Search

Understanding and controlling the sintering behavior of gold nanoparticles is important for applications such as printed electronics, catalysis and sensing that utilise these materials. Here we examine the processes by which thiol-protected gold nanoparticles thermally sinter under a variety of atmospheres. We find that upon sintering, the surface-bound thiyl ligands exclusively form the corresponding disulfide species when released from the gold surface. Experiments conducted using air, hydrogen, nitrogen, or argon atmospheres revealed no significant differences between the temperatures of the sintering event nor on the composition of released organic species. When conducted under high vacuum, the sintering event occurred at lower temperatures compared to ambient pressures in cases where the resulting disulfide had relatively high volatility (dibutyl disulfide). Hexadecylthiol-stabilized particles exhibited no significant differences in the temperatures of the sintering event under ambient pressures compared to high vacuum conditions. We attribute this to the relatively low volatility of the resultant dihexadecyl disulfide product.

The unexpected growth of highly aligned and optically polarizing metallic fins during physical vapor deposition under modestly oblique conditions is investigated. The fins exhibit nanoscale dimensions and are formed when Al is co-sputtered with any of V, Cr, Nb, Mo, Ta, W, Ru, Fe, Ni, Pt, Zr, Mg, and Ti. It is proposed that the phenomenon is caused by anomalously low atomic mobility in the alloys and intermetallic compounds formed by co-depositing with Al. In contrast, when Cu, Ag, and Au (which diffuse more rapidly in Al) are deposited, no fins form. There is a sharp visible transition in optical properties as the ratio of Al to other element is decreased: the color of the sample changes from black to silver-white for compositions containing less than about 55 atom % Al. The region over which the color change occurs is associated with a very strongly polarized reflectance. Cross-sectional elemental mapping and Monte Carlo simulations suggest that growth of the fins may be nucleated by Al hillocks and enhanced by shadowing effects. The diversity of suitable metals makes this a versatile technique for producing nanoscale polarizing surfaces suitable for high-flux and high-temperature applications.

A proof-of-principle double-layer symmetrical supercapacitor with nanoporous copper/copper oxide electrodes and an aqueous electrolyte is investigated. The electrodes are manufactured by selective dissolution of Al from a eutectic composition of Cu17.5Al82.5 using 5 M NaOH. The ostensible (i.e., net external) capacitance of a symmetrical two-electrode cell with 0.1 M KNO3 electrolyte is assessed over a series of charge/discharge cycles and is about 2 F per gram of Cu in this simple prototype. Capacitance varies during a discharge cycle due evidently to the deeply buried surfaces and pseudocapacitive reactions contributing charge toward the end of a discharge cycle. In principle such a device should have very low ohmic losses due to its highly conductive backbone and would be suitable for applications requiring maximum energy efficiency over repeated cycling. The aqueous electrolyte ensures fire safety but this comes at the cost of lower energy content. Graphical abstract: [Figure not available: see fulltext.]

A late detection of pathogenic microorganisms in food and drinking water has a high potential to cause adverse health impacts in those who have ingested the pathogens. For this reason there is intense interest in developing precise, rapid and sensitive assays that can detect multiple foodborne pathogens. Such assays would be valuable components in the campaign to minimize foodborne illness. Here, we discuss the emerging types of assays based on gold nanoparticles (GNPs) for rapidly diagnosing single or multiple foodborne pathogen infections. Colorimetric and lateral flow assays based on GNPs may be read by the human eye. Refractometric sensors based on a shift in the position of a plasmon resonance absorption peak can be read by the new generation of inexpensive optical spectrometers. Surface-enhanced Raman spectroscopy and the quartz microbalance require slightly more sophisticated equipment but can be very sensitive. A wide range of electrochemical techniques are also under development. Given the range of options provided by GNPs, we confidently expect that some, or all, of these technologies will eventually enter routine use for detecting pathogens in food. This article is categorized under: Diagnostic Tools > Biosensing.

