Advancements in fractal plasmonics: structures, optical properties, and applications.

The structural characteristics of plasmonic nanostructures directly influence their plasmonic properties, and therefore, their potential role in applications ranging from sensing and catalysis to light- and energy-harvesting. For a structure to be compatible with a selected application, it is critical to accurately tune the plasmonic properties over a specific spectral range. Fabricating structures that meet these stringent requirements remains a significant challenge as plasmon resonances are generally narrow with respect to the considered selected spectral range. Adapted from their well-established role in GHz applications, plasmonic fractal structures have emerged as architectures of interest due to their ability to support multiple tunable resonances over broad spectral domains. Here, we review the advancements that have been made in the growing field of fractal plasmonics. Iterative and space-filling geometries that can be prepared by advanced nanofabrication techniques, notably electron-beam lithography, are presented along with the optical properties of such structures and metasurfaces. The distributions of electromagnetic enhancement for some of these fractals is shown, along with how the resonances can be mapped experimentally. This review also explores how fractal structures can be used for applications in solar cell and plasmon-based sensing applications. Finally, the future areas of physical and analytical science that could benefit from fractal plasmonics are discussed

Plasmon-Mediated Drilling in Thin Metallic Nanostructures

Thin and ultraflat conductive surfaces are of particular interest to use as substrates for tip-enhanced spectroscopy applications. Tip-enhanced spectroscopy exploits the excitation of a localized surface plasmon resonance mode at the apex of a metallized atomic force microscope tip, confining and enhancing the local electromagnetic field by several orders of magnitude. This allows for nanoscale mapping of the surface with high spatial resolution and surface sensitivity, as demonstrated when coupled to local Raman measurements. In gap-mode tip-enhanced spectroscopy, the specimen of interest is deposited onto a flat metallic surface and probed by a metallic tip, allowing for further electromagnetic confinement and subsequent enhancement. We investigate here a geometry where a gold tip is used in conjunction with a silver nanoplate, thus forming a heterometallic platform for local enhancement. When irradiated, a plasmon-mediated reaction is triggered at the tip-substrate junction due to the enhanced electric field and the transfer of hot electrons from the tip to the nanoplate. This resulting nanoscale reaction appears to be sufficient to ablate the thin silver plates even under weak laser intensity. Such an approach may be further exploited for patterning metallic nanostructures or photoinduced chemical reactions at metal surfaces

Microencapsulation by in situ polymerization of amino resins

By surrounding small droplets with a coating, one can obtain micrometer-size capsules (microcapsules), and combine multiple properties into a single system. This technology has allowed the design of advanced and functional materials. Amino resins are composed principally of urea and/or melamine and formaldehyde, and exhibit advantages as wall-forming materials, such as high mechanical strength and chemical resistance. In this review, a general description of the encapsulation process by in situ polymerization of amino resins is given. Characterization methods, and the influence of the physical and design parameters are discussed. A mechanistic description, and some of the promising avenues of research are also presented

Dendritic Plasmonics for Mid-Infrared Spectroscopy

Metallic nanostructures that exhibit tailored optical resonances spanning from the near to mid-infrared spectral range are of particular interest for spectroscopic and optical measurements in these spectral domains that can benefit from localized surface-enhancement effects. Plasmon resonances shifted in the near or mid-infrared range could be used to further enhance the excitation and/or the emission of an optical process. Surface-enhanced infrared absorption (SEIRA) is one of such processes and can particularly benefit from plasmon-enhanced local fields yielding an increase in sensitivity towards the detection of an analyte. Herein, we have fabricated a series of gold dendritic nanostructures, prepared by electron-beam lithography, that exhibit plasmon resonances spanning the near and mid-infrared spectral regions. We explore the influence of the number of branches of the dendritic structures, as well as the length of each generation together with the overall effect of the shape and symmetry on the resulting optica

