- Title
- Effects of annealing on the structural and optical properties of nanostructured TiO2
- Creator
- Talla, Assane
- Creator
- Urgessa, Zelalem
- Subject
- Titanium dioxide
- Subject
- Nanostructured materials
- Subject
- Nanotubes
- Date Issued
- 2023-12
- Date
- 2023-12
- Type
- Doctorial theses
- Type
- text
- Identifier
- http://hdl.handle.net/10948/62655
- Identifier
- vital:72907
- Description
- In this thesis, the structural, morphological and optical properties of titanium dioxide (TiO2) are investigated. Titanium dioxide (TiO2) nanotubes are prepared by anodic oxidation of titanium foil. The as-anodised samples are thermally annealed at various temperatures in nitrogen, air, oxygen and vacuum. The purpose is to study how the annealing conditions affect the properties of the nanostructures, including the anatase to rutile phase transformation. In all annealing atmospheres, except in vacuum, the dominant phase is found to be anatase when annealing is performed up to 600 oC. Above 700 oC the rutile phase becomes dominant. The anatase phase is stable above 600 oC in vacuum and does not evolve significantly up to 900 oC. The morphologies of the tubes tend to deteriorate with increased annealing temperature, in nitrogen, air and oxygen atmospheres, due to sintering effects. However, the integrity of the nanotubes is maintained up to 900 oC in vacuum. The photoluminescence (PL) spectra suggest mainly the presence of oxygen vacancies and self-trapped excitons, with respective emission bands around 2.5 eV and 2.3 eV. The results show that both the annealing temperature and atmosphere strongly influence the crystalline and optical properties of the TiO2 nanotubes. In addition, the phase transformation from anatase to rutile for samples annealed in an oxygen-rich environment is investigated in detail. Complementary structural information obtained from transmission electron microscopy and Raman analysis for oxygen-annealed samples reveals that the nucleation of the rutile phase starts from the titanium substrate and then propagates along the tubes. The results provide suitable annealing conditions to control the phase content and morphology of anodic TiO2 nanotubes. The PL characteristics of bulk crystalline anatase TiO2, namely virgin and hydrogen-annealed at 600 oC for 1 h, are studied. The low temperature PL spectra at 5.5 K shows near band edge (NBE) emissions with two dominant lines ascribed to shallow donor bound exciton and possibly free to bound recombination. The two main transitions are assisted by optical phononmodes. Temperature-dependent PL measurements performed on these anatase crystals reveal that the donor bound exciton is stable below 90 K. Hydrogen trapped in oxygen vacancies is proposed to be the shallow donor. In addition, two activation processes are involved for the thermal quenching of donor bound excitons. The total activation energy is found to correlate well with the localisation energy of the bound exciton. Site-selective PL spectra obtained from anodic TiO2 tubes reveals that the luminescence of the nanostructures depends on the morphology. The result shows unusual near-band edge emission (NBE) for these structures, which is rarely observed in indirect band gap TiO2.
- Description
- Thesis (PhD) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2023
- Format
- computer
- Format
- online resource
- Format
- application/pdf
- Format
- 1 online resource (xvi, 126 pages)
- Format
- Publisher
- Nelson Mandela University
- Publisher
- Faculty of Science
- Language
- English
- Rights
- Nelson Mandela University
- Rights
- All Rights Reserved
- Rights
- Open Access
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