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NANO

LETTERS

Microstructure-Hardened Silver
Nanowires

2006
Vol. 6, No. 3
468-472

Bin Wu, Andreas Heidelberg, and John J. Boland*


School of Chemistry and the Centre for Research on AdaptiVe Nanostructures and
NanodeVices (CRANN), Trinity College Dublin, Dublin 2, Ireland

John E. Sader
Department of Mathematics and Statistics, The UniVersity of Melbourne, Australia

XiaoMing Sun and YaDong Li


Chemistry Department, Tsinghua UniVersity, Beijing, 100871, P R China
Received December 8, 2005; Revised Manuscript Received January 20, 2006

ABSTRACT
To exploit the novel size-dependent mechanical properties of nanowires, it is necessary for one to develop strategies to control the strength
and toughness of these materials. Here, we report on the mechanical properties of silver nanowires with a unique fivefold twin structure using
a lateral force atomic force microscopy (AFM) method in which wires are held in a double-clamped beam configuration. Force-displacement
curves exhibit super elastic behavior followed by unexpected brittle failure without significant plastic deformation. Thermal annealing resulted
in a gradual transition to weaker, more ductile materials associated with the elimination of the twinned boundary structure. These results
point to the critical roles of microstructure and confinement in engineering the mechanical properties of nanoscale materials.

Metal nanowires have stimulated great interest as potential


building blocks in nanoelectronic and nanoelectromechanical
devices because of their high conductivities and high
strengths. Although a variety of metal nanowires such as
gold, copper, and silver have been synthesized successfully
via wet chemistry or template-directed approaches, much less
is known about the chemical or physical properties of freestanding nanomaterials at a single-object level. One of the
main issues involved in the assembly of functional structures
using these nano building blocks, however, is the relationship
between material properties and structural elements such as
size, geometry, and microstructure. Many earlier studies have
focused on size-dependent properties.1-7 For example,
micrometer-sized whiskers and nanowires have ultrahigh
strength compared with that of their bulk counterparts.1-3
The exceptional strength is believed to originate from a
decreased defect density resulting from reduced wire size.
However, it is well established that microstructures such as
crystallinity, defects, and grain boundaries play important
roles in bulk material properties. Metals in bulk form can
be engineered to have high strengths by cold-work hardening,
grain-boundary hardening, and precipitation hardening, techniques that rely on restricting and hindering dislocation
motion.8 However, on the nanometer scale strengthening
methods that rely on the incorporation of impurities may be
* To whom correspondence should be addressed. E-mail: jboland@tcd.ie.
10.1021/nl052427f CCC: $33.50
Published on Web 02/21/2006

2006 American Chemical Society

ineffective because of facile surface segregation and expulsion. This leaves microstructure as the best candidate route
for controlling material strength. To date, single crystalline,
polycrystalline, and twin structured nanowires9-12 have been
synthesized, but the correlation between the microstructures
and mechanical properties is poorly understood, principally
because of the difficulties in performing standard tensile or
bending tests on individual wires.
Here in this work we demonstrate that microstructure
control is a particularly effective means for controlling
mechanical properties in nanowire systems. Using a fivefold
twinned Ag nanowire system, we show that the precisely
controlled grain orientation and grain-boundary organization
within these wires is responsible for their anomalous strength
and brittle failure. The principle slip directions in these grains
intersect with the twinning boundaries that extend along the
entire wire length to produce a uniformly hardened structure.
These results demonstrate that, in the case of free-standing
nanoscale materials, grain-boundary hardening is extraordinarily effective because of the ability to completely control
the orientation and boundaries of the limited numbers of
grains in these materials.
Nanowire mechanical properties were measured using a
AFM lateral bending technique developed recently,2 which
in contrast to earlier methods,3,13-23 allows the full spectrum
of mechanical properties to be measured, ranging from
elasticity to plasticity and failure. Figure 1a shows a low-

Figure 1. (a) TEM image of pentagonal silver nanowires. (b)


Cross-sectional high-resolution TEM image of pentagonal silver
nanowires. (c) Schematic of slip systems for faced-centered cubic
fivefold twinned Ag nanowires, showing that one of the slip planes
(111) together with three possible slip directions 110 inevitably
intersect the grain boundaries. Shaded planes indicate fivefold
twinned boundaries.

