Electrospun metallic nanowires: Synthesis, characterization, and

applications
Abdullah Khalil, Boor Singh Lalia, Raed Hashaikeh, and Marwan Khraisheh
Citation: J. Appl. Phys. 114, 171301 (2013); doi: 10.1063/1.4822482
View online: http://dx.doi.org/10.1063/1.4822482
View Table of Contents: http://jap.aip.org/resource/1/JAPIAU/v114/i17
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JOURNAL OF APPLIED PHYSICS 114, 171301 (2013)

APPLIED PHYSICS REVIEWS

Electrospun metallic nanowires: Synthesis, characterization, and

applications
Abdullah Khalil, Boor Singh Lalia, Raed Hashaikeh,a) and Marwan Khraisheh
Materials Science and Engineering Program Masdar Institute of Science and Technology, Abu Dhabi,
United Arab Emirates

(Received 10 March 2013; accepted 26 June 2013; published online 1 November 2013)
Metals are known to have unique thermal, mechanical, electrical, and catalytic properties. On the
other hand, metallic nanowires are promising materials for variety of applications such as
transparent conductive film for photovoltaic devices, electrodes for batteries, as well as
nano-reinforcement for composite materials. Whereas varieties of methods have been explored
to synthesize metal nanowires with different characteristics, electrospinning has also been found
to be successful for that purpose. Even though electrospinning of polymeric nanofibers is
a well-established field, there are several challenges that need to be overcome to use the
electrospinning technique for the fabrication of metallic nanowires. These challenges are mainly
related to the multi-steps fabrication process and its relation to the structure evolution of the
nanowires. In addition to reviewing the literature, this article identifies promising avenues for
further research in this area with particular emphasis on the applications that nonwoven metal
C 2013 AIP Publishing LLC.
wires confined in a nano-scale can open. V
[http://dx.doi.org/10.1063/1.4822482]

TABLE OF CONTENTS

I. INTRODUCTION
A. Scope of the review

I. INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . .
A. Scope of the review . . . . . . . . . . . . . . . . . . . . . .
B. Article organization . . . . . . . . . . . . . . . . . . . . . .
II. ELECTROSPINNING OF METALLIC
NANOWIRES (MNWS) . . . . . . . . . . . . . . . . . . . . . .
III. CHALLENGES IN ELECTROSPINNING OF
MNWS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
A. Precursor optimization . . . . . . . . . . . . . . . . . .
B. Jet instabilities . . . . . . . . . . . . . . . . . . . . . . . . .
C. Length . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
D. Alignment . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
E. Reduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
F. Control of microstructure . . . . . . . . . . . . . . . .
IV. PROPERTIES AND APPLICATIONS . . . . . . . . .
A. Compositional and morphological analysis .
B. Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . .
C. Magnetic properties . . . . . . . . . . . . . . . . . . . . .
D. Optical properties. . . . . . . . . . . . . . . . . . . . . . .
E. Mechanical properties . . . . . . . . . . . . . . . . . . .
F. Sensing characteristics . . . . . . . . . . . . . . . . . . .
G. Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
V. OUTLOOK . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

a)

1
1
2
2
5
5
6
6
7
7
7
8
8
10
11
11
11
13
14
14

Author to whom correspondence should be addressed. Electronic mail:

rhashaikeh@masdar.ac.ae

0021-8979/2013/114(17)/171301/16/$30.00

Nanotechnology, the technology which has the highest

potential to shape the future of mankind,1 involves manipulating the matter at the nano (or even atomic) scale. Whereas
nanotechnology has promised to address almost all the scientific domains, the field of materials science and engineering
was found to be one among the most highly influenced by
this rapidly emerging technology. The term nanomaterials
evolved as a consequence of the marriage between nanotechnology and materials science. Among various classes of 1D
nanomaterials, the nanofiber is one where the fiber diameter is 100 nm or less. Different types of materials like polymers, ceramics, as well as metals have been successfully
synthesized in the form of nanofibers using different fabrication techniques. The term nanowire (NW) is commonly
used in case of metals. Due to their 1D-anisotropic structure,
size dependent properties and great potential to act as key
performers in future, microelectromechanical systems
(MEMS) and nanoelectromechanical systems (NEMS), metallic NWs have gained tremendous attention during last decade. However, very limited real time applications have been
proposed so far due to difficulties encountered in their
reliable characterization and integration with other materials
and systems. Moreover, the cost associated with the current
sophisticated methods for synthesizing metal NWs is a key
hurdle in their commercial use. These include electrochemical approaches,28 nanoimprint lithography,914 synthetic
chemical routes,1521 template assisted techniques,22,23

114, 171301-1

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Khalil et al.

chemical vapor deposition,24,25 and electric arc discharge26

methods. Other sophisticated and unconventional methods
for producing metallic NWs have also been proposed in
several studies. Adelung et al.2729 have demonstrated the
deposition of Rb NW networks on different semiconducting
substrates using the concept of 1D self-assembly of metal
atoms along the narrow strain zones created across the surface. Similarly, electron beam irradiation under ultra-high
vacuum conditions to produce extremely thin Au NWs (four
atomic rows thick) has also been demonstrated by Kondo
and Takayanagi.30
It can be seen that there are variety of routes which can
be followed for synthesizing metallic NWs keeping in mind
that each method has its own benefits and limitations. The
complexities and cost involved in these methods, however,
make them unsuitable from the view point of economy,
efficiency, and mass production. That is why the large scale
production of metal NWs for commercial usage has not been
made possible so far. Recently, electrospinning, which is a
low cost and scalable technique31 for producing nanofibers,
has been employed for synthesizing metallic NWs. This process is not only relatively low cost but also provides a better
control over various process parameters which directly affect
the physical and morphological properties of the nanofiber.
So far, we found nine experimental studies3240 which are
related to the synthesis of metallic NWs via electrospinning.
The reported results are very encouraging in terms of the
NW quality and properties. However, there are different
aspects which need to be addressed and several challenges
which need to be overcome in electrospinning of metal
NWs and this is the subject of current article. The scope of
this article is to address these issues comprehensively and
highlight various potential applications of these low cost
electrospun metallic NWs in near future.
B. Article organization

The article is composed of three major sections: In

Sec. II, we describe how the electrospinning process is
employed to obtain metal NWs; in Sec. III, we addresses
several issues and problems associated with fabrication of
electrospun metal NWs; and in Sec. IV, we discuss their
reported properties and possible future applications.

J. Appl. Phys. 114, 171301 (2013)

flow rate, electric potential, etc., which directly affect the

properties of the nanofiber. Figure 1 shows the schematics of
the electrospinning process. The process involves the application of strong electric field to generate electrically charged
jet from the solution through a tiny nozzle. When the electrical potential overcomes the surface tension of the solution
droplet coming out of the nozzle, the jet emerges from the
droplet end and continues to thin as it approaches the collector. The solvents evaporate from the jet to form fibers before
approaching the grounded collector. The collector can have
any suitable geometry. During electrospinning, the fibers
are subjected to a complex system of forces comprising tensile, gravitational, inertial, and aerodynamic components.
Moreover, depending upon the liquid precursor, the solution
viscosity effect could be significant. However, the primary
force responsible for electrospinning is the tensile force acting in the axial direction with respect to the fiber flow.43
This tensile component originates due to the induced charges
in the presence of strong electric field. In general, the solution droplet at the tip of the nozzle is conical in shape, and
the jet is ejected from the vertex of the cone once the applied
electric field crosses the critical value to overcome the surface tension of the solution. This conical region, with a half
angle of 49.3 , was later referred to as the Taylor Cone as
it was discovered by Taylor.44 The magnified view of the
Taylor cone is shown in Fig. 2. However, other stable droplet
shapes with different half angles determined by the equilibrium of electric and surface tension forces are also possible
for various Newtonian and viscoelastic fluids.45 If the viscosity of the solution is very high, it travels to the collector as a
single fiber jet. However, under most practical circumstances, the jet usually undergoes instabilities causing further
stretching and elongation of fiber resulting in much thinner
fibers. In general, for sufficiently low viscosity solutions,
the solution breaks up into droplets46,47 rather than fibers
and hence electrospinning becomes impossible. Due to the
viscoelastic nature of a polymer solution, the jet maintains
continuity and resists the droplet formation during electrospinning. It can be understood that there are several parameters which will strongly influence the structure and the
properties of the electrospun fibers. These include the
applied electric field (or voltage), nozzle-collector distance,

