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X-band frequency response and electromagnetic interference shielding in

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 X-band frequency response and electromagnetic interference shielding in multiferroic
BiFeO3 nanomaterials
Hilal Ahmad Reshi, Avanish Pratap Singh, Shreeja Pillai, Touseef Ahmad Para, S. K. Dhawan, and Vilas Shelke

Citation: Applied Physics Letters 109, 142904 (2016); doi: 10.1063/1.4964383

View online: http://dx.doi.org/10.1063/1.4964383
View Table of Contents: http://scitation.aip.org/content/aip/journal/apl/109/14?ver=pdfcov
Published by the AIP Publishing

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 APPLIED PHYSICS LETTERS 109, 142904 (2016)

X-band frequency response and electromagnetic interference shielding

in multiferroic BiFeO3 nanomaterials
Hilal Ahmad Reshi,1 Avanish Pratap Singh,2 Shreeja Pillai,1 Touseef Ahmad Para,1
S. K. Dhawan,3 and Vilas Shelke1,a)
1
Novel Materials Research Laboratory, Department of Physics, Barkatullah University, Bhopal 462026, India
2
Department of Physics, Atma Ram Sanatan Dharma College, Dhaula Kuan, New Delhi 110021, India
3
Polymeric and Soft Materials Section, CSIR-National Physical Laboratory, Dr. K. S. Krishnan Road,
New Delhi 440012, India
(Received 28 August 2016; accepted 21 September 2016; published online 5 October 2016)
The presence of electric dipoles, magnetic dipoles and mobile charges is a prerequisite for
electromagnetic interference (EMI) shielding materials. Here, we demonstrate that multiferroic
compound with incipient ensemble of electric and magnetic dipoles can perform as an EMI shielding
material. We synthesized single phase BiFeO3 nanomaterial and studied complex electromagnetic
properties in an X-band frequency region. A shielding effectiveness up to 11 dB with a major contri-
bution from absorption was observed in the BiFeO3 nanomaterials. An auxiliary functionality of radi-
ation shielding is revealed in the multiferroic BiFeO3 compound. Published by AIP Publishing.
[http://dx.doi.org/10.1063/1.4964383]

The effect of non-ionizing radiations on biological pro-
cesses, including human health, has always been a topic of
debate. The International Agency for Research on Cancer
(IARC), a subsidiary of the World Health Organization, has
classified radio frequency (RF) radiation as possibly carcino-
genic to humans.1 An acute RF signal exposure can affect a
brain glucose metabolism, a marker of brain activity.2 The
nuclear magnetic resonance (NMR) imaging of bovine brain
tissue confirmed the thermo-physical effect of radiation
absorption.3 The man made electromagnetic noise disrupts
magnetic compass orientation in migratory birds.4 The RF
signals also tend to interfere with sensitive medical and navi-
gation electronic devices. In spite of the perilous conse-
quences of radiation pollution, the use of electronic gadgets
like cellular phone, radar, Bluetooth devices, etc., cannot be
prohibited completely. Therefore, a quest for efficient elec-
tromagnetic interference (EMI) shielding materials has been
triggered. Conventionally, metals are good EMI shielding
materials. However, their weight, corrosiveness, less effec-
tiveness under harsh environment, etc., placed limitations on
their use in civil, commercial and aerospace applications. In
the recent years, carbon based materials have been exten-
sively studied for EMI shielding applications.5 The carbon
allotrope like carbon nanotube,6,7 2D layered graphene,8 and
graphene oxide9–11 exhibited various degrees of shielding
effectiveness.
In all such materials, the shielding effectiveness is fun-
damentally governed by the reflection and absorption mecha-
nisms.12 The electromagnetic fields of radiation interact with
the mobile charge carriers of materials and get reflected, as
delineated in Fig. 1(a). The absorption of radiation takes
place through interaction with electric and magnetic dipoles
present in the material. Occasionally, multiple reflections
can be secondary mechanism in case of materials with large
a)
Author to whom correspondence should be addressed. Electronic mail:
drshelke@gmail.com
surface/interface areas. Therefore, a doctrine for finding
good shielding material is to make a pool of mobile charges,
electric dipoles and magnetic dipoles. Combining materials
with mobility (e.g., graphene, carbon nanotube) and dielec-
tricity (e.g., polymer) has been a good strategy.13 Similarly,
functionalization or decoration by magnetic ions can also
enhance electromagnetic radiation absorption.14–16 In some
cases, oxide compounds with magnetic character showed
potential for effective radiation shielding.17–21 Surprisingly,
multiferroic compounds have not been explored so far in this
direction. Multiferroic materials have concomitant existence
of electric and magnetic orderings, which are otherwise con-
flicting phenomena.22–24
BiFeO3 (BFO) is a classic example of multiferroic mate-
rial with high ferroelectric Curie temperature (Tc  1100 K),
high magnetic Neel temperature (TN  643 K) and lead-free
composition.25–27 In principle, it should be a potential EMI
shielding material for use in extreme conditions. Our previous
studies were focused on reducing leakage current,28 increasing
polarization,29 reducing coercive field,29 stabilizing different
structure,30 domain scaling31 and enhancing magnetization32
in this material. It has been a tough task to obtain good ferro-
electric behavior in bulk or nanocrystalline BFO mainly due to
heavy leakage current. Nevertheless, a “dirty multiferroic”
with some amount of leakage current may be suitable for EMI
shielding. In accordance with Fig. 1(a), the leakage current
(mobile charges) can contribute to reflection losses and the
electric/magnetic dipoles can effectively absorb electromag-
netic radiation. We tried to execute this strategy by synthesiz-
ing BiFeO3 nanomaterial samples using a sol-gel route. The
phase purity, crystal structure, vibrational modes, and micro-
structure were analyzed through X-ray diffraction, the Raman
spectroscopy and transmission electron microscopy techni-
ques, respectively. The complex permittivity and permeability
parameters were studied in an X band frequency region using
vector network analyzer. We observed shielding effectiveness
up to 11 dB with a major contribution from absorption losses.

