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High resolution quantitative piezoresponse force microscopy of BiFeO3
nanofibers with dramatically enhanced sensitivity
Published on 21 November 2011. Downloaded by University of Windsor on 31/10/2014 06:56:21.
Shuhong Xie,ab Anil Gannepalli,c Qian Nataly Chen,b Yuanming Liu,b Yichun Zhou,a Roger Prokschc
and Jiangyu Li*b
Received 14th August 2011, Accepted 26th October 2011
DOI: 10.1039/c1nr11099c
Piezoresponse force microscopy (PFM) has emerged as the tool of
choice for characterizing piezoelectricity and ferroelectricity of low-
dimensional nanostructures, yet quantitative analysis of such low-
dimensional ferroelectrics is extremely challenging. In this
communication, we report a dual frequency resonance tracking
technique to probe nanocrystalline BiFeO3 nanofibers with
substantially enhanced piezoresponse sensitivity, while simulta-
neously determining its piezoelectric coefficient quantitatively and
correlating quality factor mappings with dissipative domain
switching processes. This technique can be applied to probe the
piezoelectricity and ferroelectricity of a wide range of low-dimen-
sional nanostructures or materials with extremely small piezoelec-
tric effects.
Piezoresponse force microscopy (PFM) is a powerful tool for probing
local piezoelectric and ferroelectric properties of ferroelectric mate-
rials at the nanoscale level,13 and has emerged as the tool of choice
for characterizing piezoelectricity and ferroelectricity of low-dimen-
sional ferroelectric nanostructures.49 In a typical PFM measurement,
an AC driving voltage Vac V0eiut is applied to the specimen through
the conductive cantilever tip, which induces a surface vibration uac
d33V0ei(ut+4) of the specimen due to its piezoelectricity, where d33 is the
out-of-plane piezoelectric coefficient of the material, and 4 is the
phase contrast reflecting its ferroelectric polarity. The deflection of
the cantilever induced by the piezoelectric vibration of the specimen,
the so-called piezoresponse, is then measured by a photodetector.
Clearly, PFM offers nanoscale resolution limited only by the size of
the cantilever tip, and is an ideal tool for probing local piezoelectric
and ferroelectric properties of low-dimensional ferroelectric nano-
structures.411 In fact, no other technique is capable of probing
piezoelectricity and ferroelectricity directly at the nanoscale level.
The AC driving voltage of PFM is limited by the breakdown
strength Ebd of the specimen and its thickness t, V0 < Ebdt. For low-
a
Faculty of Materials, Optoelectronics and Physics, and Key Laboratory of
Low Dimensional Materials and Application Technology of Ministry of
Education, Xiangtan University, Xiangtan, Hunan, 411105, China
b
Department of Mechanical Engineering, University of Washington,
Seattle, WA, 98195-2600, USA. E-mail: jjli@uw.edu
c In this communication, we report a dual frequency resonance
Asylum Research, 6310 Hollister Ave., Santa Barbara, California, 93117,
USA
These authors contributed equally to the work.
408 | Nanoscale, 2012, 4, 408413
COMMUNICATION
dimensional ferroelectrics, the thickness is extremely small, typically
in the range of nanometres, and thus only a small AC driving voltage
can be applied to the specimen to avoid electric breakdown. In
addition, the piezoelectric coefficient is known to decrease with the
feature size of ferroelectric nanostructures, and is usually much
smaller than that of bulk materials.1215 As a result, the intrinsic
piezoresponse amplitude A d33V0 of low-dimensional ferroelectric
nanostructures is extremely small, often in the picometre region. This
raises a formidable task for detecting piezoresponse by photodiodes,
which have a lower bound on detectable cantilever deflection of
around 30 pm, limited by thermal noise and shot noise.16,17 Clearly, in
order to probe the piezoelectricity and ferroelectricity of low-
dimensional ferroelectric nanostructures or materials with extremely
small piezoelectric effect such as biopolymers,18 the piezoresponse of
the specimen has to be substantially magnified, and the PFM sensi-
tivity has to be dramatically enhanced.
