This thesis explores structural and electronic properties of layered materials at the nanometre scale. Room temperature and low temperature ultrahigh vacuum scanning probe microscopy (scanning tunneling microscopy, scanning tunneling spectroscopy, atomic force microscopy) is used as the primary characterization method. The main findings in this thesis are: (a) observations of the atomic lattice and imaging local lattice defects of semiconducting ReS2 by scanning tunneling microscopy, (b) measurement of the electronic band gap of ReS2 by scanning tunneling spectroscopy, and (c) scanning tunneling microscopy study of 1T-TaS2 lattice and chemically functionalizing its defects with magnetic molecules.

The doping of rhenium into molybdenum disulfide was achieved by Aerosol Assisted Chemical Vapour Deposition (AACVD) from single source precursors. Rhenium can be studied as a model for immobilization of radioactive technetium-99 (99Tc) in MoS2. The metals Mo(IV), Re(IV), and Tc(IV) have similar ionic radii 0.65, 0.63 and 0.65 Å respectively, and their Shannon-Prewitt crystal radii 0.79, 0.77 and 0.79 Å Hence demonstrating the potential storage of nuclear waste in geologic like formations in of groundwater may be possible. The interaction between the nuclear waste forms and groundwater, which could lead to release and transport low concentrations or vapour of radionuclides to the near field, as a result, decomposition of engineered barriers. The molecular precursors [Mo(S2CNEt2)4], [Re3(μ-SiPr)3(SiPr)6], [Re(S2CC6H5)(S3CC6H5)2], and [Re2(μ-S)2(S2CNEt2)4] have been used to deposit Re-doped MoS2 thin films. Mo-doped ReS2 alloyed, polycrystalline thin films were synthesised using [Re(S2CC6H5)(S3CC6H5)2], [Mo(S2CNEt2)4] via AACVD, adding with a low concentration of Mo source for the first time . We reported as well a new way for production of ultrathin ReS2 nanosheets by coupling bottom up processing AACVD with top-down LPE. This is important in synthetic pathways for the production of rare transition dichalcogenide, also, our processing methodology is potentially scalable and thus could be a way to commercial exploitation. Characterisation of produced materials performed by pXRD, SEM, TEM, STEM, EDX, ICP and Raman spectroscopy.