The distribution of Si dopant at the Au/GaAs interface after heat treatment has been studied using spatially resolved secondary‐ion mass spectrometry. Previously it has been shown that heat treatment changes as deposited Au thin film from Schottky contacts to ohmic contacts. The present study shows that the transition to an ohmic contact results from segregation of dopants in areas where GaAs is decomposed by reacting with the Au overlayer. Thus the ohmic contact is spatially very inhomogeneous at the metal/semiconductor interface. The mechanism leading to concentrations of the Si and nonuniform ohmic contacts is discussed, and segregation to the solid during decomposition of the GaAs is the most likely mechanism.