
nal (281 K), orthorhombic (193 K), and rhombohedral (ground
state) structures. Furthermore the structural phase transition
in BaTiO3 is not an ideal displactive type, but a displactive
type with an order–disorder behavior [20,21]. BaTiO3 has five
atoms and fifteen degrees of freedom per unit cell. In cubic
phase it has Oh symmetry, and the 15 degrees of freedom
divided into the optical representations 3F1u + F2u , while an-
other F1u symmetry mode corresponds to acoustical branch. At
room temperature BaTiO3 is tetragonal and has C4v symmetry.
Then each of the F1u modes splits into modes of symme-
try A1 + E, and the F2u splits into B1 + E. The A1 phonon
modes are infrared active for the extraordinary ray, while the
E modes are infrared active for ordinary ray. The B1 mode
is infrared in both the cubic and tetragonal phases of BaTiO3 .
So the optical branches irreducible representation of tetrago-
nal phase could be 3A1 + B1 + 4E. There is further splitting
of the vibration modes due to long-range electrostatic forces
A1 and E modes splits into pairs of TO and LO modes, i.e.,
A1 → A1 (TO) + A1 (LO) and E → E(TO) + E(LO). However
according to previous reports [22–24], the TO–LO splitting is
small for most of the vibration modes, especial E modes. For
example, the E(TO1)–E(LO1) band is near 180 cm−1 , so it is
not the CPHP model but the FPSQ model employed to fit the
experimental data of BaTiO3 .
3.4. Raman spectrum
However, terahertz TDS does not cover up to 180 cm−1 due
to the limit of measurement range. Therefore, Raman light scat-
tering is utilized as a complement of terahertz TDS to extend
the spectral range. In order to facilitate in-depth understand-
ing of the far-infrared dielectric and properties of BaTiO3 , the
2140 F. Wan et al. / Physics Letters A 372 (2008) 2137–2140

TDS study implicates that the dielectric constant of BaTiO3

is highly correlated with the lowest optical phonon modes at
180 cm−1 . The combination of terahertz TDS and Raman light
scattering is demonstrated as a powerful approach to explore
the low-frequency dielectric properties associated with optical
phonon resonances in semiconductors and composite materials.

Acknowledgements

The authors acknowledge the efforts of T. Ji, M. Ge and

Z.Y. Zhang. This project was partially supported by the major
project of knowledge innovation project of Chinese Academy
of Sciences (No. KJCX3-SYW-N10).

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Fig. 3. Completed low frequency optical response of BaTiO3 : the open circles
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