Acta Materialia 165 (2019) 15e25

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Acta Materialia
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Full length article

Dewetted nanostructures of gold, silver, copper, and palladium with

enhanced faceting
Arin S. Preston a, Robert A. Hughes a, Trevor B. Demille a, Victor M. Rey Davila a,
Svetlana Neretina a, b, c, *
a
College of Engineering, University of Notre Dame, Notre Dame, IN, 46556, USA
b
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN, 46556, USA
c
Center for Sustainable Energy at Notre Dame, Notre Dame, IN, 46556, USA

a r t i c l e i n f o a b s t r a c t

Article history: At the foundation of nanoscience and nanotechnology is the ability to shape-engineer nanometric ob-
Received 28 September 2018 jects so as to exert control over their physical and chemical properties. Architectural control is achieved
Received in revised form by manipulating thermodynamic and kinetic factors that are able to guide reactions along pathways that
13 November 2018
lead to the formation or elimination of particular crystal facets. While the dewetting of ultrathin metal
Accepted 18 November 2018
Available online 20 November 2018
films provides a straightforward method for generating substrate-based metallic nanostructures, the
ability to shape-engineer these structures is limited to such an extent that even the formation of highly
faceted equiaxed structures often proves challenging. This, however, is not the case for colloidal syn-
Keywords:
Chemical synthesis
theses where the exquisite chemical controls and synthetic ease offered by liquid-phase chemistry has
Facets led to the generation of a diverse library of nanostructure architectures. Here, it is demonstrated that the
Epitaxial growth faceting of dewetted structures of gold, silver, copper, and palladium can be enhanced by subjecting them
Thermal diffusion to a liquid-phase chemical environment in which metal ions are reduced to a neutral state and deposited
Tetrahexahedron on the nanostructure surface in manner that leads to facet formation. The faceting procedure, which can
be carried out in minutes, is also shown to be amenable to a templated dewetting approach in which
lithographically-defined metal discs formed in an array each agglomerate to form a single nanostructure.
The work has the potential to increase the functionality of dewetted nanostructures by enabling facet-
dependent chemical reactivity and plasmonic hot spots.
© 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

1. Introduction properties of the nanostructure. The facet is, hence, integral to a

The crystallographic facet is of central importance to the syn-
thesis and application of metallic nanostructures. The ability to
grow specific facets while eliminating others is, to a large extent,
the means by which nanostructures are shape-engineered. The
resulting architectural control is, for example, responsible for the
rich nature of plasmonic phenomena, yielding highly tunable
plasmon resonances, anisotropic optical properties, and the gen-
eration of near-field hot spots at the vertices where facets meet. The
exposed facet also plays a critical role in determining the chemical
* Corresponding author. College of Engineering, University of Notre Dame, Notre
Dame, IN, 46556, USA.
E-mail addresses: apresto3@nd.edu (A.S. Preston), rhughes6@nd.edu
(R.A. Hughes), tdemille@nd.edu (T.B. Demille), vreydavi@nd.edu (V.M. Rey Davila),
sneretina@nd.edu (S. Neretina).
wide a range of nanotechnologies including catalysis [1e3],
chemical and biological sensing [4e6], biomedicine [7,8], and
photovoltaics [9]. Fully exploiting these applications require the
shape-control of nanostructures both as colloids and as substrate-
immobilized entities, with the latter being of specific relevance to
the current study.
The solid-state dewetting [10e13] of a room temperature
deposited ultrathin metal film is, by far, the simplest method for
obtaining substrate-bound nanostructures. Such films are far from
pristine, instead being a highly defected metastable layer
comprised of polycrystalline grains formed in a VolmereWeber
growth mode that sees nanoscale islands strain toward each
other as they coalesce [14e16]. When heated, such films are un-
stable to a dewetting process that is driven by grain boundaries and
a minimization of the surface energy of the metalesubstrate sys-
tem. The process first sees the formation of isolated pinholes in the

https://doi.org/10.1016/j.actamat.2018.11.036
1359-6454/© 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
16 A.S. Preston et al. / Acta Materialia 165 (2019) 15e25
film that then grow in size as irregularly shaped islands detach
from the retracting edges and then evolve into more energetically
favorable configurations. By the end of the process, the film has
been transformed into nanoscale islands with a wide size distri-
bution and randomized placement [17]. The overall process is
influenced by a multitude of factors [10e13], with recent studies
indicating that grain boundaries play a more important role than
previously realized [18e21]. Kim et al. [22] was the first to show
that control could be exerted over the dewetting process by sub-
dividing a continuous film into smaller units through lithography.
When heated, the dewetting process is triggered not by random
instabilities that lead to hole formation but by lithographically-
defined edges. In doing so, the erratic natural tendencies of the
dewetting process are overridden by preprogrammed instabilities
that exert order over the assembly process. This so-called tem-
plated dewetting process has since been widely used where pat-
terns have been generated through the use photo- and e-beam
lithography [23e26], nanoimprint lithography [27], shadow masks
[28], and self-assembled patterns derived from close packed poly-
styrene spheres [29,30] or diblock copolymers [31,32].
