Nicholas W. Bigelow

Characterization of the electron- and photon-driven plasmonic excitations of metal nanorods.

A computational analysis of the electron- and photon-driven surface-plasmon resonances of monomer and dimer metal nanorods is presented to elucidate the differences and similarities between the two excitation mechanisms in a system with well-understood optical properties. By correlating the nanostructures simulated electron energy-loss spectrum and loss-probability maps with its induced polarization and scattered electric field we discern how certain plasmon modes are selectively excited and how they funnel energy from the excitation source into the near- and far-field. Using a fully retarded electron-scattering theory capable of describing arbitrary three-dimensional nanoparticle geometries, aggregation schemes, and material compositions, we find that electron energy-loss spectroscopy (EELS) is able to indirectly probe the same electromagnetic hot spots that are generated by an optical excitation source. Comparison with recent experiment is made to verify our findings.

Single-Molecule Surface-Enhanced Raman Scattering: Can STEM/EELS Image Electromagnetic Hot Spots?

Since the observation of single-molecule surface-enhanced Raman scattering (SMSERS) in 1997, questions regarding the nature of the electromagnetic hot spots responsible for such observations still persist. For the first time, we employ electron-energy-loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM) to obtain maps of the localized surface plasmon modes of SMSERS-active nanostructures, which are resolved in both space and energy. Single-molecule character is confirmed by the bianalyte approach using two isotopologues of Rhodamine 6G. Surprisingly, the STEM/EELS plasmon maps do not show any direct signature of an electromagnetic hot spot in the gaps between the nanoparticles. The origins of this observation are explored using a fully three-dimensional electrodynamics simulation of both the electron-energy-loss probability and the near-electric field enhancements. The calculations suggest that electron beam excitation of the hot spot is possible, but only when the electron beam is located outside of the junction region.

Spatially Mapping Energy Transfer from Single Plasmonic Particles to Semiconductor Substrates via STEM/EELS

Energy transfer from plasmonic nanoparticles to semiconductors can expand the available spectrum of solar energy-harvesting devices. Here, we spatially and spectrally resolve the interaction between single Ag nanocubes with insulating and semiconducting substrates using electron energy-loss spectroscopy, electrodynamics simulations, and extended plasmon hybridization theory. Our results illustrate a new way to characterize plasmon-semiconductor energy transfer at the nanoscale and bear impact upon the design of next-generation solar energy-harvesting devices.

Signatures of Fano Interferences in the Electron Energy Loss Spectroscopy and Cathodoluminescence of Symmetry-Broken Nanorod Dimers

Through numerical simulation, we predict the existence of the Fano interference effect in the electron energy loss spectroscopy (EELS) and cathodoluminescence (CL) of symmetry-broken nanorod dimers that are heterogeneous in material composition and asymmetric in length. The differing selection rules of the electron probe in comparison to the photon of a plane wave allow for the simultaneous excitation of both optically bright and dark plasmons of each monomer unit, suggesting that Fano resonances will not arise in EELS and CL. Yet, interferences are manifested in the dimers scattered near- and far-fields and are evident in EELS and CL due to the rapid π-phase offset in the polarizations between super-radiant and subradiant hybridized plasmon modes of the dimer as a function of the energy loss suffered by the impinging electron. Depending upon the location of the electron beam, we demonstrate the conditions under which Fano interferences will be present in both optical and electron spectroscopies (EELS and CL) as well as a new class of Fano interferences that are uniquely electron-driven and are absent in the optical response. Among other things, the knowledge gained from this work bears impact upon the design of some of the worlds most sensitive sensors, which are currently based upon Fano resonances.

Thermal Signatures of Plasmonic Fano Interferences: Toward the Achievement of Nanolocalized Temperature Manipulation.

A consequence of thermal diffusion is that heat, even when applied to a localized region of space, has the tendency to produce a temperature change that is spatially uniform throughout a material with a thermal conductivity that is much larger than that of its environment. This implies that the degree of spatial correlation between the heat power supplied and the temperature change that it induces is likely to be small. Here, we show, via theory and simulation, that through a Fano interference, temperature changes can be both localized and controllably directed within certain plasmon-supporting metal nanoparticle assemblies. This occurs even when all particles are composed of the same material and contained within the same diffraction-limited spot. These anomalous thermal properties are compared and contrasted across three different nanosystems, the coupled nanorod-antenna, the heterorod dimer, and the nanocube on a substrate, known to support both spatial and spectral Fano interferences. We conclude that the presence of a Fano resonance is not sufficient by itself to induce a controllably nanolocalized temperature change. However, when present in a nanosystem of the right composition and morphology, temperature changes can be manipulated with nanoscale precision, despite thermal diffusion.

Examining Substrate-Induced Plasmon Mode Splitting and Localization in Truncated Silver Nanospheres with Electron Energy Loss Spectroscopy.

Motivated by the need to study the size dependence of nanoparticle-substrate systems, we present a combined experimental and theoretical electron energy loss spectroscopy (EELS) study of the plasmonic spectrum of substrate-supported truncated silver nanospheres. This work spans the entire classical range of plasmonic behavior probing particles of 20-1000 nm in diameter, allowing us to map the evolution of localized surface plasmons into surface plasmon polaritons and study the size dependence of substrate-induced mode splitting. This work constitutes the first nanoscopic characterization and imaging of these effects in truncated nanospheres, setting the stage for the systematic study of plasmon-mediated energy transfer in nanoparticle-substrate systems.

Nanoscopic imaging of energy transfer from single plasmonic particles to semiconductor substrates via STEM/EELS

Localized surface plasmon resonances (LSPRs), the collective oscillations of conduction electrons in metallic nanoparticles, can produce intense near-fields at the resonance wavelengths. Plasmonic nanoparticles have been incorporated in the design of photovoltaic (PV) and photocatalytic devices, where they have been shown to enhance solar energy harvesting efficiency. Research has shown that the addition of plasmonic nanoparticles improves the efficiency of solar light harvesting via one or more of the following mechanisms1: (1) LSPR excitation leads to an increase in path length for incoming light via scattering, thereby increasing light absorption by the semiconductors; (2) energy transfer from the decay of an LSPR directly creates an electron-hole pair in the semiconductor, a process known as plasmon-induced resonant energy transfer (PIRET). Its efficiency relies on the overlap between the LSPR emission and the band gap absorption of the semiconductor2; (3) direct electron transfer (DET) from the nanoparticle to a semiconductor, in which an LSPR decays, through Landau damping, into a “hot” electron that may then scatter into the semiconductor if it has sufficient energy to overcome the Schottky barrier formed at the interface3. Mechanism (1) is only effective for photon energies above the band gap, while mechanism (2) and (3) involve photons with energies below or above the band gap, therefore, are of particular interest and importance. However, despite its importance, little is known about how PIRET and DET operate at the nanoscale, particularly at the level of a single nanoparticle.