There has been an ongoing quest to optimize the materials used to build plasmonic devices: first the elements were investigated, then alloys and intermetallic compounds, later semiconductors were considered, and, most recently, there has been interest in using more exotic materials such as topological insulators and conducting oxides. The quality of the plasmon resonances in these materials is closely correlated with their structure and properties. In general gold and silver are the most commonly specified materials for these applications but they do have weaknesses. Here, it is shown how, in specific circumstances, the selection of certain other materials might be more useful. Candidate alternatives include Tix N, VO2 , Al, Cu, Al-doped ZnO, and Cu-Al alloys. The relative merits of these choices and the many pitfalls and subtle problems that arise are discussed, and a frank perspective on the field is provided.

© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim An iterative algorithm is used to design a spectrally selective thin-film stack to provide maximum solar-to-thermal conversion efficiency at the very high operating temperatures associated with high solar concentrations. The resulting stack is then fabricated by magnetron sputtering and characterized. It is composed of two Ta:SiO2 layers with differing Ta nanoparticle contents on a refractory metal substrate. A SiO2 antireflecting overlayer completes the stack. Optical and microstructural characterizations indicate that the stack achieves 97.6% solar absorptance up to 900 °C. Spectral selectivity and thermal stability improve on annealing in two ways, first, due to recrystallization of Pt or Ta back reflectors which lowers room temperature thermal emittance to 0.15 from 0.18, and to 0.14 from 0.21, respectively; and second, due to alloying of substrate atoms with the Ta nanoparticles of the cermet.

© 2019 Acta Materialia Inc. High-entropy alloys (HEAs) with high melting points and low thermal neutron cross-section are promising new cladding materials for generation III+ and IV power reactors. In this study a recently developed high throughput computational screening tool Alloy Search and Predict (ASAP) has been used to identify the most likely candidate single-phase HEAs with low thermal neutron cross-section, from over a million four-element equimolar combinations. The selected NbTiVZr HEA was further studied by density functional theory (DFT) for moduli and lattice parameter, and by CALPHAD to predict phase formation with temperature. HEAs of NbTiVZr x (x = 0.5, 1, 2) were produced experimentally, with Zr varied as the dominant cross-section modifier. Contrary to previous experimental work, these HEAs were demonstrated to constitute a single-phase HEA system; a result obtained using a faster cooling rate following annealing at 1200 °C. However, the beta (BCC) matrix decomposed following aging at 700 °C, into a combination of nano-scale beta, alpha (HCP) and C15 Laves phases.

© 2019 Elsevier B.V. Spectrally-selective solar absorbing coatings based on the Ti1-xAlxN system were deposited using DC magnetron sputtering. Due to their refractory nature and very suitable optical properties, these were considered for high temperature solar thermal energy conversion. The composition of Ti1-xAlxN, (effectively, the Ti/Al ratio) was optimized to achieve a maximized solar absorptance. The optimum composition was then tested in a tandem absorber which included anti-reflective layers. A stainless steel substrate was used in order to simulate service in parabolic trough-based power plants that use stainless steel pipe to carry the heat-transfer fluid. High temperature annealing of the stack caused structural modifications but the solar absorptance of 92% was retained even after annealing at 900 °C.

© 2018 IOP Publishing Ltd. 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.

© 2018 American Chemical Society. PbS submicron crystals were formed by thermolysis of two different lead dithiocarbamate complexes. These precursors were readily synthesized and fully characterized, and in situ synchrotron powder diffraction experiments were performed to characterize their decomposition. The structure and purity of resultant PbS was examined using scanning electron and transmission electron microscopies, powder X-ray diffraction, and infrared spectroscopy. Submicron crystalline PbS was used to create a new PbS thermistor with excellent sensitivity and an ultrarapid thermal response time.

