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Copyright 2013 by American Scientic Publishers
All rights reserved.
Printed in the United States of America
Advanced Science,
Engineering and Medicine
Vol. 5, pp. 17, 2013
(www.aspbs.com/asem)
Electromagnetic Behavior of Lead Free
Ferroelectrics at Microwave Frequencies
S. N. Mathad
1
, R. N. Jadhav
2
, R. P. Pawar
2
, and Vijaya Puri
2,
1
KLE Institute of Technology, Hubli 580030, India
2
Department of Physics, Shivaji University, Kolhapur 416004, Maharashtra, India
Strontium barium niobates (Sr
x
Ba
1x
Nb
2
O
6
) have been synthesized by solid state sintering technique. The
structural aspects were studied by X-ray diffraction, FTIR, Raman spectroscopy. The grains of crystallites having
diverse shapes have been observed. The microwave properties like microwave absorption, dielectric constant
and conductivity of strontium barium niobate ceramics (0.04 x 0.75) has been investigated from 8 GHz to
18 GHz frequencies. The permittivity shows a large variation with strontium content and found maximum for
x =0.50. The dielectric constant lies in the range 3.9 to 23.8. Microwave conductivity decreases with increase
in strontium content and in the range 0.17 to 6.5 S/cm. The microwave conductivity measurement reveals the
loss of polaron conduction which supports the dielectric loss in the microwave region where minima at 10.8
and 16 GHz has been obtained.
KEYWORDS: XRD, Raman, FTIR, Dielectric Properties, Microwave Absorption, Penetration Depth, Microwave Conductivity.
1. INTRODUCTION
Todays wireless communications and information sys-
tems are heavily based on microwave technology. Current
trends indicate that in the future along with microwaves,
the millimeter wave and terahertz technologies will be
used to meet the growing bandwidth and overall perfor-
mance requirements. Moreover, motivated by the needs
of the society, new industry sectors are gaining ground;
such as wireless sensor networks, safety and security sys-
tems, automotive, medical, environmental, food monitor-
ing, radio tags etc. Ceramic materials and single crystals
showing ferroelectric behavior are being used in many
applications in electronics and optics. Each and every
material has its own set of electrical characteristics related
to its dielectric properties. Materials which can absorb
microwaves can eliminate electromagnetic wave pollution.
Wide spread applications of electromagnetic absorbers,
have inspired engineers to explore about optimal design
with available algorithms.
1
Knowing these properties pre-
cisely enables scientists and engineers to use the appropri-
ate materials for intended applications, such as the design
of ferroelectrics.
23
The dielectric constant is an essential
property of dielectric materials hence its determination is
very important. The most used technique depends on the
measurement of either reection coefcients or resonant

Author to whom correspondence should be addressed.

Email:
Received: 20 June 2012
Revised/Accepted: 4 December 2012
frequencies. In the later case material is used to load a res-
onant cavity and the sample permittivity is evaluated from
the shift of the resonant frequency value, compared to that
of the empty cavity.
49
A large number of applications of ferroelectric ceram-
ics also exploit properties that are an indirect consequence
of ferroelectricity, such as dielectric, piezoelectric, pyro-
electric and electro-optic properties. In 1970, the Bell
Telephone Laboratories had published successive thorough
investigations of the optical, electrical, and structural prop-
erties of SBN crystals. SBN belongs to the group of
relaxor ferroelectrics. A typical phenomenon for this class
is a broadened phase transition which is probably caused
by the wide variation of the nonequivalent crystallographic
positions in its structure. The high values of the electro-
optic and pyroelectric coefcients oriented further work
mainly towards holographic data storage, photorefractive
devices and pyroelectric applications. Thus SBN is very
good candidate with large number of other applications
like semiconductor and in photo optic applications.
1012
Microwave absorbing materials have an important appli-
cation in the military and the civil technology such as the
stealth, microwave darkroom and electromagnetic interfer-
ence protection. The complex permittivity is an important
factor which can be altered to achieve maximum absorp-
tion of the electromagnetic waves. Permittivity relates to
the materials ability to transmit (or permit) an electric
eld. Permittivity also depends on the physical properties
such as density and composition of the material and it
change with temperature and frequency.
13
Adv. Sci. Eng. Med. 2013, Vol. 5, No. xx 2164-6627/2013/5/001/007 doi:10.1166/asem.2013.1347 1
Electromagnetic Behavior of Lead Free Ferroelectrics at Microwave Frequencies Mathad et al.
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Another main reason that SBN is found most impor-
tant due to environmental concerns safety and health view
point, that lead free materials are being considered for
many applications as mentioned above. The objective of
this work is the synthesis of SBN ferroelectric material
by low cost solid state reaction route at low temperature
In the present case we report the synthesis of SBN fer-
roelectric material by solid-state reaction synthesis route
14
along with the electromagnetic behavior in the microwave
frequency band. To the authors knowledge there are no
reports on the microwave properties of SBN ceramics,
perturbations by wave guide (absorbance and reectance)
as well as VSWR methods (complex permittivity) at X and
Ku band.
2. EXPERIMENTAL DETAILS
2.1. Synthesis
AR grade chemicals of high purity SrCO
3
(99.95%),
BaCO
3
(99.95%) and Nb
2
O
5
(99.999%) were used as start-
ing materials. Powder was crushed for homogenization
using agate mortar in acetone medium for 1 hour to get the
ne powder. This powder was again mixed in stoichiomet-
ric proportion and ground for 4 hours in acetone medium
to obtain desired stoichiometry in the resultant compounds.
This mixture was initially sintered at 1200

