The morphology studies of the interlayer surface (0001) were carried out by the method of scanning tunneling microscopy in the n–Bi1.6Sb0.4Te2.94Se0.06, n- Bi1.8Sb0.2Te2.82Se0.09S0.09, p-Bi0.8Sb1.2Te2.91Se0.09 and p-Bi0.7Sb1.3Te2.91Se0.09 solid solutions. On the surface (0001), impurity and native defects were found (vacancies of tellurium, antisite defects, adatoms), formed in the compositions due to substitutions of atoms in the Bi2Te3 sublattices. The average values of HM and the standard deviations of HS in height in the distribution of atoms on the surface are determined depending on the composition of the solid solution. The effect of detected defects on the thermoelectric properties of solid solutions has been established.