© 2018 American Chemical Society. The changes in optical properties that occur as gold nanoparticles (AuNPs) are thermally converted to a continuous thin film were studied with the purpose of determining the roles of particle coarsening and temperature. In situ reflectance spectroscopy, electron microscopy, and synchrotron X-ray diffraction (XRD) were applied to provide complementary information on the changes in particle size and shape. The AuNPs studied were stabilized with 1-butanethiol, 1-octanethiol, oleylamine (OA), or 4-(pyren-1-yl)butane-1-thiol (PyBuSH). Initially, the films were dark brown or purple because of the plasmon resonance of the AuNPs. As the temperature was increased, the AuNPs started to coalesce and percolate, thereby changing the color of the films to that of bulk gold. Films of AuNPs stabilized with alkanethiols sintered very rapidly, measured as a rapid change in the reflectance spectrum. In contrast, films of AuNPs stabilized with OA or PyBuSH sintered more gradually and at a higher temperature. This permitted the transition to be studied in greater detail than for the alkanethiols. Red-shifted plasmon peaks and increased intensity in the reflectance data and XRD and electron microscopy measurements revealed that a prolonged process of nanoparticle coarsening occurred prior to sintering. The effect of temperature on the optical properties was isolated by monitoring samples as they cooled. The insulator-to-metal transition in these types of composites offers a very flexible platform for controlling spectral properties in the near-infrared region.

© 2018 John Wiley & Sons, Ltd. We investigate the spontaneous reduction of a photochromic surfactant/polyoxotungstate hybrid during repeated X-ray photoelectron spectroscopy (XPS) scans and show how this effect may confound attempts to use soft X-rays to characterise materials of this nature. The W4f core-level spectra revealed a progressive increase of W5+ and W4+ species at the expense of W6+ as irradiation time increased. The samples developed a blue colour attributed to the presence of W4+ and/or W5+. The progressive photoreduction is also associated with a shift of the W6+ peak within the W4f spectrum to lower binding energies. This work highlights the need to consider inadvertent changes in oxidation state during X-ray photoelectron spectroscopy characterisation of samples containing photoreducible transition metals.

© 2017 Informa UK Limited, trading as Taylor & Francis Group. Whereas the application of optically or magnetically heated nanoparticles to destroy tumours is now well established, the extension of this concept to target pathogens has barely begun. Here we examine the challenge of targeting pathogens by this means and, in particular, explore the issues of power density and heat transfer. Depending on the rate of heating, either hyperthermia or thermoablation may occur. This division of the field is fundamental and implies very different sources of excitation and heat transfer for the two modes, and different strategies for their clinical application. Heating by isolated nanoparticles and by agglomerates of nanoparticles is compared: hyperthermia is much more readily achieved with agglomerates and for large target volumes, a factor which favours magnetic excitation and moderate power densities. In contrast, destruction of planktonic pathogens is best achieved by localised thermoablation and very high power density, a scenario that is best delivered by pulsed optical excitation.

© 2018 The Royal Society of Chemistry. The photochromic properties of a hybrid compound comprised of the surfactant cation cetyltrimethylammonium [(C16H33)N(CH3)3]+ (CTA+) and the isopolytungstate anion [H2W12O40]6- is investigated. The compound, which has the nominal formula (CTA)7[H2W12O40]Cl·2H2O, changes from white to blue when exposed to UV radiation. The sample returns to the bleached state if stored in the dark-ambient. Application of XPS indicates that the coloring species are WV and WIV. The CTA+ component is found by XPS and FTIR to undergo progressive and irreversible oxidation during this cycle. Examination of FTIR suggests that the changes occur at multiple sites across the amphiphile. Surprisingly, the photochromic cycle is correlated with changes in the X-ray diffraction pattern, indicating partially reversible changes in the ordering of the Keggin ions and their spacing. In particular, application of the UV radiation causes the progressive accumulation of strain in the [001] direction. This is due to permanent oxidative changes in the CTA+ accumulating from cycle to cycle, resulting in an increase in interlamellar-distance due to less interdigitation of the chains. This provides a controllable photomechanical response.

