Spontaneous growth of polarizing refractory metal 'nano-fins'.

Traditional polymer polarizers degrade in harsh environments and at high temperatures, reducing the polarization effect. In contrast, polarizers produced with refractory metals have vastly improved thermal stability and resistance to harsh environments but are expensive to fabricate. Here we demonstrate prototype refractory metal wire grid polarizers produced by co-sputtering molybdenum and aluminum under specific conditions. Removal of the aluminum through selective dissolution enables the nanostructure array to transmit light. The polarization spans 500-1100 nm and the extinction ratio significantly increases to >100. Possessing broadband polarization and sufficient extinction ratios, the new polarizing film has potential applications in coatings for sunglasses, windows, pyrometers, scientific instruments, and LCD panels.

Thermal stability of mesoscopic compounds of cetyltrimethylammonium and Keggin metatungstates.

A hybrid surfactant/polyoxometalate compound was synthesized by combining isopolytungstate anions with the cationic surfactant cetyltrimethylammonium bromide (CTA-Br) to produce a hierarchical compound that we identify as (CTA)7[H2W12O40]Cl·2H2O. At room temperature the compound consisted of hexagonally ordered sheets of Keggin ions, with an intervening gallery containing alkyl-chains of the organic cations. The synthesis was highly dependent on solution pH, reaction time and the order in which the reactants were added. We examined the effect of temperature on the stability of (CTA)7[H2W12O40]Cl·2H2O using thermal gravimetric analysis, differential scanning calorimetry, FT-IR spectroscopy and in situ synchrotron X-ray diffraction, and found a step-wise conversion to monoclinic WOxvia a series of intermediates. Heating under nitrogen atmospheres accelerated transition events by ∼100 °C when compared to heating in air. During heating, the interplanar gallery at first expanded in a series of steps starting at 90 °C as the CTA+ amphiphiles changed orientation, before collapsing rapidly at 240 °C, a temperature coinciding with the removal of about 40% of the organic material. Between 240 and 320 °C, the material consisted of fragments of the Keggin ion cores, arranged in 2D hexagonally-packed sheets. At ∼330 °C, the Keggin ions were completely destroyed and replaced by bulk W17O47 which, upon further heating, transformed to bulk WO2 or WO3 depending on the environment.

Anomalously strong plasmon resonances in aluminium bronze by modification of the electronic density-of-states.

We use a combination of experimental measurements and density functional theory calculations to show that modification of the band structure of Cu by additions of Al causes an unexpected enhancement of the dielectric properties. The effect is optimized in alloys with Al contents between 10 and 15 at.% and would result in strong localized surface plasmon resonances at suitable wavelengths of light. This result is surprising as, in general, alloying of Cu increases its DC resistivity and would be expected to increase optical loss. The wavelengths for the plasmon resonances in the optimized alloy are significantly blue-shifted relative to those of pure Cu and provide a new material selection option for the range 2.2-2.8 eV.

The effect of vacancies on the optical properties of AuAl2.

AuAl2 is an intermetallic compound with a vivid purple colour attributable to a bulk plasmon energy in the visible part of the spectrum. However, the colour of as-deposited thin films is not as strong and only develops upon annealing. Density functional theory calculations of the dielectric function are presented for a variety of vacancy types and concentrations. The results support the view that the effect of annealing on colour is correlated with a reduction in concentration of Al vacancies. The effect of vacancies on the optical properties can be understood as arising from the complex interplay between interband transitions around the Fermi level and the plasmon energy.

First principles calculations of the optical and plasmonic response of Au alloys and intermetallic compounds.

Pure Au is widely used in plasmonic applications even though its use is compromised by significant losses due to damping. There are some elements that are less lossy than Au (e.g. Ag or Al) but they will normally oxidize or corrode under ambient conditions. Here we examine whether alloying Au with a second element would be beneficial for plasmonic applications. In order to evaluate potential alternatives to pure Au, the density of states (DOS), dielectric function and plasmon quality factor have been calculated for alloys and compounds of Au with Al, Cd, Mg, Pd, Pt, Sn, Ti, Zn and Zr. Substitutional alloying of Au with Al, Cd, Mg and Zn was found to slightly improve the plasmonic response. Of the large number of intermetallic compounds studied, only AuAl2, Au3Cd, AuMg, AuCd and AuZn were found to be suitable for plasmonic applications.

Optical properties and plasmon resonances of titanium nitride nanostructures.

We examine the optical properties of nanostructures comprised of titanium nitride, TiN, an electrically conducting intermetallic-like compound. This material can be deposited in the form of durable films by physical vapor deposition. Use of nanosphere templating techniques extends the range of nanostructures that can be produced to include the versatile semi-shell motif. The dielectric properties of TiN(1-x) depend upon stoichiometry and are favorable for plasmon resonance phenomena in the mid-visible to near-infrared range of the spectrum and for x approximately 0. We analyze the optical phenomena operating in such structures using a combination of experiment and simulation and show that semi-shells of TiN exhibit a tunable localized plasmon resonance with light. The material is, however, unsuitable for applications in which a long-distance surface plasmon polariton is desired.

Rectification in donor-acceptor molecular junctions.

We perform density functional theory (DFT) calculations on molecular junctions consisting of a single molecule between two Au(111) electrodes. The molecules consist of an alkane or aryl bridge connecting acceptor, donor or thiol endgroups in various combinations. The molecular geometries are optimized and wavefunctions and eigenstates of the junction calculated using the DFT method, and then the electron transport properties for the junction are calculated within the non-equilibrium Green's function (NEGF) formalism. The current-voltage or i(V) characteristics for the various molecules are then compared. Rectification is observed for these molecules, particularly for the donor-bridge-acceptor case where the bridge is an alkane, with rectification being in the same direction as the original findings of Aviram and Ratner (1974 Chem. Phys. Lett. 29 277-83), at least for relatively large negative and positive applied bias. However, at smaller bias rectification is in the opposite direction and is attributed to the lowest unoccupied orbital associated with the acceptor group.

Effect of composition and packing configuration on the dichroic optical properties of coinage metal nanorods.

When nanorods of Au, Ag and some other elements are aligned with a preferred orientation with respect to light, their optical extinction characteristics become dependent on the polarization and angle of incidence of the light. This effect is explored here and it is shown that it could potentially be exploited to produce a 'colour-change coating'. However, particle-particle interactions are also likely to occur in such coatings, with red shifting of extinction spectra occurring for end-on-end configurations of monodisperse rods, and blue shifting for side-by-side configurations. Surprisingly, the particle-particle interactions are attenuated if they are between rods of differing aspect ratios, and this offers a useful new means of control of the optical properties of coatings of nanorods.