Charles Cherqui

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.

Characterizing Localized Surface Plasmons Using Electron Energy-Loss Spectroscopy.

Electron energy-loss spectroscopy (EELS) offers a window to view nanoscale properties and processes. When performed in a scanning transmission electron microscope, EELS can simultaneously render images of nanoscale objects with subnanometer spatial resolution and correlate them with spectroscopic information at a spectral resolution of ∼10-100 meV. Consequently, EELS is a near-perfect tool for understanding the optical and electronic properties of individual plasmonic metal nanoparticles and few-nanoparticle assemblies, which are significant in a wide range of fields. This review presents an overview of basic plasmonics and EELS theory and highlights several recent noteworthy experiments involving the interrogation of plasmonic metal nanoparticle systems using electron beams.

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.

Effect of Localized Surface-Plasmon Mode on Exciton Transport and Radiation Emission in Carbon Nanotubes

We report on a general theoretical approach to study exciton transport and emission in a single-walled carbon nanotube (SWNT) in the presence of a localized surface-plasmon (SP) mode within a metal nanoparticle interacting via near-field coupling. We derive a set of quantum mechanical equations of motion and approximate rate equations that account for the exciton, SP, and the environmental degrees of freedom. The material equations are complemented by an expression for the radiated power that depends on the exciton and SP populations and coherences, allowing for an examination of the angular distribution of the emitted radiation that would be measured in experiment. Numerical simulations for a (6,5) SWNT and cone-shaped Ag metal tip (MT) have been performed using this methodology. Comparison with physical parameters shows that the near-field interaction between the exciton-SP occurs in a weak coupling regime, with the diffusion processes being much faster than the exciton-SP population exchange. In such a case, the effect of the exciton population transfer to the MT with its subsequent dissipation (i.e., the Förster energy transfer) is to modify the exciton steady state distribution while reducing the equilibration time for excitons to reach a steady sate distribution. We find that the radiation distribution is dominated by SP emission for a SWNT-MT separation of a few tens of nanometers due to the fast SP emission rate, whereas the exciton-SP coherences can cause its rotation.

Noninvasive Cathodoluminescence-Activated Nanoimaging of Dynamic Processes in Liquids

In situ electron microscopy provides remarkably high spatial resolution, yet electron beam irradiation often damages soft materials and perturbs dynamic processes, requiring samples to be very robust. Here, we instead noninvasively image the dynamics of metal and polymer nanoparticles in a liquid environment with subdiffraction resolution using cathodoluminescence-activated imaging by resonant energy transfer (CLAIRE). In CLAIRE, a free-standing scintillator film serves as a nanoscale optical excitation source when excited by a low energy, focused electron beam. We capture the nanoscale dynamics of these particles translating along and desorbing from the scintillator surface and demonstrate 50 ms frame acquisition and a range of imaging of at least 20 nm from the scintillator surface. Furthermore, in contrast with in situ electron microscopy, CLAIRE provides spectral selectivity instead of relying on scattering alone. We also demonstrate through quantitative modeling that the CLAIRE signal from metal nanoparticles is impacted by multiplasmonic mode interferences. Our findings demonstrate that CLAIRE is a promising, noninvasive approach for super-resolution imaging for soft and fluid materials with high spatial and temporal resolution.

Multipolar Nanocube Plasmon Mode-Mixing in Finite Substrates

Facile control of the radiative and nonradiative properties of plasmonic nanostructures is of practical importance to a wide range of applications in the biological, chemical, optical, information, and energy sciences. For example, the ability to easily tune not only the plasmon spectrum but also the degree of coupling to light and/or heat, quality factor, and optical mode volume would aid the performance and function of nanophotonic devices and molecular sensors that rely upon plasmonic elements to confine and manipulate light at nanoscopic dimensions. While many routes exist to tune these properties, identifying new approaches-especially when they are simple to apply experimentally-is an important task. Here, we demonstrate the significant and underappreciated effects that substrate thickness and dielectric composition can have upon plasmon hybridization as well as downstream properties that depend upon this hybridization. We find that even substrates as thin as ∼10 nm can nontrivially mix free-space plasmon modes, imparting bright character to those that are dark (and vice versa) and, thereby, modifying the plasmonic density of states as well as the systems near- and far-field optical properties. A combination of electron energy-loss spectroscopy (EELS) experiment, numerical simulation, and analytical modeling is used to elucidate this behavior in the finite substrate-induced mixing of dipole, quadrupole, and octupole corner-localized plasmon resonances of individual silver nanocubes.

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.