Aluminum and nickel contacts were prepared by evaporation on sulfur-passivated n-and p-type Si͑100͒ substrates. The Schottky diodes were characterized by current-voltage, capacitance-voltage, and activation-energy measurements. Due to the passivation of Si dangling bonds by S, surface states are reduced to a great extent and Schottky barriers formed by Al and Ni on Si͑100͒ substrates show greater sensitivity to their respective work functions. Aluminum, a low work function metal, shows a barrier height of Ͻ0.11 eV on S-passivated n-type Si͑100͒ and ϳ0.80 eV on S-passivated p-type Si͑100͒, as compared to 0.56 and ϳ0.66 eV for nonpassivated n-and p-type Si͑100͒, respectively. Nickel, a high work function metal, shows ϳ0.72 and ϳ0.51 eV on S-passivated n and p-type Si͑100͒, respectively, as compared to ϳ0.61 and ϳ0.54 eV on nonpassivated n and p-type Si͑100͒, respectively. Though a surface dipole forms due to the adsorption of S on Si͑100͒, our experimental results indicate that the effect of surface states is the dominant factor in controlling the Schottky barrier height in these metal-Si systems.