The behavior of boron incorporation into GaAs has been studied by x-ray photoelectron spectroscopy, x-ray diffraction, and atomic force microscopy. As the boron content of the film was increased, both the characteristic peak for the B 1s core level at 188 eV and As Auger transition (260 eV) could be detected by XPS. At 550–600 °C, single crystalline films could only be grown for x≤0.06. Upon increasing the diborane flux in the gas phase, the film stoichiometry and the boron surface composition evolved rapidly towards a boron-rich subarsenide compound. This trend is followed by a clear degradation of the surface morphology and an increase in the surface roughness. A surface segregation of boron is suggested due to the high diborane vapor supersaturation needed during growth. © 2003 American Institute of Physics.