Vidyadhar Singh

Coalescence-induced crystallisation wave in Pd nanoparticles

Palladium nanoparticles offer an attractive alternative to bulk palladium for catalysis, hydrogen storage and gas sensing applications. Their performance depends strongly on surface structure; therefore, nanoparticle coalescence can play an important role, as it determines the resultant structure of the active sites where reactions (e.g. catalysis) actually take place, i.e. facets, edges, vertices or protrusions. With this in mind, we performed classical molecular dynamics (MD) simulations and magnetron-sputtering inert gas condensation depositions of palladium nanoparticles, supported by high-resolution transmission electron microscopy (HRTEM), to study the mechanisms that govern their coalescence. Surface energy minimisation drove the interactions initially, leading to the formation of an interface/neck, as expected. Intriguingly, at a later stage, atomic rearrangements triggered a crystallisation wave propagating through the amorphous nanoparticles, leading to mono- or polycrystalline fcc structures. In the case of crystalline nanoparticles, almost-epitaxial alignment occurred and the formation of twins and surface protrusions were observed.

Inoculation of silicon nanoparticles with silver atoms

Silicon (Si) nanoparticles were coated inflight with silver (Ag) atoms using a novel method to prepare multicomponent heterostructured metal-semiconductor nanoparticles. Molecular dynamics (MD) computer simulations were employed, supported by high-resolution bright field (BF) transmission electron microscopy (HRTEM) and aberration-corrected scanning transmission electron microscopy (STEM) with a resolution ≤0.1 nm in high angle annular dark field (HAADF) mode. These studies revealed that the alloying behavior and phase dynamics during the coating process are more complex than when attaching hetero-atoms to preformed nanoparticles. According to the MD simulations, Ag atoms condense, nucleate and diffuse into the liquid Si nanoparticles in a process that we term “inoculation”, and a phase transition begins. Subsequent solidification involves an intermediate alloying stage that enabled us to control the microstructure and crystallinity of the solidified hybrid heterostructured nanoparticles.

Coalescence behaviour of amorphous and crystalline tantalum nanoparticles: a molecular dynamics study

Porous films of tantalum (Ta) and its oxides exhibit numerous properties suitable for high surface area applications, mainly in the semiconductor and bio-implant industries. Such films can be developed by Ta nanoparticle deposition using DC magnetron sputtering with gas aggregation. In order to engineer films of desirable properties, accurate control and in-depth understanding of the processes and parameters of nanoparticle growth, deposition and coalescence are crucial. Of utmost importance is to control the film’s porosity, since it determines many of the other physical properties. To this end, we performed a number of classical Molecular Dynamics simulations to study the coalescence of two or more Ta nanoparticles. Temperature, relative size and crystallographic orientation, defect content, degree of crystallinity and deposition rate effects were taken into account, and a mapping of the sintering processes was acquired. A broad range of possible interaction mechanisms were observed, from simple nanoparticle reorientation in order to achieve epitaxial configuration, to atomic adsorption, neck formation, twinning within the nanoparticles and full consolidation into a single, larger nanoparticle. The parameters studied are directly linked to experimental deposition parameters; therefore, fitting them accordingly can lead to growth of films with bespoke properties.

Single CuO nanowires decorated with size-selected Pd nanoparticles for CO sensing in humid atmosphere

We report on conductometric gas sensors based on single CuO nanowires and compare the carbon monoxide (CO) sensing properties of pristine as well as Pd nanoparticle decorated devices in humid atmosphere. Magnetron sputter inert gas aggregation combined with a quadrupole mass filter for cluster size selection was used for single-step Pd nanoparticle deposition in the soft landing regime. Uniformly dispersed, crystalline Pd nanoparticles with size-selected diameters around 5 nm were deposited on single CuO nanowire devices in a four point configuration. During gas sensing experiments in humid synthetic air, significantly enhanced CO response for CuO nanowires decorated with Pd nanoparticles was observed, which validates that magnetron sputter gas aggregation is very well suited for the realization of nanoparticle-functionalized sensors with improved performance.

Smart composite nanosheets with adaptive optical properties.

We report efficient design and facile synthesis of size-tunable organic/inorganic nanosheets, via a straightforward liquid exfoliation-adsorption process, of a near percolating gold (Au) thin film deposited onto a branched polyethylenimine (bPEI) matrix. The nanosheets are stiff enough to sustain their two-dimensional (2D) nature in acidic conditions, yet flexible enough to undergo a perfect reversible shape transformation to 1D nanoscrolls in alkaline conditions. The shape transformations, and associated optical property changes, at different protonation states are monitored by transmission electron microscopy (TEM), atomic force microscopy (AFM), UV-visible spectroscopy and zeta potential measurements. Because of their large surface area, both nanosheets and nanoscrolls could be used as capturing substrates for surface-enhanced Raman scattering (SERS) applications.

