Vibrational properties of epitaxial silicene on Ag(111)

This dissertation works out the vibrational properties of epitaxial silicene, which was discovered by Vogt et al. in 2012 by the epitaxial synthesis on the silver substrate. Its two-dimensional (2D) character is modified in comparison to the free-standing silicene due to its epitaxial nature, since the underlying substrate alters the physical properties of silicene as a result of the strong hybridization of the electronic levels of the substrate and adlayer. The growth of silicene layers is complicated by the sensitivity of the Si structures to the experimental conditions, mainly temperature, resulting in the formation of several seemingly different surface reconstructions. Another Si structure appears on the Ag surface at a supramonolayer coverage. The Raman spectroscopy was utilized to understand the relation between different Si structures and reveal their origin as well as to investigate the phonon-related physical properties of two-dimensional Si sheets. The central core of this work is the growth and characterization of these 2D silicene monolayers on the Ag (111) surface as well as the formation of silicene multilayer structures. The characterization of these materials was performed using in situ surface-sensitive measurement methods such as Raman spectroscopy and low-energy electron diffraction under ultra-high vacuum conditions due to high chemical reactivity of epitaxial silicene. Additional characterization was done ex situ by means of scanning force microscopy. The experimentally determined spectral signature of the prototypical epitaxial (3x3)/(4x4) silicene structure was confirmed by ab initio calculations, in collaboration with theory groups. The Raman signatures of the other 2D and 3D Si phases on Ag (111) were determined which allowed us to provide a clear picture of their formation depending on the preparation conditions. The monitoring of the silicene multi-layer growth yielded the vibrational signature of the top layer, reconstructed in a (√3x√3) fashion. It was compared to the inverse, (√3x√3)-Ag/Si(111), system showing the vast amount of similarities, which suggest that the (√3x√3) reconstruction belong to the silver layer. The chemical and physical properties of this surface structure additionally strengthen this equivalence. The possibility of functionalization of epitaxial silicene was demonstrated via exposure to the atomic hydrogen under UHV conditions. The adsorbed hydrogen covalently bonds to the silicene lattice modifying it and reducing its symmetry. As shown by Raman spectroscopy, such modification can be reversed by thermal desorption of hydrogen. The excitation-dependent Raman measurements also suggest the change of the electronic properties of epitaxial silicene upon hydrogenation suggesting that its originally semi-metallic character is modified into a semiconducting one.