Stabilization of Gold Nanoparticle Films on Glass by Thermal Embedding

The poor adhesion of gold nanoparticles (NPs) to glass has been a known obstacle to studies and applications of NP-based systems, such as glass/Au-NP optical devices. Here we present a simple scheme for obtaining stable localized surface plasmon resonance (LSPR) transducers based on Au NP films immobilized on silanized glass and annealed. The procedure includes high-temperature annealing of the Au NP film, leading to partial embedding in the glass substrate and stabilization of the morphology and optical properties. The method is demonstrated using citrate-stabilized Au NPs, 20 and 63 nm mean diameter, immobilized electrostatically on glass microscope cover slides precoated with an aminosilane monolayer. Partial thermal embedding of the Au NPs in the glass occurs at temperatures in the vicinity of the glass transition temperature of the substrate. Upon annealing in air the Au NPs gradually settle into the glass and become encircled by a glass rim. In situ transmission UV−vis spectroscopy carried out during the annealing in a specially designed optical oven shows three regions: The most pronounced change of the surface plasmon (SP) band shape occurs in the first ca. 15 min of annealing; this is followed by a blue-shift of the SP band maximum (up to ca. 5 h), after which a steady red-shift of the SP band is observed (up to ca. 70 h, when the experiment was terminated). The development of the SP extinction spectrum was correlated to changes in the system structure, including thermal modification of the NP film morphology and embedding in the glass. The partially embedded Au NP films pass successfully the adhesive-tape test, while their morphology and optical response are stable toward immersion in solvents, drying, and thiol self-assembly. The enhanced adhesion is attributed to the metal NP embedding and rim formation. The stabilized NP films display a refractive index sensitivity (RIS) of 34−48 nm/RIU and 0.1−0.4 abs.u./RIU in SP band shift and extinction change, respectively. The RIS can be improved significantly by electroless deposition of Au on the embedded NPs, while the system stability is maintained. The method presented provides a simple route to obtaining stable Au NP film transducers

Chiroptical Effects in Planar Achiral Plasmonic Oriented Nanohole Arrays

Chiroptical effects are routinely observed in three dimensional objects lacking mirror symmetry or quasi-two-dimensional thin films lacking in-plane mirror symmetry. Here we show that symmetric plasmonic planar arrays of circular nanoholes produced strong chiroptical responses at visible wavelengths on tilting them with respect to the incident light beam due to the collective asymmetric nature of their surface plasmon excitations. This extrinsic chiroptical effect can be stronger than the local chiroptical response in arrays of intrinsically chiral nanoholes and may be useful for chiral sensing and negative refraction

Chiroptical Effects in Planar Achiral Plasmonic Oriented Nanohole Arrays

Chiroptical effects are routinely observed in three dimensional objects lacking mirror symmetry or quasi-two-dimensional thin films lacking in-plane mirror symmetry. Here we show that symmetric plasmonic planar arrays of circular nanoholes produced strong chiroptical responses at visible wavelengths on tilting them with respect to the incident light beam due to the collective asymmetric nature of their surface plasmon excitations. This extrinsic chiroptical effect can be stronger than the local chiroptical response in arrays of intrinsically chiral nanoholes and may be useful for chiral sensing and negative refraction

Chiroptical Effects in Planar Achiral Plasmonic Oriented Nanohole Arrays

Chiroptical effects are routinely observed in three dimensional objects lacking mirror symmetry or quasi-two-dimensional thin films lacking in-plane mirror symmetry. Here we show that symmetric plasmonic planar arrays of circular nanoholes produced strong chiroptical responses at visible wavelengths on tilting them with respect to the incident light beam due to the collective asymmetric nature of their surface plasmon excitations. This extrinsic chiroptical effect can be stronger than the local chiroptical response in arrays of intrinsically chiral nanoholes and may be useful for chiral sensing and negative refraction

Chiroptical Effects in Planar Achiral Plasmonic Oriented Nanohole Arrays

Chiroptical effects are routinely observed in three dimensional objects lacking mirror symmetry or quasi-two-dimensional thin films lacking in-plane mirror symmetry. Here we show that symmetric plasmonic planar arrays of circular nanoholes produced strong chiroptical responses at visible wavelengths on tilting them with respect to the incident light beam due to the collective asymmetric nature of their surface plasmon excitations. This extrinsic chiroptical effect can be stronger than the local chiroptical response in arrays of intrinsically chiral nanoholes and may be useful for chiral sensing and negative refraction

Chiroptical Effects in Planar Achiral Plasmonic Oriented Nanohole Arrays

Chiroptical effects are routinely observed in three dimensional objects lacking mirror symmetry or quasi-two-dimensional thin films lacking in-plane mirror symmetry. Here we show that symmetric plasmonic planar arrays of circular nanoholes produced strong chiroptical responses at visible wavelengths on tilting them with respect to the incident light beam due to the collective asymmetric nature of their surface plasmon excitations. This extrinsic chiroptical effect can be stronger than the local chiroptical response in arrays of intrinsically chiral nanoholes and may be useful for chiral sensing and negative refraction