0003-6951/2016/109(14)/142904/4/$30.00 109, 142904-1 Published by AIP Publishing.

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 142904-2 Reshi et al.
This study demonstrates that multiferroic materials can be
suitable for shielding electromagnetic radiation and it may add
different saga to the multifunctionality of BiFeO3 compound.
The BiFeO3 nanostructures were synthesized by a conven-
tional solution chemistry (sol-gel) route. In a typical protocol,
stoichiometric amount of high purity Bi(NO3)35H2O and
Fe(NO3)39H2O were separately dissolved in a mixture of ethyl-
ene glycol (EG), nitric acid and deionized water to form trans-
parent precursors. These precursors were thoroughly mixed and
stirred continuously at 80  C till the solution becomes green
puffy porous mass. The mass was ground into fine powder and
pressed into 10 mm diameter pellets. The pellets were sintered
at 600  C for 2 h in air ambient. The phase purity and crystal
structure of the samples were investigated through X-ray dif-
fraction (D8 Advanced Bruker) technique using CuKa radiation
in the range 15  2h  60 . The Raman spectroscopy measure-
ment was performed on Horiba JY HR800 micro Raman set up.
The grain morphology was observed using the transmission
electron microscopy technique. We used the Agilent E8362B
vector network analyzer to measure complex parameters and
shielding efficiency in the X-band (8.2–12.4 GHz) frequency
range. For this purpose, the pressed powder of rectangular
shape with a 2 mm thickness was inserted in the copper sample
holder, which was connected between the waveguide flanges of
network analyzer.
A Rietveld fitted X-ray diffraction pattern of BiFeO3
nanomaterial is shown in Fig. 1(b). Single phase nature of
the sample is evident from the absence of impurity peaks. In
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12:13:34
Appl. Phys. Lett. 109, 142904 (2016)
FIG. 1. (a) Schematic representation
of EMI shielding through a pool of
mobile charges, electric dipoles and
magnetic dipoles; (b) Rietveld fitted
X-ray Diffraction pattern; (c) Raman
spectrum; and (d) transmission emis-
sion microscopic image of BiFeO3
nanomaterial sample.
particular, Bi2Fe4O9 is a notorious secondary phase with
Gibb’s free energy near that of BiFeO3 phase, and both can
coexist with zero degrees of freedom.33 The structural refine-
ment revealed rhombohedral R3c space group with lattice
parameters a ¼ 5.57 Å and c ¼ 13.83 Å. The Raman spectrum
of the sample is shown in Fig. 1(c). The group theory has
predicted 13 active Raman modes represented by CRaman
¼ 4A1 þ 9E for BFO.34 Three sharp peaks around 139, 169,
and 221 cm1 and a low intensity peak at 430 cm1 were
assigned to A1 modes. The peak at 139 cm1 is associated
with Bi-O vibration, while the peaks at 169 and 221 cm1
are due to Fe-O vibrations in FeO6 octahedra.35 A prominent
peak at 74 cm1 and weak signals around 260, 279, 305,
345, 367, 429, 528 and 598 cm1 signify 9E Raman modes.
The nanodimensional grain morphology of the sample is evi-
dent from the transmission electron microscopic image
shown in Fig. 1(d). The average grain size is around 103 nm.
The EMI shielding efficiency of a material is closely
coupled with complex permittivity and permeability. The
electromagnetic wave absorption results from effective com-
plementarities between relative permittivity and permeabil-
ity. The complex electromagnetic parameters are relative
permittivity e* ¼ e0  ie00 and relative permeability l* ¼ l0
 il00 . These parameters are obtained from experimental
scattering parameters (S11 and S22) using the Nicolson-Ross
and Weir algorithms.36,37 The variation of complex electro-
magnetic parameters with frequency is shown in Figs.
2(a)–2(f). The real part (e0 or l0 ) is mainly associated with
 142904-3 Reshi et al. Appl. Phys. Lett. 109, 142904 (2016)

