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| Author(s): |
Naiara Letícia Marana
Total Authors: 1
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| Document type: | Doctoral Thesis |
| Press: | Bauru. 2017-06-28. |
| Institution: | Universidade Estadual Paulista (Unesp). Faculdade de Ciências. Bauru |
| Defense date: | 2017-04-25 |
| Advisor: | Julio Ricardo Sambrano |
| Abstract | |
Computational chemistry has proved to be a very useful tool in the scientific field and has been increasingly used in the research of new materials. Among the many systems studied with the aid of computational chemistry, we highlight zinc oxide (ZnO), widely used in many electronic devices such as sensors, solar cells, UV light emitting diodes and laser diodes. At room temperature and pressure, the most stable crystalline structure of ZnO is hexagonal of the wurtzite type, in which the zinc atoms are coordinated to four oxygen atoms. Due to the tetrahedral coordination and lack of center of symmetry of this structure, the ZnO presents piezoelectric properties and can be applied in piezoelectric sensors, for example. Currently, there are many papers related to ZnO, however the number of theoretical articles in relation to the experimental works are still small. In this sense, this project aimed the analysis of ZnO properties in three different morphologies, bulk, surfaces and nanotubes, applying the main techniques of computational modeling to solid state such as the choice of density functional and basic functions, optimization of geometry, doping by atom replacement, calculation of elastic and piezoelectric constants, hydrostatic pressure simulation applied to unit cell, bulk section to generate surfaces, replacement of atoms to form interfaces, nanotubes and adsorption of molecules in nanotubes. The calculations were performed applying the Density Functional Theory, with the help of the CRYSTAL14 program, using the hybrid function B3LYP, with the set of all-electron base functions. The applied methodology preserves the periodicity of the crystalline systems (1D for nanotubes, 2D for surfaces or 3D for bulk), in which the building blocks are composed of unit cells and can be replicated by the symmetry operator. The topological reviews were performed applying the Quantum Theory of atoms in Bader's Molecules. After choosing the level of theory, the structural, electronic, vibrational, topological and elastic and piezoelectric constants were analyzed for bulk. From the optimized structure, the zinc atoms were replaced by Mn2+ and Al3+, simulating doped systems. In parallel, a study of the behavior of the elastic and piezoelectric constants was conducted due to the hydrostatic pressure variation, which showed that the piezoelectric response of ZnO increases according to the pressure. After the bulk study, the surfaces (101 ̅0), (112 ̅0) and (0001) were analyzed and studied through their surface energy, structural, electronic and topological properties. From the surface monolayer (0001), the armchair, zigzag and chiral nanotubes were generated and studied according to their obtainment, stability and different properties. The adsorption of NH3 molecules to the wall of the armchair and zigzag nanotubes was studied and an investigation of the changes in the adsorption properties was carried out, showing that ZnO nanotubes are possible to be applied in ammonia gas sensors. Finally, the study of systems with ZnO/GaN interface was conducted for the surfaces (101 ̅0) and (112 ̅0), and armchair and zigzag nanotubes. At the end, it was concluded that the interface systems can be applied in LEDs, for example, because the control of thickness and material belonging to the outer layer of the interface leads to different emissions in the electromagnetic spectrum, going from UVA to green. This study aimed to investigate the maximum of three ZnO morphologies in the wurtzite phase and to suggest some possible applications. (AU) | |
| FAPESP's process: | 13/19713-7 - Computational study of zinc oxide pure and doped with transition metals: bulk, surfaces, interfaces and nanotubes |
| Grantee: | Naiara Letícia Marana |
| Support Opportunities: | Scholarships in Brazil - Doctorate |