The final stage of the dewetting process, in which irregularly-
shaped islands reorganize into more favorable configurations, is
crucial in terms of determining nanostructure faceting. For a free-
standing metal nanostructure, the equilibrium configuration,
commonly referred to as the Wulff shape, is the shape which
minimizes the surface energy. The most common equilibrium
configuration for a face-centered-cubic (fcc) metal is a cuboctahe-
dron with six (100) facets and eight (111) facets that results from a
surface energy hierarchy of g111 < g100 < g110 [33]. It is, however,
noted that more complex equilibrium crystal shapes can exist for
fcc metals [34]. When formed on a low surface energy substrate,
the nanostructure equilibrium shape still resembles the Wulff
shape, but where it is truncated by the substrate surface (for con-
venience, this will also be referred to as the Wulff shape) [33]. With
the equilibrium shape often being a highly faceted structure, it
would appear that the formation of such structures is straightfor-
ward. This, however, is not the case. Dewetted structures typically
show significant deviations from the substrate-truncated cuboc-
tahedron in the form of rounding [35,36], the appearance of high-
index facets [37e39], and the formation of oblong and flat-
topped geometries [38,39]. Even when such features represent
deviations from the equilibrium shape, they can still show
remarkable stability as was demonstrated in study by Müller and
Spolenak [40] where they annealed dewetted Au nanostructures at
800
C for 14 days and found that less than 1% attained the equi-
librium shape. They described the non-equilibrium structures as
being kinetically trapped in metastable states. This sensitivity to
kinetic influences is not surprising since any change in shape is the
result of surface diffusion, and as such, is influenced by a variety of
confounding factors that include Ehrlich-Schwoebel barriers [41],
adsorbed species [34,42,43], impurities [34,44], defects [45,46],
grain boundaries [38,47], substrate surface roughness [48], and
interface reconstructions [49]. Moreover, alterations to the equi-
librium shape occur at small sizes [48,50] and for temperatures
approaching the melting point of the metal since the anisotropy in
the surface energies of the various facets lessens [33]. As a result, it
is a challenging task to formulate processing conditions that give
rise to a population of highly faceted equiaxed nanostructures in
high yield.
While the shape-control of metal nanostructures has proved
difficult when carrying out solid-state dewetting, this same syn-
thetic challenge has long ago been met when using colloidal syn-
thesis [51e53]. Such syntheses routinely generate nanostructures
with controlled geometries in high yield using aqueous environ-
ments comprised of metal ion precursors, facet-selective capping
agents, pH-altering acids and bases, and reducing agents that
collectively guide growth modes along kinetic and thermodynamic
pathways. Seed-mediated colloidal syntheses [54,55], in which
nucleation events are triggered by the introduction of preformed
metal seeds, have proved particularly effective in achieving shape-
control. Previously, we have shown that these same synthetic wet
chemistry protocols can be adapted to substrate-based synthesis by
treating substrate-immobilized nanostructures as seeds [56e59].
Here, we demonstrate that dewetting and solution-based growth
modes can be synergistically combined to obtain highly faceted
equiaxed structures of Au, Ag, Cu, and Pd. The overall strategy is to
use processing conditions during dewetting that give rise to equi-
axed structures that are then exposed to a solution-based growth
mode promoting facet growth. By providing a rapid, inexpensive,
and straightforward means for obtaining substrate-immobilized
metal nanostructures with faceted-dependent properties, the
work expands the opportunities available when using dewetted
nanostructures.
2. Experimental
2.1. Chemicals and materials
Au, Cu, Ag, and Pd sputter targets were cut from 0.5 mm thick
foils (Alfa Aesar) with purities of 99.9985, 99.9999, 99.9985, and
99.95þ %, respectively, while the Sb and Bi targets were cut from
rods with 99.999% purity (ESPI Metals). [0001]-oriented sapphire
substrates (MTI) were diced from larger wafers to sizes of
10 mm  10.5 mm  0.65 mm (arrayed structures) and
5 mm  7 mm  0.5 mm (random structures). Dewetting experi-
ments were carried out in either ultrahigh purity Ar or in a 10%:90%
H2:Ar gas mixture. Aqueous syntheses utilized poly-
vinylpyrrolidone (PVP) (Sigma Aldrich, average molecular weight
40,000), chloroauric acid (HAuCl4) (99.99%, Alfa Aesar), copper ni-
trate (Cu(NO3)2) (98.0%, Sigma Aldrich), silver nitrate (AgNO3)
(99.9þ%, Alfa Aesar), sodium tetrachloropalladate (II) (Na2PdCl4)
(98.0% Sigma Aldrich), ʟ-Ascorbic acid (AA) (99.0þ%, Sigma
Aldrich), hexadecyltrimethylammonium bromide (CTAB) (98.0%,
Alfa Aesar), sodium hydroxide (NaOH) (98.0þ%, Sigma Aldrich),
nitric acid (HNO3) (2.0 N Alfa Aesar), and sulfuric acid (H2SO4)
(6.0 N Alfa Aesar). Aqueous solutions were prepared with deionized
(DI) water with a resistivity of 18.2 MU cm1. All glassware was
cleaned with aqua regia and thoroughly rinsed in DI water prior to
use. All chemicals were used as received.