II. ELECTROSPINNING OF METALLIC NANOWIRES

(MNWs)

Electrospinning is a process of fabricating very thin

fibers through an electrically charged jet of a liquid precursor. The concept was demonstrated by Formhals41 to produce
extremely thin polymeric fibers via electrically charged
liquid. A similar approach was shown earlier by Morton42
for separating the volatile liquid from a solution under the
influence of an electric field resulting in the solidification
of the less volatile phase in the form of filaments. In electrospinning, the precursor is usually a solution of different
chemicals, in a mixture of solvent and non-solvent, depending upon the desired fiber material. This process is not only
relatively cost-effective but also provides a better control
over various process parameters, viz., solution viscosity,

FIG. 1. Schematics of electrospinning.

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Khalil et al.

FIG. 2. Image showing formation of Taylor cone. Reproduced by permission from Han et al., Polymer 49, 1651 (2008). Copyright 2008 by Elsevier
Ltd.

and the solution flow rate. In addition, the spinning environment and the solution properties could have significant
impact on the electrospun fibers formation, alignment, and
diameter. The electrospinning process has been successfully
employed to synthesize various polymeric, ceramic, and
metallic nanofibers.
One of the earliest successes in electrospinning polymer
fibers was reported by Baumgarten48 who was able to electrospun acrylic fibers having diameter in the sub-micron
range. Although the fiber diameter was in 500 to 1100 nm
range, which is too large to fall within the nanometer range.
Baumgarten concluded many important aspects which served
as a foundation for future researchers. One important experimental finding was the relationship between jet diameter and
applied field. It was also found that the proper spinning environment is necessary. The relative humidity should be less
than 60% so that the fibers can dry sufficiently before reaching the collector. Comprehensive studies were carried out
later by Larrondo and Manley.49,50 They electrospun polyethylene and polypropylene fibers and observed that the fiber
diameter decreases with increasing melt temperature and the
applied voltage. Fiber diameter observed to be decreased
with increasing melt temperature and the applied voltage.
Hayati et al.51 showed that optimum solution conductivity is
required for formation of smooth and continuous jets during
electrospinning. The high conductivity of solution results in
the formation of unstable jets resulting in nonuniform fibers.
On the other hand, the solution with lower conductivity,
such as those having paraffinic oil as solvent, forms relatively stable jets and consequently formed uniform fibers. A
major breakthrough in the electrospinning was achieved by
Doshi and Reneker52 who were able to produce electrospun
polyethylene oxide nanofibers with a smallest diameter of
50 nm. They found the nozzle-collector distance as a key
parameter affecting the jet diameter. Inverse relation was
observed between the nozzle-collector distance and the jet
diameter. Another important finding was that an optimum solution viscosity is required to form a stable jet. Porous fibers
can also be formed while electrospinning by controlling the
evaporation rate of the solvent which depends upon the flow
rate,53 polymers molecular weight, and the relative humidity

J. Appl. Phys. 114, 171301 (2013)

of the environment in which the electrospinning is carried

out.54 A number of reports have been published afterwards
revealing successful electrospinning of different polymeric
nanofibers. Interested readers may follow the Refs. 43 and
5557 where detailed reviews were carried out on the electrospinning of wide variety of polymeric nanofibers. The
potential applications of electrospun polymeric nanofibers
have been found to be in the areas of optical fiber technology,58 advanced textiles,46,59 membrane filtration technology,60,61 and various bio-medical applications such as drug
delivery62 and scaffolds for tissue engineering.63
Because of better flow ability, viscoelasticity, and
solubility in different chemicals, the polymers were the first
to be electrospun. However, the electrospinning technique
has been successfully employed to synthesize various
ceramic and metallic nanofibers. Larsen et al.64 have demonstrated successfully the electrospinning of titania, silica, and
alumina nanofibers using viscous inorganic sols. Others6567
have also demonstrated the synthesis of PZT and silica nanofibers using same approach. In order to improve the viscoelasticity required for electrospinning, a solution consisting
of a polymer as a host for carrying ceramic precursor has
been employed by Li and Xia.68 The polymeric phase is
selectively removed via calcination at high temperature in
air leaving behind the titania nanofibers. This method turned
out to be much better in terms of control of final fiber diameter which can be controlled from tens to hundreds of nanometers. The fiber diameter was found to increase with the
increasing polymer/ceramic concentration in the solution.
Direct relation was also observed between the final fiber
diameter and the solution flow rate, whereas the opposite
trend was observed for applied field. Nanofibers of several
ceramics have been synthesized following the same
approach.6974 Moreover, nanofibers of a non-oxide ceramic,
such as silicon carbide, have been synthesized using the
same technique.64 Several potential applications of ceramic
nanofibers have been proposed. These include structural
reinforcement, sensors/actuators, membranes, catalysis, and
electrodes in energy management devices.43 Interested readers may follow the Ref. 75 where the processing, characterization and applications of electrospun ceramic nanofibers
have been discussed comprehensively.
As mentioned previously, limited attempts have been
made to utilize this method for producing pristine metallic
NWs. The reason behind this may be the difficulty associated
with the formation of suitable precursor and obtaining reasonable microstructure of the NW. However, the primary
benefits offered by electrospinning are its simplicity, economic feasibility, and mass production capability,31,35 which
justifies an extensive research for obtaining high quality
metallic NWs through this process. In all the reported work
related to the electrospun metallic NWs, similar approach
has been followed which comprise of three steps: (1) A metal
salt is selected as precursor, e.g., copper nitrate, copper acetate, etc. The appropriate amount of salt is mixed with a suitable polymer such as polyvinyl acetate (PVA) in an aqueous
or other solvent. The purpose of polymer is to provide the
structural support to hold the metal ions during electrospinning and to provide a viscoelastic behavior to the solution

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Khalil et al.

which is mandatory for electrospinning. (2) The electrospun

composite fibers are then calcined at high temperature under
suitable inert environment to selectively remove the polymer
component. This results in the obvious decrease in fiber
diameter. (3) The calcined fibers are usually metallic oxide
and further reduction to metallic nanofibers is needed. The
reduction of metal oxide nanofibers was achieved using a
reducing agent such as hydrogen gas at 300  C. The overall
process is schematically illustrated in Figure 3.The third step
was found to be inapplicable in some cases because the calcination step turned out to be enough for oxygen removal.
This aspect will be discussed in detail in later sections. The
first successful attempt to synthesize metallic NW via electrospinning was made by Bognitzki et al.33 Copper NWs
with average diameter of 270 nm were fabricated using the
above mentioned procedure. Wu et al.34,36 synthesized Cu,
Fe, Ni, and Co NWs having diameters of 40 to 100 nm range.
Graeser et al.32 synthesized Fe and Co electrospun NWs of
100 to 200 nm fiber diameters. Barakat et al.35 also synthesized nearly 200 nm Ni NWs. Recently, Hansen et al.37 have
carried out a much comprehensive work on the fabrication of
Cu, Fe, Ni, and Co NWs having diameters 100 to 200 nm.
Kim et al.38,39 have obtained very thin Pt nanowires, 30 nm
diameter, via electrospinning. Barakat et al.35 also synthesized about 200 nm diameter Ni NWs. In another study, Kim
et al.40 obtained Pt nanowires in the diameter range of
100150 nm via electrospinning. Recently, Hansen et al.37
have carried out a much comprehensive work on the fabrication of Cu, Fe, Ni, and Co NWs having diameters 100 to
200 nm.
Table I summarizes the important aspects of the work
done so far related to electrospinning of metallic NWs. It can
be seen that the work done so far is encouraging in terms of
the results. However, there are plenty of aspects which need
to be addressed regarding the electrospinning, characterization, as well as the applications of electrospun metallic NWs.
As already mentioned, electrospinning has plenty of
controllable parameters which directly affect the properties
of the produced NWs. However, all the studies related to
electrospun metallic NWs, used a single set of parameters
(applied voltage, solution flow rate, collector distance, environment), i.e., the optimization of these parameters for
obtaining the metallic NWs with finest microstructure and

FIG. 3. Steps involved in obtaining metal NWs via electrospinning.

