Growth of Bismuth Oxide and Bismuth Ferrite Thin Films via CVD

This thesis describes the growth of bismuth oxide (Bi2O3) and multiferroic bismuth ferrite (BiFeO3) films via chemical vapour deposition (CVD). The synthesis of a range of bismuth(III) β-diketonate complexes was carried out via a ligand-exchange reaction between [Bi(N(SiMe3)2)3] and the respective free ligand, and crystal structures of [Bi(dbm)3]2 and [Bi(acac)3] are reported. The decomposition of these complexes was studied via DSC-TGA to assess their potential as single-source precursors to Bi2O3, and the mass transport characteristics of the volatile complexes [Bi(mmp)3], [Bi(thd)3] and [Bi(OtBu)3] were studied. Bi2O3 films were grown via the LPCVD reaction of the single-source precursor [Bi(OtBu)3]; the crystalline phase (and band-gap) of the resultant films depended strongly upon the reactor conditions. Films were tested for photo-oxidation of water under UV-light, revealing high activities comparable to those of TiO2 films described previously. [Bi(dbm)3]2 was utilised as a single-source precursor to β-Bi2O3 films via AACVD, together with the growth of Pt(0) films using H2PtCl6.6H2O as a precursor. Pt-nanoparticle Bi2O3 films were grown via a ‘one-pot’ AACVD reaction of both precursors; composite Pt-Bi2O3 films were able to evolve hydrogen via the photo-reduction of water, a property not observed for films containing either Pt or Bi2O3 alone. BiFeO3 films were grown via a multi-source LPCVD reaction between [Fe(acac)3], [Bi(OtBu)3] and air, as well as via the dual-source reaction of [Bi(OtBu)3] and [Fe(OtBu)3]2 without oxidising gas, and, furthermore, via the single-source precursor [{Cp(CO)2Fe}BiCl2] using AACVD. Magnetometry revealed low temperature ferromagnetism and spin-glass behaviour, characteristic of larger particle sizes. Ferroelectric measurements revealed low polarisation but nevertheless indicated films were multiferroic at room temperature. A selection of these films were tested for photo-oxidation of water under visible-light; films displayed high photoactivities with rates in excess of those from optimised TiO2 films measured under UV-light, highlighting the potential of BiFeO3 films as strong visible-light active photocatalysts