The piezoresponse and PFM sensitivity can usually be enhanced
by driving the AC modulation voltage near the resonance of the
cantileverspecimen system,1921 and thus magnify the piezoresponse
amplitude A d33V0Q by orders of magnitude, where Q is the quality
factor of the system typically in the range of 10 to 100 s. This makes it
possible to probe ferroelectric nanostructures using PFM, but such
a resonance enhancement comes with a penalty that compromises
quantitative analysisthe quality factor Q is usually unknown,
varying from sample to sample and even varying from point to point
in the same sample. As a result, the piezoelectric coefficient d33 can no
longer be determined quantitatively for ferroelectric nanostructures,
even with careful calibration against standard references, since the
quality factors would be different. In fact, it even becomes ambiguous
to make a meaningful qualitative comparison of piezoresponses from
sample to sample. This makes it extremely difficult to probe, for
example, the size effects in ferroelectric nanostructures using PFM,
since reliable quantitative information can no longer be extracted.
For that matter, it has been noticed that the piezoelectric coefficient
d33 correlates with the spontaneous polarization through the elec-
trostrictive coefficient,22 one of the key parameters of interest to
ferroelectric nanostructures, and there are no other techniques to
probe the spontaneous polarization directly with nanoscale
resolution.
tracking (DFRT) technique that allows us to magnify the piezores-
ponse sensitivity by orders of magnitude while determining its quality
This journal is The Royal Society of Chemistry 2012

factor Q simultaneously, and thus enable high resolution quantitative
PFM for low-dimensional ferroelectric nanostructures with high
sensitivity. To understand the technique, let us examine how reso-
nance enhancement works first. The cantilever and sample can be
viewed as a damped harmonic oscillator driven by an applied electric
field Vac, as shown in Fig. 1(a). Due to the piezoelectricity of the
ferroelectric sample, a surface vibration uac is induced, which in turn
drives the vibration of the cantilever that is in contact with the sample
surface through the tip. The deflection of the cantilever z is governed
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by the following motion equation:23
u0
z z_ u20 z d33 V0 eiut4 ; (1)
Q
where u0 is the resonance frequency of the harmonic oscillator. The
steady state solution for the deflection is given by:
z Aei(ut+4+f),
with the piezoresponse amplitude A given by:
d33 V0
A q; (3)
1  u =u20 u=u0 Q2
2 2
and its phase shift f given by:
p h i solved analytically in general, they can be easily solved by numerical
f tan1 Qu=u0  u0 =u :
2
From eqn (3), it is clear that if a quasi-static voltage is applied, the tip
deflection is given by A d33V0, while if the AC modulation voltage
is driven at resonance frequency, the tip deflection is given by A
d33V0Q, magnified by a factor of Q compared to the quasi-static
response, as schematically shown in Fig. 1(b) and confirmed by our
fitting of experimental data using eqn (3) and (4). This is the principle
behind the resonance enhancement technique. Since Q is generally
unknown, and usually varies from sample to sample or point to
Fig. 1 Schematics of dual frequency resonance tracking (DFRT) tech-
nique: (a) tip-nanofiber harmonic oscillation system; (b) resonance
enhancement using single frequency; and (c) schematics of dual frequency
resonance tracking using actual experimental data of piezoresponses
versus AC driving frequency.
This journal is The Royal Society of Chemistry 2012
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point, such resonance enhancement is achieved at the expense of
quantitative information.20
To overcome this difficulty, let us examine the cantileversample
system in Fig. 1(a) in more detail. For such a damped harmonic
oscillator, we have four unknown parameters: resonance frequency
u0, quality factor Q, amplitude An and phase shift fn, both to be
determined at resonance frequency u0. Yet we only have two
measurements, the amplitude Ad and phase shift fd measured at
driving frequency ud, making it impossible to solve for the four
unknown parameters from eqn (3) and (4). However, if we measure
the amplitude A1,2 and phase shift f1,2 at two distinct frequencies u1,2
across resonance, as schematically shown in Fig. 1(c) using actual
experimental data, then four measurements will be obtained, making
it possible to solve for u0, Q, An, and fn simultaneously from the
measured A1,2 and f1,2 using eqn (3) and (4). This is the essence of our
proposed approach, which would enable the quantitative PFM
(2) together with dramatically enhanced sensitivity, a combination that
would be impossible to achieve under the conventional single
frequency resonance enhancement technique. As evident from Fig. 1
(c), eqn (3) and (4) fit the experimental data very well, especially for
the amplitude data, where the error between the fitted resonance peak
and highest response measured is less than 5%. This validates the
quantitative analysis with DFRT. While eqn (3) and (4) cannot be
(4) iterations.
