Aniekan Magnus Ukpong

Theoretical study of strain fields and local order in hydrogenated amorphous silicon

This paper presents the results of a tight-binding molecular-dynamics simulation which demonstrates that the local order and intrinsic stress in hydrogenated amorphous silicon are influenced by the hydrogen concentration. Snapshots of the atomic-level stresses in the simulated structures show that amorphous silicon exhibits a broad distribution in the magnitude of the local stress, rather than a uniform stress field over the whole simulated structure. The corresponding spatial and temporal correlations of the stress fields are interpreted to provide information on the effects of hydrogen on the short- and medium-range order.

Atomic-Scale Modelling and its Application to Catalytic Materials Science

Computational methods are a burgeoning science within industry. In particular, recent advances have seen first-principles atomic-scale modelling leave the realm of the academic theory lab and enter mainstream industrial research. Herein we present an overview, focusing on catalytic applications in fuel cells, emission control and process catalysis and looking at some real industrial examples being undertaken within the Johnson Matthey Technology Centre. We proceed to discuss some underpinning research projects and give a perspective on where developments will come in the short to mid-term.

First principles molecular dynamics study of nitrogen vacancy complexes in boronitrene

We present the results of first principles molecular dynamics simulations of nitrogen vacancy complexes in monolayer hexagonal boron nitride. The threshold for local structure reconstruction is found to be sensitive to the presence of a substitutional carbon impurity. We show that activated nitrogen dynamics triggers the annihilation of defects in the layer through formation of Stone-Wales-type structures. The lowest energy state of nitrogen vacancy complexes is negatively charged and spin polarized. Using the divacancy complex, we show that their formation induces spontaneous magnetic moments, which is tunable by electron or hole injection. The Fermi level s-resonant defect state is identified as a unique signature of the ground state of the divacancy complex. Due to their ability to enhance structural cohesion, only the divacancy and the nitrogen vacancy carbon-antisite complexes are able to suppress the Fermi level resonant defect state to open a gap between the conduction and valence bands.

Computer simulation of the influence of hydrogen on stress–order correlations in amorphous silicon

This paper reports the computational simulation of the correlations between atomic-level stress and local structure fluctuations in a computational model of amorphous silicon. A single parameter has been identified, which uniquely characterises the structural order in these structures. This parameter is the linear combination of the SDs of the first and second nearest neighbour separations. The stress fluctuations, under progressive hydrogen incorporation, show two clear dependences on this parameter, and therefore on the structural order. This dual dependency clearly alludes to structural network configurations that contain low and high hydrogen concentrations. The implications of the results on the local geometry of tetrahedrally bonded amorphous solids are discussed.

Ab initio studies of coherent spin transport in Fe-hBN/graphene van der Waals multilayers

This paper presents the results of ab initio studies of the electronic spin inversion and filtering in a ferromagnetic multilayer heterostructure. Spin-polarized electronic structure calculations are performed based on van der Waals density functional theory to give unique insights in to the generation, manipulation and transport of coherent spin conductance. By using an exact theory of the self-consistent ground state of the Fe-hBN/graphene multilayer as a model of the magnetic tunnel junction, hidden asymmetries are unraveled in the spin-resolved charge densities. It is shown that the injection of spin into the graphene/boron nitride tunnel layer from a ferromagnetic contact gives rise to coherent spin current. The projected Fermi surfaces of the up and down spin channels are analyzed to reveal Fermi arc topologies and spin anisotropies. It is also demonstrated that the coherent transport of pure spin-down current in the topological Weyl semimetal phase is robust. The implications of the results on out-of-plane transport of spin polarized conductance in van der Waals multilayer spintronic devices is discussed. The insights derived from this study are expected to open up prospects for further exploration of van der Waals magnetic multilayer heterostructures as a versatile platform for developing materials for Weyltronic applications.

Tight-binding molecular dynamics study of the hydrogen-induced structural modifications in tetrahedral amorphous carbon

A tight-binding molecular dynamics study of the structural evolution in tetrahedral amorphous carbon networks under dynamic hydrogen saturation is presented. The incorporation of hydrogen results in higher degrees of network disorder in second-neighbour distances, and initiates orbital re-hybridization that relaxes network stress. Using the simulated structures, numerical tests are performed to verify the effectiveness of a new structural order parameter for tetrahedrally-bonded solids. It is found that the island of accessible information, within the order parameter field shows a linear dependence between the fluctuations in first- and second-nearest-neighbour distances at a preferred orientation of 36°. A comparison with similar studies on hydrogenated amorphous silicon suggests that the local network structure of tetrahedrally-bonded amorphous solids obey the same ordering rule irrespective of differences in chemical species.

Density functional studies of the defect-induced electronic structure modifications in bilayer boronitrene

The van der Waals interaction-corrected density functional theory is used in this study to investigate the formation, energetic stability, and inter-layer cohesion in bilayer hexagonal boronitrene. The effect of inter-layer separation on the electronic structure is systematically investigated. The formation and energetic stability of intrinsic defects are also investigated at the equilibrium inter-layer separation. It is found that nonstoichiometric defects, and their complexes, that induce excess nitrogen or excess boron, in each case, are relatively more stable in the atmosphere that corresponds to the excess atomic species. The modifications of the electronic structure due to formation of complexes are also investigated. It is shown that van der Waals density functional theory gives an improved description of the cohesive properties but not the electronic structure in bilayer boronitrene compared to other functionals. We identify energetically favourable topological defects that retain the energy gap in the electronic structure, and discuss their implications for band gap engineering in low-n layer boronitrene insulators. The relative strengths and weaknesses of the functionals in predicting the properties of bilayer boronitrene are also discussed.

Studies of the electronic and vibrational signatures of the unusual bonding geometries in melt-quenched amorphous silicon

Tight-binding molecular dynamics simulations have been performed to investigate the effect of quenching rate of the Si melt on the resulting local structure of amorphous silicon. Different quenching rates were used to cool liquid silicon in the simulations to demonstrate that the choice of quenching rates significantly influences the resulting local structure. The calculated pair correlation functions show that the local structure is sensitive to the thermal processing of the liquid silicon melt. The use of cooling rates higher than 10−13 K s−1 appears to prevent the activation of the required structural re-arrangements necessary to stabilise the networks, causing unexpected bonding geometries to develop. The electronic signatures of the defects show that only the triangular defect structure contributes resonance states to the conduction band tail. Also, the vibrational signature of the triangular structure shows a high energy transverse optical mode at 95 meV, indicating that the defect is likely to be unstable at 300 K, although both defects contribute minimal states to the mid-gap level.

Computational studies of the effect of hydrogen on the thermalized positron state in amorphous silicon

The two-component density functional theory is applied to the study of the thermalized positron state in simulated structures of hydrogenated amorphous silicon. Results show that positron properties in bulk and ad hoc defect structures are sensitive to the defect free-volume. Using the normalized positron density, it is determined that the thermalized positron state is weakly localized at hydrogen-decorated vacancy-like complexes, and not at microscopic open volume defects. These defect complexes form as clusters of hydrogen-passivated dangling bonds. It is also found that hydrogen enhances the delocalization of positron density in the simulated structures. The relevance of the present results to the interpretation of actual positron lifetime spectroscopy in real materials is discussed.