Engineering of nanoscale defect patterns in CeO2 nanorods via ex situ and in situ annealing.

Single-crystalline ceria nanorods were fabricated using a hydrothermal process and annealed at 325 °C-800 °C. As-synthesized CeO2 nanorods contain a high concentration of defects, such as oxygen vacancies and high lattice strains. Annealing resulted in an improved lattice crystalline quality along with the evolution of novel cavity-shaped defects in the nanorods with polyhedral morphologies and bound by e.g. {111} and {100} (internal) surfaces, confirmed for both air (ex situ) and vacuum (in situ) heating. We postulate that the cavities evolve via agglomeration of vacancies within the as-synthesized nanorods.

Environment-mediated structure, surface redox activity and reactivity of ceria nanoparticles.

Nanomaterials, with potential application as bio-medicinal agents, exploit the chemical properties of a solid, with the ability to be transported (like a molecule) to a variety of bodily compartments. However, the chemical environment can change significantly the structure and hence properties of a nanomaterial. Accordingly, its surface reactivity is critically dependent upon the nature of the (biological) environment in which it resides. Here, we use Molecular Dynamics (MD) simulation, Density Functional Theory (DFT) and aberration corrected TEM to predict and rationalise differences in structure and hence surface reactivity of ceria nanoparticles in different environments. In particular we calculate reactivity 'fingerprints' for unreduced and reduced ceria nanoparticles immersed in water and in vacuum. Our simulations predict higher activities of ceria nanoparticles, towards oxygen release, when immersed in water because the water quenches the coordinative unsaturation of surface ions. Conversely, in vacuum, surface ions relax into the body of the nanoparticle to relieve coordinative unsaturation, which increases the energy barriers associated with oxygen release. Our simulations also reveal that reduced ceria nanoparticles are more active towards surface oxygen release compared to unreduced nanoceria. In parallel, experiment is used to explore the activities of ceria nanoparticles that have suffered a change in environment. In particular, we compare the ability of ceria nanoparticles, in an aqueous environment, to scavenge superoxide radicals compared to the same batch of nanoparticles, which have first been dried and then rehydrated. The latter show a distinct reduction in activity, which we correlate to a change in the redox chemistry associated with moving between different environments. The reactivity of ceria nanoparticles is therefore not only environment dependent, but is also influenced by the transport pathway or history required to reach the particular environment in which its reactivity is to be exploited.

Nanopatterning by ion implantation through nanoporous alumina masks.

The important problem of how to generate lateral order for ion implantation patterning of substrates is solved by using a nanoporous anodic alumina membrane as a mask. Co and Pt implantation is used at two implantation doses. In order to observe the achieved implantation zones free from artifacts, electron transparent thin nitride and oxide films are used as substrates, which allows the quality of pattern transfer from the mask to the thin film to be assessed by plan-view transmission electron microscopy. Characteristic density variations of implanted elements across projected pore-regions of the mask, such as ring and dome shapes, and corresponding variation of cluster size are discussed, and therefore the method also serves as a suitable test bed for ion beam focusing studies by cylindrical or conical pores.

Cationic surface reconstructions on cerium oxide nanocrystals: an aberration-corrected HRTEM study.

Instabilities of nanoscale ceria surface facets are examined on the atomic level. The electron beam and its induced atom migration are proposed as a readily available probe to emulate and quantify functional surface activity, which is crucial for, for example, catalytic performance. In situ phase contrast high-resolution transmission electron microscopy with spherical aberration correction is shown to be the ideal tool to analyze cationic reconstruction. Hydrothermally prepared ceria nanoparticles with particularly enhanced {100} surface exposure are explored. Experimental analysis of cationic reconstruction is supported by molecular dynamics simulations where the Madelung energy is shown to be directly related to the binding energy, which enables one to generate a visual representation of the distribution of "reactive" surface oxygen.

Stability of embedded indium nanoclusters in silica under thermal treatment and ion irradiation.

