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A new method is proposed to modify the Schottky barrier height (SBH) for nickel silicide/Si contact.Chemical and electrical properties for NiSi2/Si interface with titanium,scandium and vanadium incorporation are investigated by first-principles calculations. The metal/semiconductor interface states within the gap region are greatly decreased,which is related to the diminutions of junction leakage when Ti-eap is experimentally used in nickel silicide/Si contact process.It leads to an unpinning metal/semiconductor interface.The SBH obeys the SchottkyMort theory. Compared to Ti substitution,the SBH for electrons is reduced for scandium and increases for vanadium.