J. Appl. Phys. 114, 171301 (2013)

highly tuned properties is still an open question. The most

important parameter of interest is the final diameter of the
obtained metallic NW. Theoretical models have been formulated to correlate the final fiber diameter with the processing
parameters during electrospinning.76 The major factors influencing the final fiber diameter were found to be solution flow
rate, current carried by the solution, and the surface tension
of the solution being electrospun. Sigmund et al.31 have
modified this theory for the electrospinning of ceramic NWs
and the experimental findings were found to be in good
agreement with the modified model. Since the procedure for
electrospinning ceramic and metallic NWs is similar, the
modified model of Sigmund et al.31 is expected to be equally
applicable for metal NWs. It is however important to realize
that the complexities posed by the variety of competing
factors during electrospinning makes it nearly impossible to
develop a versatile model which can predict the final fiber
diameter for variety of precursors. For example, the fiber
diameter is supposed to decrease with increasing applied
voltage (or current) due to greater stretching of jet. However,
Deitzel et al.46 showed that high voltage causes an alteration
in the Taylor cone configuration and the produced nanofibers
are composed of high density of beads causing thicker and
nonuniform nanofiber geometry. The studies realized that
electrospinning is not a single stage process. It is rather a
combination of multiple stages involving formation of
Taylor cone, jet emission, and then the whipping region. In
case where the precursor is composed of different components or solutes having different electrical properties (for
example, the polymer molecules and salt ions), the localized
attraction/repulsion due to inhomogeneous charge distribution can cause localized instabilities which can further complicate the electrospinning process. All these aspects make it
very difficult to develop a single versatile model which can
be applicable irrespective of the solution properties. In case
of metallic NWs, the final wire diameter is the one which is
obtained after the removal of polymer as well reduction
of metal oxide NWs. Therefore, besides the processing
variables, the final diameter of a metallic NW is largely
influenced by the solution chemistry which defines the compositional properties of electrospun composite wires containing polymeric as well as metallic phase. This aspect is
evident from the literature3237 that in spite of using almost
similar electrospinning parameters, the final metal NW diameter was found to be very different in these studies. This is
most likely due to vast difference in the precursor chemistry
and composition. Hence, it is logical to carry out the systematic study which can give an indication that how the diameter
of electrospun metal NW is affected by solution composition. In a similar fashion, the morphology and crystalline
structure of electrospun metal NWs can be correlated to solution properties and processing variables. For example, highly
imperfect crystalline structure and surface of the NWs have
been reported to be the major reasons for their lower magnetization and conductivity.3335,37 Therefore, it is important to
develop the NWs with fine and highly oriented crystalline
structure to overcome these issues. This will be dependent
upon not only the electrospinning parameters but also
the precursor composition and the post heat treatment of

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Khalil et al.

J. Appl. Phys. 114, 171301 (2013)

TABLE I. Summary of the literature related to electrospinning of metallic NWs.

Solution composition

Reference
Graeser et al.32

Metal

Polymer
matrix

Solvent

Diameter of
NW (nm)

PVB

Bognitzki et al.33 Cu

Cobalt dinitrate, iron

trinitrate
Cu nitrate

PVB

Water-isopropyl
200
alcohol
Water and isopropanol 270

Wu et al.34

Fe, Co, Ni

Fe, Co, Ni nitrate

PVA

Water

4054

Kim et al.38,39

Pt

PVP

Water and ethanol

30

Barakat et al.35

Ni

PVA

Water

200

Wu et al.36

Cu

Hexachloroplatinic
acid hydrate
Nickel(II) acetate tetrahydrate
Cu acetate

PVA

Water

100

Kim et al.40

Pt

Hexachloroplatinic
acid hydrate
Cu, Ni, Fe, Co Cu, Ni, Fe, Co acetate

PVP

Water and ethanol

100150

PVA

Water-acetic acid

100200

Hansen et al.37

Fe, Co

Precursor salt

composite wires which is done for selective removal of polymer and oxygen.
III. CHALLENGES IN ELECTROSPINNING OF MNWS

Although electrospinning process is quite simple in terms

of its setup and theory, yet there are several challenges which
need to be overcome for obtaining smooth and continuous
metal NWs. These are discussed separately in Secs. III AIII F.
A. Precursor optimization

As mentioned previously, the precursor which is used

for producing electrospun metallic NWs primarily composed
of three components: A soluble metal salt, a solvent, and a
soluble polymer. The salt acts as a source of metal ions
which later integrate up to yield metal NW and the sole purpose of a polymer is to provide viscosity to the solution as
well as fiber-like connectivity of the electrospun salt. Hence
the interaction of salt and polymer inside the solution is not
chemical. However, depending upon the type of polymer and
salt used, there is a possibility of polymer hydrolysis by the
salt ions. For example, if PVA is used as a polymer and
copper acetate as salt, the PVA will get hydrolyzed due to
the action of acetate ions. To avoid this, acetic acid is usually
added in certain proportion to maximize the solution stability, as in case of copper acetate-PVA combination for producing copper NWs.37 This causes an increase in the acetate
ion concentration shifting the equilibrium in backward direction. Acetic acid has also been found very beneficial for
precursor stability in several other electrospinning attempts
for producing niobium oxide,77 titania,78 and barium titanate79 nanofibers.
The interaction of salt and polymer in the precursor can
depend upon the polymer-salt combination used. For

Comments
NWs showed higher coercivity with high
anisotropy
NWs showed high electrical conductivity, however, much lower than bulk Cu wires which was
attributed to irregular surface of NW
NWs showed lower magnetization but almost
double coercivity as compared with bulk wires
due to their anisotropic and single domain nature
Nanowires showed higher catalytic activity than
nanoparticles
NWs showed lower magnetization but higher
coercivity
NWs showed high photo-current and high flexibility due to very high aspect ratio
Nanowires showed higher catalytic activity than
nanoparticles
NWs showed high coercivity which was found to
decrease with increasing temperature and decreasing crystal size

example, in case of copper acetate-PVA combination, the

chelation of PVA chain is most likely to be caused by copper acetate via Cu atoms.80,81 The Cu atoms are held across
the adjacent PVA chains via oxygen atoms through dative
bond. This will also increase the cross-linking across the
PVA chains shown below.80
As the polymer is selectively removed, the Cu atoms
combine to yield pure Cu NWs. This chelating interaction is
the most probable type of interaction which could happen in
the precursor used for obtaining metallic NWs.
The type of salt selected for obtaining metal NW seems
to largely influence the final product as evident from literature. If metal nitrate is selected, the obtained product after
polymer burning is the metal oxide.33,34,36 However, if metal
acetate is used as a precursor salt, the likelihood of oxidation
reduces and the final product is pure metal NW without any
further need of reduction.35,37 Similarly, it is also interesting
to note that using PVA as a polymer also results in pure
metal NWs after polymer burning.35,37 Whereas the use of
other polymers such as polyvinyl butyral (PVB)32,33 and
PVA34,36 leads to the production of metal oxide NWs. This
gives an indication that selecting a proper polymer-salt combination and optimizing the precursor chemistry can have
significant effect on the product composition which is
obtained after the polymer removal step. Moreover, the role
of stabilizers, such as acetic acid, as described before, and
organic solvents such as Isopropanol,33 Isopropyl alcohol,32
and ethanol,79 which are added to improve the volatility of
liquid, can also be significant in this regard but all these
aspects can be clarified only after carrying out exhaustive
experimentation to develop a relationship between precursor
chemistry and the final product. The available literature does
not address these issues and therefore this is an important
direction for research.

