We used the Monte Carlo code EGSnrc to simulate electron energy loss profiles as well as angle resolved x-ray spectra for metal-layer/substrate combinations in the primary electron energy range of 60-160 keV. We were furthermore able to separate the bremsstrahlung fraction originating in the substrate from that of the metal layer. The simulations were accompanied by experimental investigations. High-energetic electrons of 60-160 keV were directed onto 1-2 μm thin tungsten layers on top of 500 μm diamond substrates. The spectra were recorded by an energy resolved detector positioned in backward direction. We compared the experimental data with the simulation results and found good agreement. An enhanced monochromaticity in backward direction however, as expected from thin film theory, has not been observed due to the influence of the substrate.