Surface-enhanced Raman spectroscopy (SERS) is now a well-established technique for the detection, under appropriate conditions, of single molecules (SM) adsorbed on metallic nanostructures. However, because of the large variations of the SERS enhancement factor on the surface, only molecules located at the positions of highest enhancement, so-called hot-spots, can be detected at the single-molecule level. As a result, in all SM-SERS studies so far only a small fraction, typically less than 1%, of molecules are actually observed. This complicates the analysis of such experiments and means that trace detection via SERS can in principle still be vastly improved. Here we propose a simple scheme, based on selective adsorption of the target analyte at the SERS hot-spots only, that allows in principle detection of every single target molecule in solution. We moreover provide a general experimental methodology, based on the comparison between average and maximum (single molecule) SERS enhancement factors, to verify the efficiency of our approach. The concepts and tools introduced in this work can readily be applied to other SERS systems aiming for detection of every single target molecule.

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The enhanced local fields around plasmonic structures can lead to enhancement of the excitation and modification of the emission quantum yield of fluorophores. So far, high enhancement of fluorescence intensity from dye molecules was demonstrated using bow-tie gap antenna made by e-beam lithography. However, the high manufacturing cost and the fact that currently there are no effective ways to place fluorophores only at the gap prevent the use of these structures for enhancing fluorescence-based biochemical assays. We report on the simultaneous modification of fluorescence intensity and lifetime of dye-labeled DNA in the presence of aggregated silver nanoparticles. The nanoparticle aggregates act as efficient plasmonic antennas, leading to more than 2 orders of magnitude enhancement of the average fluorescence. This is comparable to the best-reported fluorescence enhancement for a single molecule but here applies to the average signal detected from all fluorophores in the system. This highlights the remarkable efficiency of this system for surface-enhanced fluorescence. Moreover, we show that the fluorescence intensity enhancement varies with the plasmon resonance position and measure a significant reduction (300×) of the fluorescence lifetime. Both observations are shown to be in agreement with the electromagnetic model of surface-enhanced fluorescence.

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We provide a detailed user guide for smarties, a suite of Matlab codes for the calculation of the optical properties of oblate and prolate spheroidal particles, with comparable capabilities and ease-of-use as Mie theory for spheres. smarties is a Matlab implementation of an improved T -matrix algorithm for the theoretical modelling of electromagnetic scattering by particles of spheroidal shape. The theory behind the improvements in numerical accuracy and convergence is briefly summarised, with reference to the original publications. Instructions of use, and a detailed description of the code structure, its range of applicability, as well as guidelines for further developments by advanced users are discussed in separate sections of this user guide. The code may be useful to researchers seeking a fast, accurate and reliable tool to simulate the near-field and far-field optical properties of elongated particles, but will also appeal to other developers of light-scattering software seeking a reliable benchmark for non-spherical particles with a challenging aspect ratio and/or refractive index contrast.

The transition-matrix (T -matrix) approach provides a general formalism to study scattering problems in various areas of physics, including acoustics (scalar fields) and electromagnetics (vector fields), and is related to the theory of the scattering matrix (S-matrix) used in quantum mechanics and quantum field theory. Focusing on electromagnetic scattering, we highlight an alternative formulation of the T -matrix approach, based on the use of the reactance matrix or K-matrix, which is more suited to formal studies of energy conservation constraints (such as the optical theorem). We show in particular that electrostatics or quasi-static approximations can be corrected within this framework to satisfy the energy conservation constraints associated with radiation. A general formula for such a radiative correction is explicitly obtained, and empirical expressions proposed in earlier studies are shown to be special cases of this general formula. This work therefore provides a justification of the empirical radiative correction to the dipolar polarizability and a generalization of this correction to any types of point or body scatterers of arbitrary shapes, including higher multipolar orders.

We study the convergence of the integrals required to be evaluated in the surface integral equation (SIE) formulation (or method of moments) for simulating the optical response of plasmonic nanostructures. We analyze how the numerical quadratures used to compute the integrals affect the accuracy of the SIE matrix elements and, in turn, that of the relevant physical quantities calculated using the method. Based on these studies, we propose an optimized algorithm for evaluation of the integrals, which improves the accuracy of the results without significantly increasing the calculation overhead.

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