DIW is supplied toward a surface of a substrate to form a lower layer liquid film, which is then frozen to form a lower layer frozen film. Further, DIW cooled down to a temperature at which the lower layer frozen film will not melt is supplied toward a surface of the lower layer frozen film to form an upper layer liquid film, which is then frozen to form an upper layer frozen film in a layered structure. DIW which is at room temperature is thereafter supplied, thereby melting the entirety of the lower layer frozen film and the upper layer frozen film to remove these films together with particles off from the surface of the substrate.