magnification transmission electron microscopy (TEM) image of pentagonal silver nanowires prepared at a lower
temperature (140 C). Details of the preparation of these
pentagonal silver nanowires can be found elsewhere.9 These
wires have typical lengths of many micrometers and diameters ranging from 16 to 35 nm. The cross-sectional TEM
image in Figure 1b shows the remarkable fivefold twinned
grain-boundary structure that exists along the entire wire
length. Note that there is a 2 nm thick carbon coating on
the surface as determined from high-resolution TEM observation9 (data is not shown here).
To perform three-point bending tests on 16-35 nm
diameter pentagonal silver nanowires, we fabricated welldefined trench patterns on a substrate that was coated with
a 10-20 nm TiN film. Typically, trenches having widths of
650 nm and depths of 475 nm were used in these experiments. This selection provides a reasonable ratio between
the pinned nanowire length and its diameter while eliminating
problems associated with wire droop. The pentagonal silver
nanowires were dispersed in ethanol and then deposited on
the prepatterned substrates after solvent evaporation. Silver
nanowires found to bridge well-defined trenches were located
by scanning electron microscopy (SEM) in a dual-beam
(electron/focused ion beam) system and subsequently doubleclamped at the trench edges by electron-beam-induced
deposition of Pt lines. Details of the experimental conditions
and the pinning procedure can be found elsewhere.2 A wellcalibrated rectangular cantilever (Budgetsensors) with an
average normal force constant of 1-3 N/m (75 kHz) was
used in the bending experiments. AFM lateral manipulations
were carried out using a Digital Instruments Nanoman
System with closed-loop x-y-z scanner. By positioning the
Nano Lett., Vol. 6, No. 3, 2006

AFM tip 450 nm into the trench, that is, 20-30 nm above
the trench floor, frictional forces between the trench floor
and tip were eliminated completely. Lateral bending measurements were then performed either as a single-shot
experiment (in which the tip engaged the wire, elastically
and then plastically deformed it, and finally broke the wire
in a single manipulation) or in a series of loading-unloading
cycles (in which the wire was increasingly loaded and
unloaded in a series of manipulations so that progressive
elastic and then plastic deformation occurred, followed by
wire failure). The normal and lateral force signals were
recorded using a Labview-based program. However, here we
focus on the lateral force because in this geometry the normal
force on the cantilever is less than 5% of the total force.2
Tip velocities were 20 nm/s throughout and all details relating
to the manipulation and tip calibration procedures can be
found elsewhere.2
Figure 2 shows a typical set of experimental data including
AFM images before bending and after failure (Figure 2a and
b) together with the F-d curves recorded during a series of
loading and unloading cycles (Figure 2c). The two curves
labeled 1 and 2 in Figure 2c (which are displaced relative to
each other for viewing purposes) are essentially nonlinear
but symmetric about the vertical dashed lines that identify
the starting point for unloading, that is, the cantilevers
turning point. This symmetry reflects the full elastic recovery
of the wire and is evident also from AFM images (not shown,
but identical to Figure 2a) recorded both before and
afterward, which reveal no permanent deformation of the
wire. However, after reloading again the wire was subject
to a large manipulation that resulted in F-d curve 3 in Figure
2c. In this curve, a sharp force-drop was observed and is
associated with wire failure, which is confirmed immediately
by the subsequent AFM image (Figure 2b). The F-d curves
are nonlinear and reproducible; both curves 1 and 2 can be
shifted to completely overlap curve 3 in Figure 2. These F-d
curves were analyzed in terms of a generalized model that
includes contributions from wire bending and tensile stretching.24 This approach has the advantage that it provides an
accurate description of the mechanical properties over the
entire range of elastic deformation. The exact analytical
solution is expressed as24
192EI
f(R)zcenter
L3
R
where f(R) )
xR
192 tanh
4
48 xR
Fcenter )

(1)

( )

R is related to  by (the detailed description of this approach


can be found elsewhere24)
 ) z2center
R)

(AI)

6(140 + )
350 + 3

(2)
(3)
469

Figure 3. Plot of Youngs modulus versus the nanowire radius in


the range of 10-15 nm for pentagonal silver nanowires. The
Youngs modulus remains essentially the same before (circle) and
after (star) thermal annealing experiments. The dashed line shows
the average value of the Youngs modulus for bulk silver.

Figure 2. (a and b) Tapping-mode AFM images of a 23.6 nm


diameter pentagonal silver nanowire before bending and after brittle
failure. All scale bars are 250 nm. (c) F-d curves recorded during
the consecutive manipulation by AFM tip-induced lateral bending
of a 23.6 nm pentagonal silver nanowire. Curves 1 and 2 show
that the wire was elastically loaded and unloaded. The unloading
points are identified as vertical dashed lines. Curve 3 is a singleshot experiment and shows nonlinear elastic behavior of silver
nanowire, followed by limited plastic deformation and then brittle
failure. Note that F-d curves are shifted for clarity. Inset: schematic
of bending test showing that the bending angle defined as the angle
between the deformed wire and its original direction. (d) Fit of
F-d curve 3 to the generalized formula, which yields a Youngs
modulus of 90 GPa.

