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The thesis discusses a fundamental question of reconstruction on the Si(100) surface as well as three material combinations, which are important for perspective microelectronics technologies: Si/Pr2O3/Si(100), W/WNx/poly-Si/SiO2/Si(100), and CoSix/Si(100). A refined mixed ad-dimer model is developed for the Si(100)-c(4ยด4) reconstruction on the basis of scanning tunnelling microscopy investigations. A thermal stability of Pr2O3/Si(100) and Si/Pr2O3/Si(100) structures is studied with ion sputtering assisted Auger electron spectroscopy. The latter technique is also applied for precise determination of O and N content in the new W/WNx/poly-Si/SiO2/Si(100) structure, and to study the preferential sputtering of Si in CoSi2, CoSi, and Co2Si phases on Si(100) surface. The WSix/poly-Si/SiO2/Si(100) system, which was previously used in microelectronics, is studied for comparison. The preferential sputtering of Si in WSix is shown to be qualitatively similar as in the CoSix case.