Near-field distribution of optical transmission of periodic subwavelength holes in a metal film

Optical transmission of a two-dimensional array of subwavelength holes in a metal film has been numerically studied using a differential method. Transmission spectra have been calculated showing a significant increase of the transmission in certain spectral ranges corresponding to the excitation of the surface polariton Bloch waves on a metal surface with a periodic hole structure. Under the enhanced transmission conditions, the near-field distribution of the transmitted light reveals an intensity enhancement greater than 2 orders of magnitude in localized (similar to 40 nm) spots resulting from the interference of the surface polaritons Bragg scattered by the holes in an array.

Optical transmission of periodic annular apertures in metal film on high-refractive index substrate: The role of the nanopillar shape

The influence of annular aperture parameters on the optical transmission through arrays of coaxial apertures in a metal film on high refractive index substrates has been investigated experimentally and numerically. It is shown that the transmission resonances are related to plasmonic crystal effects rather than frequency cutoff behavior associated with annular apertures. The role of deviations from ideal aperture shape occurring during the fabrication process has also been studied. Annular aperture arrays are often considered in many applications for achieving high optical transmission through metal films and understanding of nanofabrication tolerances are important. (C) 2010 American Institute of Physics.

Light tunneling via resonant surface plasmon polariton states and the enhanced transmission of periodically nanostructured metal films: An analytical study

An analytical treatment of optical transmission through periodically nanosructured metal films capable of supporting surface-plasmon polaritons is presented. The optical properties of such metal films are governed by surface polariton behavior in a periodic surface structure forming a surface polaritonic crystal. Due to different configurations of the electromagnetic field of surface polariton modes, only states of even Brillouin zones are responsible for the optical transmission enhancement at normal incidence. The transmission enhancement is related to photon tunneling via resonant states of surface polariton Bloch modes in which the energy buildup takes place. Surface polariton states of at least one of the film interfaces contribute to the transmission resonance which occurs due to tunnel coupling between photons and surface polaritons on the opposite interfaces. Under double-resonance conditions, resonant tunneling between surface polariton states of both interfaces is achieved, which leads to further enhancement of the transmission efficiency. The double-resonance conditions occur not only in the case of a film in symmetric environment but can also be engineered for a film on a substrate. Light tunneling via surface polariton states can take place directly through a structured metal film and does not necessarily require holes in a film.

SURFACE-PLASMON ENHANCED LASER-ABLATION OF THIN METAL-FILMS

Surface plasmon enhancement of laser ablation of thin Al films is examined with a view to its application in metal film patterning and nano-structuring. Al films, deposited on silica prisms, are first characterized by attenuated total reflection using a broadband UV source and appropriate interference filter. The films are subsequently subjected to excimer laser radiation of wavelength 248 nm under conditions both of direct incidence from the air side of the film, and of surface plasmon excitation in which light is incident through the prism at greater than critical angle. For a given level of ablation damage in a particular film the fluence required using the surface plasmon technique is 3-5 times less than that needed when direct incidence is used. This is roughly in line with the energy absorbed in the film. From a practical standpoint it is clear that ablation of metal films can be achieved with much lower fluences than has hitherto been possible, thus reducing the requirements on laser output and relaxing the power handling constraints on any input optical elements.

CHARACTERIZATION OF SURFACE-PLASMONS ON METAL-OXIDE-SEMICONDUCTOR STRUCTURES

Using the Otto (prism-air gap-sample) configuration p-polarized light of wavelength 632.8 nm has been coupled with greater than 80% efficiency to surface plasmons on the aluminium electrode of silicon-silicon dioxide-aluminium structures. The results show that if the average power per unit area dissipated on the metal film exceeds approximately 1 mW mm-2, then the coupling gap and thus the characteristics of the surface plasmon resonance are noticeably altered. In modelling the optical response of such systems the inclusion of both a non-uniform air coupling gap and a thin cermet layer at the aluminium surface may be necessary.

Electrochemical promotion of a metal catalyst supported on a mixed-ionic conductor

It has been found that the catalytic activity and selectivity of a metal film deposited on a solid electrolyte could be enhanced dramatically and in a reversible way by applying an electrical current or potential between the metal catalyst and the counter electrode (also deposited on the electrolyte). This phenomenon is know as NEMCA [S. Bebelis, C.G. Vayenas, Journal of Catalysis, 118 (1989) 125-146.] or electrochemical promotion (EP) [J. Prichard, Nature, 343 (1990) 592.] of catalysis. Yttria-doped barium zirconate, BaZr_0.9Y_0.1O_{3 - α} (BZY), a known proton conductor, has been used in this study. It has been reported that proton conducting perovskites can, under the appropriate conditions, act also as oxide ion conductors. In mixed conducting systems the mechanism of conduction depends upon the gas atmosphere that to which the material is exposed. Therefore, the use of a mixed ionic (oxide ion and proton) conducting membrane as a support for a platinum catalyst may facilitate the tuning of the promotional behaviour of the catalyst by allowing the control of the conduction mechanism of the electrolyte. The conductivity of BZY under different atmospheres was measured and the presence of oxide ion conduction under the appropriate conditions was confirmed. Moreover, kinetic experiments on ethylene oxidation corroborated the findings from the conductivity measurements showing that the use of a mixed ionic conductor allows for the tuning of the reaction rate. © 2006 Elsevier B.V. All rights reserved.