2.2. Au syntheses
Seeds with a random size and placement were formed by first
sputter depositing Au films with a thickness of 11 nm onto [0001]-
oriented sapphire substrates followed by their immediate insertion
into a quartz tube furnace. The air in the tube was then purged for
30 min with Ar gas at a flow rate of 120 cm3 min1, after which the
flow was reduced to 60 cm3 min1. The temperature regimen used
to dewet the Au saw it heated to 1085
C in 27 min followed by a
slow cool to room temperature lasting 3 h. The nanoimprint
lithography (NIL) procedure used to form periodic arrays of Au
seeds is described in detail elsewhere [27]. In this process, a poly-
mer resist is first spin coated onto a substrate. A NIL stamp was then
used to define either a (i) hexagonal pattern of circular openings
with a diameter of 240 nm and a center-to-center distance of
700 nm through which 24 nm Au is deposited or (ii) square pattern
of circular openings with a diameter of 275 nm and a center-to-
center distance of 600 nm through which 18 nm of Au was depos-
ited. The lithographically-defined Au discs were then heated to
high temperatures using the same heating regimen. Once removed
 A.S. Preston et al. / Acta Materialia 165 (2019) 15e25
from the furnace, the seeds were immediately subjected to a liquid-
phase synthesis. The Wulff-shaped structures with random size
and placement were formed by first placing the Au seeds into 4 mL
aqueous PVP (1 mM) heated to 95
C. After a 15 s duration, which
allowed the seeds to equilibrate with their surroundings, the re-
action was initiated through the rapid injection of 1 mL aqueous
HAuCl4 (1 mM, 20
C) and allowed to continue for 4 min. The
sample was then gently sonicated in DI water and dried in a flow of
N2 gas. Triangular-shaped structures were formed using a similar
procedure, but where the concentration of HAuCl4 was raised to
1.5 mM. When forming arrayed structures with enhanced faceting,
the HAuCl4 concentrations for the Wulff- and triangular-shaped
structures were reduced to 0.8 and 1.2 mM, respectively. Lower
concentrations are required to compensate for the smaller number
of seeds present when using arrays.
2.3. Cu syntheses
Seeds of Cu with random size and placement were produced in
much the same manner as Au, but where key differences exist due
to its propensity for oxidation. After the deposition of 13 nm of Cu,
the films were rapidly transferred to a tube furnace through which
an H2eAr gas mixture was flowed. Once the air was purged from
the quartz tube, the sample was heated to 1030
C in 25 min and
then allowed to cool to room temperature. The fabrication of
arrayed Cu seeds also required a somewhat different procedure if
heteroepitaxy with the substrate was to be promoted. A continuous
Cu film with a thickness of 23 nm was deposited onto a sapphire
substrate followed by the application of a resist. The resist was
patterned into an array of cylinders using a NIL stamp with a pe-
riodic pattern of cylindrical holes (diameter ¼ 290 nm, center-to-
center distance ¼ 700 nm) into which the resist flowed. After
stamp removal, a reactive ion etch (RIE) was used to expose the Cu
film in all locations except those occupied by the cylinders. The
exposed film was then etched using borohydride (10 mM, 3 min)
followed by nitric acid (5 mM, 4 min). The role of the borohydride is
to remove a Cu oxide layer formed during RIE. After the resist was
removed, the exposed Cu discs were dewetted using the afore-
mentioned procedure, removed from the furnace, inserted into
1 mL of 90
C AA (10 mM), and allowed to equilibrate. Cu deposition
onto the seeds to enhance faceting was then initiated by adding
3 mL of 1 mM Cu(NO3)2 and allowed to continue for 5 min.
2.4. Ag syntheses
The synthesis of facet-enhanced Ag nanostructures proved more
difficult than Cu or Au (vida infra), and as a result, key differences in
seed fabrication were required. Seeds were only fabricated in the
arrayed format where, prior to NIL, a continuous 6 nm thick layer of
sacrificial Sb was deposited onto the substrate. The lithographic
procedure was then carried out using the NIL stamp with a hex-
agonal patterned and a 30 nm Ag deposition. The resist is then
removed, leaving behind 30 nm thick Ag discs on a continuous film
of Sb. The exposed Sb was then removed through a wet etching
procedure that sequentially exposed it to sulfuric (2 mL, 6.0 N,
3.5 min) and nitric (2 mL, 5 mM, 30 s) acid where the former
removes Sb and its oxides and the latter etches the Ag surface to
expose an uncontaminated surface. During this procedure the Ag
discs act as an etch block for the Sb layer that lies beneath them.
These AgeSb bilayer discs are then heated in flowing Ar gas to a
temperature of 945
C in 17 min, followed by a 15 min anneal at
700
C. After this procedure, the Sb has sublimated leaving behind
an array of Ag seeds. The Sb layer, while sacrificial, proved crucial in
promoting a heteroepitaxial relationship between the Ag and
sapphire. We suspect that its role is to prevent the substrate surface
17
from being damaged during the reactive ion etching (RIE) proced-
ure used when carrying out NIL [27]. The Ag seed faceting was
enhanced by first placing them in a 1.5 mL aqueous solution of AA
(6.67 mM) and NaOH (0.33 mM) heated to 95
C to which 3 mL of
AgNO3 (1 mM, 95
C) was added. The ensuing reaction was allowed
to proceed for 5 min, after which the sample was rinsed and dried
in the usual manner.
