Phys. Status Solidi RRL 6, No. 6, 244–246 (2012) / DOI 10.1002/pssr.

201206135

pss
Nanoscale magnetoelectric coupling www.pss-rapid.com
in multiferroic BiFeO3 nanowires
K. Prashanthi*, 1, P. M. Shaibani1, A. Sohrabi1, T. S. Natarajan2, and T. Thundat1
1
Dept. of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta, Canada
2
Dept. of Physics, Indian Institute of Technology Madras, Chennai, India

Received 29 March 2012, revised 25 April 2012, accepted 25 April 2012

Published online 27 April 2012

Keywords BiFeO3, magnetic force microscopy, MFM, multiferroics, magnetoelectric effects

*
Corresponding author: e-mail kovur@ualberta.ca, Phone: +1780 492 8664, Fax: +1780 492 2881

Nanoscale magnetoelectric (ME) coupling has been observed
in multiferroic BiFeO3 (BFO) nanowires (NWs) synthesized
by sol–gel based electrospinning technique. Under externally
imposed electric fields these NWs exhibit the systematic evo-
lution of a magnetic domain pattern as established by mag-
netic force microscopy (MFM), confirming the presence of
ME coupling. Interestingly, the effect persists even after the
electric field is removed, thereby implying an electric-field-
induced magnetic hysteresis phenomenon in BFO NWs. The
estimated ME coupling coefficient from tip–sample interac-
tions is α33 = 2.2 × 10−10 sm−1, and the equivalent ME voltage
coefficient is 0.49 V cm–1 Oe−1. The obtained values of the
ME coupling coefficient are higher than the reported values
for BFO bulk and thin films. These results promise one-
dimensional (1D) multiferroic BFO NWs as potential candi-
date for manipulating magnetism through electric field at the
nanoscale and provide great opportunities towards magneto-
electrically tunable multiferroic devices.

© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1 Introduction Bismuth ferrite (BiFeO3, BFO) is
one of the very few room temperature multiferroic materi-
als with a simultaneous coexistence of ferroelectric
(TC = 810 °C) and antiferromagnetic order (TN = 380 °C)
parameters. It is also reported that even though BFO has an
antiferromagnetic spin ordering, it displays a weak mag-
netic moment arising from a canted spin structure [1, 2].
Extensive work has been reported on growth and charac-
terization of BFO thin films due to their immense applica-
tion potential in spintronics [3], non-volatile memories
[4], microelectromechanical systems (MEMS) [5], and
switchable photovoltaics [6]. However, one-dimensional
(1D) nanostructures, such as nanowires [7, 8], nanotubes
[9] and nanofibers [10, 11] are expected to show excellent
properties compared to the conventional structures due to
the large surface area [12] and quantum size effects [13].
Several efforts therefore, have been directed towards fabri-
cating BFO nanostructures using the template technique
[9], hydrothermal synthesis [14], sol–gel combustion
method [15], soft chemical methods [16], and electrospin-
ning technique [10, 11]. Controlling magnetism with an
external electric field and electric polarization by an exter-
nal magnetic field in nanostructured BFO is one of the
most important attempts in order to realize nanoscale de-
vices with unique functionalities utilizing the coupling be-
tween two parameters. Though there are several literature
reports on magnetoelectric (ME) coupling of pure and
modified BFO bulk and thin films [17–19], however, to the
best of our knowledge, there are no literature reports on lo-
cal ME coupling of nanostructured BFO. In this Letter, we
report on the local probing of ME coupling in BFO NWs
prepared by sol–gel based electrospinning technique. Us-
ing magnetic force microscopy, the evolution of a mag-
netic domain pattern with application of external electric
field has been observed confirming the ME coupling in
BFO NWs.
2 Experimentation The BFO sol–gel precursor solu-
tion was prepared by dissolving Bi(NO3)3 ⋅5H2O and
Fe(NO3)3 ⋅9H2O salts in stoichiometric proportions in
2-methoxyethanol. The pH value of the solution was ad-
justed to 4 by adding ethanolamine. This mixture was
magnetically stirred for 2 hours at room temperature. The
polymer solution of 15 wt% was prepared by dissolving
nylon-6 crystals to formic acid. The prepared BFO solution
was added to this polymer solution drop by drop to obtain

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Research Letter

Phys. Status Solidi RRL 6, No. 6 (2012) 245

a homogeneous BFO precursor solution for the electro-

spinning process. A home-made electrospinning unit was
used for the fabrication of BFO NWs. The obtained nylon-
6/BFO gel was electrospun onto the Pt/Ti/SiO2/Si sub-
strates with an applied voltage of 20 kV and feeding rate of
0.3 ml/h. The distance between the needle tip and the tar-
get was kept at 20 cm. The as-spun fibers were then dried
at 100 °C for 2 h in a vacuum oven. The dried fibers were
then calcinated at 600 °C in furnace for 2 h in presence of
air to form BFO NWs. The size of the BFO NWs and the
lattice spacing were analyzed using transmission electron
microscopy (TEM) (JEOL JEM-2100). X-ray diffraction
(XRD) (Rigaku, Cu Kα radiation, λ = 1.5405 Å) was used
for structural phase identification. The local probing of ME
coupling was carried out using magnetic force microscopy
(MFM) (MFP 3D, Asylum Research). To study the evolu-
tion of the magnetic domain structure with an applied elec-
tric field, the sample was biased during MFM imaging.