The stability of embedded Indium (In) nanoclusters (NCs) in silica under thermal annealing and ion irradiation was investigated. The In NCs were prepared by implantation of 890 keV indium ions in silica matrix at room temperature. Post implantation annealing resulted in the shifting of the size distribution to higher side. On the other hand 140 keV Nitrogen ion irradiation at elevated temperature resulted in the reduction of NCs size, with significant narrowing of the size distribution. The paper discusses the results of the study in the light of the models pertaining to the stability of NCs under ion irradiation conditions.

Oxide mediated liquid-solid growth of high aspect ratio aligned gold silicide nanowires on Si(110) substrates.

Silicon nanowires grown using the vapor-liquid-solid method are promising candidates for nanoelectronics applications. The nanowires grow from an Au-Si catalyst during silicon chemical vapor deposition. In this paper, the effect of temperature, oxide at the interface and substrate orientation on the nucleation and growth kinetics during formation of nanogold silicide structures is explained using an oxide mediated liquid-solid growth mechanism. Using real time in situ high temperature transmission electron microscopy (with 40 ms time resolution), we show the formation of high aspect ratio ( approximately 15.0) aligned gold silicide nanorods in the presence of native oxide at the interface during in situ annealing of gold thin films on Si(110) substrates. Steps observed in the growth rate and real time electron diffraction show the existence of liquid Au-Si nano-alloy structures on the surface besides the un-reacted gold nanostructures. These results might enable us to engineer the growth of nanowires and similar structures with an Au-Si alloy as a catalyst.

Chlorine gas sensors using one-dimensional tellurium nanostructures.

Tellurium nanotubes have been grown by physical vapor deposition under inert environment at atmospheric pressure as well as under vacuum conditions. Different techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and optical absorption have been utilized for characterization of grown structures. Films prepared using both types of tellurium nanotubes were characterized for sensitivity to oxidizing and reducing gases and it was found that the relative response to gases depends on the microstructure. Nanotubes prepared at atmospheric pressure (of argon) showed high sensitivity and better selectivity to chlorine gas. Impedance spectroscopy studies showed that the response to chlorine is mainly contributed by grain boundaries and is therefore enhanced for nanotubes prepared under argon atmosphere.

Formation of aligned nanosilicide structures in a MBE-grown Au/Si(110) system: a real-time temperature-dependent TEM study.

Thin Au films (∼2 nm) were deposited on an Si(110) substrate epitaxially under ultra-high vacuum (UHV) conditions in a molecular beam epitaxy (MBE) system. Real-time in situ transmission electron microscopy (TEM) measurements were carried out at various temperatures (from room temperature to 700 °C), which shows the formation and growth of aligned gold silicide nanorod-like structures. The real-time selected-area electron diffraction patterns show the presence of silicon and unreacted gold at lower temperatures (up to 363 °C), while at higher temperatures only the signature of silicon has been observed. The diffraction analysis from room temperature cooled systems show the presence of gold silicide structures. Around 700 °C, 97% of the nanostructures were found to be aligned nanosilicide-rod-like structures with a longer side of ≈37 nm and aspect ratio of 1.38. For a high temperature annealed system (at 600 °C), selected-area diffraction (SAD) and high resolution lattice (after cooling down to room temperature) confirmed the formation of nano- Au(5)Si(2) structures. The alignment of gold silicide structures has been explained on the basis of lattice matching between the substrate silicon and silicide structures.

Synthesis of gold nanorods in organic media.

A seed mediated approach for the synthesis of anisotropic rod shaped gold nanoparticles in organic media (toluene) is demonstrated. Pre-formed gold nanoparticles stabilized in toluene by 4-hexadecylaniline (HDA) are used as seeds. These when reacted with 1-octadecylamine (ODA) hydrophobised chloroaurate ions in toluene lead to the formation of gold nanorods. ODA or alkylamines of different chain lengths which are the chloroaurate ion phase transfer agent have been found to play a key role in the formation of the nanorods. The gold nanorods that have a five-fold symmetry evolve from multiply twinned particles and are bound at the tips by [1 11] faces and at the sides by [100] faces. The gold nanorods have been shown to grow under the shape directing effect of the alkylamines which stabilize the high energy [100] faces. The concentration of the alkylamines has been found to play a critical role in the formation of the gold nanorods. Higher concentrations of the alkylamines lead to formation of spherical particles, at times of narrow size distribution.