171301-6

Khalil et al.

Whereas the type of chemicals used in the precursor

defines the chemical composition of final product; the relative proportion of chemicals governs the morphology of final
product. Using higher proportion of polymer will lead to
increased solution viscosity which will ultimately cause the
formation of much thinner fibers, whereas lower polymer
concentration will decrease the solution viscosity and more
beaded fibers will be produced46 leading to more defective
and discontinuous metal NWs. Although the viscosity is also
enhanced by the addition of salt, the contribution of polymer
is much more pronounced. Hansen et al.37 used very high
salt loading (far above the maximum solubility limit) and
very high metal salt to polymer mass ratio for the precursor.
They proposed that such approach could be advantageous for
obtaining much longer and continuous NWs. However, in
such case, since the significant proportion of salt particles is
suspended instead of dissolved, the inhomogeneity in solution will increase the instabilities and also the final microstructure of the metal NWs will become very defective due
to nonuniform distribution of metal atoms. This was evident
from the TEM micrographs shown by Hansen et al., where
the NW structure was extremely defective and the various
crystalline domains were poorly connected. Thus, an ideal
precursor would be one which is saturated with salt without
suspended particles and having such polymer concentration
which can impart good electrospinability to the precursor. It
is worth mentioning that polymer less electrospinning has
been demonstrated by Choi et al.82 for obtaining silica nanofibers. They showed that the viscosity of a sol-gel comprising
a salt and solvents only can be brought to an electrospunable
level through its aging. This approach eliminates the polymer burning step and is thus expected to improve the morphology of metal NWs. However, there would be another
chemical step needed to convert the sol-gel fibers into the
pure metal NWs. This polymer less electrospinning for
obtaining metal NWs could be an interesting direction of
research.

J. Appl. Phys. 114, 171301 (2013)

FIG. 4. Different types of jet instabilities during electrospinning. (a)

Bending or whipping. Reprinted with permission from Yarin et al., J. Appl.
Phys. 89, 3018 (2001). Copyright 2001 American Institute of Physics. (b)
Rayleigh. Raleigh instability image. Reproduced by permission from Y. J.
Kim, Ph.D. thesis, University of Washington, 2011. Copyright University of
Washington Libraries 20092013. (c) Axisymmetric. Reproduced by permission from C. P. Carroll and Y. L. Joo, J. Non-Newtonian Fluid Mech.
153, 130 (2008). Copyright 2008 by Elsevier BV.

instability increases with decreasing charge density of the

solution which causes the modulation in surface charge density of the jet. As a result, undesirable periodic beads are
formed along the fiber axis causing defects and discontinuities in fiber structure. The Rayleigh axisymmetric instability, governed by the surface tension of the liquid, is the most
general type of instability encountered by the falling stream
of fluids even in the absence of the electric field. This instability results in the splitting of liquid stream into tiny droplets and thus could play major role in bead formation. In
electrospinning, the surface tension of the fluid is usually
low enough to avoid this Rayleigh instability. However,
the electric field induced instability is strongly the function
of solution charge density. In case of metallic NWs, this
instability is expected to be less due to an increase in solution charge density. Since the precursor has significant proportion of the salt, the ions will increase the charge density
and hence less axisymmetric instability is expected to be
observed. This increased charge density is also expected to
cause greater whipping instability and hence more ultrafine
fibers are expected.

B. Jet instabilities

As the jet is ejected from the cone, it continues to thin

down as it moves towards the collector. However, as the jet
narrows down, the radial charge repulsion may become dominant due to the variation in the charge density.83 This results
in a chaotic motion of the jet about the jet axis resulting in
the instability which is usually referred to as bending or
whipping instability. Thanks to this instability as the major
fiber extension and reduction in the diameter occurs in this
instability region. The radial charge repulsion may also
cause the splitting of primary jet into much thinner jets (a
phenomenon called as splaying) resulting in the formation
of much thinner fibers.84 However, the other two types of
axisymmetric instabilities, i.e., the classical Rayleigh
instability and the electric field induced instability have
also been observed during the electrospinning process. These
three types of instabilities are shown in Fig. 4. Shin et al.85
have shown that the relative contribution of each of the three
instabilities depends upon the fluid properties and the operating parameters. The electric field induced axisymmetric

C. Length

Electrospinning is capable of producing extremely long

fibers having length of several kilometers. However, such
length scales have been reported in case of polymers only
due to high homogeneity of the precursor having only single
polymeric phase. In case of metallic NWs, such length
scales are not expected due to the presence of different
components in the precursor which will cause discontinuity
and instabilities during the electrospinning process.
Moreover, the polymer burning step is also expected to
cause some microstructural defects and length discontinuities in the metallic NWs. This aspect has not been explicitly highlighted in the available literature on electrospun
metallic NWs. However, the obtained lengths so far for the
reported metallic NWs were found to be ranging from 100
lm (Ref. 34) to couple of centimeters.36 The desired length
of the NW depends upon the target application, and means
to precisely control the NW length during electrospinning is
equally important.

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D. Alignment

Not only from the application aspect but also for convenient and reliable characterization, it is desirable to have the
electrospun NWs in a highly oriented form. Unfortunately,
because of the instabilities, the NWs are collected in random
orientations in the form of meshes and nonwoven mats. To
overcome this difficulty, several approaches have been used.
Some authors have proposed a collector in the form of rotating drum88 and rotating wheel.89 These methods somehow
turned out to be better for improving fiber alignment over the
larger length scale. However, the alignment was still not up
to the level so that these NWs could be studied and applied in
an isolated manner. A much efficient way was proposed by
Li et al.90 They used a split electrode with a gap of few millimeters to centimeters. Such configuration results in the collection of uniaxially aligned fibers, however, over a smaller
length scales (few mm to a cm). This makes the handling and
characterization of nanofibers very easy. Moreover, the
aligned arrays can be easily and accurately transferred to
various substrates for fabricating different devices such as
electrodes. Similarly, these aligned metallic NWs can be
sandwiched between two electron beams deposited metallic
nanolayers to form nano laminates. However, in case of metallic NWs, it is important to ensure that the lateral welding
of these aligned NWs does not occur during the polymer
burning and reduction steps. Fig. 5 shows the different collector geometries which have been discussed.

J. Appl. Phys. 114, 171301 (2013)

studies have shown that metallic phase NWs are obtained

directly after the polymer burning step.35,37 It is interesting
to note that these studies used the metal acetate salt, whereas
those required reduction as a necessary step used metal
nitrate salts. Wu et al.36 also used copper acetate salt but
they reported reduction as a necessary step for converting
copper oxide NWs to pure copper NWs. However, the reduction time and temperature was much lower than other
studies.
Although hydrogen is the most common and active gas
for the reduction of metal oxide nanostructures91 and thin
films,92 there are several other possibilities besides conventional reduction in hydrogen atmosphere which does not
only consumes more time and energy but also unsafe from
environmental perspective. Using suitable reducing agents,
such as hydrazine, the reduction of metal oxides can be
done much quickly and in a much cheaper way. It has been
shown that hydrazine acts as an effective reducing agent for
converting metal oxides to pure metals.93,94 Similarly, other
reducing agents such as alcohols, carboxylic acid, and aldehydes have been reported as effective reducing agents for
metal oxide films.95 In addition to these purely chemical
techniques, electrochemical methods96,97 have also been proposed to be very effective for converting metal oxides to
pure metals. We believe that these reduction techniques can
also be applied for reducing metallic oxide NWs. Since these
techniques are much faster and less energy consuming, they
can be more practical when it comes to commercial production of metallic NWs.

