Synthesis and Characterisation of Ultra Thin Film Oxides for Energy Applications

• This thesis describes studies of materials which can be exploited for hydrogen production from water and sunlight. The materials investigated are maghemite (γ-Fe2O3), magnetite (Fe3O4) and especially hematite (α-Fe2O3), which is an iron oxide with most promising properties in this field. Hematite has been deposited using Atomic Layer Deposition (ALD) - a thin-film technique facilitating layer-by-layer growth with excellent thickness control and step coverage. The iron oxides were deposited using bis-cyclopentadienyl iron (Fe(Cp)2) or iron pentacarbonyl (Fe(CO)5) in combination with an O2 precursor. Since it is crucial to have good control of the deposition process, the influence of substrate, process temperature, precursor and carrier gas have been investigated systematically. By careful control of these deposition parameters, three polymorphs of iron oxide could be deposited: hematite (α-Fe2O3), maghemite (γ-Fe2O3) and magnetite (Fe3O4).The deposited materials were characterized using X-ray Diffraction, Raman and UV-VIS Spectroscopy, and Scanning Electron Microscopy. Hard X-ray Photoelectron Spectroscopy (HAXPES) was also used, since it is a non-destructive, chemically specific, surface sensitive technique – the surface sensitivity resulting from the short mean escape depth of the photoelectrons. The depth probed can be controlled by varying the excitation energy; higher photoelectron energies increasing the inelastic mean-free-path in the material.HAXPES studies of atomic diffusion from F-doped SnO2 substrates showed increased doping levels of Sn, Si and F in the deposited films. Diffusion from the substrate was detected at annealing temperatures between 550 °C and 800 °C. Films annealed in air exhibited improved photocatalytic behavior; a photocurrent of 0.23 mA/cm2 was observed for those films, while the as-deposited hematite films showed no photo-activity whatsoever.The optical properties of low-dimensional hematite were studied in a series of ultra-thin films (thicknesses in the 2-70 nm range). The absorption maxima were shifted to higher energies for films thinner than 20 nm, revealing a different electronic structure in thin films.

Ämnesord

TEKNIK OCH TEKNOLOGIER  -- Materialteknik (hsv//swe)

ENGINEERING AND TECHNOLOGY  -- Materials Engineering (hsv//eng)

Nyckelord

Atomic Layer Deposition

Iron oxides

Hematite

Solar Water Splitting

Hard X-Ray Photoelectron Spectroscopy

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