Apparatus and methods for second harmonic generation with a waveguide. In one embodiment, a method includes the steps of providing a waveguide, wherein the waveguide has a substrate, and a polydomain epitaxial thin film on the substrate, wherein the polydomain epitaxial thin film defines a plane and has a first surface and a second, opposite surface defining a body portion of the polydomain epitaxial thin film therebetween with a film thickness, l, and wherein the polydomain epitaxial thin film has a coherence length, lc, and exposing the waveguide to an incident photon beam with a wavelength and a focal point such that the incident photon beam is incident to the plane of the polydomain epitaxial thin film with an angle θ that is formed between the incident beam and the plane of the polydomain epitaxial thin film and satisfies the condition of 0