C for 10 hrs
and further at 850

C for 48 hours in a mufe furnace. The
schematic representation given below emphasis the growth
mechanism and owchart of synthesis of tungsten bronze
structured SBN.
2.2. Characterization
The single phase formation of the compounds was con-
rmed by X-ray diffraction patterns obtained using Cr-K
o
radiations, (Philips Diffract meter PW 3710). The sur-
face morphology was studied using scanning electron
Fig. 1. Growth mechanism of SBN ceramics.
microscope (SEM JEOL-JSM 6360). Further the samples
were characterized by using IR spectrophotometer (Perkin
Elmer Model No. 783) to identify and understand the
aspect of bonding in the present samples in the range
of 4004000 cm
1
with KBr solvent. The Raman spec-
tra of the samples were recorded in the spectral range of
363600 cm
1
using Fourier-Transform Raman spectrom-
eter (Bruker Multi-RAM, Germany Make) Nd:YAG laser
source with excitation wavelength of 1064 nm and resolu-
tion of 4 cm
1
at 336 mW laser power. Transmission of
microwaves due to SBN ceramics was measured by reec-
tometer set up consisting of the X and Ku band generator,
isolator, attenuator, directional coupler and RF detector.
3. RESULTS AND DISCUSSION
3.1. XRD Analysis
Figure 2 shows the X-ray diffraction pattern for the
Sr
x
Ba
1x
Nb
2
O
6
powder samples with x = 0.4, 0.5, 0.61
and 0.75, respectively. It is seen that all peaks are attributed
to the tetragonal bronze structure without extra lines, indi-
cating that all samples are actually single phase. The cal-
culated lattice parameters for all samples (o = 12.639 ,
l = 12.639 , c = 3.978 ) were found to be in good
agreement with earlier reported values with JCPDS card
no. 00-039-0265.
3.2. Surface Morphology Studies
The SEM micrographs of SBN sample are as shown
in Figure 3. The surface is rough and grains of crys-
tallites having diverse shapes and micrometric sizes are
seen. These crystallites are randomly distributed and irreg-
ularly oriented. Microstructure reveals that Sr40 has an
interesting structure like net like morphology. Sr50 has
microstructure of different shaped rod of length of 1 jm
Fig. 2. X-ray diffraction pattern of SBN ceramics.
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Fig. 3. Scanning electron micrograph of SBN ceramics.
to 5 jm and width of 0.6 jm. The Sr61 and Sr75 samples
shows different shaped platelet like structure with little
more porosity compared to other samples and we observed
that grain size increases as a function of strontium concen-
tration due to increase in grain growth. The voids appear
to be more pronounced with increase in strontium con-
centration due to the smaller ionic radii of Sr
+2
(1.54 )
as compared to Ba
+2
(1.74 ) which may be due partial
replacement of Ba
+2
with Sr
+2
causing the shrinkage.
15
The sintering temperature and time also exercises strong
effects on the surface morphology. These different mor-
phologies are reported for the rst time as per authors
knowledge.
3.3. FTIR and Raman Studies
The ferroelectric SBN belongs to the structure type of
tetragonal tungsten bronze (TTB) with the space group
P4bm at room temperature. Sr and Ba occupy the A
1
and
A
2
positions; while the smaller 12-fold coordinated A
1
site
is occupied only by Sr, both Sr and Ba are found in the
larger 15-fold coordinated A
2
site. SBN has a tetragonal
structure belonging to the space group C
2
4v
. A complete
unit cell of the tetragonal tungsten bronze-type struc-
ture has the general formula (A
1
)
2
(A
2
)
4
C
4
(B
1
)
2
(B
2
)
8
O
30
.
In SBN crystal this complex formula is reduced to the
general formula (A
1
)
2
(A
2
)
4
(B
1
)
2
(B
2
)
8
O
30
with B
1
and B
2
sites fully occupied by niobium atoms, while A
1
sites
are partially occupied by Sr and A
2
sites are randomly
occupied by Sr and Ba. As a consequence, the atoms are
distributed in 46 crystallographic sites giving rise to 138
normal modes distributed among the irreducible represen-
tations of the C4v factor group A
1
, A
2
(Raman inactive),
B
1
, B
2
and E. The vibrational normal modes and they can
be classied according to the following irreducible repre-
sentations due to complex crystal structure of the material
!
total
=19A
1
(z)+15A
2
+14B
1
+18B
2
+36E(x)+36E(,),
Where x, ,, and z indicate the polarization direction of the
infrared active modes (z is the ferroelectric axis). Three
modes belonging to the A
1
, E(x), and E(,) representa-
tions are acoustic modes and the other modes, except A
2
modes, are Raman active; the number of such modes is
120.
14
In order to comprehend the spectra of SBN ceramics
DFT calculations of NbO
7
6
anion and rst approximation,
the dynamics of isolated NbO
7
6
anions have been taken
into account plays an important role.
16
Assuming the O
h
symmetry of NbO
7
6
anion, we may
observe 15 internal modes of vibrations, i.e., the total
symmetric stretching mode A
1g
, doubly degenerate the
antisymmetric, stretching E
g
mode, the triply degenerate
antisymmetric, stretching and bending T
1u
modes, triply
degenerate T
2u
modes and the triply degenerate bend-
ing T
2g
modes. The T
2u
mode is IR and Raman active
mode, where as A
1g
, E
g
and T
2g
modes are Raman active,
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Fig. 4. FTIR spectra of SBN ceramics.
T
1u
mode and A
1g
modes are IR active. The detailed study
of IR and Raman analysis are given below.
At room temperature absorption spectra (FTIR) of SBN
samples shown in Figure 4. We have observed that SBN
crystals studied so far contained only a small amount
of hydroxyl ions (OH

