A lithographic patterning method includes forming a multi-layer patterning material film stack on a semiconductor substrate, the patterning material film stack including a resist layer formed over one or more additional layers, and forming a metal-containing top coat over the resist layer. The method further includes exposing the multi-layer patterning material film stack to patterning radiation through the metal-containing top coat to form a desired pattern in the resist layer, removing the metal-containing top coat, developing the pattern formed in the resist layer, etching at least one underlying layer in accordance with the developed pattern, and removing remaining portions of the resist layer. The metal-containing top coat can be formed, for example, by atomic layer deposition or spin-on deposition over the resist layer, or by self-segregation from the resist layer.