E. Reduction

The composite electrospun fibers comprising metallic

salt and polymeric phase, obtained after evaporation of volatile liquid, are heated under high temperature to selectively
remove the polymeric phase. Most of the studies33,34,36 have
shown that the metallic NWs end up in the form of their
oxide after the polymer burning step. As a result, these
oxides need to be reduced through a suitable way to be converted into metallic form. The method used so far involves
reducing the oxide NWs in a hydrogen atmosphere for suitable duration under elevated temperatures. However, some

F. Control of microstructure

The microstructure of electrospun metallic NWs has

been found quite defective as revealed from TEM images.
The defects and irregularities across the electrospun NWs
are produced primarily due to two reasons. First, as the jet
undergoes instability, the composite fiber is stretched in random directions due to simultaneous action of various force
components. This causes the inherent microscopic defects
inside the nanofiber and consequently in the final metallic
NW. Second, and more importantly, it is the selective

FIG. 5. Different types of collector geometries: (a) Rotating drum. Reproduced

by permission from Kenawy et al., J.
Controlled Release 81, 57 (2002).
Copyright 2002 by Elsevier BV. (b)
Rotating wheel. Reprinted with permission from J. Kameoka and H. G.
Craighead, Appl. Phys. Lett. 83, 371
(2003). Copyright 2003 American
Institute of Physics. (c) Split electrode.
Reproduced by permission from Nano
Lett. 3, 1167 (2003). Copyright 2003 by
American Chemical Society.

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removal of polymer which results in unevenness across the

NW, especially at the NW exterior. No matter how uniform
the solution is, there will always be a slight heterogeneity in
polymer-metal distribution at the microscopic level. Fig. 6
compares the morphology of solution processed and electrospun metallic NWs. Whereas, solution processed NWs are
very homogenous and uniform throughout their length, the
electrospun NWs are inhomogeneous, defective and nonuniform in diameter across their length. This nonuniform and
defective morphology is one of the current main drawbacks
of electrospun metallic NWs. By subjecting these metal
NWs to controlled annealing treatments, it is expected to get
improvement in microstructures and hence various physical
properties of metallic NWs.
As far as the diameter of Electrospun metal NW is concerned, there is significant amount of variance in the reported
literature. The minimum average diameter was reported as
40 to 50 nm by Wu et al.,34 whereas diameters as large as
270 nm were reported by Bognitzki et al.33 The value of 100
to 200 nm was observed by others.3537,98 The large variance
is obvious due to the different solution compositions and
electrospinning parameters used in these studies. It is interesting to note, this key benefit of electrospinning, that by
varying the solution properties and electrospinning
parameters, metal NWs of desired diameter can be obtained
which may be suitable for particular application. The diameters reported by Wu et al.,34 i.e., 40 to 50 nm are comparable
with those reported by the authors who used more sophisticated techniques such as soft solution processing18 and nanoimprint lithography.14 This shows that electrospinning has
equal potential for producing ultra-fine metallic NWs.

FIG. 6. Morphology of solution processed Ag [Reproduced by permission

from Sun et al., Nano Lett. 2, 165 (2002). Copyright 2002 by American
Chemical Society] and electrospun Fe. Reproduced by permission from Wu
et al., Chem. Mater. 19, 3506 (2007). Copyright 2007 by American
Chemical Society and Reproduced by permission from Hansen et al., Small
8, 1510 (2012). Copyright 2012 by Wiley-VCH Verlag GmbH & Co KGaA.
And metallic NWs as observed through TEM.

J. Appl. Phys. 114, 171301 (2013)

IV. PROPERTIES AND APPLICATIONS

A. Compositional and morphological analysis

The compositional and morphological characteristics of

electrospun metal NWs have been determined using the conventional approaches such as SEM, TEM, XRD, and energy
dispersive spectroscopy (EDS). However, it is important to
realize the limitations of some conventional techniques while
using them for evaluating nanostructures. For example, the
SEM can give rough estimate about the true diameter of the
NW due to limitation posed by maximum resolution, and
very little information can be obtained about the morphology
and crystalline structure even for very well prepared samples. The use of TEM is thus inevitable if one needs reliable
information about NW diameter and structure. Even the
images of TEM have to be carefully analyzed due to artifacts produced as the wire diameter approaches 10 nm or
below.99 Atomic Force Microscope (AFM) has also turned
out to be useful in estimating the NW diameter. The profile
generated by AFM tip while scanning the surface in contact
mode can give good indication about the average diameter
of NWs.36
The compositional analysis of electrospun metal NWs
has been carried out using XRD and EDS.35,36 The most
important aspect of interest is to determine whether the
obtained NWs after the polymer removal step are pure metal
or metal oxide. It can be understood that due to limitations
posed by resolution of these techniques, there could be significant level of uncertainty in the results. For example, if
one is using SEM based EDS for point analysis over the
length of NW, the results could be unreliable due to inaccuracy in pin-pointing the desired location and consequently
the error caused by substrate elements. This error can be
minimized by depositing a very dense mesh of NWs on the
substrate which can be easily done by simply increasing the
electrospinning duration. Then the area analysis rather than
point encompassing larger amount of NWs and operating at
lower accelerating voltage will maximize the probability that
the collected signals represent the NWs. Using lower accelerating voltage will limit the electron penetration to NWs,
and the substrate effects will be minimized.
Similarly, XRD will be more informative about phase
determination in NWs if the substrate used for collecting
NWs is amorphous in nature, e.g., glass, so that the XRD signals are not overlapped by the crystalline substrate. Taking
care of these aspects, both EDS and XRD35,36 were found to
be useful for compositional analysis of electrospun metal
NWs. A modified form of XRD which is called as grazing
incidence XRD (GIXRD) (also called glancing incidence
XRD) is a more practical choice if one wants to carry out
the phase analysis of NWs lying randomly over the substrate.
This technique, which was originally developed to analyze
very thin films deposited over a substrate,100 relies on the
principle of total external reflection.101 Since the refractive
index for most of the materials is less than 1 in case of
X-Rays, one can achieve the total external reflection by keeping the incident angle to a very low value. This limits the
X-ray penetration in the specimen to only fraction of nanometers rather than few microns and hence the contribution of

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substrate becomes negligible in the diffracted signals. Further

optimization of slit configuration before the detector allows
only the parallel beam of X-rays to reach the detector and
hence highly tuned signals can be obtained representing the
nanomaterial only lying over a substrate.102 Several studies
have shown the effectiveness and importance of GIXRD in
analyzing different NWs such as ZnO (Ref. 103) and Pd
(Ref. 104) lying over different substrates.
The distribution of metal ions (or salt molecules) across
the polymer molecules is an important aspect which does not
only affect the electrospinning process itself but also the final
morphology of the metal NW. In this regard, TEM could be
a good tool in analyzing the morphology of electrospun composite nanofibers comprising both the metallic and polymeric
phase. For example, Fig. 7(a) shows the TEM image of the
electrospun titania/PVP (poly-vinyl pyrrolidone) composite
nanofiber and Fig. 7(b) shows the TEM image of the same
nanofiber after calcination.105 It can be seen that no discrete
domains are visible in the composite nanofibers which reflect
the high degree of homogeneity in the salt/polymer distribution. As a consequence, the calcined nanofibers, which are
pure titania, have very fine morphology and very high uniformity in diameter throughout the length. Similarly, Fig. 8
shows the TEM micrograph of electrospun PEO (poly-ethylene oxide) nanofibers containing 28 wt. % magnetite nanoparticles.106 The dark regions in this image represent the
domains where the magnetite concentration is high and vice
versa. However, such TEM imaging of electrospun composite nanofibers has not been presented in any of the studies
related to metallic NWs. Hansen et al.37 showed the TEM
images of electrospun metal salt/PVA composite nanofibers
calcined at 400  C. As an example, the images for Cu and Fe
are shown in Figs. 9(a) and 9(b). The authors argued that
these fibers are pure metal NWs, however, their morphology
suggest that the unevenly distributed darker spots may be the
residues left after polymer burning because the temperature
required for complete degradation of PVA including all the
bi-products is around 500  C (Ref. 107), whereas the calcination temperature selected by Hansen et al. was only 400  C.
When the same composite fibers were calcined at 800  C, the
morphology of obtained NWs was found to be highly defective as depicted by TEM images shown in Figs. 9(c) and
9(d). This may be attributed to uneven polymer/metal distribution due to very high loading of salt content, as discussed
previously. One possible reason for the lack of TEM analysis
of composite nanofibers could be the irradiation sensitivity

