Solid state dewetting of ultrathin films is the most straightforward means of fabricating substrate-supported noble metal nanostructures. This assembly process is, however, quite inflexible, yielding either densely packed smaller structures or widely spaced larger structures. Here, we demonstrate the utility of introducing a sacrificial antimony layer between the substrate and noble metal overlayer. We observe an agglomeration process which is radically altered by the concurrent sublimation of antimony. In stark contrast with conventional dewetting, where the thickness of the deposited metal film determines the characteristic length scales of the assembly process, it is the thickness of the sacrificial antimony layer which dictates both the nanoparticle size and interparticle spacing. The result is a far more flexible self-assembly process where the nanoparticle size and areal density can be varied widely. Demonstrations show nanoparticle areal densities which are varied over four orders of magnitude assembled from the identical gold layer thickness, where the accompanying changes to nanostructure size see a systematic shift in the wavelength of the localized surface plasmon resonance. As a pliable self-assembly process, it offers the opportunity to tailor the properties of an ensemble of nanostructures to meet the needs of specific applications.
The
galvanic replacement of sacrificial templates offers one of
the most synthetically viable approaches for generating platinum-based
nanostructures with impressive catalytic activity. Here, we present
template design criteria for the synthesis of morphologically smooth
platinum nanoshells which undergo minimal alloying with the template
material. The criteria is founded on comparisons of nanoshells derived
from reacting substrate-immobilized templates of silver, lead, copper,
nickel, and cobalt with aqueous H2PtCl6. It
is shown that template-surface modifications are the primary mode
by which smooth Pt nanoshells are obtained, with template composition
playing a secondary role. The degree of alloying is strongly dependent
upon whether the template applies tensile or compressive heteroepitaxial
strains to the depositing nanoshell. On the basis of these findings,
we propose a mechanistic framework and an overall strategy for the
synthesis of advanced templates for substrate-based galvanic replacement
reactions.
A substrate-based templated assembly route has been devised which offers large-area, high-throughput capabilities for the fabrication of periodic arrays of sub-micrometer and nanometer-scale structures. The approach overcomes a significant technological barrier to the widespread use of substrate-based templated assembly by eliminating the need for periodic templates having nanoscale features. Instead, it relies upon the use of a dynamic template with dimensions that evolve in time from easily fabricated micrometer dimensions to those on the nanoscale as the assembly process proceeds. The dynamic template consists of a pedestal of a sacrificial material, typically antimony, upon which an ultrathin layer of a second material is deposited. When heated, antimony sublimation results in a continuous reduction in template size where the motion of the sublimation fronts direct the diffusion of atoms of the second material to a predetermined location. The route has broad applicability, having already produced periodic arrays of gold, silver, copper, platinum, nickel, cobalt, germanium and Au-Ag alloys on substrates as diverse as silicon, sapphire, silicon-carbide, graphene and glass. Requiring only modest levels of instrumentation, the process provides an enabling route for any reasonably equipped researcher to fabricate periodic arrays that would otherwise require advanced fabrication facilities.
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