Harnessing the energy from hot charge carriers is an emerging research area with the potential to improve energy conversion technologies. − Here we present a novel plasmonic photoelectrode architecture carefully designed to drive photocatalytic reactions by efficient, nonradiative plasmon decay into hot carriers. In contrast to past work, our architecture does not utilize a Schottky junction, the commonly used building block to collect hot carriers. Instead, we observed large photocurrents from a Schottky-free junction due to direct hot electron injection from plasmonic gold nanoparticles into the reactant species upon plasmon decay. The key ingredients of our approach are (i) an architecture for increased light absorption inspired by optical impedance matching concepts, (ii) carrier separation by a selective transport layer, and (iii) efficient hot-carrier generation and injection from small plasmonic Au nanoparticles to adsorbed water molecules. We also investigated the quantum efficiency of hot electron injection for different particle diameters to elucidate potential quantum effects while keeping the plasmon resonance frequency unchanged. Interestingly, our studies did not reveal differences in the hot-electron generation and injection efficiencies for the investigated particle dimensions and plasmon resonances.

Refractory nanophotonics, or nanophotonics at high temperatures, can revolutionize many applications, including data storage and waste heat recovery. In particular, nanophotonic devices made from hyperbolic materials are promising due to their nearly infinite photonic density of states (PDOS). However, it is challenging to achieve a prominent PDOS in existing refractory hyperbolic materials, especially in a broad spectral range. Here, we demonstrate that macroscopic films and architectures of aligned carbon nanotubes work as excellent refractory hyperbolic materials. We found that aligned carbon nanotubes are thermally stable up to 1600 • C and exhibit extreme anisotropy -metallic in one direction and insulating in the other two directions. Such extreme anisotropy makes this system a hyperbolic material with an exceptionally large PDOS over a broadband spectrum range (longer than 4.3 µm) in the midinfrared, exhibiting strong resonances in deeply subwavelength-sized cavities. We observed polarized, spectrally selective thermal emission from aligned carbon nanotube films as well as indefinite cavities of aligned carbon nanotubes with volume as small as ∼ λ 3 /700 operating at 700 • C. These experiments suggest that aligned carbon nanotubes possess naturally large PDOS that leads to thermal photon densities enhanced by over two orders of magnitude, making them a promising refractory nanophotonics platform. * guru@rice.edu † These authors contributed equally. arXiv:1903.06063v1 [physics.optics]

Since the discovery of the laser, optical nonlinearities have been at the core of efficient light conversion sources. Typically, thick transparent crystals or quasi-phase matched waveguides are utilized in conjunction with phase-matching techniques to select a single parametric process. In recent years, due to the rapid developments in artificially structured materials, optical frequency mixing has been achieved at the nanoscale in subwavelength resonators arrayed as metasurfaces. Phase matching becomes relaxed for these wavelength-scale structures, and all allowed nonlinear processes can, in principle, occur on an equal footing. This could promote harmonic generation via a cascaded (consisting of several frequency mixing steps) process. However, so far, all reported work on dielectric metasurfaces have assumed frequency mixing from a direct (single step) nonlinear process. In this work, we prove the existence of cascaded second-order optical nonlinearities by analyzing the second- and third-wave mixing from a highly nonlinear metasurface in conjunction with polarization selection rules and crystal symmetries. We find that the third-wave mixing signal from a cascaded process can be of comparable strength to that from conventional third-harmonic generation and that surface nonlinearities are the dominant mechanism that contributes to cascaded second-order nonlinearities in our metasurface.

The effect of terahertz (THz) pulse generation has revolutionized broadband coherent spectroscopy and imaging at THz frequencies. However, THz pulses typically lack spatial structure, whereas structured beams are becoming essential for advanced spectroscopy applications. Nonlinear optical metasurfaces with nanoscale THz emitters can provide a solution by defining the beam structure at the generation stage. We develop a nonlinear InAs metasurface consisting of nanoscale optical resonators for simultaneous generation and structuring of THz beams. We find that THz pulse generation in the resonators is governed by optical rectification. It is more efficient than in ZnTe crystals, and it allows us to control the pulse polarity and amplitude, offering a platform for realizing binary-phase THz metasurfaces. To illustrate this capability, we demonstrate an InAs metalens, which simultaneously generates and focuses THz pulses. The control of spatiotemporal structure using nanoscale emitters opens doors for THz beam engineering and advanced spectroscopy and imaging applications.