Crystalline structure and composition of the ZnO films grown by atomic layer deposition (ALD) on the n- and p-type Si (100) substrates with a SiC buffer layer were studied. The SiC buffer layers have been synthesized by a novel method of atomic substitution (partial chemical replacement) of Si atoms by carbon atoms in the subsurface layer of the Si substrate. A four-component epitaxial texture of ZnO in a direction close to [101] on the n- and p-type (100) Si vicinal substrates with a SiC buffer layer has been revealed and investigated with electron diffraction. Formation mechanism of the epitaxial textures of ZnO was found to depend on the conductivity type (n- or p-type) of the Si (100) substrates. A theoretical model explaining the effect of the texture formation and its dependence on the type of Si substrate conductivity has been proposed. The effect is associated with the transformation of the vicinal Si (100) surfaces into the SiC surfaces during its synthesis by the atomic substitution method. Significant differences have been found between the structures and between the growth mechanisms of the ZnO layers on the SiC/Si (111) and (100) substrates.