The dual frequencies adopted here also allow us to overcome other
difficulties associated with resonance enhancement techniques,
particularly the cross-talk with topography and the loss of sensitivity
when contact stiffness varies while scanning over sample surfaces.
For the single frequency resonance enhancement technique, the
frequency is locked at the resonance in a particular location. As the
resonance shifts during scanning due to the change of contact stiff-
ness, such a lock-in will actually drive the oscillator away from the
resonance at the current location, resulting in loss of enhanced
sensitivity, as schematically shown in Fig. 1(b). This also leads to
cross-talk with topography, and severely compromises PFM resolu-
tion.20,21,24,25 The dual frequencies adopted, on the other hand, allow
us to track resonance when it varies over the sample surface and
minimize the cross-talk with topography, as schematically shown in
Fig. 1(c). Instead of locking in at a single frequency, we have two
frequencies u1,2 on both sides of the resonance, and use the difference
in the amplitudes, A1  A2, for the feedback control, which is
maintained to be zero in our implementation.21,26 When the resonance
shifts during scanning, the amplitude difference deviates from zero,
and the dual frequencies are adjusted through feedback control to
bring this difference back to zero. This allows us to track the reso-
nance frequency during PFM scanning and minimize cross-talk with
topography, while simultaneously enables high resolution quantita-
tive PFM with high sensitivity. Other approaches developed to track
resonance include frequency sweeps27 and band excitation28
techniques.
To demonstrate the concept, we applied the proposed quantitative
DFRT PFM to probe a single BiFeO3 nanofiber synthesized using
solgel based electrospinning.2931 BiFeO3 belongs to the so-called
multiferroic materials,32,33 and ferroelectricity is essential for its
magnetoelectric coupling. The fiber has a diameter around 200 nm,
and due to such a small size, PFM is the only method capable of
probing its piezoelectricity and ferroelectricity at the nanoscale level
directly. A 1 mm by 1 mm PFM scan was carried out using DFRT
Nanoscale, 2012, 4, 408413 | 409

under an AC modulation voltage of 1.76 V, from which mappings of
amplitude A1,2 and phase shift f1,2 are obtained under u1,2. These two
frequencies vary spatially due to the variation of contact stiffness of the
sample, and are adjusted to track the resonance via feedback control.
This allows us to solve for u0, Q, fn, and An at each point and map their
spatial distributions, as shown in Fig. 2, where the resonance frequency
u0 (a), quality factor Q (b), phase shift fn (c), and amplitude An/Q (d)
mappings are imposed on top of the three-dimensional nanofiber
topography. Indeed, it is observed in Fig. 2(a) that the resonance
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frequencies vary over the surface of the nanofiber, ranging between
227 kHz and 235 kHz. While this seems to be a rather small variation, it
can result in a reduction of sensitivity by one order of magnitude if
a conventional single frequency resonance enhancement technique is
used during scanning. For example, if we lock in at 235 kHz, while the
actual resonance at a particular point is 227 kHz, then the piezores-
ponse is approximately 15d33V according to eqn (3) for a typical
quality factor of 100 instead of 100d33V as expected at resonance. This
would not only result in loss of sensitivity, but also lead to false contrast
in piezoresponse mapping. In addition to the relative small variation in
resonance frequency, we also observe a large variation in quality factor
Q ranging between 60 and 90, as shown in Fig. 2(b). This underscores
the importance of accurate determination of quality factor for the
quantitative PFM characterization, without which even a qualitative
comparison of piezoresponse at different points of a sample would be
difficult to interpret. The PFM phase contrast is clearly observed in
Fig. 2(c) and corresponds to the amplitude mapping in Fig. 2(d) well,
indicating different polarity in different domains. No obvious cross-
talk with topography is observed, and it appears that the domains in
the nanofiber span multiple grains, indicating a strong intergranular
interaction. Most importantly, the intrinsic piezoresponse of the
nanofiber can be now determined by correcting the quality factor Q,
making it possible to map the spatial distribution of piezoelectric
coefficient d33 quantitatively, as shown in Fig. 2(d). It is observed that
Fig. 2 Mapping of (a) frequency, (b) quality factor, (c) phase shift, and (d) amplitude of a BiFeO3 nanofiber superimposed on its three-dimensional
topography, derived using the DFRT technique proposed.
