Structural and functional characterization of nanoporous thin films through advanced scanning-transmission electron microscopies and optical spectroscopies

Resumen

Nano-structuration of materials at the mesoscale to give rise to porosity-controlled coatings represents an important breakthrough in the area of Materials Science and Engineering, offering new and enhanced functionalities of interest in fields such as optics, optronics and optoelectronics. In order to optimize their performances, in-depth analyses are required: local information about the morphology, composition and atomic structure, the compactness distribution, but also layer homogeneity, interface and interpenetration between stacked layers or oxidation are extremely important factors that can ruin their way of operation. In this particular context, the objective of the present PhD Thesis is to make significant contributions to the study and development of multifunctional porous nanostructured systems, from their design and elaboration, to the maximum knowledge of their structure and properties, through advanced (S)TEM methods, including 3D reconstructions, elemental analyses at the nanoscale and atomic-scale imaging, combined with optical spectroscopy techniques. In the first instance, given the great potential of the slanted nanostructures generated by means of oblique angle depositions, in which the refractive index gradient can be tuned by the columns tilt and density imposed via the growth angles and parameters, OAD broadband antireflective coatings based on Si, Ge or SiO2 OAD films have been designed, manufactured, and extensively characterized with the aim of maximizing the performance of the optical elements in the vis-IR wavelength range. This same approach has also been implemented to enhance the antireflective capabilities of transparent conductive ITO thin films in the near-IR window without compromising too much their electrical response. On the other hand, the advanced structural and functional characterization of porosity-controlled GaN NW arrays grown by plasma-assisted MBE through (S)TEM methods and vis-IR SE elliposmetry, has helped not only to improve growth processes but also to optimize their resulting optical and electrical properties. Finally, the knowledge and methodologies acquired during the study and optimization of the previous porous systems have been transferred to the development of a two-step procedure, based on the deposition and the subsequent fast oxidation of vanadium-based OAD films in open air atmosphere, for the synthesis of thermochromic VO2 coatings of tunable metal-to-insulator response and controlled grain sizes and crystallinities.