2.5. Pd syntheses
The formation of equiaxed Pd seeds required the deposition of a
14 nm thick sacrificial Bi layer onto which a 16 nm thick Pd film is
deposited. This bilayer is the then exposed to a heating regimen in
flowing Ar that sees the temperature raised to 1100
C in 30 min,
annealed for 40 min, and then cooled to room temperature. Seed
faceting was altered by placing the sample in a 40
C aqueous so-
lution formed through the addition of 3 mL of AA (25 mM) to 1 mL
of CTAB (200 mM). After a 15 s interval in which the sample
equilibrated with its surroundings, the reaction was initiated
through the rapid injection of 1 mL of aqueous Na2PdCl4 (2 mM,
20
C) and allowed to continue for 15 min. The sample was then
removed from the solution, rinsed and sonicated in DI water, and
dried under a N2 gas flow.
2.6. Instrumentation and characterization
SEM images and the associated elemental analysis were ob-
tained using a Magellan 400 FEI field emission scanning electron
microscope equipped with a Bruker XFlash energy dispersive X-ray
detector. The images were taken using a secondary electron de-
tector operating in immersion mode with a voltage, current, and
working distance of 10 keV, 13 pA, and 4.5 mm, respectively. Films
were sputter deposited using a Gatan Model 681 High-Resolution
Ion Beam Coater. Dewetting and annealing experiments were car-
ried out in a Lindberg Blue M quartz tube furnace equipped with
the vacuum fittings needed to place the sample under a regulated
gas flow. A dedicated quartz tube was used for each of the four
elements studied so as to avoid cross-contamination. Absorbance
spectra were acquired using a Jasco V730 Spectrophotometer. The
XRD data was obtained using a Bruker D8 Advance Davinci
Diffractometer with a Cu Ka1 radiation source (l ¼ 1.54056 Å).
Particle size distributions were generated using Fiji ImageJ
software.
3. Results and discussion
3.1. Scheme for enhancing nanostructure faceting
Fig. 1 shows two variations of a scheme that is designed to
enhance the faceting of Au nanostructures derived from the (i)
dewetting of an ultrathin film of Au (Fig. 1a) and (ii) templated
dewetting of lithographically-defined Au discs (Fig. 1b). In the first
scenario, a polycrystalline Au film is deposited onto a substrate and
heated to elevated temperatures. The processing conditions used
are optimized to not only induce the dewetting phenomenon but to
do so in manner that realizes equiaxed structures with a single
crystalline character. At this stage, the structures are roundish and
show only weak faceting. The substrate-immobilized nano-
structures are then exposed to a liquid-state chemical environment
that is designed to deposit additional Au on the dewetted struc-
tures using a seed-mediated growth mode adapted from one of the
many synthetic protocols that are routinely used to obtain highly
faceted colloidal nanostructures. After several minutes of deposi-
tion, the substrate is removed from its liquid environment to reveal
somewhat enlarged structures with pronounced facets. The second
18 A.S. Preston et al. / Acta Materialia 165 (2019) 15e25
Fig. 1. Schematic showing the processing steps used to form substrate-based metallic nanostructures with (a) random size and position from a continuous metallic film and (b)
near-identical size in periodic arrays using templated dewetting.
scenario proceeds in much the same manner as the first, except that
the Au is deposited not as a continuous film but as nanoscale
islands produced by lithographically defining a polymer resist
through which Au is deposited. The resist and the Au is then
removed in a lift-off procedure in which the resist is dissolved as
the Au on its surface is washed away. When heated, each island
coalesces into a single crystal structure that is then exposed to the
same liquid-state chemistry to obtain a periodic array of
identically-sized nanostructures with pronounced faceting. In the
subsequent sections of this report, results are presented that
demonstrate these schemes as applied to nanostructures of Au, Cu,
Ag, and Pd. For each case, the relevant literature pertaining to the
dewetting of each metal is briefly described to provide a context
from which the results can be viewed.
3.2. Gold
Au is, by far, the most extensively studied metal from the
standpoint of the dewetting of both continuous [17,18,38,40,42,45]
and patterned thin films [22,26,27,29,31,32] As such, the film
thickness, substrate material, and heating regimens have been
varied widely. While the results of these studies vary considerably
due to variable kinetic and thermodynamic influences, trends of
significance have nevertheless emerged since the outcome is
reliant on the same underlying solid-state dewetting phenomenon.
As the film thickness is increased, there is an evolution from
densely packed smaller nanostructures to widely spaced larger
structures where in all cases there is a considerable size distribu-
tion [17]. Regardless of the substrate material, Au shows a strong
tendency toward the formation of dewetted structures with their
[111]-axis normal to the substrate surface, a tendency attributable
to both a weak interaction with the substrate surface and the
energetically favorable bonding arrangement associated with close
packed (111) Au planes. Structures heated to temperatures well in
excess of those where dewetting occurs show greater shape uni-
formity while lesser temperatures typically give rise to a range of
shapes including those with an oblong or planar character. Briefly
heating dewetted structures to temperatures in excess of the Au
melting temperature (i.e., 1065
C) leads to equiaxed structures, but
where the structures have a round morphology with weak faceting
[36,60]. Larger structures, in general, show faceting that is more
pronounced. There also exist several notable studies that have used
conditions that lead to structures with pronounced faceting. Sadan
and Kaplan [47] and Kovalenko and Rabkin [45] produced highly
faceted structures on [0001]-oriented sapphire using extended
anneal times of 24 h at 900
C and 100 h at 1000
C, respectively.