Optoelectronic, Aggregation, and Redox Properties of Double-Rotor Boron Difluoride Hydrazone Dyes

We develop the chemistry of boron difluoride hydrazone dyes (BODIHYs) bearing two aryl substituents and explore their properties. The low-energy absorption bands (λmax = 427–464 nm) of these dyes depend on the nature of the N-aryl groups appended to the BODIHY framework. Electron-donating and extended p-conjugated groups cause a red shift, whereas electron-withdrawing groups result in a blue shift. The title compounds were weakly photoluminescent in solution and strongly photoluminescent as thin films (λPL = 525–578 nm) with quantum yields of up to 18% and lifetimes of 1.1–1.7 ns, consistent with the dominant radiative decay through fluorescence. Addition of water to THF solutions of the BODIHYs studied causes molecular aggregation which restricts intramolecular motion and thereby enhances photoluminescence. The observed photoluminescence of BODIHY thin films is likely facilitated by a similar molecular packing effect. Finally, cyclic voltammetry studies confirmed that BODIHY derivatives bearing para-substituted N-aryl groups could be reversibly oxidized (Eox1 = 0.62–1.02 V vs. Fc/Fc+) to their radical cation forms. Chemical oxidation studies confirmed that para-substituents at the N-aryl groups are required to circumvent radical decomposition pathways. Our findings provide new opportunities and guiding principles for the design of sought-after multifunctional boron difluoride complexes that are photoluminescent in the solid state

Photocontrolled Degradation of Stimuli-Responsive Poly(ethyl glyoxylate): Differentiating Features and Traceless Ambient Depolymerization

The depolymerization of coatings prepared from a 6-nitroveratryl carbonate end-capped poly(ethyl glyoxylate) (PEtG) self-immolative polymer was studied. This polymer undergoes end-to-end depolymerization following cleavage of the end-cap by UV light. Several important fundamental diff erences between this class of polymers and conventional degradable polymers were revealed. For example, polymer backbone cleavage and depolymerization exhibited different dependencies on pH, emphasizing the decoupling of these processes. Probing of the coating erosion mechanism illustrated an interesting combination of features from surface erosion and bulk degradation mechanisms that arise from the end-to-end depolymerization mechanism and further differentiate these polymers from convention degradable polymers. It was also demonstrated that, unlike backbone cleavage, PEtG depolymerization did not exhibit a dependence on water and that PEtG could depolymerize back to the volatile monomer ethyl glyoxylate at ambient temperature and pressure. This unusual feature was utilized to perform facile polymer reprogramming/recycling via an irradiation− trapping− repolymerization sequence as well as polymer patterning by a simple irradiation− evaporation sequence

Fabrication and In-Situ Cross-linking of Carboxylic Acid-Functionalized Poly(ester amide) Scaffolds for Tissue Engineering

Three-dimensional (3D) scaffolds are important tools for tissue engineering, and should ideally provide both biochemical cues and biomechanical support for cells. Poly(ester amide)s (PEAs) have emerged as promising materials for the preparation of tissue engineering scaffolds and the pendant side chains of residues such as ʟ-lysine and ʟ-aspartic acid can provide sites for the conjugation of biochemical signals. However, it has been challenging to combine scaffold morphological stability with the presentation of reactive groups on PEA scaffolds. We describe here a new approach involving the functionalization of a ʟ-lysine-containing PEA with maleic anhydride to simultaneously introduce cross-linkable alkenes and carboxylic acid conjugation sites. Maleic-acid-functionalized PEA was processed to form 3D scaffolds using a salt leaching method and the scaffolds were cross-linked in situ using a poly(ethylene glycol) dimethacrylate cross-linking agent by thermal free radical curing. Micro-computed tomography analysis indicated that the cross-linked scaffolds had higher polymer volume fraction, lower porosity, and smaller pore size than the non-cross-linked scaffolds, but both scaffolds exhibited high morphological stability and negligible mass loss upon incubation in phosphate buffered saline for 5 days. The Young’s moduli of the cross-linked and non-cross-linked scaffolds were 28 and 9 kPa respectively. Fluorescein-labeled bovine serum albumin was successfully conjugated to the scaffolds using a carbodiimide-based coupling. Finally, it was shown that the scaffolds supported the attachment and proliferation of mouse embryonic mesenchymal multipotent cells, showing their promise as platforms for tissue engineering applications