3 Results and discussion The size and crystalline

morphology of BFO NWs calcinated at 600 °C studied by
TEM is shown in Fig. 1(a). The average diameter of BFO
NWs is ~150 nm with crystallite size ~25 nm. Figure 1(b)
shows the high resolution TEM (HRTEM) image of BFO
crystals. The interplanar spacing observed from Fig. 1(b) is
about 0.396 nm (012) and 0.278 nm (110) showing the
polycrystalline nature of BFO NWs. XRD in Fig. 1(c)
shows that BFO NWs are polycrystalline and have R3c
rhombohedral distorted perovskite structure (JCPDS: 01-
071-2494) with a small trace of Bi2Fe4O9 (secondary
phase).
(a)
(110)
Figure 2 (online colour at: www.pss-rapid.com) MFM imaging
of BFO NWs calcinated at 600 °C. (a) Topography image at 0 V,
(b) phase image at 0 V, (c) phase image at 5 V, (d) phase image
at 10 V, (e) phase image at back to 0 V.
Figure 2 shows the evaluation of magnetic domain
structure in the presence of an electric field. The topo-
graphy and MFM phase image of BFO NWs when no
electric field is applied are shown in Fig. 2(a) and (b),
respectively. When no electric field is applied (Fig. 2(b)),
an indistinct domain structure dominated by topographic
features is observed in the MFM phase image. Conversely,
when a bias of 5 V is applied, a clear change in the
magnetic domain structure is seen with distinct, elongated
(b) and multiple domain patterns (Fig. 2(c)). Further, if voltage
is increased to 10 V, in certain regions the multiple domain
pattern in BFO NWs is changed into a single domain
pattern with an excellent phase contrast (Fig. 2(d)). Quite
remarkably, this domain pattern remains even after the
electric field is switched off (Fig. 2(e)). Here it should be
noted that the MFM phase image shown in Fig. 2(e) was
captured after multiple scans when the electric field was
removed. This apparently shows an electric-field-induced
magnetic hysteresis in BFO NWs. It was also ascertained

(c) * Bi2Fe4O9
that this response does not depend on the polarity of the
applied electric field which is essential by symmetry
Intensity (a.u)

considerations. By symmetry, an electric-field-induced

(012)

magnetic easy axis can only be parallel or perpendicular to

(202)

the applied electric field and therefore, does not depend

(300)
(024)
(006)

on the sign of the applied electric field. In a polycrystalline

(116)

* material, with an uniaxial magnetic easy axis, the

20 30 40 50 60 individual crystals tend to align along a certain crystallo-
2theta graphic axis making it easier to magnetize the sample in
Figure 1 (online colour at: www.pss-rapid.com) (a) Bright field one direction than it would be if the individual crystals
TEM image of BFO NWs calcinated at 600 °C. (b) HRTEM oriented randomly. Therefore, for an isotropic case, the
image of BFO nanocrystal showing the interplanar spacing. (c) associated strain, s, due to a change in the magnetization
XRD spectra of BFO NWs. direction is related to the angle (θ) between the directions

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246 K. Prashanthi et al.: Nanoscale magnetoelectric coupling in multiferroic BiFeO3 nanowires

(a) where ΔM is the difference of magnetization of sample at

8
0 V and 10 V, E is the applied electric field. From the ob-
MFM Response (a.u)

6 tained magnetization values at different applied electric

phase shift (θ)

fields, the calculated ME coupling coefficient using Eq. (3)
is α33 = 2.2 × 10−10 sm−1, and the equivalent ME voltage
coefficient, αE, is 0.49 V cm−1 Oe−1. These ME coefficient
0V 4
5V
10 V values are higher than the reported values for bulk and
back to 0 V 2 (b) thin films of BFO [18, 19]. In a single phase multiferroic,
0 50 100 150 200 250 0 2 4 6 8 10 like BFO, which is both ferroelectric and magnetic, the
Lateral distance (nm) Applied Voltage (V) orientation of the magnetic axis can be rotated by
Figure 3 (online colour at: www.pss-rapid.com) (a) Sectional application of an electric field [4]. Nevertheless, our results
analysis of MFM phase signal of BFO NWs at different applied indicate that BFO NWs are potential candidates for
voltages. Inset: local MFM image where the signal was measured. manipulating magnetic domain structures through electric-
(b) Phase shift with applied voltage and corresponding domain field-induced strain and provide great opportunities for
evolution. magnetoelectrically tunable multiferroic devices.
In conclusion, the local ME coupling in 1D multifer-
roic BiFeO3 (BFO) NWs has been demonstrated by apply-
of magnetization and the strain in which it is measured and
ing electric field and observing the change in magnetic
is given by [20]
domain structure. A significant change in the magnetic
domain pattern with externally applied electric field has
s = 32 λs (cos θ - 13 ) ,
2
(1)
been observed. More remarkably, the effect persists even
after the electric field is removed, thereby implying an
where λs is the magnetoelastic coupling coefficient.
electric-field-induced magnetic hysteresis phenomenon in
Figure 3(a) shows the cross-sectional analysis of
BFO NWs. The observed results establish an in-principle
MFM response at different applied volatges. The inset in
applicability of BFO NWs towards magnetoelectrically
Fig. 3(a) shows the portion of MFM image where the
tunable device applications.
signal was measured. It is possible to estimate the magneti-
zation value of the sample from MFM phase shift using the Acknowledgements The authors acknowledge the support
MFM probe–sample interaction [21, 22]. It can be shown, of the CERC. The authors also thank ACSES and the Cell
using the small cantilever oscillation amplitude approxi- Imaging Facility at University of Alberta for characterization fa-
mation, that the phase shift (Δφ) resulting from the dipolar cilities.
probe–sample interaction is expressed as

μ0 12πQ 180 ˆ References

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