Müller et al. [29] studied the templated dewetting of Au on silicon
nitride surfaces using anneal times as long as 120 h at 950
C. While
they also demonstrated that long anneal times can lead to
increased faceting, it resulted in arrays with an exaggerated size
distribution and even the loss of structures, influences attributed to
sublimation, diffusion, and Ostwald Ripening [61].
Fig. 2a shows an SEM image of the Au nanostructures formed by
depositing an 11 nm thick film followed by heating to temperatures
in excess of the Au melting point. Nanostructures produced in this
manner are equiaxed and show weak faceting that trends toward
that expected for [111]-orientated Wulff-shaped structures. The so-
formed structures were then placed in a 95
C aqueous solution of
HAuCl4 and PVP for 4 min. A reaction ensues in which Au3þ ions
derived from HAuCl4 are reduced by PVP to Au0, a neutral species
that readily deposits on the dewetted Au. Under these conditions,
PVP not only acts as a mild reducing agent but also as a capping
agent that promotes the preferential formation of {111} facets [62].
When a small amount of Au is added the {100} facets on Wulff-
shaped structures persist, but eventually give way to {111} facet-
ing if the deposition is allowed to continue (Fig. S1, Supplemental
material). Fig. 2(bec) shows top- and tilted-view images of the
dewetted Au structures after being exposed to this reaction. It re-
veals that the rounded structures have undergone a dramatic shape
transformation in which weakly faceted structures have been
transformed into Wulff-shaped nanostructures with sharp faceting.
Important to note is that this 4 min procedure leads to faceting that
 A.S. Preston et al. / Acta Materialia 165 (2019) 15e25 19

Fig. 2. SEM image of (a) dewetted Au and (b) top- and (c) tilted-view images of similarly formed structures that were further subjected to a solution-based growth mode that
enhances nanostructure faceting. (d) Nanostructure size distribution histograms, (e) XRD scans (offset for clarity), and (f) LSPR absorbance spectra for the dewetted (blue) and facet-
enhanced structures (red). SEM images of periodic arrays of Au nanostructures formed using (g) templated dewetting and similarly formed arrays where the faceting is enhanced to
form (h) Wulff-shaped and (i) triangular nanostructures. Inset scale bars are 100 nm. (For interpretation of the references to colour in this figure legend, the reader is referred to the
Web version of this article.)

is more pronounced than that which occurred for structures
annealed for 100 h or more [29,47]. Histograms of the nano-
structure size distribution taken before and after the solution-
based deposition show Gaussian-like distributions where the
average nanostructure size has increased by 30 nm (Fig. 2d). XRD
scans using the Bragg-Brentano Ɵe2Ɵ configuration (Fig. 2e) show
that the Au structures are oriented with their [111]-axis perpen-
dicular to the (0001) Al2O3 surface where the (111) and (222) Au
reflections for the faceted structures show more counts due to the
larger quantity of Au present. A comparison of the absorbance
spectra of the weakly and strongly faceted structures (Fig. 2f) shows
that the absorbance peak strengthens and red shifts from 570 to
605 nm, a result consistent with Discrete Dipole Approximation
(DDA) [63,64] simulations (Fig. S2, Supplemental material). The
same synthesis scheme was also applied to Au nanostructures
produced using templated dewetting. Fig. 2(g-h) show SEM images
of the structures obtained before and after undergoing the
enhanced faceting procedure. The result is similar to that obtained
for the dewetted film except that the more organized nature of the
templated assembly procedure gives rise to arrayed structures of
similar size. By carrying out the solution-based growth mode with a
higher HAuCl4 concentration, it is possible to increase the amount
of Au deposited and fully exploit the PVP capping so as to generate a
periodic array of triangular structures with {111} facets. The square
pattern accentuates the fact that both upward and downward
pointing triangles are formed due to the existence of two
geometrically equivalent epitaxial orientations, an occurrence that
is typical for fcc metals formed on (0001)-oriented sapphire sub-
strates [65].
3.3. Copper
The dewetting of Cu films is far more challenging because even
residual levels of oxygen at high temperatures leads to its oxida-
tion. Even when dewetted in an oxygen-free environment, the slow
degradation of structures when exposed to air limits their useful-
ness. As a result, there exist few studies describing the dewetting of
Cu films [37,66e69], where most have formed large structures with
micrometer-scale dimensions. Reports showing the successful
dewetting of Cu have been carried out in the presence of a back-
ground gas with a partial pressure of H2 gas. At elevated temper-
atures, H2 reacts with O2 to form water vapor that is then flushed
20 A.S. Preston et al. / Acta Materialia 165 (2019) 15e25

away in the gas flow. Others have carried out dewetting under
vacuum conditions. Significant faceting was observed by Curiotto
et al. [37,66] in which 50e100 nm thick Cu films were deposited on
sapphire and exposed to dewetting regimes in which they were
heated to 980
C for 78 h or to 1083
C for 5 min. These faceted
structures are, however, quite large (diameter z 1 mm). The other
studies showed weak to no faceting.
