Power Spectral Density Analysis for Optimizing SERS Structures

The problem of optimizing the topography of metal structures allowing Surface Enhanced Raman Scattering (SERS) sensing is considered. We developed a model, which randomly distributes hemispheroidal particles over a given area of the glass substrate and estimates SERS capabilities of the obtained structures. We applied Power Spectral Density (PSD) analysis to modeled structures and to atomic force microscope images widely used in SERS metal island films and metal dendrites. The comparison of measured and calculated SERS signals from differing characteristics structures with the results of PSD analysis of these structures has shown that this approach allows simple identification and choosing a structure topography, which is capable of providing the maximal enhancement of Raman signal within a given set of structures of the same type placed on the substrate.

EXPRESS: Probing Heterogeneity in Attenuated Total Reflection Surface-Enhanced Infrared Absorption Spectroscopy (ATR SEIRAS) Response with Synchrotron Infrared Microspectroscopy

The heterogeneity of metal island films electrodeposited on conductive metal oxide modified internal reflection elements is shown to provide a variable ATR-SEIRAS (attenuated total reflection surface enhanced infrared absorption spectroscopy) response. A self-assembled monolayer of a ferrocene-terminated thiol monolayer (FcC11SH) was formed on the gold islands covering a single substrate, which was measured using both a conventional spectrometer and a custom-built horizontal microscope. Cyclic voltammetry and ATR-SEIRAS results reveal that the FcC11SH modified substrate undergoes a reversible electron transfer and an associated re-orientation of both the ferrocene/ferrocenium headgroup and the hydrocarbon backbone. The magnitude of the absorption signal arising from the redox changes in the monolayer, as well as the IR signature arising from the ingress/egress of the perchlorate counterions, is shown to depend significantly on the size of the infrared beam spot when using a conventional FTIR spectrometer. By performing equivalent measurements on a horizontal microscope, the primary cause of the differences in the signal level is found to be the hetereogeneity in the density of gold islands on the conductive metal oxide.

Plasmonic Nanoparticles and Island Films for Solar Energy Harvesting: A Comparative Study of Cu, Al, Ag and Au Performance

Alternative materials that can potentially replace Au and Ag in plasmonics and broaden its application potential have been actively investigated over the last decade. Cu and Al have been usually overlooked as plasmonic material candidates because they are prone to oxidisation. In this work the plasmonic performance of Cu and Al is investigated using numerical simulations of different nanostructures (spheres, cubes, rods and particle dimers) and taking into account the presence of oxidisation. It is shown that geometry can play a dominant role over material properties and the performance of Cu and Al becomes comparable to that of Ag and Au for systems of non-spherical particles and strong electromagnetic coupling among particles. This observation is experimentally confirmed by the fabrication and characterisation of Cu and Al metal island films. Optical characterisation of the samples reveals a comparable performance of these metals to that obtained for Ag and Au and suggests that Cu and Al metal island films can offer an efficient low-cost platform for solar energy harvesting, as shown in water vapour generation proof of concept experiments.

Periodic array-based substrates for surface-enhanced infrared spectroscopy

At the beginning of the 1980s, the first reports of surface-enhanced infrared spectroscopy (SEIRS) surfaced. Probably due to signal-enhancement factors of only 101 to 103, which are modest compared to those of surface-enhanced Raman spectroscopy (SERS), SEIRS did not reach the same significance up to date. However, taking the compared to Raman scattering much larger cross-sections of infrared absorptions and the enhancement factors together, SEIRS reaches about the same sensitivity for molecular species on a surface in terms of the cross-sections as SERS and, due to the complementary nature of both techniques, can valuably augment information gained by SERS. For the first 20 years since its discovery, SEIRS relied completely on metal island films, fabricated by either vapor or electrochemical deposition. The resulting films showed a strong variance concerning their structure, which was essentially random. Therefore, the increase in the corresponding signal-enhancement factors of these structures stagnated in the last years. In the very same years, however, the development of periodic array-based substrates helped SEIRS to gather momentum. This development was supported by technological progress concerning electromagnetic field solvers, which help to understand plasmonic properties and allow targeted design. In addition, the strong progress concerning modern fabrication methods allowed to implement these designs into practice. The aim of this contribution is to critically review the development of these engineered surfaces for SEIRS, to compare the different approaches with regard to their performance where possible, and report further gain of knowledge around and in relation to these structures.