The surface structure of GaAs(100), (111)A, and (111)B substrates nitrided through the wet chemical treatment in hydrazine-sulfide solution have been studied by scanning tunneling microscopy (STM) under annealing in UHV. Such treatment has earlier been shown to produce a monolayer of gallium nitride on the (100) GaAs surface. The as-nitrided substrates of all surface orientations were found to be covered by an overfilm, which contains thioarsenic compounds and has a smooth relief. Thermal desorption of the overlfilm at about 530 degrees C opens the own relief of the nitrided surfaces. For the (100) orientation such relief is not microscopically planar and consists of nano-scale vicinal hillocks. These hillocks occur due to surface microetching which proceeds simultaneously with the formation of the surface nitride layer. We have shown that the wet nitridation procedure forms a monolayer of surface nitride on the (111)B surface. During nitridation the (111)B surface, as well as the (100) one, is affected by the microetching in the hydrazine-sulfide solution. Therefore, it exhibits a characteristic relief formed by triangular vicinal pyramids. At the same time the nitride film is not formed on the (111)A surface, which is more chemically inert, and where the surface etching is almost absent. (C) 2008 Published by Elsevier B. V.