From anti-counterfeiting to biotechnology applications, there is a strong demand for encoded surfaces with multiple security layers that are prepared by stochastic processes and are adaptable to deterministic fabrication approaches. Here, we present dewetting instabilities in nanoscopic (thickness <100 nm) polymer films as a form of physically unclonable function (PUF). The inherent randomness involved in the dewetting process presents a highly suitable platform for fabricating unclonable surfaces. The thermal annealinginduced dewetting of poly(2-vinyl pyridine) (P2VP) on polystyrenegrafted substrates enables fabrication of randomly positioned functional features that are separated at a microscopic length scale, a requirement set by optical authentication systems. At a first level, PUFs can be simply and readily verified via reflection of visible light. Area-specific electrostatic interactions between P2VP and citrate-stabilized gold nanoparticles allow for fabrication of plasmonic PUFs. The strong surface-enhanced Raman scattering by plasmonic nanoparticles together with incorporation of taggants facilitates a molecular vibration-based security layer. The patterning of P2VP films presents opportunities for fabricating hybrid security labels, which can be resolved through both stochastic and deterministic pathways. The adaptability to a broad range of nanoscale materials, simplicity, versatility, compatibility with conventional fabrication approaches, and high levels of stability offer key opportunities in encoding applications.
Spatially
defined assembly of colloidal metallic nanoparticles
is necessary for fabrication of plasmonic devices. In this study,
we demonstrate high-resolution additive jet printing of end-functional
polymers to serve as templates for directed self-assembly of nanoparticles
into architectures with substantial plasmonic activity. The intriguing
aspect of this work is the ability to form patterns of end-grafted
poly(ethylene glycol) through printing on a hydrophobic layer that
consists of fluoroalkylsilanes. The simultaneous dewetting of the
underlying hydrophobic layer together with grafting of the printed
polymer during thermal annealing enables fabrication of spatially
defined binding sites for assembly of nanoparticles. The employment
of electrohydrodynamic jet printing and aqueous inks together with
reduction of the feature size during thermal annealing are critically
important in achieving high chemical contrast patterns as small as
∼250 nm. Gold nanospheres of varying diameters selectively
bind and assemble into nanostructures with reduced interparticle distances
on the hydrophilic patterns of poly(ethylene glycol) surrounded with
a hydrophobic background. The resulting plasmonic arrays exhibit intense
and pattern-specific signals in surface-enhanced Raman scattering
(SERS) spectroscopy. The localized seed-mediated growth of metallic
nanostructures over the patterned gold nanospheres presents further
routes for expanding the composition of the plasmonic arrays. A representative
application in SERS-based surface encoding is demonstrated through
large-area patterning of plasmonic structures and multiplex deposition
of taggant molecules, all enabled by printing.
Demanding applications in sensing, metasurfaces, catalysis, and biotechnology require fabrication of plasmonically active substrates. Herein, we demonstrate a bottom-up, versatile, and scalable approach that relies on direct growth of silver nanostructures from seed particles that were immobilized on polymer brush-grafted substrates. Our approach is based on (i) the uniform and tunable assembly of citrate-stabilized gold nanoparticles on poly(ethylene glycol) brushes to serve as seeds and (ii) the use of hydroquinone as a reducing agent, which is extremely selective to the presence of seed particles, confining the growth of silver nanostructures on the surface of the substrate. The diameter of the seed particles, concentration, as well as ratio of reactants and duration of the growth process are investigated for large-area growth of silver nanostructures with high surface coverage and plasmonic activity. The resulting silver nanostructures exhibit high levels of surface-enhanced Raman scattering activity at two different laser lines and allow detection of molecules at concentrations as low as 10 pM. The plasmonic properties of the silver nanostructures are further studied using ultrafast pump-probe spectroscopy. Spatially defined silver nanostructures are fabricated through the seed particles that are patterned via soft lithography, showing the capabilities of the presented approach in device applications.
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