Advanced Science,

Engineering and Medicine

Vol. 5, pp. 17, 2013
(www.aspbs.com/asem)

Copyright 2013 by American Scientic Publishers

All rights reserved.
Printed in the United States of America

Electromagnetic Behavior of Lead Free

Ferroelectrics at Microwave Frequencies
S. N. Mathad1 , R. N. Jadhav2 , R. P. Pawar2 , and Vijaya Puri2

1
2

KLE Institute of Technology, Hubli 580030, India

Department of Physics, Shivaji University, Kolhapur 416004, Maharashtra, India

KEYWORDS: XRD, Raman, FTIR, Dielectric Properties, Microwave Absorption, Penetration Depth, Microwave Conductivity.

1. INTRODUCTION
Todays wireless communications and information systems 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 performance requirements. Moreover, motivated by the needs
of the society, new industry sectors are gaining ground;
such as wireless sensor networks, safety and security systems, automotive, medical, environmental, food monitoring, 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 precisely enables scientists and engineers to use the appropriate 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

Adv. Sci. Eng. Med. 2013, Vol. 5, No. xx

frequencies. In the later case material is used to load a resonant 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 ceramics also exploit properties that are an indirect consequence
of ferroelectricity, such as dielectric, piezoelectric, pyroelectric and electro-optic properties. In 1970, the Bell
Telephone Laboratories had published successive thorough
investigations of the optical, electrical, and structural properties 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 electrooptic 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 application in the military and the civil technology such as the
stealth, microwave darkroom and electromagnetic interference protection. The complex permittivity is an important
factor which can be altered to achieve maximum absorption 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

2164-6627/2013/5/001/007

doi:10.1166/asem.2013.1347

ARTICLE

Strontium barium niobates (Srx Ba1x Nb2 O6  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.

Electromagnetic Behavior of Lead Free Ferroelectrics at Microwave Frequencies

Another main reason that SBN is found most important 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 ferroelectric material by solid-state reaction synthesis route14
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.

Mathad et al.

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 cm1 with KBr solvent. The Raman spectra of the samples were recorded in the spectral range of
363600 cm1 using Fourier-Transform Raman spectrometer (Bruker Multi-RAM, Germany Make) Nd:YAG laser
source with excitation wavelength of 1064 nm and resolution of 4 cm1 at 336 mW laser power. Transmission of
microwaves due to SBN ceramics was measured by reectometer set up consisting of the X and Ku band generator,
isolator, attenuator, directional coupler and RF detector.

3. RESULTS AND DISCUSSION

2. EXPERIMENTAL DETAILS

ARTICLE

2.1. Synthesis
AR grade chemicals of high purity SrCO3 (99.95%),
BaCO3 (99.95%) and Nb2 O5 (99.999%) were used as starting 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 stoichiometric 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 conrmed by X-ray diffraction patterns obtained using Cr-K
radiations, (Philips Diffract meter PW 3710). The surface morphology was studied using scanning electron

Fig. 1.

Growth mechanism of SBN ceramics.

3.1. XRD Analysis

Figure 2 shows the X-ray diffraction pattern for the
Srx Ba1x Nb2 O6 powder samples with x = 04
05
061
and 0.75, respectively. It is seen that all peaks are attributed
to the tetragonal bronze structure without extra lines, indicating that all samples are actually single phase. The calculated lattice parameters for all samples (a = 12639 ,
b = 12639 , c = 3978 ) 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 crystallites having diverse shapes and micrometric sizes are
seen. These crystallites are randomly distributed and irregularly oriented. Microstructure reveals that Sr40 has an
interesting structure like net like morphology. Sr50 has
microstructure of different shaped rod of length of 1 m

Fig. 2. X-ray diffraction pattern of SBN ceramics.

Adv. Sci. Eng. Med., 5, 17, 2013

Mathad et al.

Scanning electron micrograph of SBN ceramics.

to 5 m and width of 0.6 m. 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 concentration due to increase in grain growth. The voids appear
to be more pronounced with increase in strontium concentration 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 morphologies 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 A1 and
A2 positions; while the smaller 12-fold coordinated A1 site
is occupied only by Sr, both Sr and Ba are found in the
larger 15-fold coordinated A2 site. SBN has a tetragonal
2
structure belonging to the space group C4v
. A complete
unit cell of the tetragonal tungsten bronze-type structure has the general formula (A1 2 (A2 4 C4 (B1 2 (B2 8 O30 .
In SBN crystal this complex formula is reduced to the
general formula (A1 2 (A2 4 (B1 2 (B2 8 O30 with B1 and B2
Adv. Sci. Eng. Med., 5, 17, 2013

sites fully occupied by niobium atoms, while A1 sites

are partially occupied by Sr and A2 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 representations of the C4v factor group A1 , A2 (Raman inactive),
B1 , B2 and E. The vibrational normal modes and they can
be classied according to the following irreducible representations due to complex crystal structure of the material
total = 19A1 z + 15A2 + 14B1 + 18B2 + 36Ex + 36Ey,
Where x
y, and z indicate the polarization direction of the
infrared active modes (z is the ferroelectric axis). Three
modes belonging to the A1 , Ex, and Ey representations are acoustic modes and the other modes, except A2
modes, are Raman active; the number of such modes is
120.14 In order to comprehend the spectra of SBN ceramics
DFT calculations of NbO7
6 anion and rst approximation,
the dynamics of isolated NbO7
anions have been taken
6
into account plays an important role.16
Assuming the Oh symmetry of NbO7
6 anion, we may
observe 15 internal modes of vibrations, i.e., the total
symmetric stretching mode A1g , doubly degenerate the
antisymmetric, stretching Eg mode, the triply degenerate
antisymmetric, stretching and bending T1u modes, triply
degenerate T2u modes and the triply degenerate bending T2g modes. The T2u mode is IR and Raman active
mode, where as A1g , Eg and T2g modes are Raman active,
3

ARTICLE

Fig. 3.