Rapid Formation of Coordination Multilayers Using Accelerated Self-Assembly Procedure (ASAP)

Layer-by-layer (LbL) assembly of multilayers on surfaces using metal−organic coordination between consecutive layers is a well-established method for multilayer construction. The basic scheme includes self-assembly of a ligand (anchor) monolayer on the surface, followed by alternate binding of metal ions and multifunctional ligand layers to form a coordination multilayer. Binding of the ligand repeat unit to form a new layer is commonly a slow process, taking typically overnight to complete. This renders the process of multilayer preparation exceedingly slow and, in many cases, impractical. Here we describe a method for LbL synthesis of self-assembled coordination multilayers denoted accelerated self-assembly procedure (ASAP), where binding of a full organic ligand layer occurs in ca. 1 min. In the new protocol a small volume of a dilute ligand solution is spread on the substrate surface and evaporated under natural convection conditions, leaving the surface covered with excess ligand. Extensive rinsing in pure solvent results in complete removal of unbound molecules from the surface, leaving only the new coordinated layer. ASAP is demonstrated here by the construction of two kinds of coordination multilayers, comprising mercaptoundecanoic acid−Cu(II) and bishydroxamate−Zr(IV). Multilayers prepared by ASAP and by the standard (overnight adsorption) procedure are compared using ellipsometry, contact-angle, and FTIR data, showing regular multilayer growth in both cases. However, the rapid binding associated with ASAP may lead to a different structure than the one reached after prolonged assembly. Study of the ASAP mechanism suggests that the fast ligand binding kinetics are attributed to a large increase of the local ligand concentration at the moving liquid front when the solvent evaporates on the surface

Solid-State Thermal Dewetting of Just-Percolated Gold Films Evaporated on Glass: Development of the Morphology and Optical Properties

Solid-state thermal dewetting of just-percolated gold films of nominal thicknesses in the range 10–16 nm, prepared by evaporation on glass slides and annealing, was systematically studied. The kinetics of thermal dewetting and transition from a percolated film to isolated islands were monitored using <i>in situ</i> transmission localized surface plasmon resonance (LSPR) spectroscopy combined with <i>ex situ</i> high-resolution scanning electron microscopy (HRSEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), X-ray diffraction (XRD), and selected-area electron diffraction (SAED) to correlate between evolution of the film morphology and development of the optical properties. Annealing at 550 °C results in transformation of the as-evaporated, percolated polycrystalline films, with mean crystallite dimensions close to the film nominal thickness, to (111) textured films comprising large separated single-crystalline islands. The dewetting scenario depends on the initial morphology of the unannealed, just-percolated Au film, in particular on the structure of the voids at the metal–ambient and metal–glass interfaces. Dewetting of films of <13 nm (nominal thickness), the latter exhibiting a majority of voids which are open at both interfaces (denoted type I films), shows faster kinetics than in-plane grain growth. In films of >13 nm (nominal thickness), in which the majority of voids do not protrude through the entire film and are closed at the metal–glass interface (denoted type II films), grain growth presents faster kinetics than dewetting. The annealed films display discrete single-crystalline Au islands with flat, (111) textured top surfaces. Island diameters range from <100 nm to submicrometer, while the surface plasmon extinction band varies over >300 nm for different average island sizes

Amplification of Chiroptical Activity of Chiral Biomolecules by Surface Plasmons

Chiral molecules are shown to induce circular dichroism (CD) at surface plasmon resonances of gold nanostructures when in proximity to the metal surface without direct bonding to the metal. By changing the molecule-Au separation, we were able to learn about the mechanism of plasmonic CD induction for such nanostructures. It was found that even two monolayers of chiral molecules can induce observable plasmonic CD, while without the presence of the plasmonic nanostructures their own CD signal is unmeasurable. Hence, plasmonic arrays could offer a route to enhanced sensitivity for chirality detection

Plasmonic Chiroptical Response of Silver Nanoparticles Interacting with Chiral Supramolecular Assemblies

Silver nanoparticles were prepared in aqueous solutions of chiral supramolecular structures made of chiral molecular building blocks. While these chiral molecules display negligible circular dichroism (CD) as isolated molecules, their stacking produced a significant CD response at room temperature, which could be eliminated by heating to 80 °C due to disordering of the stacks. The chiral stack-plasmon coupling has induced CD at the surface plasmon resonance absorption band of the silver nanoparticles. Switching between two plasmonic CD induction mechanisms was observed: (1) Small Ag nanoparticles coated with large molecular stacks, where the induced plasmonic CD decayed together with the UV molecular CD bands on heating the solution, indicating some type of electromagnetic or dipole coupling mechanism. (2) Larger Ag nanoparticles coated with about a monolayer of molecules exhibited induced plasmonic CD that was temperature-independent. In this case it is estimated that the low chiroptical response of a molecular monolayer is incapable of inducing such a large chiroptical effect, and a model calculation shows that the plasmonic CD response may be the result of a slight chiral shape distortion of the silver nanoparticles