No abstract

We show that the structure demonstrated by Feng et al. (Reports, 5 August 2011, p. 729) cannot enable optical isolation because it possesses a symmetric scattering matrix. Moreover, one cannot construct an optical isolator by incorporating this structure into any system as long as the system is linear and time-independent and is described by materials with a scalar dielectric function.

Hot charge carriers from plasmonic nanomaterials currently receive increased attention because of their promising potential in important applications such as solar water splitting. While a number of important contributions were made on plasmonic charge carrier generation and their transfer into the metal's surrounding in the last decades, the local origin of those carriers is still unclear. With our study employing a nanoscaled bicontinuous network of nanoporous gold, we take a comprehensive look at both subtopics in one approach and give unprecedented insights into the physical mechanisms controlling the broadband optical absorption and the generation and injection of hot electrons into an adjacent electrolyte where they enhance electrocatalytic hydrogen evolution. This absorption behavior is very different from the well-known localized surface plasmon resonance effects observed in metallic nanoparticles. For small ligament sizes, the plasmon decay in our network is strongly enhanced via surface collisions of electrons. These surface collisions are responsible for the energy transfer to the carriers and thus the creation of hot electrons from a broad spectrum of photon energies. As we reduce the gold ligament sizes below 30 nm, we demonstrate an occurring transition from absorption that is purely exciting 5d-electrons from deep below the Fermi level to an absorption which significantly excites "free" 6sp-electrons to be emitted. We differentiate these processes via assessing the internal quantum efficiency of the gold network photoelectrode as a function of the feature size providing a size-dependent understanding of the hot electron generation and injection processes in nanoscale plasmonic systems. We demonstrate that the surface effect, compared with the volume effect, becomes dominant and leads to significantly improved efficiencies. The most important fact to recognize is that in the surface photoeffect presented here, absorption and electron transfer are both part of the same quantum mechanical event.

High temperature stable selective emitters can significantly increase efficiency and radiative power in thermophotovoltaic (TPV) systems. However, optical properties of structured emitters reported so far degrade at temperatures approaching 1200 °C due to various degradation mechanisms. We have realized a 1D structured emitter based on a sputtered W-HfO 2 layered metamaterial and demonstrated desired band edge spectral properties at 1400 °C. To the best of our knowledge the temperature of 1400 °C is the highest reported for a structured emitter, so far. The spatial confinement and absence of edges stabilizes the W-HfO 2 multilayer system to temperatures unprecedented for other nanoscaled W-structures. Only when this confinement is broken W starts to show the well-known self-diffusion behavior transforming to spherical shaped W-islands. We further show that the oxidation of W by atmospheric oxygen could be prevented by reducing the vacuum pressure below 10 −5 mbar. When oxidation is mitigated we observe that the 20 nm spatially confined W films survive temperatures up to 1400 °C. The demonstrated thermal stability is limited by grain growth in HfO 2 , which leads to a rupture of the W-layers, thus, to a degradation of the multilayer system at 1450 °C.

Hot electron generation in a metal and injection into a semiconductor is a crucial mechanism to convert sub band gap photons into free electrical charges inside a semiconductor. This process is of paramount importance for solar photocatalysis since the semiconductors involved often have a band gap too large for direct excitation with sun light, thus requiring a carrier transfer from an adjacent effective absorber, which in our case is a metal, to the semiconductor in order to initiate the envisaged photochemical reactions. Single interaction of a hot electron with a metal−semiconductor boundary is described by Fowler's law. In nanometer sized metals hot electrons, before they lose their energy, can interact several times with the boundary, which increases the probability of injection. To understand the efficiency of this process, to find ways to optimize it, and to determine its limits, an electron transport model based on a Monte Carlo approach is proposed. The numerical calculations provide an indepth understanding of the impact of size and shape of the metal on the injection efficiency. Values are obtained that exceed the usual efficiency limits described by Fowler's theory.

Non-iridescent structural colors based on disordered arrangement of monodisperse spherical particles, also called photonic glass, show low color saturation due to gradual transition in the reflectivity spectrum. No significant improvement is usually expected from particles optimization, as Mie resonances are broad for small dielectric particles with moderate refractive index. Moreover, the short range order of a photonic glass alone is also insufficient to cause sharp spectral features. We show here, that the combination of a well-chosen particle geometry with the short range order of a photonic glass has strong synergetic effects. Using a first-order approximation and an Ewald sphere construction the reflectivity of such structures can be related to the Fourier transform of the permittivity distribution. The Fourier transform required for a highly saturated color can be achieved by tailoring the substructure of the motif. We show that this can be obtained by choosing core-shell particles with a non-monotonous refractive index distribution from the center of the particle through the shell and into the background material. The first-order theoretical predictions are confirmed by numerical simulations.

The spectral properties of nanoporous gold are distinguished by two peaks in the transmission spectrum. Unlike earlier works, we do not attribute the peaks in the transmission to two separate localized plasmon resonances. Instead we show that the spectral shape can be understood as that of diluted gold with a spectrally narrow dip in transmission that arises from the averaged electric field approaching zero. Thus, the transmission characteristics are rather featured by a dip in one broad transmission curve than by two distinct peaks. Nanoporous gold is approximated by the effective medium model of a cubic grid of gold wires.

Using optical in-situ measurements in an electrochemical environment, we study the electrochemical tuning of the transmission spectrum of films from the nanoporous gold (NPG) based optical metamaterial, including the effect of the ligament size. The long wavelength part of the transmission spectrum around 800 nm can be reversibly tuned via the applied electrode potential. The NPG behaves as diluted metal with its transition from dielectric to metallic response shifted to longer wavelengths. We find that the applied potential alters the charge carrier density to a comparable extent as in experiments on gold nanoparticles. However, compared to nanoparticles, a NPG optical metamaterial, due to its connected structure, shows a much stronger and more broadband change in optical transmission for the same change in charge carrier density. We were able to tune the transmission through an only 200 nm thin sample by 30%. In combination with an electrolyte the tunable NPG based optical metamaterial, which employs a very large surface-to-volume ratio is expected to play an important role in sensor applications, for photoelectrochemical water splitting into hydrogen and oxygen and for solar water purification.