where Fcenter is the measured lateral force, E is Youngs


modulus, I is the moment of inertia, and zcenter is the
displacement of the wire of suspended length L and crosssectional area A. Because the wires have a circular cross
section as seen from the TEM image in Figure 1b, the
moment of inertia is I ) r4/4. AFM was used to determine
the diameter and the suspended length of pinned wires. The
diameter was measured at several points along the wires
length and average values based on a typical scatter of (1
nm were used for fitting the curves. A complete analysis
470

also requires a detailed calibration of the AFM tip dimensions


and a determination of cantilever lateral spring constant, the
procedures for which are described elsewhere.2
The F-d curves in Figure 2 were fitted using eqs 1-3 to
determine the mechanical properties of the nanowire: Youngs
modulus, elastic deformation, yield point, and failure. The
data analysis was performed using a MATHEMATICA 5.2based algorithm that inputted all measured parameters (wire
diameter, the suspended length of wires, lateral force constant
of the cantilever, etc.) and in which the Youngs modulus,
E, was the only adjustable parameter. Analysis involved
initially fitting data at small displacement and then extending
the range to include increasingly larger displacements. The
value of the modulus obtained by this method remained
constant until the yield point associated with the onset of
plastic deformation was reached and after which the apparent
value of the modulus dropped and the fit became increasingly
poorer. This approach is possible only because the generalized formula provides a complete description of the elastic
properties over the entire range of displacements. Curve 3
in Figure 2c is replotted in Figure 2d together with the
corresponding fit to the generalized theory. The excellent
fit demonstrates that these pentagonal silver nanowires
exhibit very good elasticity up to displacements of 80 nm;
that is, these wires can be bent elastically up to an angle of
13.2 from the wire original direction (see the inset in
Figure 2c). The axial strain induced by bending is related to
the bending angle by  ) (1/cos ) - 1. After the yield
point, Figure 2d indicates that the wire undergoes only 30
nm of plastic deformation prior to failure. Significantly, we
measure 30 nm permanent displacement of wire in the postfailure AFM image Figure 2b, which underscores the validity
of this analysis in the determination of both the modulus
and yield point.
We have measured the mechanical properties of 24 single
wires, and Figure 3 shows values of the Youngs modulus
determined for a range of pentagonal silver nanowires with
diameters from 22 to 35 nm. The data scatter falls within
that typically found using this technique, and details of the
Nano Lett., Vol. 6, No. 3, 2006

error propagation can be found elsewhere.2 The average value


of the modulus is 102 ( 23 GPa and is higher than that of
bulk silver (83 GPa). Oxygen plasma experiments that
removed the 2 nm carbon coating indicated that the coating
is not responsible for the high modulus values of the
pentagonal silver nanowires (see the Supporting Information).
At present, the physical origin of the increased Youngs
modulus is unknown, but similar observations have been
reported for other nanoscale systems.5-7
The observation in Figure 2d that the extent of plastic
deformation at failure is less than 40% of the elastic
deformation is exceptional for a pure metal. In the case of
gold nanowires, the total plastic deformation during bending
is up to 450% of the elastic deformation, an order of
magnitude greater than that observed for the present silver
wires.2 For bulk metals, strengthening typically involves the
incorporation of impurities or the modification of the
microstructure. Although the former method is effective for
engineering bulk materials, it has limited application on the
nanoscale because impurities can be expelled easily from
the material. The effectiveness of the microstructure modification, however, is limited by physical size in bulk
specimens because there will always be grains with favorable
orientations for plastic deformation. In contrast, the finite
physical dimensions and limited numbers of highly orientated
nanoscale grains within the present Ag nanowires make them
particularly amenable to strengthening by microstructure
modification. We hypothesize here that the novel fivefold
twin microstructure of the nanowires is responsible for the
unique mechanical properties seen in Figure 2. Wire growth
occurs along the <011> direction of the face-centered cubic
(FCC) crystal structure, which is characterized by a slip
system of four (111) slip planes, along the three <1-10>
directions (see Figure 1c). Consequently, the fivefold grain
boundaries in these wires necessarily intersect with all of
the possible slip systems and so the motion of dislocations
associated with the initiation of plastic deformation along
any slip direction is restricted by the twinning boundaries
that extend into the center of the wire. In this manner, the
fivefold twinned silver nanowires are effectively grainboundary hardened materials, which sacrifices ductility for
strength. Because the twin boundaries exist along the entire
length of wire, the whole wire is uniformly hardened and
there are no defects that limit the strength of the wire.
To test this hypothesis, we carried out nanowire annealing
experiments at 240-250 C in nitrogen gas and then let them
cool slowly to room temperature before removing and
mechanically testing the samples. These annealing conditions
are sufficient to induce recrystallization even for bulk silver.
As a result, atoms at the grain boundaries diffuse rapidly to
reduce the interfacial energy, resulting in the gradual
elimination of the unique pentagonal grain-boundary structure. Figure 4 shows single-shot mechanical measurements
for pentagonal silver nanowires that were annealed for 17
and 48 h, respectively. These data, which are representative
of a study involving 15 nanowires, illustrate several important
points, which are summarized in Table 1. First, the Youngs
modulus remains essentially unchanged before and after
Nano Lett., Vol. 6, No. 3, 2006

