Unlike silver and gold, aluminum has material properties that enable strong plasmon resonances spanning much of the visible region of the spectrum and into the ultraviolet. This extended response, combined with its natural abundance, low cost, and amenability to manufacturing processes, makes aluminum a highly promising material for commercial applications. Fabricating Al-based nanostructures whose optical properties correspond with theoretical predictions, however, can be a challenge. In this work, the Al plasmon resonance is observed to be remarkably sensitive to the presence of oxide within the metal. For Al nanodisks, we observe that the energy of the plasmon resonance is determined by, and serves as an optical reporter of, the percentage of oxide present within the Al. This understanding paves the way toward the use of aluminum as a low-cost plasmonic material with properties and potential applications similar to those of the coinage metals.
The optical properties of a high quality bulk ZnO, thermally post treated in a forming gas environment are investigated by temperature dependent continuous wave and time-resolved photoluminescence (PL) measurements. Several bound and free exciton transitions along with their first excited states have been observed at low temperatures, with the main neutral-donor-bound exciton peak at 3.3605 eV having a linewidth of 0.7 meV and dominating the PL spectrum at 10 K. This bound exciton transition was visible only below 150 K, whereas the A-free exciton transition at 3.3771 eV persisted up to room temperature. A-free exciton binding energy of 60 meV is obtained from the position of the excited states of the free excitons. Additional intrinsic and extrinsic fine structures such as polariton, two-electron satellites, donor-acceptor pair transitions, and longitudinal optical-phonon replicas have also been observed and investigated in detail. Time-resolved PL measurements at room temperature reveal a biexponential decay behavior with typical decay constants of ϳ170 and ϳ864 ps for the as-grown sample. Thermal treatment is observed to increase the carrier lifetimes when performed in a forming gas environment.
The use of aluminum for plasmonic nanostructures opens up new possibilities, such as access to short-wavelength regions of the spectrum, complementary metal-oxide-semiconductor (CMOS) compatibility, and the possibility of low-cost, sustainable, mass-producible plasmonic materials. Here we examine the properties of individual Al nanorod antennas with cathodoluminescence (CL). This approach allows us to image the local density of optical states (LDOS) of Al nanorod antennas with a spatial resolution less than 20 nm and to identify the radiative modes of these nanostructures across the visible and into the UV spectral range. The results, which agree well with finite difference time domain (FDTD) simulations, lay the groundwork for precise Al plasmonic nanostructure design for a variety of applications.
Photocatalysis has not found widespread industrial adoption, in spite of decades of active research, because the challenges associated with catalyst illumination and turnover outweigh the touted advantages of replacing heat with light. A demonstration that light can control product selectivity in complex chemical reactions could prove to be transformative. Here, we show how the recently demonstrated plasmonic behaviour of rhodium nanoparticles profoundly improves their already excellent catalytic properties by simultaneously reducing the activation energy and selectively producing a desired but kinetically unfavourable product for the important carbon dioxide hydrogenation reaction. Methane is almost exclusively produced when rhodium nanoparticles are mildly illuminated as hot electrons are injected into the anti-bonding orbital of a critical intermediate, while carbon monoxide and methane are equally produced without illumination. The reduced activation energy and super-linear dependence on light intensity cause the unheated photocatalytic methane production rate to exceed the thermocatalytic rate at 350°C.
The practical efficacy of technologically promising metals for use in ultraviolet plasmonics (3−6 eV) is assessed by an exhaustive numerical analysis. This begins with estimates of the near-and far-field electromagnetic enhancement factors of isolated hemispherical and spherical metallic nanoparticles deposited on typical dielectric substrates like sapphire, from which the potential of each metal for plasmonic applications may be ascertained. The ultraviolet plasmonic behavior of aluminum, chromium, copper, gallium, indium, magnesium, palladium, platinum, rhodium, ruthenium, titanium, and tungsten was compared with the well-known behavior of gold and silver in the visible. After exploring this behavior for each metal as a function of nanoparticle shape and size, the deleterious effect caused by the metal's native oxide is considered, and the potential for applications such as surface-enhanced Raman spectroscopy, accelerated photodegradation and photocatalysis is addressed.
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