410 | Nanoscale, 2012, 4, 408413
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the maximum piezoresponse amplitude, after the correction, is only
15.3 pm, and without the resonance enhancement, this would be
impossible to detect! The dual frequency resonance tracking (DFRT)
technique, on the other hand, makes it possible to not only detect such
small piezoresponse, but also quantitatively determine its intrinsic
piezoelectric coefficient, which is estimated to be 8.70 pm V1.
The value of this piezoelectric coefficient is much smaller than that
of bulk BiFeO3 for a couple of reasons. First of all, the grains in the
nanofiber are randomly oriented, and their spontaneous polarization
prefers to be aligned in-plane to minimize the depolarization energy,34
resulting in a much smaller out-of-plane piezoelectric response. In
addition, the local piezoelectric response of the nanofiber underneath
the conductive tip is severely constrained by its neighbors that are
subjected to a much weaker electric field, and thus is much smaller
than the piezoelectric response of a bulk material or thin film sub-
jected to a homogeneous electric field. Nevertheless, the small pie-
zoresponse of the BiFeO3 nanofiber raises important questionsis it
ferroelectric, and is it possible to switch its spontaneous polarization
using a conductive PFM tip? To answer these questions, we applied
a series of DC voltages up to 60 V in two complete cycles as shown in
Fig. 3(a) and (b) at two different spots marked by 1 and 2 on the
nanofiber, and probed the corresponding piezoresponse using a AC
voltage of 1.76 V before and after the application of cyclic electric
loading.35 Before the application of electric field, the two spots have
opposite phases, as seen in Fig. 3(c), indicating upward polarization
(purple) at 1 and downward polarization (yellow) at 2. Thus, one of
the spots should have its phase contrast reversed after the electric
loading, if the polarization is switched by the conductive tip. Inter-
estingly, the phase contrasts of these two spots remain unchanged
after the electric cycle, as seen in Fig. 3(d). This again suggests that the
nanoscale electromechanical response of the BiFeO3 nanofiber is
severely constrained by its neighboring area, making it rather difficult
to have either local piezoresponse or domain switching due to this
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Fig. 3 Polarization switching in BiFeO3 nanofibers: (a) the DC bias
voltage applied to the cantilever tip as a function of time; (b) the detailed
variation of the DC bias voltageat every step, the DC bias is reduced to
zero, and then increases to the next step; (c and d) the PFM phase image
of BiFeO3 nanofiber before (c) and after (d) the electric cycle.
constraint.36 The polarization reversal may still occur during the
application of electric field, yet the switched domain is simply
unstable after the removal of electric field, and reverses back to its
original configuration. Nevertheless, ferroelectricity of the nanofiber
is confirmed by domain switching in areas adjacent to these two
spots, as highlighted in the marked boxes before and after the electric
cycle. Note that polarizations in boxes 3, 5, and 7 are switched from
upward to downward, while areas in boxes 4 and 6 are switched from
downward to upward, suggesting that different domain stabilities
exist in different areas. These areas presumably have less constraint
and more favorable orientation for domain switching, and their
switching also indicates that the electric field is not confined to the
conductive tip. It is also interesting to note that box 3 is more than
200 nm away from spot 1, where the electric field was applied, indi-
cating rather long range interactions among grains and domains.
Domain switching is a dissipative process that increases dissipation
and decreases quality factor, which can also be investigated using
DFRT PFM. This is indeed confirmed by the mappings of quality
factor before and after application of electric field, as shown in Fig. 4.
