The interfacial structures resulting from the metallurgical reactions between a Ni/Au/Ge/Au film and (100) GaAs substrate were studied by cross-section TEM. Annealing at 300 – 350°C causes a complicated solid-solid phase reaction, resulting in the multilayer structure of Ni2Ge/Au7Ga2/NiAs/Au7Ga,/GaAs. The contact shows non-ohmic character, since most of the doping element Ge is trapped in the surface Ni2Ge layer When the contact is annealed at above 400°C. the layered structure is destroyed because one of the phases (Au-Ga) becomes liquid but other phases (Ni-Ge, Ni-As) remain solid Ge, which is captured in the surface layer, diffuses out of the Ni2Ge phase into the contact/GaAs interface through the Au-rich melt. Above this temperature, a Ge-doped n+ region is probably formed at the NiAs/GaAs interface and the contact becomes ohmic. With increasing annealing temperature, continuous grain growth of NiAs is found to occur and the NiAs/GaAs interface area increases. Thus the ohmic behavior of Au-Ge-Ni on n-GaAs can be explained by the low barrier height of the NiAs/GaAs interface and the formation of Ge-doped n+ region under the NiAs phase.