This thesis explores different physical phenomena observed in, or involving thin surface films. Thin surface layers are ubiquitous. Found in nature and used in almost every aspect of daily life, thin surface films are invaluable. While the applications and roles may be varied, to be used effectively, the physical properties of these films and the factors influencing their stability need to be well understood. Surfaces can have a strong effect on the stability of thin films. In thin films of polymer blends, wetting layers rich in one component often form at the film interface prior to phase separation. Here the formation of these wetting layers are seen to result in destabilisation of the film, even when the blend is far from phase coexistence. A spinodal like instability with a characteristic wavelength is shown to form. A theoretical model is developed, which describes the observed behaviour in terms of coupled height and composition fluctuations in the wetting layer. Spin coating is a common technique for the formation of thin polymer films. Films formed in this way however, are often seen to exhibit anomalous properties, which strongly differ from that of the bulk behaviour of the material. Here the rheological properties and stored stresses in spin cast films are explored, with focus on the role that the casting solvent plays in the properties of the film. The results suggest that the observed deviation comes from a lowered density of chain entanglements. The effective viscosity and residual stresses in the as-spun film are seen to strongly depend on the casting solvent properties and the solvent-polymer interactions. The use of organometallic polymers as precursors for the formation of magnetic ceramics is investigated. Emphasis is placed on doping the polymers with metallic compounds prior to pyrolysis, allowing for the formation of technologically interesting metallic alloys, without the need for new polymers to be synthesised. The formation of iron-palladium alloys is demonstrated using this method. These are highly desirable due to their potential use in hard-disk drive technologies. Thin films can be used to influence the optical signature of a material and are widely used in nature to produce vibrant, pure, iridescent colours. Here the optical properties of the tropical plant Selaginella willdenowii are explored. The bright blue colouration is seen to arise from a multilayer lamella structure on the upper surface of the leaves. Light is important to plants, who use it both as an energy source and an environmental signal. Blue iridescence occurs in a wide range of plant species, suggesting that it has some adaptive benefit. These are considered and discussed.

Electrochemical ellipsometry is employed to determine the real and imaginary parts of the refractive index and the thickness of thin films as functions of the potential applied to the electrode upon which the film is grown. The relatively recent advent of an analyser with no moving parts, the Stokesmeter, has removed previous time restraints and allows microsecond resolution. The Newcastle system is extremely novel, using a Stokesmeter, and thus being capable of 325 gs resolution, and also being electrochemically interfaced. The ellipsometric studies have concentrated on the growth and behaviour of a series of electroactive polymers derived from salicylaldehydes (Salens). [Ni(SaltMe)] and [Ni(SaIdMe)] were found to yield stable homogeneous films upon polymerisation, however while the behaviour during film growth was similar, marked differences were observed during potential cycling, poly[Ni(SaIdMe)] showing a marked decrease in thickness near the anodic limit not observed for poly[Ni(Saltme)], indicating that even minor changes to ligand structure well away from the site of polymerisation may have significant effects on the resulting film. The behaviour of poly[Ni(OMeSaltMe)] during polymerisation is more complicated; initially a homogeneous film is produced, however about half way through the growth process the film becomes inhomogeneous, and remains so during subsequent potential cycling. This behaviour was also observed for poly[Pd(OMeSalen)], indicating electron donating groups around the phenyl rings of the ligand have a profound effect on the nature of the polymer films, possibly far more so than the identity of the central metal.

The processing and properties of novel polymer-based nano-composite (PNC) dielectrics for capacitor applications has been studied. PNCs were fabricated via a vacuum based deposition technique and their micro/nano-structure, chemical and dielectric properties investigated. After process development and optimisation, co-deposited Al and nylon-6 PNCs had a dielectric constant k∼7 at an approximate Al volume fraction of 0.3 that agreed with analytical predictions if it was assumed that the Al transformed to an oxide in-situ and/or after deposition. The significant effect of absorbed water vapour and temperature on PNC dielectric properties was revealed using different types of post-deposition heat treatment. Alternately-deposited PNCs consisting of Al or Ag 2-20 nm layers sandwiched between nylon-6 layers were fabricated in which the overall PNC Al or Ag volume fraction was controlled by varying the nominal Al or Ag layer thickness. Ag layers comprised of discrete nano-islands that produced a nano-capacitor network effect that increased k to ∼11. In the case of Al layers, when the layer thickness was ≥ 5 nm, corresponding to a nominal volume fraction of 0.1, Al (core)-oxide (shell) nanoparticles were formed and the PNC dielectric constant increased to ∼19. The detailed nano-structure of the core-shell particles was studied using various types of transmission electron microscopy (TEM), and the elevations in dielectric constant ascribed to multiple-interface polarisation effects dependent on the formation of the core-shell structure. PNCs based on alternate deposition of Ti sandwiched in nylon-6, and then both Ti and Ag in nylon-6 were also fabricated, with k reaching ∼73 for Ag+Ti/nylon-6 PNCs. As well as Ti-based core (metal)-shell (oxide) particles, the Ag volume fraction was sufficiently high in the 10 nm nylon-6 layers to again form a nano-capacitor network that contributed to the overall device capacitance and effective dielectric constant. Again, various types of high magnification TEM were critical in resolving the Ti-based core-shell structure and its role in high-k behaviour. The vacuum-based alternate deposition technique has been developed to offer ease of operation, reliability, flexibility and applicability to chemically different filler and matrix systems in the fabrication of high-k PNC based capacitors, in which high-k performance relies critically on the formation of core (metal)-shell (oxide) particles in both Al and Ti based systems.