© 2017 The Royal Society of Chemistry. 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.

Crown Copyright © 2015 Published by Elsevier Ltd on behalf of Acta Materialia Inc. A method for rapidly predicting the formation and stability of undiscovered single phase high-entropy alloys (SPHEAs) is provided. Our software implementation of the algorithm uses data for 73 metallic elements and rapidly combines them - 4, 5 or 6 elements at a time - using the Miedema semi-empirical methodology to yield estimates of formation enthalpy. Approximately 186,000,000 compositions of 4, 5 and 6 element alloys were screened, and ∼1900 new equimolar SPHEAs predicted. Of the 185 experimentally reported HEA systems currently known, the model correctly predicted the stability of the SPHEA structure in 177. The other sixteen are suggested to actually form a partially ordered solid solution - a finding supported by other recent experimental and theoretical work. The stability of each alloy at a specific temperature can also be predicted, allowing precipitation temperatures (and the likely precipitate) to be forecast. This combinatorial algorithm is described in detail, and its software implementation is freely accessible through a web-service allowing rapid advances in the design, development and discovery of new technologically important alloys.

© 2016 IOP Publishing Ltd. 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.

© 2015, Springer Science+Business Media New York. Ag triangular nanoplates are known to generate strong plasmonic resonances when excited by both light and electron beams. Experimental electron energy-loss spectra (EELS) and maps were acquired using an aberration-corrected JEOL-ARM microscope. The corner, edge and centre modes that are often observed in such structures were also observed in these measurements. In addition, novel higher order internal modes were observed and were found to be well reproduced by theoretical calculations using boundary element method (BEM). These modes are “dark modes” so are not observed in the optical extinction spectra. They are confined surface propagating modes and are analogous to laser cavity modes.

Excessive corrosion of silver nanoparticles is a significant impediment to their use in a variety of potential applications in the biosensing, plasmonic and antimicrobial fields. Here we examine the environmental degradation of triangular silver nanoparticles (AgNP) in laboratory air. In the early stages of corrosion, transmission electron microscopy shows that dissolution of the single-crystal, triangular, AgNP (side lengths 50–120 nm) is observed with the accompanying formation of smaller, polycrystalline Ag particles nearby. The new particles are then observed to corrode to Ag2S and after 21 days nearly full corrosion has occurred, but some with minor Ag inclusions remaining. In contrast, a bulk Ag sheet, studied in cross section, showed an adherent corrosion layer of only around 20–50 nm in thickness after over a decade of being exposed to ambient air. The results have implications for antibacterial properties and ecotoxicology of AgNP during corrosion as the dissolution and reformation of Ag particles during corrosion will likely be accompanied by the release of Ag+ ions.

© 2016 The Royal Society of Chemistry. Nanoporous gold sponges are useful for a variety of applications but the kinetics of the dissolution process used to make them is not well understood. Here we show how optical transmittance can be used to determine the rate at which sponges form from thin film precursors. The technique also provides a means by which de-alloying can be terminated at a target thickness. Analysis revealed three stages during the de-alloying process: initial depassivation, bulk dissolution and, finally, delamination. The dissolution rate is linear with hydroxide concentration, and exponential with temperature, with an activation energy of approximately 0.5 eV.

© 2015 SPIE. The optical and electrical responses of open, nanoscale, metal networks are of interest in a variety of technologies including transparent conducting electrodes, charge storage, and surfaces with controlled spectral selectivity. The properties of such nanoporous structures depend on the shape and extent of individual voids and the associated hyper-dimensional connectivity and density of the metal filaments. Unfortunately, a quantitative understanding of this dependence is at present only poorly developed. Here we address this problem using numerical simulations applied to a systematically designed series of prototypical sponges. The sponges are produced by a Monte Carlo simulation of the dealloying of Ag-Al alloys containing from 60% to 85% Al. The result is a series of Ag sponges of realistic morphology. The optical properties of the sponges are then calculated by the discrete dipole approximation and the results used to construct an 'effective medium' model for each sponge. We show how the resulting effective medium can be correlated with the associated morphological characteristics of each target and how the optical properties are primarily controlled by the density of the sponge and its state of percolation.