Single-Beam Inscription of Plasmon-Induced Surface Gratings

The formation of gratings on gold nanoprisms arrays by plasmon-mediated reduction of a diazonium salt is investigated. Nanosphere lithography (NSL) is used to produce large surfaces of gold nanoprisms that are effective at reducing diazonium salts by producing hot electrons through excitation of localized surface plasmon resonances (LSPRs). Using single beam irradiation, we report here on the formation of periodic structures formed from the diazonium salts and that follow the NSL structures. On plasmonically active nanoprism substrates, the electric field enhancement promotes chemical reduction and hence modifies the grafting direction and grating properties of the ripples. The nanoprisms act as a plasmon guide which widens the pitch of the self-organized gratings and can even alter it from straight lines into a crisscross pattern

Tunable 3D Plasmonic Cavity Nanosensors for Surface-enhanced Raman Spectroscopy with Sub Femtomolar Limit of Detection

Metallic nanohole arrays (NHAs) with a high hole density have emerged with potential applications for surface-enhanced Raman spectroscopy (SERS) including the detection of analytes at ultra-low concentrations. However, these NHA structures generally yield weak localized surface plasmon resonance (LSPR) which is a prerequisite for SERS measurements. In this work, a compact three-dimensional (3D) tunable plasmonic cavity with extraordinary optical transmission properties serves as a molecular sensor with sub-femtomolar detection. The 3D nanosensor consists of a gold film containing a NHA with an underlying cavity and a gold nanocone array at the bottom of the cavity. These nanosensors provide remarkable surface plasmon polariton (SPP) and LSPR coupling resulting in a significantly improved detection performance. The plasmonic tunability is evaluated both experimentally and theoretically. A SERS limit of detection of 10-16 M for 4-Nitrothiophenol (4-NTP) is obtained along with distribution mapping of the molecule on the 3D plasmonic nanosensor. This results in an improved SERS enhancement factor (EF) of 106 obtained from a femtolitre plasmonic cavity volume. The tunability of these sensors can give rise to a potential opportunity for use in optical trapping while providing SERS sensing of a molecule of interest

Carving Plasmon Modes in Silver Sierpiński Fractals

The surface plasmon resonance (SPR) modes of the first three generations of a Sierpiński fractal triangle are investigated using electron energy loss spectroscopy (EELS) complemented with finite difference time domain simulations. The Sierpiński fractal geometry is created in a subtractive manner, by carving triangular apertures into the triangular prism of the previous fractal generation. The ability of the fractal antenna to efficiently utilize space in coupling to long wavelength excitations is confirmed on the single nanostructure level via redshifting of the primary dipole mode as the fractal generation is increased. Through application of the Babinet principle, it is demonstrated that this spectral shift is caused by coupling of two orthogonal dipolar modes of a single triangle with two orthogonal dipole modes of the triangular aperture occupying the centre of the first generation fractal. It is also shown that the spectral position and strength of the dipole mode can be tuned by altering the size of the central 1 aperture, and thus the capacitance of the equivalent circuit, and the width of the conductive channels joining different fractal building blocks, thereby altering the circuit inductance. Importantly, placing the aperture on an anti-node of the SPR mode causes a shift in energy of this mode without changing the charge configuration; placing the aperture on a node of the SPR mode causes no shift in energy, but changes the field configuration, as revealed through EELS measurements. These fractal-specific properties provide new strategies to design, predict, and effectively exploit highly tunable SPR modes using simple building blocks