IMAGING OF SURFACE-PLASMON PROPAGATION AND EDGE INTERACTION USING A PHOTON SCANNING TUNNELING MICROSCOPE

We report the direct imaging of surface plasmon propagation on thin silver films using the photon scanning tunneling microscope. It is found that the surface plasmon remains tightly confined in the original launch direction with insignificant scattering to other momentum states. A propagation length of 13.2 mum is measured at lambda = 632.8 nm. We also present images showing the interaction of a surface plasmon with the edge of the metal film supporting it. The most remarkable feature is the absence of a specularly reflected beam.

Enhancing the Efficiency of Slit-Coupling to Surface-Plasmon Polariton via Dispersion Engineering

We describe a simple method for enhancing the efficiency of coupling from a free-space transverse-magnetic (TM) plane-wave mode into a surface-plasmon-polariton (SPP) mode. The coupling structure consists a metal film with a dielectric-filled slit and a planar, dielectric layer on the slit-exit side of the metal film. By varying the dielectric layer thickness, the wavevector of the SPP mode on the metal surface can be tuned to match the wavevector magnitude of the modes emanating from the slit exit, enabling high-efficiency radiation coupling into the SPP mode at the slit exit. An optimal dielectric layer thickness of approximately 100 nm yields a visible-frequency SPP coupling efficiency approximately 4 times greater than the SPP coupling efficiency without the dielectric layer. Commensurate coupling enhancement is observed spanning the free-space wavelength range 400 nm < or = lambda(0) < or = 700 nm. We map the dependence of the SPP coupling efficiency on the slit width, the dielectric-layer thickness, and the incident wavelength to fully characterize this SPP coupling methodology

BROAD-BAND EXCITATION AND EMISSION OF SURFACE-PLASMONS

The well known advantages of using surface plasmons, in particular the high sensitivity to surface adsorbates, are nearly always compromised in practice by the use of monochromatic excitation and the consequent lack of proper spectroscopic information. This limitation arises from the angle/wavelength selective nature of the surface plasmon resonance. The work described here uses an elegant broadband excitation/decay scheme in a substrate(silica)-grating profiled photoresist-Ag film geometry. Laser radiation of wavelength 488 nm, incident through the silica substrate, excites by near-field coupling a broad band of surface plasmons at the photoresist-Ag interface within the spectral range of the photoresist fluorescence. With a judicious choice of grating period this mode can cross-couple to the mode supported at the Ag-air interface. This latter mode can, in turn, couple out to light by virtue of the same grating profile. The spectral distribution of the light emitted due to this three-step process has been studied as a function of the angle of emission and depth of the grating profiled surface for each polarization. It is found that the optimum emission efficiency occurs with a groove depth in the region of 65 nm. This is considerably greater than the optimum depth of 40 nm required for surface plasmon-photon coupling at a Ag-air interface or, in other words, for the last step of the process in isolation.

Synthesis of Epitaxial Metal Oxide Nanocrystals via a Phase Separation Approach

Perovskite phase instability of BiMnO3 has been exploited to synthesize epitaxial metal oxide magnetic nanocrystals. Thin film processing conditions are tuned to promote the breakdown of the perovskite precursor into Bi2O3 matrix and magnetic manganese oxide islands. Subsequent cooling in vacuum ensures complete volatization of the Bi2O3, thus leaving behind an array of self-assembled magnetic Mn3O4 nanostructures. Both shape and size can be systematically controlled by the ambient oxygen environments and deposition time.As such, this approach can be extended to any other Bi-based complex ternary oxide system as it primarily hinges on the breakdown of parent Bi-based precursor and subsequent Bi2O3 volatization.

Capillary microreactors wall-coated with mesoporous titania thin film catalyst supports

A new method for catalyst deposition on the inner walls of capillary microreactors is proposed which allows exact control of the coating thickness, pore size of the support, metal particle size, and metal loading. The wall-coated microreactors have been tested in a selective hydrogenation reaction. Activity and selectivity reach values close to those obtained with a homogeneous Pd catalyst. The catalyst activity was stable for a period of 1000 h time-on-stream.