The development of therapeutic nucleic acids has led to new strategies for treating various diseases. Non-viral, synthetic nano-vectors in gene therapy have attracted increasing attention due to their low immunogenicity and low toxicity compared to viral counterparts. Due to the molecular structure of nucleic acids, they are very prone to degradation in pH sensitive biological environments. Therefore, synthetic nano-vehicles for therapeutic delivery, known as ‘nano-vectors’, need to be cleverly designed and engineered to protect and deliver appropriate therapeutic nucleic acids to the targeted sites for action. In this chapter, a brief overview of various types of therapeutic nucleic acids is first provided, followed by analysis of the synthetic nanomaterials under development as delivery systems to carry nucleic acids. The nucleic acid-encapsulated nano-vectors discussed here open a window for a new generation of nanomedicine.

© 2015 Optical Society of America. Dark-mode plasmon resonances can be excited by positioning a suitable nano-antenna above a nanostructure to couple a planar incident wave-front into a virtual point source. We explore this phenomenon using a prototypical nanostructure consisting of a silver nanotriangle into which a hole has been drilled and a rod-like nano-antenna of variable aspect ratio. Using numerical simulations, we establish the behavior of the basic drilled nanotriangle under plane wave illumination and electron beam irradiation to provide a baseline, and then add the nano-antenna to investigate the stimulation of additional dark-mode plasmon resonances. The introduction of a suitably tuned nano-antenna provides a new and general means of exciting dark-mode resonances using plane wave light. The resulting system exhibits a very rich variety of radiant and sub-radiant resonance modes.

© 2015 IOP Publishing Ltd. 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.

© 2015 SPIE. Titanium nitride is a golden-colored semiconductor with metallic optical properties. It is already widely used in room temperature spectrally-selective coatings. In contrast, aluminum nitride is a relatively wide-band gap, non-metallic material. Both nitrides have exceptional thermal stability, to over 1000 °C, but are susceptible to oxidation. We will show here that composite coatings consisting of these materials and their complex oxides have considerable potential for spectrally-selective applications, including at elevated temperatures. In particular, we examine the metastable materials produced by magnetron sputtering. The effective dielectric functions of these materials can be tuned over a wide range by manipulation of their microstructure. This provides a strategy to assemble materials with tunable dielectric functions using a 'bottom-up' approach. The results are compared to those achievable by conventional, 'top-down', planar optical stacks comprised of alternating layers of TiNx and AlN.

© 2015 by the authors; licensee MDPI, Basel, Switzerland. Nanoporous “Raney gold” sponge was prepared by de-alloying an Au-Al precursor alloy. Catalytic tests using a micro-reactor confirmed that Raney gold can serve as an active heterogeneous catalyst for CO oxidation, reduction of NO to N2, and oxidation of NO to NO2. In general, the specific surface area of a heterogeneous catalyst has an influence on its catalytic efficacy. Unfortunately, gold sponges coarsen readily, leading to sintering of their structure and reduction in surface area. This potentially places constraints on their upper operating temperature in catalytic reactors. Here we analyzed the behavior of Raney gold when the temperature was raised. We examined the kinetics and mechanism of coarsening of the sponge using a combination of in situoptical measurements and Metropolis Monte Carlo modeling with a Lennard-Jones interatomic potential. Modeling showed that the sponges started with an isotropic “foamy” morphology with negative average “mean curvature” but that subsequent thermally activated coarsening will drive the morphology through a bi-continuous fibrous state and on, eventually, to a sponge consisting of sintered blobs of predominantly positive “mean curvature”.