Fig. 3a shows an SEM image of the Cu nanostructures formed by
dewetting a 13 nm thick film in a 10% H2 (balance Ar) gas flow using
a heating regimen that sees the temperature raised to 1030
C, a
value that is 55
C below the Cu melting point. The resulting
structures are equiaxed and exhibit mild faceting. It is noted that
heat treatments that melt the Cu yield more variance in structure
orientation and shape, a result that is likely due to an interaction
between molten Cu and the sapphire substrate that leads to the
formation of polycrystalline structures [37]. The dewetted struc-
tures were then transferred to a 95
C aqueous solution of Cu(NO3)2
and ʟ-ascorbic acid (AA) and allowed to react for 5 min. This reac-
tion reduces the Cu2þ ions from the copper nitrate to Cu0, which
then deposits on the dewetted Cu. Fig. 3b shows an SEM image of
the resulting structures which appear highly faceted and show a
Wulff-like shape, where the square {100} facets are overexpressed
to the point that the normally hexagonal {111} facets appear
triangular. The faceting is consistent with [111]-oriented structures
that are heteroepitaxial aligned with the substrate. Fig. 3c shows
histograms of the nanostructure size distribution for both the
dewetted Cu (blue) and Wulff-like structures (red). With peaks at
110 and 185 nm, the dewetted structures show the bimodal dis-
tribution associated with Ostwald ripening [70]. The absence of the
two peaks for the faceted structures is attributable to the smaller
structures growing in diameter at a faster rate than the larger ones.
The result is not unexpected since larger structures require the
addition of far more Cu atoms for the same increase in diameter.
XRD scans (Fig. 3d) confirm that the Cu structures are oriented with
their [111]-axis perpendicular to the (0001) sapphire surface.
Noteworthy, is that there are no reflections associated with CuO or
CuO2. The influence of the regrowth on the Cu plasmon is much the
same as that observed for Au, showing both an increase in absor-
bance and a red shift (Fig. 3e). The templated dewetting procedure
was also applied to Cu to form periodic arrays of dewetted struc-
tures that were then exposed to same liquid phase chemistry to
form highly faceted structures (Fig. 3f).
3.4. Silver
The formation of rounded Ag nanostructures through dewetting
is challenging because the temperatures needed to promote suffi-
cient diffusion also result in its sublimation and Ostwald ripening.
These issues are well-exemplified by the work of Quan et al. [71]
who carried out a systematic study showing the influence of tem-
perature on the dewetting characteristics of 20 nm thick Ag films
deposited on SiO2. As the maximum temperature is varied from 200
to 1000
C, the Ag nanostructures show a progression that sees the
generation of (i) irregular shapes with elongated geometries, (ii)
somewhat rounded structures but where many are oblong, (iii)
more rounded structures but where the size distribution is dis-
rupted by Ostwald Ripening and sublimation, and (iv) an empty
substrate resulting from the complete loss of Ag from the surface.

Fig. 3. SEM image of (a) dewetted Cu and (b) similarly formed structures that were further subjected to a solution-based growth mode that promotes (100) and (111) faceting. (c)
Nanostructure size distribution histograms, (d) XRD scans, and (e) LSPR absorbance spectra for the dewetted (blue) and facet-enhanced structures (red). (f) SEM image of a periodic
array of Cu nanostructures with enhanced faceting. Inset scale bars are 100 nm. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web
version of this article.)
 A.S. Preston et al. / Acta Materialia 165 (2019) 15e25
Equiaxed structures were formed by Kunwar et al. [72] by dewet-
ting 60 nm thick films at 750
C where the resulting structures were
quite large (z400 nm). Near-spherical geometries were also ob-
tained by Farzinpour et al. [17] when dewetting Ag films deposited
on a sacrificial Sb layer. In none of these accounts, however, does Ag
form any obvious facets. Mild faceting was observed for the larger
diameter structures (>200 nm) formed by Ruffino and Grimaldi
[60] when dewetting 20 and 40 nm thick films through shadow
masks, but where the process resulted in a large size distribution.
Our attempts to establish processing conditions that consis-
tently yielded equiaxed Ag structures through the dewetting of
continuous Ag films proved unsuccessful. While such structures
were occasionally obtained when using temperatures approaching
the melting point of Ag, the high levels of Ostwald ripening and
sublimation led to severe irreproducibility. Producing such struc-
tures through templated dewetting, however, proved far more
controllable. The advantage stems from the deposition of Ag discs
of equal size where each undergoes the same degree of sublima-
tion. Moreover, the process of Ostwald ripening is frustrated by a
uniform size distribution as well as a substantial interparticle
spacing. Fig. 4a shows an SEM image of a periodic array of mildly
faceted Ag nanostructures formed through templated dewetting.
