Atomic short-range order, optical and electronic properties of amorphous transition metal oxides : An experimental and theoretical study of amorphous titanium aTiO2 and tungsten aWO3 solid thin-film oxides

• Main Author: Triana, Carlos A
• Format: Doctoral Thesis
• Language: English
• Published: Uppsala universitet, Fasta tillståndets fysik 2017
• Subjects: X-ray-Absorption; Reverse Monte Carlo; Molecular dynamics; Electronic structure; Condensed Matter Physics; Den kondenserade materiens fysik
• Online Access: http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-318193; http://nbn-resolving.de/urn:isbn:978-91-554-9866-5

Amorphous transition metal oxides [aTMOs], have emerged as innovative functional materials for wide-ranging electronic, optical and energy-related applications. However, no systematic and broadly applicable method exists to assess their atomic-scale correlations, and since the optical and electronic processes are local structure-dependent, still there are not well-stablished mechanisms that suitably explain the physical properties of aTMOs. This thesis presents experimental and theoretical studies of the atomic short-range order, optical and electronic properties, and state-defects induced by Li+-ion-intercalation and oxygen-vacancies in amorphous titanium aTiO2 and tungsten aWO3 thin-film oxides. Those properties play a key role for application in high energy-density Li+-ion batteries and in switchable dynamical modulation of solar-irradiation transmittance for energy efficient "smart windows", where the disorder-dependent Li+-ion-intercalation and oxygen-vacancy-induced defect-states influence charge-carrier transfer mechanisms. After introducing the scope of this thesis, the fundamental theoretical concepts describing the experimental findings on amorphous solids are reviewed. Thereafter, a comprehensive analysis on the optical absorption phenomena experimentally observed in oxygen-deficient and Li+-ion-intercalated aLixTiO2−y and aLixWO3−y thin-films and a discussion on the electrochromic properties are presented. The optical absorption is described in the framework of the small polaron absorption model. Finally, a state-of-the-art systematic procedure involving theory and experiment in a self-consistent computational framework is implemented to unveil the atomic-scale structure of aTiO2 and aWO3, and its role for the electronic properties. The procedure is based in Reverse Monte Carlo [RMC] and Finite Difference Method [FDM] simulations of X-ray-Absorption spectra to construct a disordered theoretical model having the same bonding and coordination distribution as the experimental system. Ab-initio molecular dynamics simulations and density functional theory are then used to assess defect-states induced by Li+-ion-intercalation and oxygen-vacancies in aTiO2 and aWO3 oxides. The schemes introduced in this study offer a consistent route to experimentally and theoretically assess the role of the atomic-scale structure on the optical and electronic properties of aTiO2 and aWO3 and could be extended to the study of other aTMOs. The final results provide crucial insight towards the understanding of optical and electronic mechanisms where disorder-dependent ion-intercalation and oxygen-vacancy-induced localized defect-states influence charge transfer mechanisms of crucial importance for wide ranging optical and energy-related application of aTiO2 and aWO3 oxides.