), probably as a result of the

humid atmosphere during the growth process at 3450 to
3600 cm
1
. We observe a broad peak in the region 400
to 850 cm
1
. These peaks are due to superposition of
fundamental modes T
2u
(triply degenerate bending mode)
and A
1g
(symmetric stretching mode) with assignments
o(ONbO) and u(NbO) respectively. At region 1600 to
1800 cm
1
and at 2800 to 3000 cm
1
. We nd that bands
due to sum of the fundamental modes of T
2u
and A
1g
.
16
Structural disorder and compositional uctuations in
solid solutions destroy translational invariance on which
Raman spectra is strongly dependent, may be due to the
observation of no soft mode in the Raman spectra, the
observation of rst-order Raman bands in forbidden cubic
symmetry well above the paraelectricferroelectric phase
transition temperature, and the breakdown of wave vector
selection rules, leading to the distribution of normal modes
among irreducible representations of factor group as an
approximate procedure As shown in Raman spectra, many
bands were observed. Due to some disorder and defects
long range translational order (for atoms as oxygen and
niobium) is preserved. Micro-Raman spectroscopy is very
useful in determining the effect of dopants in such struc-
tures because of the shorter coherence length and timescale
of the phonons.
17
The room temperature Raman spectra of the samples
are Sr40 and Sr75 are shown in Figure 5. From the graph
we observe that both spectra are identical but Sr75 shows
intense peaks as compared to Sr40. The other composi-
tions lie in between these two. The main features of the
spectra are the ve peaks about 100 cm
1
, 280 cm
1
,
400 cm
1
, 650 cm
1
, and 850 cm
1
regions. The bands
at 100 cm
1
may be due to vibrational and translational
Fig. 5. Raman spectra of Sr40 and Sr75 samples.
Raman-active external modes. The strong bands 280 cm
1
about 650 cm
1
regions are attributed to o(ONbO)
bending and u(NbO) symmetric stretching vibrational
modes. The doubly degenerate antisymmetric, stretching
u
os
(NbO) E
g
mode is responsible for the weak bands
at 400 cm
1
. The very weak bands about 850 cm
1
is
assigned to a silent mode which is due to o(ONbO)
bending vibrations. Further it is noted that the weak bands
observed at 400 and 850 cm
1
are due to a superposition
of silent T
2u
and A
1g
stretching modes. The Sr75 show-
ing intense peaks compared to Sr40. may be due ionic
radii of Sr
+2
(1.54

