RESUMEN
The concept of plasmonic "hotspots" is central to the broad field of nanophotonics. In surface-enhanced Raman scattering (SERS), hotspots can increase Raman scattering efficiency by orders of magnitude. Hotspot dimensions may range from a few nanometers down to the atomic scale and are able to generate SERS signals from single molecules. However, these single-molecule SERS signals often show significant fluctuations, and the concept of intense, localized, yet static hotspots has come into question. Recent experiments have shown these SERS intensity fluctuations (SIFs) to occur over an extremely wide range of timescales, from seconds to microseconds, due to the various physical mechanisms causing SERS and the dynamic nature of light-matter interaction at the nanoscale. The underlying source of single-molecule SERS fluctuations is therefore likely to be a complex interplay of several different effects at different timescales. A high-speed acquisition system that captures a full SERS spectrum with microsecond time resolution can therefore provide information about these dynamic processes. Here, we show an acquisition system that collects at a rate of 100,000 SERS spectra per second, allowing high-speed characterization. We find that while each individual SIF event will enhance a different portion of the SERS spectrum, including a single peak, over 10s to 100s of microseconds, the SIF events overall do not favor one region of the spectrum over another. These high-speed SIF events can therefore occur with relatively equal probability over a broad spectral range, covering both the anti-Stokes and the Stokes sides of the spectrum, sometimes leading to anomalously large anti-Stokes peaks. This indicates that both temporally and spectrally transient hotspots drive the SERS fluctuations at high speeds.
RESUMEN
Propagating surface plasmon waves have been used for many applications including imaging and sensing. However, direct in-plane imaging of micro-objects with surface plasmon waves suffers from the lack of simple, two-dimensional lenses, mirrors, and other optical elements. In this paper, we apply lensless digital holographic techniques and leakage radiation microscopy to achieve in-plane surface imaging with propagating surface plasmon waves. As plasmons propagate in two-dimensions and scatter from various objects, a hologram is formed over the surface. Iterative phase retrieval techniques applied to this hologram remove twin image interference for high-resolution in-plane imaging and enable further applications in real-time plasmonic phase sensing.
RESUMEN
The observation of single molecule events using surface-enhanced Raman scattering (SERS) is a well-established phenomenon. These events are characterized by strong fluctuations in SERS intensities. High-speed SERS intensity fluctuations (in the microsecond time scale) have been reported for experiments involving single metallic particles. In this work, the high-speed SERS behavior of six different types of nanostructured metal systems (Ag nanoshells, Ag nanostars, Ag aggregated spheres, Au aggregated spheres, particle-on-mirror, and Ag deposited on microspheres) was investigated. All systems demonstrated high-speed SERS intensity fluctuations. Statistical analysis of the duration of the SERS fluctuations yielded tailed distributions with average event durations around 100 µs. Although the characteristics of the fluctuations seem to be random, the results suggest interesting differences between the system that might be associated with the strength distribution and density of the localized SERS hotspots. For instance, systems with more localized fields, such as nanostars, present faster fluctuation bursts compared to metallic aggregates that support spread-out fields. The results presented here appear to confirm that high-speed SERS intensity fluctuations are a fundamental characteristic of the SERS effect.
