PbS layer growth by laser ablation on slightly misoriented Si and NaCl substrates has been investigated. An analysis of the substrate atom core level XPS spectra dependence on layer growth indicated a "flat" layer growth on terrace-step surface. The influence of substrate surface morphology on layer growth and on layer component electron spectra was observed. An additional structure of Pb core levels in the photoelectron spectra was observed in PbS layers grown on misoriented substrate. The additional components of Pb core levels have a shift equal to 1.0 eV. The formation of clusters with excess of Pb is considered to be responsible for the new lines.