) being smaller as compared to Ba
+2
(1.74

). Due to increase in concentration of Sr
+2
in SBN
the average ionic radius of NbO
7
6
environment decreases.
There may be stronger deformation of niobate octahedra
for higher strontium content.
17
3.4. Microwave Reection and
Absorption Measurements
The transmission and reection of microwave due to SBN
were measured by waveguide reectometer technique in
X-band (812 GHz) and Ku-band (1318 GHz) region
and the microwave absorption calculated. The schematic
of microwave reectometer set up is shown in Figure 6
which consists of oscillator, isolator, attenuator, two 3 dB
directional coupler and detector.
The microwave reection loss of SBN in X-band and
Ku-band region were calculated by reection coefcient
of the sample using the formula,
Reection loss =20log
10

V
R
V
I

Where, V
R
is reected output power by SBN, V
I
is the
incident power on SBN.
Figure 7 shows the reection loss of SBN with differ-
ent Sr concentration in X band and Ku band region. In X
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Fig. 6. Microwave Reectometer set up for microwave characterization.
band, it is observed that composition dependent variations
are not drastic. Above 10.8 GHz reection loss of the
Sr50 sample increases (lower reection) from 3.19 dB
to 24.55 dB up to 12 GHz. In Ku band, composition
dependent small variations are observed. As Sr content
increases reection loss also increases. For high strontium
concentration (Sr75) high reection loss are observed.
In X band composition dependent small variations are
observed in the absorption loss. At high Sr content (Sr75)
absorption loss is high and it decreases with increase in
frequency. For all the compositions microwave absorption
loss is low in between 9 GHz to 10.8 GHz frequency
Fig. 7. Reection loss of SBN in (a) X-band (8 GHz12 GHz) (b) Ku-
band (13 GHz18 GHz).
Fig. 8. Absorption loss of SBN in (a) X-band (8 GHz12 GHz) (b) Ku-
band (13 GHz18 GHz).
range. In Ku band Sr75 shows the lower absorption loss
in whole 13 GHz to 15.8 GHz frequency range and
it is 2 dB. High microwave absorption loss peak
(14.3 dB) is observed at frequency 14.3 GHz.
3.5. Dielectric Dispersion Studies
The complex permittivity of SBN was measured using
VSWR measurement setup. The VSWR measurement
setup was almost the same as the waveguide reectome-
ter setup; instead of two 3 dB directional couplers VSWR
slotted section was used. Initially the slotted section was
calibrated with air. The SBN samples acts as a load to the
transmission of the microwaves and microwaves reected
back from that load.
The positions of the minima of the standing wave were
compared with that of air. As impedance is mismatched,
the position of the minima is shifted by placing the SBN
as load. The reection coefcient was also measured. The
Smith chart was used to nd the phase change due to the
SBN samples in the path of microwaves and dielectric con-
stant (a

) and dielectric loss (a

) of complex permittivity
measured in X and Ku bands by using the formula.
18
a

1+
A\
0
360J

2
And a

=
A\
0

8.686rJ
Where J is the thickness of the sample, \
0
wave-
length, A phase shift of materials from VSWR slotted
section.
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Fig. 9. Dispersion behavior of SBN in the 8 GHz to 18 GHz.
Using calculated dielectric constant (a

