Preparation of transition metal oxide thin films used as solar absorbers

Abstract : The present thesis deals with the synthesis and structural characterization of transition metals doped cobalt and manganese based spinel oxides MxCo2-xMnO4 (with M = Ni, Cu, Zn and x = 0, 0.15, 0.30, 0.60), in relationships with their conduction and optical properties. These materials are good p-type semiconductors and light absorbers in the UV and visible regions, therefore interesting for photo-catalysis and photovoltaics. The first chapter is a brief overview of the energy context and nature of global warming, renewable energy resources and a literature review of materials used for solar cells including the newly studied system type based on all-oxide photovoltaics. Chapter two presents all the experimental methods and characterization techniques used for this research work. The inorganic polycondensation method optimized in our laboratory and used for synthesizing spinel oxide powders at low temperature (T < 120 °C) without complex organic agents is described. Then, the preparation of colloidal dispersions stabilized at room temperature using an azeotrope solution based on absolute ethanol and water only is described, in order to obtain homogenous oxide thin films by the dip-coating technique. The third chapter presents detailed results on the atomic and electronic structures of the materials under study performed by using a full density functional theory investigation thanks to a collaboration with the CEMES. First principles electronic structure calculations were performed for the first time to our knowledge over the whole spinel oxide solid solution range MnxCo3-xO4 (0 = x = 3), and compared with our experimental data. A small band gap of ~ 0.8 eV is calculated, due to metal-metal transitions in B sites. The experimental band gaps observed at 1.5 and 2.2 eV, which increase with the amount of manganese, would correspond to B-A and O-B transitions, respectively. The magnetic properties of these materials are also discussed. Chapter four shows the experimental details of the preparation and characterization of the spinel oxide powders, colloidal dispersions and thin films. All samples (Ni, Cu or Zn-doped Co2MnO4) are well crystallized with a single cubic spinel oxide phase. Nanoparticles are spherical and their diameters vary from 20 to 50 nm, doping with Zn, Ni to Cu, mainly due to steric effects. Homogenous oxide thin films were deposited on quartz, alumina, titanium nitride and platinum in order to measure their optical and electrical properties, and to increase the film compactness (thus electrical conductivity and light absorbance) after thermal treatment. Thin films are well preserved up to 900 °C in air and can handle higher temperatures (up to 1000 ºC) on platinum without reaction with the substrate. Chapter five deals with the optical and electrical properties of thin films before and after sintering. The optical properties were measured over a wide range of wavelengths (UV-VIS). The optical properties of spinel oxide thin films show two strong absorption band gaps for each composition at the UV front and close to 700 nm in wavelength. These band gaps are direct and mostly lower than 2 eV for the first band. Both band gaps increase with further doping and decrease after annealing. Thin film resistivity is about 105 .cm at room temperature and decreases with increasing temperature (a few tens of 20cm at 300 ºC). In parallel to the soft chemistry method and dip-coating technique used to prepare our spinel oxide thin layers, Pulsed Laser Deposition technique was used to prepare pure Co2MnO4 and Cu2O dense thin films. Their structural and optical main features are discussed.
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Thi Ly Le. Preparation of transition metal oxide thin films used as solar absorbers. Materials. Université Paul Sabatier - Toulouse III, 2016. English. ⟨NNT : 2016TOU30120⟩. ⟨tel-01578163⟩

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