Plasmon-induced charge transfer causes electron-hole spatial separation at the metal-semiconductor interface, which plays a key role in photocatalytic and photovoltaic applications. The Schottky barrier formed at the metal-semiconductor interface can modify the hot carrier dynamics. Taking the Ag-TiO2 system as an example, we have investigated plasmon-induced charge transfer at the Schottky junction using quantum mechanical simulations. We find that the Schottky barrier induced by n-type doping enhances the electron transfer and that induced by p-type doping enhances the hole transfer, which is attributed to the shift of the Fermi energy and the band bending of the Schottky junction at the interface. The Schottky barrier also modifies the layer distribution of hot carriers. In particular, for the system with a large band bending, there exists electron-hole spatial separation inside the TiO2 substrate. Our results reveal the mechanism and dynamics of charge transfer at the Schottky junction, and pave the way for manipulating plasmon-assisted photocatalytic and photovoltaic applications.