FIG. 7. TEM images of electrospun PVP/titania nanofibers. (a) Before calcination and (b) after calcination. Reproduced by permission from D. Li and
Y. Xia, Nano Lett. 3, 555 (2003). Copyright 2003 by American Chemical
Society.

J. Appl. Phys. 114, 171301 (2013)

FIG. 8. TEM micrograph of electrospun PEO nanofibers containing 28 wt.

% magnetite nanoparticles. Reproduced by permission from Wang et al.,
Polymer 45, 5505 (2004). Copyright 2004 by Elsevier Ltd.

of polymers. The polymer at the nanoscale will quickly degrade upon exposure to high energy electron beam in
TEM.108 A much better technique, therefore, to analyze the
polymer/metal distribution could be AFM operating in
dynamic mode.109 The phase contrast images obtained in
amplitude modulation AFM can give comprehensive information about the different elements present in the medium at
the nanoscale without affecting the compositional or morphological features of the medium. An example of such
approach was given by Aviles et al.67 where they identified
different domains within an electrospun PZT microfiber
through phase contrast images using scanning probe microscope as shown in Fig. 10. Similarly, other composite electrospun fibers can also be characterized in terms of
compositional homogeneity following same approach. Since
the nanofiber might be too thin for informative phase contrast images, an alternative approach could be the dynamic
AFM analysis of the precursor prepared for electrospinning.
The precursor may be applied over a glass substrate and after
drying, the phase images of the precursor can be obtained

FIG. 9. TEM image of electrospun (a) Cu and (b) Fe NW after calcination at

400  C. (c) and (d) are the images of wires shown in (a) and (b), respectively, but after calcination at 800  C. Scale bar is 200 nm. Reproduced by
permission from Hansen et al., Small 8, 1510 (2012). Copyright 2012 by
Wiley-VCH Verlag GmbH & Co. KGaA

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FIG. 10. SPM phase contrast image of electrospun PZT microfibers.

Reproduced by permission from Santiago-Aviles et al., Appl. Phys. A:
Mater. Sci. Process. 78, 1043 (2004). Copyright 2004 by Springer-Verlag

via AFM giving information about compositional homogeneity which is vital for obtaining uniform and defect free electrospun metallic NWs. However, it is important to realize
that AFM is more of a surface characterization technique
and limited information can be obtained about the interior of
the structure. Therefore, AFM could be useful as long as the
different phases are uniformly distributed across the nanofiber. If the salt/metal ions are mostly concentrated towards
the center of the nanofiber and are enclosed in a polymeric
shell, little information can be obtained about
the distribution quality. In such case, TEM will be more
effective.
B. Conductivity

Metals are well known for their high electrical and thermal conductivity and the reason behind this behavior is well
understood. The electrical conductivity for metals is higher
because of high density of free electrons. As far as thermal
conductivity is concerned, it is a function of both free electron density and the contribution from lattice vibrations (also
called phonons). Since the metals have highly ordered
lattice structure, the contribution of phonons is also significant and as consequence, metals display very high thermal
conductivity. However, at the nanoscale, the metals were
found to exhibit lower thermal and electrical conductivity.
The lower electrical conductivity of NWs has been explained
in terms of quantum dissipations110 and electron scattering
from the wire boundary. These effects become more pronounced as the wire diameter approaches the mean free electron path of the bulk material. Also, the electron scattering
from the uneven wire boundaries, especially in case of electrospun metal NWs,33 has been proposed as another reason
for this behavior. It should be noted that the role of atomic
defects is negligible when we talk about the electrical conductivity of bulk metals. However, when the diameter of the
wire is in the nanoscale, few defects can play important role
in electron scattering as these defects could be significant
proportion of the total NW diameter.

J. Appl. Phys. 114, 171301 (2013)

Even with lower electrical conductivities, the future of

low cost MEMS and NEMS seems to be largely driven by
these metallic NWs. The expensive techniques, such as
lithography which are used to pattern the micron and nano
sized conducting paths, hinder the mass production and commercial usage of MEMS and NEMS. With much cheaper
techniques like electrospinning, it will be possible to produce
the metallic NWs in mass quantity and make their widespread usage in various MEMS and NEMS. However, there
are two main hindrances in using electrospun metallic NWs
in these miniaturized systems. The first aspect is the controlled deposition of the NWs which is very difficult in conventional electrospinning process. However, Sun et al.111
have demonstrated that it is possible to deposit the nanofibers
in a fairly controlled fashion using near-field electrospinning technique. This approach involves using very
small nozzle-collector distances (few millimeters) and application of very low applied voltages to minimize the inherent
instabilities in the electrospinning process. The second difficulty is the reliable measurement of their electrical properties before they can be applied. The isolation of single NW
from the electrospun nonwoven and then measuring its
conductivity is a very complicated process and requires
some custom designed setup. For instance, Bognitzki et al.33
utilized low-energy electron point source (LEEPS) microscope for measuring electrical conductivity of single Cu NW
as shown in Fig. 11. They measured the conductivity to be
8500 S/cm. However, in the other studies conducted by Wu
and Hansen et al., a conventional two probe37 and four
probe36 method was employed to measure the electrical
characteristics of electrospun Cu NW sheet and due to uncertainty in NW length, only the sheet resistance or conductivity
was reported which is a representative of combined effect
produced by various NWs in random directions with fused
junctions. At the same time, due to poor crystalline structure,
the reported values may not be the ideal ones for a NW. We
believe that a controlled and prolonged heat treatment of
electrospun metallic NWs can lead to their better crystalline
structure and hence enhanced conductivity.
Thermal conductivity of the NWs has also been found to
be less as compared to bulk materials due to similar reasons.
At nanoscale, the effects of mean free path and mean free
time available for phonons to transfer thermal energy
become significant as opposed to macroscopic scale where
these effects get averaged out and play negligible role. It has
been shown for silicon that despite fine crystalline structure,
the NWs have nearly half of the thermal conductivity as
compared to bulk silicon.112 The possible reasons proposed

FIG. 11. LEEPS setup for measuring electrical conductivity of a single NW.
(a) Schematic representation and (b) image taken during conductance measurement. Reproduced by permission from Bognitzki et al., Adv. Mater. 18,
2384 (2006). Copyright 2006 by John Wiley and Sons

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for this were the increased phonon scattering at the boundaries and modification in phonon spectrum at the nanoscale.
The thermal conductivity was, however, found to increase
with increased temperature. Zhou et al.113 have obtained
similar results for the thermal conductivity of indium arsenide NWs and they explained their results in the similar
context. Using molecular dynamic simulations, Kosevich
and Savin114 have demonstrated how the phonon scattering
becomes dominant in case of NWs with rough surfaces and
edges.
Although their efficiency is less, the metallic NWs have
tremendous potential to act as heat conductors in future
MEMS and NEMS. The lower thermal conductivity of
NWs does not affect their potential application as nano heat
transfer elements because of the huge surface area offered
by them which is another key property for efficient heat
transfer. There has been an increasing interest in developing
micro and nano heat exchangers for enhancing heat transfer
in miniaturized electronic devices.115 The size reduction
of heat exchangers offered by metallic NWs will overcome
the disadvantage of their lower heat transfer efficiency.
Moreover, further refinement in their microstructure and
reduction in surface defects can further improve their efficiency to the level where they can be applied in advanced
engineering systems with more reliability.
C. Magnetic properties

A very interesting property of electrospun metal NWs

has been found to be their extremely high coercivity as compared to their bulk counterparts. This is the key property
required for high density data storage and therefore these
NWs are expected to have important applications in mass
data storage devices,32,34,35,37 Fig. 12. The high coercivity of
NWs has been explained in terms of their ID-single domain
nature. Although there are several other challenges regarding
the integration of these randomly oriented NWs in data
storage devices, the low cost of electrospinning and progress
in micro/nanofabrication technologies can lead to their

FIG. 12. High coercivity of electrospun Ni NWs. Reproduced with permission from Barakat et al., J. Phys. Chem. C 113, 531 (2009). Copyright 2009
by American Chemical Society.

