Effects of annealing on the structural and optical properties of nanostructured TiO2
- Talla, Assane, Urgessa, Zelalem
- Authors: Talla, Assane , Urgessa, Zelalem
- Date: 2023-12
- Subjects: Titanium dioxide , Nanostructured materials , Nanotubes
- Language: English
- Type: Doctorial theses , text
- Identifier: http://hdl.handle.net/10948/62655 , 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. , Thesis (PhD) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2023
- Full Text:
- Date Issued: 2023-12
- Authors: Talla, Assane , Urgessa, Zelalem
- Date: 2023-12
- Subjects: Titanium dioxide , Nanostructured materials , Nanotubes
- Language: English
- Type: Doctorial theses , text
- Identifier: http://hdl.handle.net/10948/62655 , 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. , Thesis (PhD) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2023
- Full Text:
- Date Issued: 2023-12
Block copolymer templates for metal oxide nanostructures
- Authors: Talla, Assane
- Date: 2019
- Subjects: Nanotechnology , Nanostructured materials Metal oxide semiconductors
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/43889 , vital:37075
- Description: Recent advances in technology have increased the need for fabrication of devices with feature sizes of tens of nanometers, such as ultra-fine filters or membranes, and high density data storage media, to name a few. For this reason, research is now focused on block copolymer nanolithographic processes, particularly the fabrication of nanoscale templates with domains well below 100 nm. Block copolymers have the tendency to self-organise into various structures, such as lamellae, spheres or cylinders on a nanometer scale. Among these possible configurations, the perpendicular cylindrical structure is most desirable, because it can be used for templates or masks for feature development, in particular, oriented wires or rods. In this work, the aim is to create a nano-mask from a di-block copolymer thin film, for zinc oxide nanorods growth. For this purpose poly (styrene-block-methylmethacrylate) (PS-b-PMMA) was investigated as a potential nano-mask. Samples were characterized using X-ray reflectometry to determine the thicknesses of the PS-b-PMMA thin films, while scanning probe microscopy and scanning electron microscopy was used to investigate the surface morphology of the samples. PS-b-PMMA thin films were produced on a random copolymer (poly (styrene-random-methylmethacrylate) (PS-r-PMMA) coated onto a silicon substrate. The PS-r-PMMA permits a non-preferential interaction between the di-block constituents and the substrate. Thermal annealing in vacuum of PS-b-PMMA on PS-r-PMMA led to perpendicular cylinders of PMMA within a PS matrix in the di-block. The typical thicknesses measured for the di-block copolymer films ranged between 33 nm and 37 nm. During this study, a perpendicular orientation of the di-block components was also produced when PS-b-PMMA was spun onto a layer of zinc oxide nanoparticles and thermally annealed in vacuum. It was shown that the ZnO nanoparticles created a corrugated surface on silicon which induced perpendicular cylinders of PMMA within the PS matrix. This was possible for a specific surface roughness parameter and film thickness. In this case, the typical thickness determined for the di-block copolymer ranged between 33 and 35 nm and the surface roughness parameter was 0.07. For the fabrication of a di-block template or PS nano-mask, the vertically oriented PMMA cylindrical nanodomains in the PS matrix were removed by exposing the film to ultraviolet radiation at an adequate dose, followed successively by washing in acetic acid and de-ionized water. It was shown that ultraviolet exposure is necessary to ensure the degradation of PMMA. A subsequent rinse in glacial acetic acid and DI water of the film exposed to ultraviolet, left an array of ordered nanoscopic pores with sizes ranging between 10 nm and 20 nm. Finally, the growth of ZnO nanorods on the di-block template produced on zinc oxide nanoparticles, was attempted using an aqueous solution based-method, namely chemical bath deposition. The rods did not grow inside the nanopores, probably due to poor capillary action. In additional experiments, the di-block template was removed by toluene (a selective solvent for PS) followed by the growth of ZnO rods on the exposed nanoparticle surface. Vertical and well separated ZnO rods formed on this surface, in places where the underlying seed layer had been attacked by the acetic acid treatment during removal of the PMMA. The observed ZnO rod morphology can be used in applications such as solar cell.
- Full Text:
- Date Issued: 2019
- Authors: Talla, Assane
- Date: 2019
- Subjects: Nanotechnology , Nanostructured materials Metal oxide semiconductors
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/43889 , vital:37075
- Description: Recent advances in technology have increased the need for fabrication of devices with feature sizes of tens of nanometers, such as ultra-fine filters or membranes, and high density data storage media, to name a few. For this reason, research is now focused on block copolymer nanolithographic processes, particularly the fabrication of nanoscale templates with domains well below 100 nm. Block copolymers have the tendency to self-organise into various structures, such as lamellae, spheres or cylinders on a nanometer scale. Among these possible configurations, the perpendicular cylindrical structure is most desirable, because it can be used for templates or masks for feature development, in particular, oriented wires or rods. In this work, the aim is to create a nano-mask from a di-block copolymer thin film, for zinc oxide nanorods growth. For this purpose poly (styrene-block-methylmethacrylate) (PS-b-PMMA) was investigated as a potential nano-mask. Samples were characterized using X-ray reflectometry to determine the thicknesses of the PS-b-PMMA thin films, while scanning probe microscopy and scanning electron microscopy was used to investigate the surface morphology of the samples. PS-b-PMMA thin films were produced on a random copolymer (poly (styrene-random-methylmethacrylate) (PS-r-PMMA) coated onto a silicon substrate. The PS-r-PMMA permits a non-preferential interaction between the di-block constituents and the substrate. Thermal annealing in vacuum of PS-b-PMMA on PS-r-PMMA led to perpendicular cylinders of PMMA within a PS matrix in the di-block. The typical thicknesses measured for the di-block copolymer films ranged between 33 nm and 37 nm. During this study, a perpendicular orientation of the di-block components was also produced when PS-b-PMMA was spun onto a layer of zinc oxide nanoparticles and thermally annealed in vacuum. It was shown that the ZnO nanoparticles created a corrugated surface on silicon which induced perpendicular cylinders of PMMA within the PS matrix. This was possible for a specific surface roughness parameter and film thickness. In this case, the typical thickness determined for the di-block copolymer ranged between 33 and 35 nm and the surface roughness parameter was 0.07. For the fabrication of a di-block template or PS nano-mask, the vertically oriented PMMA cylindrical nanodomains in the PS matrix were removed by exposing the film to ultraviolet radiation at an adequate dose, followed successively by washing in acetic acid and de-ionized water. It was shown that ultraviolet exposure is necessary to ensure the degradation of PMMA. A subsequent rinse in glacial acetic acid and DI water of the film exposed to ultraviolet, left an array of ordered nanoscopic pores with sizes ranging between 10 nm and 20 nm. Finally, the growth of ZnO nanorods on the di-block template produced on zinc oxide nanoparticles, was attempted using an aqueous solution based-method, namely chemical bath deposition. The rods did not grow inside the nanopores, probably due to poor capillary action. In additional experiments, the di-block template was removed by toluene (a selective solvent for PS) followed by the growth of ZnO rods on the exposed nanoparticle surface. Vertical and well separated ZnO rods formed on this surface, in places where the underlying seed layer had been attacked by the acetic acid treatment during removal of the PMMA. The observed ZnO rod morphology can be used in applications such as solar cell.
- Full Text:
- Date Issued: 2019
- «
- ‹
- 1
- ›
- »