The behavior of metals across a broad frequency range from microwave to ultraviolet frequencies is of interest in plasmonics, nanophotonics, and metamaterials. Depending on the frequency, losses of collective excitations in metals can be predominantly classical resistive effects or Landau damping. In this context, we present first-principles calculations that capture all of the significant microscopic mechanisms underlying surface plasmon decay and predict the initial excited carrier distributions so generated. Specifically, we include ab initio predictions of phonon-assisted optical excitations in metals, which are critical to bridging the frequency range between resistive losses at low frequencies and direct interband transitions at high frequencies. In the commonly used plasmonic materials, gold, silver, copper, and aluminum, we find that resistive losses compete with phonon-assisted carrier generation below the interband threshold, but hot carrier generation via direct transitions dominates above threshold. Finally, we predict energy-dependent lifetimes and mean free paths of hot carriers, accounting for electron-electron and electron-phonon scattering, to provide insight toward transport of plasmonically generated carriers at the nanoscale.

Empowering silicon (Si) with optical functions constitutes a very important challenge in photonics. The scalable fabrication capabilities for this earth-abundant, environmentally friendly material are unmatched in sophistication and can be unleashed to realize a plethora of high-performance photonic functionalities that find application in information, bio-, display, camouflage, ornamental, and energy technologies. Nanofashioning represents a general strategy to turn Si into a useful optical material and Si structures have already been engineered to enable light emission, optical cloaking, waveguiding, nonlinear optics, enhanced light absorption, and sensing. Here, we demonstrate that a wide spectrum of colors can be generated by harnessing the strong resonant light scattering properties of Si nanostructures under white light illumination. The ability to engineer such colors in a predetermined fashion through a choice of the structure size, dielectric environment, and illumination conditions opens up entirely new applications of Si and puts this material in a new light.

The conversion of optical power to an electric potential is of general interest for energy applications and is typically obtained via optical excitation of semiconductor materials. We developed a method for achieving electric potential that uses an all-metal geometry based on the plasmon resonance in metal nanostructures. In arrays of gold nanoparticles on an indium tin oxide substrate and arrays of 100-nanometer-diameter holes in 20-nanometer-thick gold films on a glass substrate, we detected negative and positive surface potentials during monochromatic irradiation at wavelengths below or above the plasmon resonance, respectively. We observed plasmoelectric surface potentials as large as 100 millivolts under illumination of 100 milliwatts per square centimeter. Plasmoelectric devices may enable the development of all-metal optoelectronic devices that can convert light into electrical energy.

Ultrafast laser measurements probe the non-equilibrium dynamics of excited electrons in metals with increasing temporal resolution. Electronic structure calculations can provide a detailed microscopic understanding of hot electron dynamics, but a parameter-free description of pump-probe measurements has not yet been possible, despite intensive research, because of the phenomenological treatment of electron-phonon interactions. We present ab initio predictions of the electrontemperature dependent heat capacities and electron-phonon coupling coefficients of plasmonic metals. We find substantial differences from free-electron and semi-empirical estimates, especially in noble metals above transient electron temperatures of 2000 K, because of the previously-neglected strong dependence of electron-phonon matrix elements on electron energy. We also present firstprinciples calculations of the electron-temperature dependent dielectric response of hot electrons in plasmonic metals, including direct interband and phonon-assisted intraband transitions, facilitating complete theoretical predictions of the time-resolved optical probe signatures in ultrafast laser experiments.