In this thesis, ultra-thin dielectric layers on metal substrates are studied mainly by scanning tunneling microscopy and scanning tunneling spectroscopy. In chapter 2, field emission resonances, i.e. bound states in the potential well between sample and tip with an applied voltage, are used to determine the local work function on a sample with patches of different structural composition. To do so, a simple theoretical model is developed and used to simulate the peak positions of the measured dI/dV spectra. In the present case the sample is a Ag(100) surface covered by up to three monolayers of NaCl. The presented method is also applicable to other systems suitable for STM measurements. Additionally, the surface potential is locally probed in the dipole layer region between domains of different work function. In chapter 3, new molecular structures on silver surfaces are presented, that are formed by a mixture of gases. This mixture contains the small molecules H2, H2O, CO, CO2, and N2. No final conclusion can be drawn on the chemical nature of these structures due to the impossibility of the scanning tunneling microscope to determine chemical species. But already the presence of these structures indicates that there is a multitude of unknown interactions, that are possible between a transition metal surface and even smallest molecules. In chapter 4, the moiré pattern is described that a BC3 film creates on a NbB2(0001) surface. As the growth of the BC3 sheet is incommensurate, a moiré pattern is formed that modulates the apparent height of the atoms on the STM images, i.e. the local density of states. The BC3 layer exhibits a completely different behavior than the closely related graphite layer, because it is transparent for the tunnel current. In the present case, the BC3 layer is visible on the STM images only by its moiré effect.