Nanoparticle design by gas-phase synthesis

Abstract Gas-phase synthesis characterizes a class of bottom-up methods for producing multifunctional nanoparticles (NPs) from individual atoms or molecules. This review aims to summarize recent achievements using this approach, and compare its potential to other physical or chemical NP fabrication techniques. More specifically, emphasis is given to magnetron-sputter gas-phase condensation, since it allows for flexible growth of complex, sophisticated NPs, owing to the fast kinetics and non-equilibrium processes it entails. Nanoparticle synthesis is decomposed into four stages, i.e. aggregation, shell-coating, mass-filtration, and deposition. We present the formation of NPs of various functionalities for different applications, such as magnetic, plasmonic, catalytic and, gas-sensing, emphasizing on the primary dependence of each type on a different stage of the fabrication process, and their resultant physical and chemical properties. Graphical Abstract

Assembly of tantalum porous films with graded oxidation profile from size-selected nanoparticles

AbstractFunctionally graded materials offer a way to improve the physical and chemical properties of thin films and coatings for different applications in the nanotechnology and biomedical fields. In this work, design and assembly of nanoporous tantalum films with a graded oxidation profile perpendicular to the substrate surface are reported. These nanoporous films are composed of size-selected, amorphous tantalum nanoparticles, deposited using a gas-aggregated magnetron sputtering system, and oxidized after coalescence, as samples evolve from mono- to multi-layered structures. Molecular dynamics computer simulations shed light on atomistic mechanisms of nanoparticle coalescence, which govern the films porosity. Aberration-corrected (S) TEM, GIXRD, AFM, SEM, and XPS were employed to study the morphology, phase and oxidation profiles of the tantalum nanoparticles, and the resultant films.Graphical AbstractDesign and assembly of tantalum nanoparticle porous films with a graded oxidation profile perpendicular to the substrate surface were fabricated by magnetron-sputter inert-gas aggregation system. At the top-most layers of the film, the larger free-surface areas of nanoparticles enable the formation of thermodynamically stable Ta2O5.

Influence of packaging on the surface oxidation and magnetic properties of cobalt nanocrystals

One frequently encountered obstacle during both ambient fabrication and the use of metal nanoclusters is spontaneous oxidation, which hampers many technological applications. In this work, we studied the influence of packaging material on the surface oxidation and magnetic properties of Co nanocrystals. We demonstrate that ?epoxy-electronic-varnish? capping (60?80?nm) effectively preserves the magnetic properties of pristine Co nanocrystals (?14?nm); without showing any exchange bias coupling over a period of >720?h, slower temperature variation of coercivity reminiscent of a Co single crystal and intercluster interaction dominated high blocking temperatures >300?K. Packaging by a silver (Ag) capping layer of similar thickness facilitates pronounced exchange bias compared to the even air exposed Co nanocrystals. Numerical fits M(H)?=?M(?)[1???(H*/H)1/2] to the high field part (10?50?kOe) of M?H loops yield a sharp rise in H* values at cryogenic temperatures (5?25?K) only in Ag capped Co nanocrystals, indicating a large induced anisotropy due to altered Co/Ag interfacial spin structures.

Enhanced magnetic behavior in carbon encapsulated nickel nanotubules through a linear polymer template

Carbon encapsulated Ni nanotubules, synthesized by a simple chemical method with linear polymer templates, reveal a high saturation magnetization (Ms) close to bulk fcc-Ni value, with larger coercivity 140Oe at 300K. An improvement in basic ferromagnetic character is reflected in the remanent magnetization (Mr), which is enhanced to be Mr∕Ms∼0.3, intrinsic of strongly ferromagnetic pseudosingle domains. The TEM images consist of fcc-Ni of ∼350nm long cylindrical tubules with an average 20nm diameter. The sample has two Raman bands of 1350cm−1 (D-band) and 1590cm−1 (G-band) characterizing the presence of a graphitic carbon (disordered).

Nanoscale Heterogeneity of Multilayered Si Anodes with Embedded Nanoparticle Scaffolds for Li-Ion Batteries

Abstract A new approach on the synthesis of Si anodes for Li‐ion batteries is reported, combining advantages of both nanoparticulated and continuous Si films. A multilayered configuration prototype is proposed, comprising amorphous Si arranged in nanostructured, mechanically heterogeneous films, interspersed with Ta nanoparticle scaffolds. Particular structural features such as increased surface roughness, nanogranularity, and porosity are dictated by the nanoparticle scaffolds, boosting the lithiation process due to fast Li diffusion and low electrode polarization. Consequently, a remarkable charge/discharge speed is reached with the proposed anode, in the order of minutes (1200 mAh g−1 at 10 C). Moreover, nanomechanical heterogeneity self‐limits the capacity at intermediate charge/discharge rates; as a consequence, exceptional cycleability is observed at 0.5 C, with 100% retention over 200 cycles with 700 mAh g−1. Higher capacity can be obtained when the first cycles are performed at 0.2 C, due to the formation of microislands, which facilitate the swelling of the active Si. This study indicates a method to tune the mechanical, morphological, and electrochemical properties of Si electrodes via engineering nanoparticle scaffolds, paving the way for a novel design of nanostructured Si electrodes for high‐performance energy storage devices.