The heating regimen sees the structures rapidly heated to 945
C
and then cooled to 700
C where they were allowed to anneal for
15 min before allowing the temperature to fall to room tempera-
ture. The short anneal leads to a mild faceting (see inset to Fig. 4a)
that proves beneficial to the liquid-phase syntheses. The faceting
was enhanced by exposing the arrayed structures to an aqueous
solution of AgNO3, ʟ-ascorbic acid, and NaOH. In this process, the
AgNO3 supplies Agþ ions, ascorbic acid is the reducing agent, and
NaOH regulates the pH of the solution to a value where faceted
growth takes place. The resulting structures, which are shown in
Fig. 4b, are heteroepitaxially aligned with the substrate and show
faceting consistent with a Wulff shape. Fig. 4c shows the changes to
the absorbance spectra that occur due to both an increased size and
the emergence of well-defined facets.
3.5. Palladium
The dewetting of Pd films requires high temperatures and long
anneal times since solid-state diffusion processes are more sluggish
for high melting point metals (Tm ¼ 1555
C). Atmospheric controls
or post-dewetting treatments are also required if the surfaces of the
dewetted structures are to remain free of oxides. In air, PdO forms
Fig. 4. SEM images of Ag nanostructures formed in a periodic array using templated dewetting and (b) identically produced structures after having their facets enhanced through a
liquid-phase deposition. (c) LSPR absorbance spectra for the dewetted (blue) and facet-enhanced structures (red). (For interpretation of the references to colour in this figure legend,
the reader is referred to the Web version of this article.)
21
above 258
C, but then decomposes back to pure Pd above 775
C
[73]. Upon cooling, however, the oxide can reform. Kracker et al.
[73] showed that this can be remedied using a hydrogen gas
treatment, but where the uptake of hydrogen by the Pd structure is
highly likely. There is also a strong tendency for Pd to form flat-
topped structures with low contact angles [74]. Equiaxed struc-
tures were obtained by Farzinpour et al. [17] by depositing a
sacrificial Bi layer between a sapphire substrate and Pd. In this case,
the dewetting diffusion kinetics are enhanced as Bi liquefies
(Tm ¼ 271
C) and evaporates from the surface. Silly et al. [75,76],
notably, demonstrated faceting and architectural control in the
formation of 4e10 nm structures on lattice-matched SrTiO3
substrates.
Our attempts to obtained equiaxed Pd nanostructures through
conventional dewetting techniques proved unsatisfactory in that
many of structures were flat-topped and few were equiaxed (Fig. S3,
Supplemental material). The preparation of high quality Pd seeds is,
however, possible if a 16 nm thick Pd film is deposited onto 14 nm
thick sacrificial Bi layer and heated to high temperatures. It is noted
that seeds formed in this manner do not lend themselves to array
formation due to a vapor-induced motion that causes them to
migrate away from their array positions [77]. An SEM image of the
nanostructures (Fig. 5a) reveals well-faceted Pd structures with an
underlying geometry that is spherical. The most frequently observed
nanostructure geometries display shapes that are consistent with the
formation of {111} and {310} facets. From the standpoint of solution-
based growth modes, such a situation presents opportunities in that
protocols can be used that exaggerate one type facet at the expense
of others to form unique geometries. Fig. 5(bec) shows top- and
tilted-view images of the dewetted Pd nanostructures after being
subjected to an aqueous solution of CTAB, ʟ-ascorbic acid, and
Na2PdCl4 for 15 min at 40
C, a synthesis that is similar to the pro-
tocol used by Liu et al. [78] in which Pd was deposited on Au seeds.
The images show a reconfigured structure where the {111} facets fill
in to form a shape that is entirely comprised of high index facets. An
analysis of the size distribution before and after the solution-based
growth reveals that the size of the structures has not markedly
changed (Fig. 5d), a likely indicator that the growth terminates once
the {111} facets are filled in. XRD scans reveal that the structures
preferentially form with their [110] axis perpendicular to the sub-
strate instead of the usual [111]-orientation expressed by most fcc
metals. The X-ray data is also consistent with the sacrificial Bi layer
being evaporated from the surface since there are no Bi peaks nor
any indication of BiePd alloying.
22 A.S. Preston et al. / Acta Materialia 165 (2019) 15e25
Fig. 5. SEM images of (a) dewetted Pd and (b) top- and (c) tilted-view images of Pd tetrahexahedrons. (d) Histograms for Pd seeds and tetrahexahedron structure size distributions,
(e) XRD scans and (f) schematic representation and SEM images of tetrahexahedrons from three different perspectives. Inset scale bars are 100 nm.
The rather complicated facet pattern expressed by the [110]-
oriented Pd structure is shown from several perspectives in
Fig. 5f along with schematic representations. The structure has a
tetrahexahedron-like appearance, but where some of the facets
have been truncated where they intercept the substrate surface. A
tetrahexahedron is a 24-sided structure that is, in essence, a cube
with a 4-sided pyramid on each face where each side of the pyra-
mid expresses a high index facet. Numerous examples exist in the
literature of such structures formed as colloids [79e81]. A close
examination of the facet pattern reveals that the final structure is
comprised of only {310} facets, but where deviations do exist.