RAMAN-SCATTERING AND SCANNING ELECTRON-TUNNELING STUDIES OF METAL LIQUID-LIKE FILMS PRODUCED FROM SILVER AND GOLD SOLS

Surface-enhanced Raman scattering (SERS) excited at several visible wavelengths and recorded using a cooled charged-coupled device detector is reported from the mobile, interfacial, liquid-like metal films (MELLFs) formed when solutions of metal complexes or pyridine in chlorocarbon solvents are mixed with aqueous sols of silver or gold. MELLF formation has not previously been reported for gold sols or for pyridine as stabilizer. Comparison of the spectra for the MELLFs formed from individual metal complexes and from 50:50 mixtures show that the spectral patterns observed for the latter are distinctive and are not generally equivalent to the sum of the spectra associated with the individual complexes, in contrast to the situation observed for sols where the individual spectra do appear to be additive. Raman scattering from both gold and silver MELLFs is readily observed at excitation wavelengths in the red, around 750 nm, but at 514 nm only that from silver films is detectable. These findings are considered in terms of particle size and absorption band intensities. A preliminary study of the film surface topography and particle size was carried out by scanning tunnelling electron microscopy (STM) of Ag MELLFs deposited on gold-coated mica substrates. Computer-processed images of the STM data show the presence on the film surface of finger-like bars, 200-400 nm long with approximately square cross-section, 40-60 nm side, together with other smaller cuboid features. The implications of these findings in relation to SERS are briefly considered.

Biosorption of toxic chromium from aqueous phase by lignin: mechanism, effect of other metal ions and salts

Surface reaction methodology was implicated in the optimization of hexavalent chromium removal onto lignin with respect to the process parameters. The influence of altering the conditions for removal of chromium(VI), for instance; solution pH, ionic strength, initial concentration, the dose of biosorbent, presence of other metals (Zn and Cu), presence of salts and biosorption-desorption studies, were investigated. It was found that the biosorption capacity of lignin depends on solution pH, with a maximum biosorption capacity for chromium at pH 2. Experimental equilibrium data were fitted to five different isotherm models by non-linear regression method, however, the biosorption equilibrium data were well interpreted by the Freundlich isotherm. The maximum biosorption capacities (q(max)) obtained using Dubinin-Radushkevich and Khan isotherms for Cr(VI) biosorption are 31.6 and 29.1 mg/g. respectively. Biosorption showed pseudo second order rate kinetics at different initial concentrations of Cr(VI). The intraparticle diffusion study indicated that film diffusion may be involved in the current study. The percentage removal of chromium on lignin decreased significantly in the presence of NaHCO3 and K2P2O7 salts. Desorption data revealed that nearly 70% of the Cr(VI) adsorbed on lignin could be desorbed using 0.1 M NaOH. It was evident that the biosorption mechanism involves the attraction of both hexavalent chromium (anionic) and trivalent chromium (cationic) onto the surface of lignin. (C) 2011 Elsevier B.V. All rights reserved.

Development of a heterogeneous catalyst for lignocellulosic biomass conversion:Glucose dehydration by metal chlorides in a silica-supported ionic liquid layer

An attempt is made to immobilize the homogeneous metal chloride/EMIMCl catalyst for glucose dehydration to 5-hydroxymethylfurfural. To this end, ionic liquid fragments were grafted to the surface of SBA-15 to generate a heterogenized mimick of the homogeneous reaction medium. Despite a decrease in the surface area, the ordered mesoporous structure of SBA-15 was largely retained. Metal chlorides dispersed in such ionic liquid film are able to convert glucose to HMF with much higher yields as is possible in the aqueous phase. The reactivity order CrCl > AlCl > CuCl > FeCl is similar to the order in the ionic liquid solvent, yet the selectivity are lower. The HMF yield of the most promising CrCl-Im-SBA-15 can be improved by using a HO:DMSO mixture as the reaction medium and a 2-butanol/MIBK extraction layer. Different attempts to decrease metal chloride leaching by using different solvents are described. © 2013 American Institute of Chemical Engineers Environ Prog.

In Situ Formation of Micron-Scale Li-Metal Anodes with High Cyclability

Scanning probe microscopy methods have been used to electrodeposit and cycle micron-scale Li anodes deposited electrochemically under nanofabricated Au current collectors. An average Li volume of 5 x 10(8) nm(3) was deposited and cycled with 100% coulombic efficiency for similar to 160 cycles. Integrated charge/discharge values agree with before/after topography, as well as in situ dilatometry, suggesting this is a reliable method to study solid-state electrochemical processes. In this work we illustrate the possibility to deposit highly cyclable nanometer thick Li electrodes by mature SPM and nanofab techniques which can pave the way for inexpensive nanoscale battery arrays.