A technique is proposed for estimation of maximal thickness of a doped semiconductor transition layer in a Schottky contact. It is based on taking spectral curves of transverse photovoltage. It is shown that in gallium arsenide crystal with starting impurity concentration of 10 16 cm 3 , a layer with doping level of 10 17 cm 3 and maximal thickness of 4 nm may exist in the space-charge region near the interface of the TiB 2-GaAs structure. At impurity concentration in the transition layer about and over 10 18 cm 3 , its thickness goes down, and it shows up as individual inclusions in the GaAs lattice. The total area of such inclusions at the metal-semiconductor interface does not exceed 1 % that of contact. In actual structures the transition layer is a superposition of layers and inclusions, with impurity concentration of 10 17 cm 3 or more and thickness below 4 nm.