Nanostructured carbon-based thin films prediction and design

Sammanfattning: Carbon-based thin films are a vast group of materials of great technological importance. Thanks to the different bonding options for carbon, a large variety of structures (from amorphous to nanostructured) can be achieved in the process of film synthesis. The structural diversity increases even more if carbon is combined with relatively small quantities of atoms of other elements. This results in a set of materials with many different interesting properties for a wide range of technological applications.This doctoral thesis is about nanostructured carbon-based thin films. In particular, the focus is set on theoretical modeling, prediction of structural features and design of sulfo carbide (CSx) and carbon fluoride (CFx) thin films.The theoretical approach follows the synthetic growth concept (SGC) which is based on the density functional theory. The SGC departure point is the fact that the nanostructured films of interest can be modeled as assemblies of low dimensional units (e.g., finite graphene-like model systems), similarly to modeling graphite as stacks of graphene sheets. Moreover, the SGC includes a description of the groups of atoms that act as building blocks (i.e., precursors) during film deposition, as well as their interaction with the growing film.This thesis consists of two main parts:Prediction: In this work, I show that nanostructured CSx thin films can be expected for sulfur contents up to 20 atomic % with structural characteristics that go from graphite-like to fullerene-like (FL). In the case of CFx thin films, a diversity of structures are predicted depending on the fluorine concentration. Short range ordered structures, such as FL structure, can be expected for low concentrations (up to 5 atomic %). For increasing fluorine concentration, diamond-like and polymeric structures should predominate. As a special case, I also studied the ternary system CSxFy. The calculations show that CSxFy thin films with nanostructured features should be possible to synthesize at low sulfur and fluorine concentrations and the structural characteristics can be described and explained in terms of the binaries CSx and CFx.Design: The carbon-based thin films predicted in this thesis were synthesized by magnetron sputtering. The results from my calculations regarding structure and composition, and analysis of precursors (availability and role during deposition process) were successfully combined with the experimental techniques in the quest of obtaining films with desired structural features and understanding their properties.