A tight-binding analysis of the electronic properties of III-nitride semiconductors

This thesis divides into two distinct parts, both of which are underpinned by the tight-binding model. The first part covers our implementation of the tight-binding model in conjunction with the Berry phase theory of electronic polarisation to probe the atomistic origins of spontaneous polarisation and piezoelectricity as well as attempting to accurately calculate the values and coefficients associated with these phenomena. We first develop an analytic model for the polarisation of a one-dimensional linear chain of atoms. We compare the zincblende and ideal wurtzite structures in terms of effective charges, spontaneous polarisation and piezoelectric coefficients, within a first nearest neighbour tight-binding model. We further compare these to real wurtzite structures and conclude that accurate quantitative results are beyond the scope of this model but qualitative trends can still be described. The second part of this thesis deals with implementing the tight-binding model to investigate the effect of local alloy fluctuations in bulk AlGaN alloys and InGaN quantum wells. We calculate the band gap evolution of Al1_xGaxN across the full composition range and compare it to experiment as well as fitting bowing parameters to the band gap as well as to the conduction band and valence band edges. We also investigate the wavefunction character of the valence band edge to determine the composition at which the optical polarisation switches in Al1_xGaxN alloys. Finally, we examine electron and hole localisation in InGaN quantum wells. We show how the built-in field localises the carriers along the c-axis and how local alloy fluctuations strongly localise the highest hole states in the c-plane, while the electrons remain delocalised in the c-plane. We show how this localisation affects the charge density overlap and also investigate the effect of well width fluctuations on the localisation of the electrons.

The role of age and emotional valence in word recognition: an ex-Gaussian analysis

The aim of this work is to evaluate the roles of age and emotional valence in word recognition in terms of ex-Gaussian distribution components. In order to do that, a word recognition task was carried out with two age groups, in which emotional valence was manipulated. Older participants did not present a clear trend for reaction times. The younger participants showed significant statistical differences in negative words for target and distracting conditions. Addressing the ex-Gaussian tau parameter, often related to attentional demands in the literature, age-related differences in emotional valence seem not to have an effect for negative words. Focusing on emotional valence for each group, the younger participants only showed an effect on negative distracting words. The older participants showed an effect regarding negative and positive target words, and negative distracting words. This suggests that the attentional demand is higher for emotional words, in particular, for the older participants.

Low valence cation doping of bulk Cr2O3: Charge compensation and oxygen vacancy formation

The different oxidation states of chromium allow its bulk oxide form to be reducible, facilitating the oxygen vacancy formation process, which is a key property in applications such as catalysis. Similar to other useful oxides such as TiO2, and CeO2, the effect of substitutional metal dopants in bulk Cr2O3 and its effect on the electronic structure and oxygen vacancy formation are of interest, particularly in enhancing the latter. In this paper, density functional theory (DFT) calculations with a Hubbard + U correction (DFT+U) applied to the Cr 3d and O 2p states, are carried out on pure and metal-doped bulk Cr2O3 to examine the effect of doping on the electronic and geometric structure. The role of dopants in enhancing the reducibility of Cr2O3 is examined to promote oxygen vacancy formation. The dopants are Mg, Cu, Ni, and Zn, which have a formal +2 oxidation state in their bulk oxides. Given this difference in host and, dopant oxidation states, we show that to predict the correct ground state two metal dopants charge compensated with an oxygen vacancy are required. The second oxygen atom removed is termed "the active" oxygen vacancy and it is the energy required to remove this atom that is related to the reduction process. In all cases, we find that substitutional doping improves the oxygen vacancy formation of bulk Cr2O3 by lowering the energy cost.