J. Appl. Phys. 114, 171301 (2013)

successful use in future mass data storage devices. The saturation magnetization was, however, found to be very low for
these electrospun metal NWs as compared to their bulk
counterparts which was attributed to the formation of magnetically dead oxide layer on the NW surface due to their
high surface area.35
D. Optical properties

Due to higher and consistent specular and diffusive

transmittance as well as very high aspect ratios, the metallic
NWs are expected to serve as transparent flexible electrodes
in solar cells and future electronic devices.16,36 Fig. 13
depicts the performance of Cu NW networks as compared
to conventional indium tin oxide (ITO) films. It can be seen
that the transmittance of NWs is not only higher but also
consistent with wavelength as compared to ITO films.
Higher aspect ratio of the electrospun metallic NWs is one of
the key characteristic which imparts them matchless flexibility which cannot be achieved even with extremely thin sputtered metallic coatings. Even if the length of the NW is only
1 cm, the diameter of the order of 100 nm results in the
aspect ratio of the orders of 100 000 which is extremely
high. This allows the NWs to easily release the built-up
strain during repeated stretching without any cracking. Thus,
another key benefit of electrospinning is obtaining very long
metal NWs as compared to other conventional techniques
which yield NWs which are only few micrometers long.
E. Mechanical properties

Another important aspect is the mechanical properties of

these electrospun metallic NWs which have not been
addressed in any of the published studies so far. Of course, it
is again due to the difficulties associated with the mechanical
characterization at the nanoscale. However, an intelligent
use of AFM can give us some idea about the nanoscale
mechanical integrity of the metallic NWs. In this way, we
will be able to analyze their potential as mechanical reinforcements. Although it is possible to cut the tensile specimens from the electrospun nonwovens, the tensile properties
will be the representative of the net effect produced by

FIG. 13. Higher and more consistent specular transmittance of Cu NWs as

compared to ITO films. Reproduced by permission from Wu et al., Nano
Lett. 10, 4242 (2010). Copyright 2010 by American Chemical Society

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J. Appl. Phys. 114, 171301 (2013)

various randomly oriented wires and very little information

can be obtained for the individual NW. Even if the nonwoven comprises highly aligned wires, the tensile tests will be
useful if the aligned nonwoven is to be used in certain application. Again, there will be a high uncertainty in the properties of single NW. Although it is almost impossible to carry
out the tensile test on a single NW, yet some nanoscale characterization devices such as AFM can be very effective for
mechanical characterization of individual NW.116 Bellan
et al.117 have demonstrated the use of AFM for measuring
the elastic modulus of poly-ethylene and silica nanofibers.
The testing configuration is similar to the 3-point bending
test in which a flat AFM tip is pressed against a NW suspending across rigid supports. The NW can be fixed from
two ends using FIB which will weld the NW end with the
support trench. This is schematically represented in Fig. 14.
Given the dimensions of NWs and the force-deflection
curves obtained from AFM, the elastic modulus can be estimated with a high degree of accuracy using the relationship
for 3-point bending test. The observed value of elastic modulus was found to be significantly higher than the bulk materials due to high degree of molecular orientation. Using a
similar 3 point bending configuration in AFM, Lee et al.118
have measured the elastic modulus of titania nanofibers.
However, the measured value was found to be significantly
lower than the bulk titania and this was attributed to high
degree of uncertainty in crystalline orientation and effects
of diffusional creep and shear deformations. Gu et al.119
have also reported extremely high elastic modulus for polyacrylonitrile (PAN) nanofibers as compared to bulk PAN.
They also used AFM for this purpose but in a different configuration. The one end of the fiber was directly attached to
the AFM tip and it was bent against a rigid support using the
other end of the fiber as an anchoring point. These studies
demonstrate that AFM can be a very useful tool for having a
good estimate for the elastic modulus of metallic NWs.
Breaking the NW in the 3-point bending configuration can
give us an estimate about its strength. The mechanical properties estimated in this way can give a good understanding
about the feasibility of these NWs in flexible applications
such as transparent flexible electrodes.

An alternative way of employing AFM for determining

mechanical properties of NWs is to directly press the NW
through AFM tip which is laterally lying on the substrate
in a horizontal position. This approach, demonstrated in
Fig. 15, has been followed by Ko et al.120 for estimating the
modulus of carbon nanotubes (CNTs) based composite nanofibers. This method was actually used by Kracke et al.121 for
determining the nanoelasticity of thin gold films. An important requirement for implementing this approach is that the
fiber diameter should be significantly larger than the tip contact radius. The deflection, Dz, for a given applied load can
be translated to the elastic modulus of the NW.
Recently, in-situ characterization techniques122127 have
turned out to be very useful for mechanical testing of NWs.
However, due to lack of standardization and several complexities, there is large variance in the reported values, and
the elastic properties for these NWs were found to be very
different from their bulk counterparts. Several metallic NWs
have been tested using in-situ electron microscopy methods.
Taking an example of Au NWs, it has been demonstrated
that the deformation mechanisms in the nanostructures are
very different from their bulk counterparts.128 Whereas the
dislocation emission and multiplication is the dominating
deformation mechanism in bulk materials, the partial dislocations emitted from the surface governs the deformation
mechanism in NWs. Similar observations have been made
elsewhere in case of Au NWs.124 In another example,
extremely high strength for individual Ni NWs was observed
through in-situ tensile testing.129 Similarly, Zhang et al.126
have carried out in-situ tensile testing of Co NWs inside
SEM, however, they observed very low modulus for these
NWs as compared to bulk Co. They attributed this behavior
to the stiffness of the soldering portions, specimen misalignment, microstructure of the NWs and the experimental measurement uncertainty. Size dependent tensile properties for
these NWs have also been an interesting topic. For example,
Asthana et al.127 have demonstrated the compressive testing
of titania nanofibers via AFM tip operating inside TEM.
They observed strong size dependence for modulus. Within

FIG. 14. Schematic illustration of 3-point bending test of NW via AFM tip.

FIG. 15. Lateral pressing of nanofiber lying on a rigid substrate.

