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Microstructure-Hardened Silver Nanowires
Microstructure-Hardened Silver Nanowires
LETTERS
Microstructure-Hardened Silver
Nanowires
2006
Vol. 6, No. 3
468-472
John E. Sader
Department of Mathematics and Statistics, The UniVersity of Melbourne, Australia
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.
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-
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)
( )
(AI)
6(140 + )
350 + 3
(2)
(3)
469
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
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%
472
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