Implant depth and silicon binding states in as-implanted and annealed ultra-shallow junction 75As+ implants were characterized using X-ray photoelectron spectroscopy (XPS). Dopant profiles were merged with secondary ion mass spectrometry (SIMS) depth profiles to complete the dopant distribution in the initial transient region. Doped regions of the implanted silicon substrate were identified using shifts in the Si2p photoelectron energy. The effects of rapid thermal annealing on Si2p energy are also presented.