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Khalil et al.

the diameter range of 40 nm to 110 nm, the modulus was

found to decrease with increasing diameter after which it
became stable. This interesting observation was explained in
terms of combined effects of surface relaxation and long
range interactions present in the ionic crystals, which led to
much stiffer surfaces than the bulk. They proposed that
for wires having larger diameter, the surface-to-volume
ratio decreases and hence the surface stiffness effect also
decreases. Fig. 16 shows some examples of in-situ mechanical testing inside electron microscopes.
It is important to realize that the characterization techniques for NWs, in fact, for all classes of nanomaterials, are at
the stage of development and researchers are evaluating different techniques to come up with a reliable testing methods.
Due to lack of standardization and high uncertainties, different and contrasting results are observed. Current trend shows
more inclination towards AFM as compared to in-situ
tensile/compression testing for mechanical characterization
of NWs. This is most probably due to the fact that most of
the AFM systems are capable of such experimentation,
whereas not all SEM and TEM systems are equipped with
specialized in-situ testing holders. Such holders are neither
economical nor standardized in terms of required sensitivity
and accuracy. It is worth mentioning that the in-situ tensile/
compressive testing of NWs could be more reliable and
practical because it treats the NW as a continuum. On the
contrary, the AFM measurements for mechanical properties
are localized in nature and do not provide good level of
confidence about the macroscopic response of NWs.
Nevertheless, AFM and in-situ electron microscopy manifest
themselves as strong and practical techniques when it comes
to the mechanical testing of these one-dimensional nanostructure. In future, we can expect some non-destructive
testing (NDT) techniques for mechanical testing of these
nanostructures. An interested reader may go through a comprehensive review article by Rohlig et al.130 where different
techniques for evaluating elastic properties of NWs have
been covered.
The electrospun metallic NWs have great potential to
act as mechanical reinforcements. This is mainly due to two
reasons. First, since the reinforcement effect is governed by
the aspect ratio, even very small length nanofibers of few
millimeters can be very effective due to extremely high
aspect ratio. Second, because of very high surface area, these

FIG. 16. In-situ mechanical testing of NWs inside SEM (left) [Reproduced
by permission from Zhang et al., Nanotechnology 20, 365706 (2009).
Copyright 2009 by IOP Publishing] and TEM (right) [Reproduced by permission from Asthana et al., Nanotechnology 22, 265712 (2011). Copyright
2011 by IOP Publishing.]

J. Appl. Phys. 114, 171301 (2013)

NWs will have very good adhesion with the matrix and the
strengthening will be at the molecular level due to the size
range of NWs. Because of better strengthening effect, lower
contents of the reinforcement are required as compared to
those when macroscopic fibers are used. Limited attempts
have been made to study the influence of polymeric nanofibers as reinforcements because of the difficulties associated
with nanofiber orientation and dispersion inside the matrix.
Bergshoef et al.131 have reported 35 times and 4 times
improvement in the stiffness and the strength, respectively,
for epoxy when reinforced with polyamide nanofibers.
Similarly, Kim et al.132 have shown around 35% improvement in the modulus of epoxy when reinforced with polybenzimidazole nanofiber mats. Based on these results,
metallic NWs are expected to have strong reinforcing effect
for different metallic and polymeric matrices. However, as
stated earlier defect free microstructure of the NWs is very
important to take their mechanical advantage.

F. Sensing characteristics

Metal NWs produced through electrochemical growth

have shown promising sensing characteristics, especially the
sensing of various gases. The higher sensitivity of NWs is
due to their very high surface energy which allows them
to reversibly react with different gases in the surrounding
environment. For example, sub-micron Pd NWs have shown
excellent hydrogen sensing properties due to reversible
hydride formation,2 Fig. 17. Similarly, the electrochemically
deposited Pd NWs133 have also shown excellent hydrogen
sensitivity as depicted in Fig. 18. The temporary change
from pure metal to metal hydride due to hydrogen exposure
causes the change in electrical properties and consequently
the change in current flowing characteristics with time which
can be measured and amplified to produce a detectable signal. To improve the reliability and functionality of these sensors, the arrays of NWs can also be employed as sensors as
shown elsewhere.134 At the same time, this higher reactivity
could turn out be disadvantageous because of oxidation of
these NWs. However, Wu et al.36 have shown that the oxidation tendency of Cu NWs is not too high and it becomes of a

FIG. 17. Hydrogen sensing characteristics of sub-micron Pd wire.

Reproduced by permission from Yun et al., Nano Lett. 4, 419 (2004).
Copyright 2004 by American Chemical Society

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J. Appl. Phys. 114, 171301 (2013)

G. Catalysts

FIG. 18. Hydrogen sensing characteristics of a Pd NW. Reproduced by

permission from Walter et al., Microelectron. Eng. 6162, 555 (2002).
Copyright 2002 by Elsevier BV.

lesser concern if the NWs are to be used in the applications

where they are embedded underneath the other material. In
addition to gas sensors, the Mo NWs containing the beads of
other metallic nanoparticles, such as gold, have also been
proposed as very effective bio-sensors.135 Depending upon
the surface chemistry of nanoparticle, the specific nano/bio
species present in the environment may interact with it causing an overall change in the current carrying capacity of the
NW. This concept is depicted in Fig. 19. The high surface
energy and hence chemical reactivity/affinity is therefore
one of the key characters of metal NW which makes them
strong candidate for future sensors and related micro/nano
devices. Moreover, the variety of electrospun metal NWs
with different diameters and morphology will further lead to
cost reduction and mass production of such sensors.
Following the same approach for obtaining aligned electrospun metal NWs across two electrodes,90 the arrays of NW
acting as sensors can be obtained. The challenge however
remains that how these electrospun NWs can be integrated
with other micro/nano devices so that low cost and reliable
sensors may be developed.

FIG. 19. Schematic diagram of a beaded NW-based sensor. Depending on

the chosen metal and/or the presence of recognition elements, the interaction
of a specific molecule with the surface of the particle induces a conductivity
change. Reproduced by permission from Walter et al., Surf. Interface Anal.
34, 409 (2002). Copyright 2002 by John Wiley & Sons Ltd.

Due to very high surface area, electrospun metal NWs

act as strong and active catalytic elements as shown in some
studies. Kim et al.38,39 have shown that electrospun Pt NWs
have much higher catalytic performance as compared to the
nanoparticles, as shown in Fig. 20. They explained this
behavior in terms of better electron transport in NWs due to
less collision across interfaces. Such NWs could thus serve
as efficient electrode materials for low temperature fuel cells.
Kim et al.40 have also shown that the rough surface and the
defective structure of electrospun Pt NWs can be advantageous for better catalysis. The rough surfaces in these NWs
serve as active sites for effective electron transport and hence
enhance the catalytic activity. Based on these observations,
metal NWs seem to have important future applications as
electrodes in low cost fuel cells as well as in several chemical and electrochemical catalytic applications.
V. OUTLOOK

Despite several challenges, electrospinning manifests

itself as the most economical method for mass production of
metallic NWs. Moreover, providing excellent control over
final NW structure and properties is one of the key benefits
of this process over other methods. However, there is a
strong need to develop three clear connections in this regard.
First, the connection between the precursor properties and
the structure of NWs. Second, the connection between
the electrospinning parameters and the structure of NWs.
Finally, the connection between the structure and the different properties of the NWs. Once these connections are well
developed and understood, the process can be commercialized for mass production of metallic NWs for desired applications. At the same time, focus is needed to optimize the
electrospinning process for obtaining highest quality NWs
and to carefully understand their nanoscale response from
various perspectives. Also, the means to integrate the electrospun metallic NWs with other materials and devices need

FIG. 20. Maximum power density for a given current in case of Pt NWs and
the Pt nanoparticles Reproduced by permission from Kim et al., Electrochem.
Commun. 11, 446 (2009). Copyright 2009 by Elsevier, Inc.

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Khalil et al.

to be explored. This will pave the way towards the successful

and large scale usage of these electrospun metallic NWs in
future engineering applications. Advancements and innovations in electrospun metal NWs can be foreseen at this stage.
For example, by using a combination of different metallic
salts, bimetallic or alloyed NWs can be produced. An example of this approach has been demonstrated by Kim et al.136
for obtaining electrospun PtRh and PtRu NWs. In future,
we can expect electrospun metallic core shell NWs (nanopipes) and porous metallic NWs (nanofoams) via similar
approaches which have already been used for producing
core shell and porous polymeric nanofibers. Such metallic
NWs with customized morphology will open new doors of
research in the area of nanomaterials.
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