Figure 4. (a) A typical single-shot F-d curve fit for a 23.2 nm


diameter pentagonal silver nanowire following 17 h thermal
annealing treatment in N2. The red curve is the best fit of the elastic
region of F-d data showing three regimes: the elastic bending,
grain-boundary hardened plastic bending and failure. The point
where the red curve departs from the data is identified as the yield
point. The curve fit gives a modulus of 121 GPa. (b) A typical
single-shot F-d curve fit for a 17 nm diameter silver nanowire
after 48 h thermal annealing. The modulus is 99 GPa in this case.
(c) AFM images of a 16.5 nm diameter silver nanowire after 48 h
thermal annealing in N2 during consecutive lateral bending tests.
All scale bars are 250 nm.

annealing (see Figure 3). This can also be clearly seen from
the solid curves in Figure 4a and b, which represents a best
fit to the generalized formula over the elastic region of the
data (see above). Second, the F-d curve fit for the 17 h
annealed sample in Figure 4a shows that the wire is
471

Table 1. Summary of the Bending Angles in Different


Samples

original Ag
nanowire
17 h annealed
Ag nanowire
48 h annealed
Ag nanowire
200-nm Au
nanowirea

maximum
elastic
bending
angles

bending
angle at
failure

ratio between
plastic and
elastic
displacements

13.2

17.9

35%

8.2

21.9

169%

6.9

27.1

304%

6.8

34.0

432%

a Typical bending angles for a 200-nm Au nanowire were shown for


comparison.2

elastically deformed up to a displacement of 50 nm, which


corresponds to a maximum elastic bending angle of 8.2,
followed by 90 nm of plastic deformation. The extended 48
h anneal resulted in an elastic displacement of 40 nm, a
reduced elastic bending angle of 6.9, and 130 nm of plastic
deformation (Figure 4b). When compared with the mechanical properties of original unannealed wire, the annealed wires
have much reduced elasticity with lower yield strengths (see
Table 1). For these annealed wires, yielding at small
deformation is induced by mechanical pure bending2 and the
yield strength can be estimated as y ) FyL/2r3, resulting
in values (7.3 GPa from Figure 4c) that are substantially
larger than that for bulk silver (55 MPa). This analysis is
not valid for the original wires because yielding involves
both stretching and bending, but is indicative of even stronger
materials. Finally, the data in Figure 4 also demonstrate that
the transition from a brittle to ductile metal is a gradual one.
Note that the yield point (the deviation point between the
fitted curves and the data) in Figures 2d, 4a, and 4b
progressively moves to smaller displacements and the smaller
the elastic recovery following plastic deformation. This is
consistent with reduced hardening as the grain boundaries
disappear during annealing and is also evident from the
variation in the bending angle at failure, which range from
17.9 for the original wire, to 21.9 and 27.1, for the 17
and 48 h annealed wires, respectively (see Table 1). This
dramatic increase in ductility can also be seen from the AFM
images in Figure 4c recorded following consecutive manipulation of the 48 h annealed wire.
These results demonstrate that the mechanical properties
of nanowires can be uniquely tailored by controlling their
microstructure. Although microstructure is a recognized
means to engineering the strength of materials, it is exceptionally effective on the nanoscale level because it is possible
to assemble materials with oriented, interlocking grains that
are both grain-boundary hardened and oriented so as to
eliminate all favorable slip orientations.

472

Acknowledgment. This work was supported by Science


Foundation Ireland under grant 00/PI.1/C077A.2.
Note Added after ASAP Publication. A coauthor was
not included in the version published ASAP February 21,
2006; the correct version was published March 3, 2006.
Supporting Information Available: The possible effect
of carbon coating on the elastic properties of pentagonal
silver wires was performed by oxygen plasma etching
experiments. AFM images, height analysis, and corresponding F-d curve fitting are shown. This material is available
free of charge via the Internet at http://pubs.acs.org.
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NL052427F

Nano Lett., Vol. 6, No. 3, 2006

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