Systems and methods for preparing freestanding films using laser-assisted chemical etch (LACE), and freestanding films formed using same, are provided. In accordance with one aspect a substrate has a surface and a portion defining an isotropically defined cavity; and a substantially continuous film is disposed at the substrate surface and spans the isotropically defined cavity. In accordance with another aspect, a substrate has a surface and a portion defining an isotropically defined cavity; and a film is disposed at the substrate surface and spans the isotropically defined cavity, the film including at least one of hafnium oxide (HfO2), diamond-like carbon, graphene, and silicon carbide (SiC) of a predetermined phase. In accordance with still another aspect, a substrate has a surface and a portion defining an isotropically defined cavity; and a multi-layer film is disposed at the substrate surface and spans the isotropically defined cavity.