represent transmitted and incident powers, respectively. The

shielding effectiveness is determined from the scattering
parameters S11 (S22) and S12 (S21) of network analyzer, as
reported previously.40 The variation of SE with frequency
for a BFO nanomaterial sample is shown in Fig. 3(a). The
shielding effectiveness due to absorption (SEA) remained
invariant around 6.5 dB over the X-band frequency range,
while that due to reflection (SER) decreased significantly at
higher frequency. The total shielding effectiveness (SET)
value up to 11 dB was observed in the BFO nanomaterial
sample. Usually, the reflection loss is the prime mechanism
for EMI shielding. However, absorption of radiation is a
dominant mechanism in our sample. It is the consequences
of the interaction of electromagnetic radiation with electric
and magnetic dipoles present in the sample. The multiferroic
BFO has intrinsic electric dipoles, magnetic dipoles and
incipient leakage current across grain/domain boundaries.28
The attenuation of electromagnetic signals is shown in
Fig. 3(b). The sample showed up to 77% attenuation of inci-
dent radiation.
According to electromagnetic theory, ac conductivity
(r) and skin depth (d) are important parameters to analyze
radiation-matter interaction.40 These parameters are plotted
FIG. 2. Frequency dependence of complex electromagnetic parameters (a) as a function of frequency in Figs. 4(a) and 4(b), respec-
e0 , (b) e00 , (c) tan de, (d) l0 , (e) l00 and (f) tan lm in X-band region for BFO tively. The ac conductivity (r) value around 3 S/m is lower
sample. as compared to that of La0.7Sr0.3MnO3 system, as reported
previously.40 In fact, La0.7Sr0.3MnO3 is conducting ferro-
the amount of polarization, and the imaginary part (e00 or l00 ) magnetic system at room temperature. The better conductiv-
is a measure of dissipated energy. The dielectric perfor- ity due to itinerant electrons and ample magnetic dipoles
mance depends on ionic, electronic, orientational and space
charge distribution. The value of e0 decreases from 34 at
8.2 GHz to 15 at 12.4 GHz. The decreasing trend with
increasing frequency in e0 and e00 is due to the dipole relaxa-
tion phenomenon.38 At higher frequency, the dipoles present
in the system cannot reorient themselves fast enough to
respond to the applied field. Consequently, the dielectric
constant decreases. The real and imaginary parts of perme-
ability indicated slightly increasing trend with frequency.
The permeability is mostly dominated by spin relaxation of
domain wall motion and electron diffusion relaxation.39
These relaxations are the attribute of 3d electron transitions
between the Fe3þ ions in the changing field. The dielectric
loss tangent (tan de ¼ e00 /e0 ) showed wide variation with fre-
quency. Several complex phenomena like dipole relaxation,
electronic polarization, natural resonance, polaron polariza-
tion, etc., contribute to the dielectric losses in BFO system.
Similarly, magnetic loss tangent (tan dm ¼ l00 /l0 ) results
from natural resonance, eddy current effect, magnetic hyster-
esis loss, domain wall resonance, exchange resonance,
anisotropy energy, etc., present in the system. The dielectric
loss tangent is much smaller than magnetic loss tangent. It
indicates that the main contribution to radiation absorption is
from the magnetic loss. Nevertheless, the presence of both
magnetic and dielectric entities ensures effective EMI
shielding.
The EMI shielding is a direct consequence of reflection,
absorption and multiple internal reflections suffered by inci-
dent electromagnetic radiation. The EMI shielding effective-
ness (SE) is defined as the ratio of transmitted power to the FIG. 3. Variation of (a) shielding effectiveness (SE) and (b) attenuation with
incident power, i.e., SE ¼ 10 log(Pt/Pi), where Pt and Pi frequency for BFO sample.

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 142904-4 Reshi et al. Appl. Phys. Lett. 109, 142904 (2016)

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