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An exploration of some early transition metal (oxy) fluoride systems using solvothermal techniques has been carried out. 30 novel materials have been synthesised, which fall into three classes based on different metal centres; vanadium (21), molybdenum (5) and niobium (4). Some of these also contain secondary metal centres, namely copper (22) and zinc (1). Simultaneously, the relationship between the SHG values and the crystal structures of the hilgardites family members Pb₂B₅O₉Cl, Pb₂B₅O₉Br, Sr₂B₅O₉Cl and Ba₂B₅O₉Cl was investigated. In particular, the Pb–containing members of the hilgardite family of borate halides exhibit an abnormally large non–linear optical response, which was analysed based on neutron powder diffraction. Using solvothermal synthesis in HF–containing media, 21 novel vanadium oxyfluorides containing interesting structural features, were synthesised at 160˚C using a range of organo-amine compounds as a ligand, template, linker or structure directing agent. The architectures of the crystal structures may be categorised into; four clusters including monomeric vanadium units, five clusters including vanadium dimers, eight 1–D chains, two 2–D layers and two 3–D networks. ‘Composition–space’ diagrams with three components were used to study the effect of stoichiometry changes of reactants and to map out the crystallisation fields. The combination of early (Nb⁵⁺, Mo⁶⁺) and late (Cu²⁺) transition metals with different organo-amines produced nine novel compounds incorporating monomers, chains and 2– D interpenetrated networks. The chains and layers were synthesised from a systematic series of reactions at 160˚C and can be subdivided into four pairs, the topologies of which are essentially unique to each ligand, containing in each case a Cu–based cationic species, but alternately either [MoO₂F₄]²⁻ or [NbOF₅]²⁻, in an isomorphous manner, as the anionic moiety. The overall structures of these materials reflect the influence of the organo–amine ligands. The materials have been studied for their magnetic properties and characterised by thermogravimetric analysis, Rietveld refinement and elemental analysis where relevant.

This work presents the development of a GaN-based dilute magnetic semiconductor (DMS) by metal organic chemical vapor deposition (MOCVD) that is ferromagnetic at room temperature (RT), electrically conductive, and possesses magnetic properties that can be tuned by n- and p-doping. The transition metal series (TM: Cr, Mn, and Fe) along with the rare earth (RE) element, Gd, was investigated in this work as the magnetic ion source for the DMS. Single- phase and strain-free GaTMN films were obtained. Optical measurements revealed that Mn is a deep acceptor in GaN, while Hall measurements showed that these GaTMN films were semi-insulating, making carrier mediated exchange unlikely. Hysteresis curves were obtained for all the GaTMN films, and by analyzing the effect of n- and p-dopants on the magnetic properties of these films it was determined that the magnetization is due to magnetic clusters. These findings are supported by the investigation of the effect of TM dopants in GaN nanostructures which reveal that TMs enhance nucleation resulting in superparamagnetic nanostructures. Additionally, this work presents the first report on the development of GaGdN by MOCVD providing an alternate route to developing a RT DMS. Room temperature magnetization results revealed that the magnetization strength increases with Gd concentration and can be enhanced by n- and p-doping, with holes being more efficient at stabilizing the ferromagnetic signal. The GaGdN films obtained in this work are single-phase, unstrained, and conductive making them suitable for the development of multifunctional devices that integrate electrical, optical, and magnetic properties.