Fig. 6a shows schematics of [110]- and [111]-oriented Pd seeds as
viewed as top-view projections where each of the visible {111} and
{310} facets is indexed. Fig. 6b schematically shows the trans-
formation that occurs during the synthesis. CTAB, which acts as a
capping agent, prevents growth from occurring on the {310} facets
while allowing deposition on the {111} facets. As Pd deposits, the
{111} facets diminish in area as the {310} facets continuously
expand until all the {111} facets are extinguished. At this point,
CTAB has capped the entire structure and no further growth can
occur. At the end of the synthesis, only {310} facets exist. Fig. 6c
shows top-view SEMs of the [110]- and [111]-oriented Pd tetra-
hexahedrons where lines have been overlaid to exaggerate the facet
pattern so as to make comparisons with the schematics
straightforward.
3.6. Significance of results
With the faceting of dewetted structures of Au, Ag, Cu, and Pd all
being enhanced in a controllable manner, this work has demon-
strated the broad applicability of our approach. It should, however,
be emphasized that the dewetting step still represents a significant
challenge in that single crystal equiaxed structures must be ob-
tained if a population of identically shaped structures is to be
realized. In the current work, this requirement has been met using
temperatures above or near the melting point of the metal or
through the use of a sacrificial layer that alters dewetting kinetics.
The solution-based growth modes used to promote faceting capi-
talize on the fact that the dewetted nanostructures have curved
surfaces. Curvature, which manifests itself on atomic length-scales
as a step-terrace morphology, is conducive to the deposition of
metal atoms from the liquid phase because of the high coordination
occurring at step-edges. From a fundamental standpoint, the
emergence of non-equilibrium shapes when a structure is subject
to a kinetically driven growth process has been described in terms
of a “kinetic Wulff shape”, which predicts shape based on a mini-
mization of anisotropic kinetic coefficients (m) as opposed to the
surface energy (g) [82]. At the same time, the use of capping agents
in solution-based growth modes alter both the kinetics and ther-
modynamics [83] to the point that a change in capping agents can
lead to the emergence of different facets. The expanded use of such
agents should lead to architectural controls beyond those demon-
strated in this report.
By resolving inadequacies in the dewetting process, wet
chemistry provides an effective means for upgrading the physico-
chemical properties accessible for these substrate-bound struc-
tures. The ability to transform nanostructure shape provides the
most obvious benefit since the shape of dewetted structures is
fundamentally limited by thermodynamics. Reconfigured struc-
tures, however, can take advantage of shape-dependent properties
that offer far greater tunability than merely changing nanoparticle
size. By transforming curved features into sharp corners, near-field
plasmonic responses are also intensified. The ability to promote
specific facets, including those with high indices, can dramatically
 A.S. Preston et al. / Acta Materialia 165 (2019) 15e25
Fig. 6. (a) Schematics of the [110]- and [111]-oriented seeds where each facet is indexed and (b) the process by which these structures are reconfigured through the capping of {310}
facets (red) as the {111} facets fill through deposition until they are extinguished. (c) SEM images of the [110]- and [111]-oriented tetrahexahedrons with lines drawn to highlight the
{310} facets. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)
alter the chemical properties of nanostructures, a property of
specific relevance to catalysis, photocatalysis, and certain sensing
modalities. Seed-mediated colloidal synthesis has also demon-
strated that, once monometallic structures are available, it opens up
the possibility for subsequent liquid-state syntheses that further
transform structures into bimetallic structures able to realize their
own distinctive chemical and optical signatures [84]. From the
standpoint of nanostructure characterization well-formed facets
provide a convenient means for identifying the orientational rela-
tionship between the dewetted nanostructure and the underlying
substrate and in assessing whether a given
nanostructureesubstrate combination provides a single hetero-
epitaxial relationship.
4. Conclusion
The study carried out demonstrates that liquid-phase chemistry
can be used to enhance the faceting of metal nanostructures
formed through dewetting or templated dewetting. The synthetic
scheme is reliant on formulating the dewetting processing condi-
tions that give rise to equiaxed single crystal structures with weak
faceting that, once locked in, can be enhanced using the chemical
controls accessible when using liquid-phase chemistry. In doing so,
the procedure provides the means by which to mitigate weak-
nesses of the dewetting process such as the need for long pro-
cessing times when trying to promote faceting, the propensity for
forming non-equiaxed structures, and an inability to exert archi-
tectural control over the assembled structures. By overcoming
these synthetic barriers using a simple, rapid, and inexpensive
procedure our approach has the potential to expand the viability of
dewetted structures in advancing studies of fundamental and
practical importance.
Acknowledgments
This work is supported by a National Science Foundation Award
(CMMI-1707595). V.M.R.D. acknowledges the support of the
Graduate School’s Summer Research Opportunities Program. The
23
authors have benefited from the facilities available through the
Notre Dame Integrated Imaging Facility (NDIIF). The authors thank
I. Lightcap and the ND Energy Materials Characterization Facility as
well as A. Oliver and the ND Molecular Structure Facility for their
expertise and assistance with X-ray diffraction. The authors would
also like to acknowledge the efforts of E. Menumerov, a former
Ph.D. student who provided guidance and training on various lab-
oratory equipment.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.actamat.2018.11.036.
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