Tunneling Spectroscopy Studies of Epitaxial Graphene on Silicon Carbide(0001) and Its Interfaces

A two dimensional network of sp2 bonded carbon atoms is defined as graphene. This novel material possesses remarkable electronic properties due to its unique band structure at the vicinity of the Fermi energy. The toughest challenge to bring use of graphene electronic properties in device geometries is that graphene is exceptionally sensitive to its electrical environment for integration into macroscopic system of electrical contacts and substrates. One of the most promising substrates for graphene is the polar surfaces of SiC for the reason it can be grown epitaxially by sublimating Si from the top-most SiC atomic layers. In this work, the interfaces of graphene grown on the Si-terminated polar surface SiC(0001) is studied in UHV using scanning tunneling microscopy (STM), scanning tunneling spectroscopy (STS), low energy electron diffraction (LEED) and auger electron Spectroscopy (AES). STM is used image the graphene surface and interfaces with the capability of atomic resolution. LEED is used to study surface atomic reciprocal ordering and AES is used to determine surface atomic composition during the graphene formation. Interfacial layer (Buffer layer), Single layer graphene and bilayer graphene are identified electronically by means of probing the first member of the image potential derived state. This state is found by dZ/dV spectroscopy in the high energy unoccupied states and is exceptionally sensitive to electrostatic changes to the surface which is detected by energy shifts of image potential states (IPS). This sensitivity is utilized to probe the graphene screening of external electric fields by varying the electric field in the tunneling junction and addresses the fact that charged impurity scattering is likely to be crucial for epitaxial graphene on SiC(0001) when it comes to transport parameters. Shifts of IPS energy position has also been used verify work function changes for identification of several Sodium Intercalation structures of epitaxial graphene. STS, STM along with DFT calculations are used to determine the interface location of Sodium, SiC-bufferlayer or bufferlayer-graphene intercalation.;In this thesis, STM, and STS are used to study the interactions of paramagnetic FePc molecules with epitaxial graphene. The molecules, FePc, is found to interact with the graphene substrate where STM images show substrate induced orientation of FePc densely packed square lattice structure. At sub-monolayer coverages, FePc form a molecular gas at room temperature suggesting a low diffusion barrier on the graphene lattice. The substrate interaction is probed by STS and show an abnormally low LUMO energy that suggest strong electronic coupling between graphene and FePc. DFT calculations support the experimental observations and predict a spin-dependent molecule-graphene hybridization close to the Fermi energy in unoccupied states. For majority spins, DFT demonstrates the Dirac cone splits and a delocalized hybrid state is found in the band gap. For minority spin the Dirac cone is intact with energy of Dirac point empty.;In addition, a novel method of improving UHV graphene growth on SiC(0001) is presented. During growth the SiC surface is exposed to atomic hydrogen which allows selective etching of Si over Carbon. This result in more uniform non-thermal formation of the buffer layer with many fewer defects and thus leads to nearly pit-free and defect-free thermal graphene layers.