In one aspect, a method is disclosed that includes providing a substrate having a topography that comprises a relief and providing an anti-reflective film conformally over the substrate using a molecular layer deposition step. The anti-reflective film may be formed of a compound selected from the group consisting of: (i) an organic compound chemically bound to an inorganic compound, where one of the organic compound and the inorganic compound is bound to the substrate and where the organic compound absorbs light at at least one wavelength selected in the range 150-500 nm, or (ii) a monodisperse organic compound absorbing light at at least one wavelength selected in the range 150-500 nm. The method further includes providing a photoresist layer on the anti-reflective film.