The mapping of phase contrast change is shown in Fig. 4(a), with five
boxes highlighted, where the phase contrast change is close to 180 ,
a signature of domain switching; this is how we identify the five boxes
shown in Fig. 3. The corresponding mapping of quality factor before
Fig. 4 Correlation between mapping of phase contrast and quality factors: (a) change of phase contrast; (b) quality factor before the electric cycle; and
(c) quality factor after the electric cycle.
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and after domain switching is shown in Fig. 4(b) and (c). While there
is no clear correlation between mappings of phase contrast change
and absolute values of quality factor, the quality factor is clearly
reduced in areas where domains are switched, confirming increased
dissipation due to domain switching. In areas away from these
switched boxes, little change in the quality factor is observed.
The ferroelectricity of the nanofiber is also confirmed by the pie-
zoresponse phasevoltage hysteresis loop and amplitudevoltage
butterfly loop as shown in Fig. 5, obtained under a series of DC
voltages similar to those shown in Fig. 3(a) and (b). While the PFM
phase is reversed when the DC voltage is reversed as shown in Fig. 5
(a), indicating a possible polarization reversal of ferroelectricity, the
PFM amplitude appears to be linear with respect to the applied
voltage and does not saturate even at large DC voltages up to 60 V.
Such a linear relationship is usually caused by strong electrostatic
interactions between the conductive tip and sample, but we believe
this is not the case here. The PFM switching measurement is carried
out when the DC voltage is brought back to zero at each step, as
shown in Fig. 3(b), and thus the effect of electrostatic interactions is
minimized. Indeed, a zoom in on the amplitudevoltage loop shows
characteristics of butterfly loop, and a relatively large coercivity of
3.5 V is observed in the hysteresis and butterfly loops, clearly shown
in the zoomed hysteresis and butterfly loops near switching in Fig. 5
(c) and (d). This is a strong indication of ferroelectricity instead of
electrostatic interactions. The overall amplitudevoltage characteris-
tics appear to be linear, which we believe is due to the difficulty in
polarization switching in the nanofiber as observed in Fig. 3(c) and
(d). As such, the switching has to proceed in a gradual incremental
manner, instead of abrupt switching as in a bulk material. In nano-
crystalline rhombohedral ferroelectrics such as BiFeO3, such an
incremental switching is caused not only by the two-step polarization
reversal process involving 71 and 109 domain switching, but also by
gradual polarization reversal in individual grains within a single
domain that spans multiple grains. As a result, the piezoresponse
amplitude does not saturate even at large electric fields. Indeed, with
a large DC voltage of 60 V, a rather small piezoresponse is measured,
only in the range of 120 pm, far smaller than the saturated piezor-
esponse expected if the domain is fully switched.
In summary, a dual frequency resonance tracking (DFET) tech-
nique is adopted to enable high resolution quantitative piezoresponse
force microscopy of nanocrystalline BiFeO3 nanofibers with high
sensitivity. The BiFeO3 nanofiber has extremely small out-of-plane
piezoresponse, which would be rather difficult to probe by conven-
tional techniques. The dual frequency resonance tracking (DFET)
technique, on the other hand, allows us to map the fine ferroelectric
domains in the nanocrystalline BiFeO3 nanofiber in detail, determine
Nanoscale, 2012, 4, 408413 | 411
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Fig. 5 PFM phasevoltage hysteresis (a) and amplitudevoltage butterfly (b) loops of BiFeO3 nanofiber; (c) and (d) show the zoomed hysteresis and
butterfly loops near the coercive voltage.
its out-of-plane piezoelectric coefficients quantitatively, and corre-
lating the change of quality factor mappings with the dissipative
domain switching process. The proposed approach can be applied to
probe the piezoelectricity and ferroelectricity of a wide range of low-
dimensional nanostructures, as well as materials with extremely small
piezoelectric responses.
Acknowledgements
We acknowledge the support of US National Science Foundation
(DMR-1006194 and CMMI-1100339) and Natural Science Foun-
dation of China (Approval nos. 10972189, 10902095, and 11090331).
S. H. Xie also acknowledges the partial support of China Scholarship
Council, Q.N. Chen acknowledges the partial support of NASAs
Space Technology Research Fellowship, and Y. M. Liu acknowl-
edges the partial support of a UIF Fellowship from the Center for
Nanotechnology, University of Washington.
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