) and dielectric
loss (a

) of complex permittivity of SBN the dispersion

behavior in X and Ku bands are plotted in Figure 9. The
dielectric constant of all the samples varies in the range
3.9 to 23.8. The permittivity is wide-ranging with stron-
tium content and found maximum for x =0.50. This may
be due to rod like morphology and increase in polar-
ization. However the observed dielectric constant also
increases and polarization is affected by structural homo-
geneity, stoichiometry, grain size and porosity. The dielec-
tric loss is little more prominent for x = 0.40. Hence
dielectric loss also follows the same pattern as that of Sr75.
However Sr40 is shows more prominent loss in X band
which is 0.13 at 12 GHz, the loss goes on decreasing
to 0.009 at 16 GHz. At 9 GHz and 16 GHz loss of all
the samples becomes minimum may be due to impedance
matching.
3.6. Microwave Conductivity and Penetration Depth
The microwave conductivity was calculated using the
equation
19
u =wa

a
0
(1)
0
1
2
3
4
5
6
7
8 9 10 11 12 13 14 15 16 17 18
M
i
c
r
o
w
a
v
e

c
o
n
d
u
c
t
i
v
i
t
y
(
S
/
c
m
)
Frequency (GHz)
Sr40 Sr50
Sr61 Sr75
Fig. 10. Microwave conductivity of SBN ceramics.
where w is angular frequency, a
0
and a

are permittivity
of free space and dielectric loss of material respectively.
The microwave conductivty of all the samples also
becomes very low at 9 GHz and 16 GHz, the same trend
as observed in dielectric loss (a

). From Figure 10 it is
observed that as strontium content increases microwave
conductivity decreases. The conductivity varies from
7 S/cm for the composition Sr40, 6 S/cm for Sr50,
5 S/cm for Sr61 and 3 S/cm for Sr75. As strontium
content increases the frequency dependent variations are
prominent. To the authors knowledge there are no reports
available on the microwave conductivity of SBN bulk in
the 818 GHz frequency range.
The penetration depth of microwave in the ceramics can
be calculated by using the following relation,
J =c,w]2a

(1+a

,a

)
1,2
1]
1,2
Where c is speed of light, w is angular frequency, a

and a

permittivity of free space and dielectric loss of

material.
20
The variation in penetration depth with fre-
quency and strontium content is shown in Figure 11. The
calculated penetration depth is high for Sr50 and lower for
Sr75. The penetration depth is nothing but the power is
reduced to 1,e of the power entering in the surface. Due
to this microwave absorption is higher for Sr75.
Fig. 11. Penetration depth of SBN ceramics.
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4. CONCLUSIONS
The Sr
x
Ba
1x
Nb
2
O
6
ceramic were successfully synthe-
sized by low cost effective, uncomplicated solid state
reaction. The XRD reveals tungsten bronze structure of
sample, SEM provide a variation in morphology and
increase in grain growth due to strontium concentration. IR
and Raman broad peak in the region 400 to 850 cm
1
due
normal modes of vibration, dynamics of isolated NbO
7
6
anions have been reported. VSWR method perturbation
technique has been used for the evaluation of dielectric
parameters of dielectric material at microwave frequencies.
The analysis of the expressions for dielectric constants
and loss factors of SBN ceramics has been reported rst
time by the author. The VSWR technique was successfully
implemented for the calculation of complex permittivity
of the SBN ceramics and it is an efcient tool capable of
detecting the changes in microwave properties. According
literature survey, there are no reports about the complete
study of complex permittivity of SBN ceramics, systemat-
ically at microwave regions. The dielectric constant lies in
the range 3.9 to 23.8. Microwave conductivity decreases
with increase in strontium content and in the range 0.17
to 6.5 S/cm.
These SBN ceramics can be a good candidate since
large dielectric constants are noteworthy because they
enable capacitors and microwave components, semicon-
ductor memory; nonvolatile memory; nonvolatile logic to
be fabricated, for use in communications, navigation, and
various types of radar.
Acknowledgments: The author Vijaya Puri gratefully
acknowledges UGC, India for the Award of Research Sci-
entist C. S. N. Mathad acknowledge to Principal and
Management of K. L. E Institute of Technology, and R. N.
Jadhav thanks DST for Award of Women Scientist-A. All
the authors also thank DST-PURSE, UGC-SAP.
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