The method of surface preparation on n-type GaAs, even with the presence of an amorphous-Si interfacial passivation layer, is shown to be a critical step in the removal of accumulation capacitance frequency dispersion. In situ deposition and analysis techniques were used to study different surface preparations, including NH4OH, Si-flux, and atomic hydrogen exposures, as well as Si passivation depositions prior to in situ atomic layer deposition of Al2O3. As–O bonding was removed and a bond conversion process with Si deposition is observed. The accumulation capacitance frequency dispersion was removed only when a Si interlayer and a specific surface clean were combined.