Electromagnetic Behavior of Lead Free Ferroelectrics at Microwave Frequencies

Electromagnetic Behavior of Lead Free Ferroelectrics at Microwave Frequencies

Fig. 4.

Mathad et al.

FTIR spectra of SBN ceramics.

ARTICLE

Fig. 5. Raman spectra of Sr40 and Sr75 samples.

T1u mode and A1g 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 cm1 . We observe a broad peak in the region 400
to 850 cm1 . These peaks are due to superposition of
fundamental modes T2u (triply degenerate bending mode)
and A1g (symmetric stretching mode) with assignments
(ONbO) and (NbO) respectively. At region 1600 to
1800 cm1 and at 2800 to 3000 cm1 . We nd that bands
due to sum of the fundamental modes of T2u and A1g .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 structures 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 compositions lie in between these two. The main features of the
spectra are the ve peaks about 100 cm1 , 280 cm1 ,
400 cm1 , 650 cm1 , and 850 cm1 regions. The bands
at 100 cm1 may be due to vibrational and translational
4

Raman-active external modes. The strong bands 280 cm1

about 650 cm1 regions are attributed to (ONbO)
bending and (NbO) symmetric stretching vibrational
modes. The doubly degenerate antisymmetric, stretching
as (NbO) Eg mode is responsible for the weak bands
at 400 cm1 . The very weak bands about 850 cm1 is
assigned to a silent mode which is due to (ONbO)
bending vibrations. Further it is noted that the weak bands
observed at 400 and 850 cm1 are due to a superposition
of silent T2u and A1g stretching modes. The Sr75 showing intense peaks compared to Sr40. may be due ionic
being smaller as compared to Ba+2
radii of Sr+2 (1.54 )

(1.74 ). Due to increase in concentration of Sr+2 in SBN

the average ionic radius of NbO7
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,


V
Reection loss = 20 log10 R
VI
Where, VR is reected output power by SBN, VI is the
incident power on SBN.
Figure 7 shows the reection loss of SBN with different Sr concentration in X band and Ku band region. In X
Adv. Sci. Eng. Med., 5, 17, 2013

Mathad et al.

Fig. 6.

Electromagnetic Behavior of Lead Free Ferroelectrics at Microwave Frequencies

Microwave Reectometer set up for microwave characterization.

Fig. 8. Absorption loss of SBN in (a) X-band (8 GHz12 GHz) (b) Kuband (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
(143 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 reectometer 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 constant (
 ) and dielectric loss (
 ) of complex permittivity
measured in X and Ku bands by using the formula.18



 0 2
 0




= 1+
And
=
360d
8686d

Fig. 7. Reection loss of SBN in (a) X-band (8 GHz12 GHz) (b) Kuband (13 GHz18 GHz).
Adv. Sci. Eng. Med., 5, 17, 2013

Where d is the thickness of the sample, 0 wavelength,  phase shift of materials from VSWR slotted
section.
5

ARTICLE

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 319 dB
to 2455 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

Electromagnetic Behavior of Lead Free Ferroelectrics at Microwave Frequencies

Mathad et al.

Microwave conductivity(S/cm)

Sr40

Sr50

Sr61

Sr75

6
5
4
3
2
1
0
8

10

11

12

13

14

15

16

17

18

Frequency (GHz)

ARTICLE

Fig. 10. Microwave conductivity of SBN ceramics.

Fig. 9.

Dispersion behavior of SBN in the 8 GHz to 18 GHz.

Using calculated dielectric constant (

 ) and dielectric
loss (
 ) 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 strontium content and found maximum for x = 050. This may
be due to rod like morphology and increase in polarization. However the observed dielectric constant also
increases and polarization is affected by structural homogeneity, stoichiometry, grain size and porosity. The dielectric loss is little more prominent for x = 040. 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.

where  is angular frequency,

0 and
 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 (
 ). 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,
dp = c/2
 1 +
 /
 1/2 11/2
Where c is speed of light,  is angular frequency,

and
 permittivity of free space and dielectric loss of
material.20 The variation in penetration depth with frequency 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.

3.6. Microwave Conductivity and Penetration Depth

The microwave conductivity was calculated using the
equation19
 = 

0
(1)
6

Fig. 11. Penetration depth of SBN ceramics.

Adv. Sci. Eng. Med., 5, 17, 2013

Mathad et al.

Electromagnetic Behavior of Lead Free Ferroelectrics at Microwave Frequencies

4. CONCLUSIONS

Acknowledgments: The author Vijaya Puri gratefully

acknowledges UGC, India for the Award of Research Scientist C. S. N. Mathad acknowledge to Principal and
Management of K. L. E Institute of Technology, and R. N.

Adv. Sci. Eng. Med., 5, 17, 2013

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ARTICLE

The Srx Ba1x Nb2 O6 ceramic were successfully synthesized 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 cm1 due
normal modes of vibration, dynamics of isolated NbO7
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, systematically 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, semiconductor memory; nonvolatile memory; nonvolatile logic to
be fabricated, for use in communications, navigation, and
various types of radar.

Jadhav thanks DST for Award of Women Scientist-A. All

the authors also thank DST-PURSE, UGC-SAP.