A method for forming a superconductive article is disclosed. According to one method, a substrate is provided, the substrate having an aspect ratio of not less than about 1×103, forming a buffer layer overlying the substrate, forming a superconductor layer overlying the buffer layer, and characterizing at least one of the substrate, the buffer layer and the superconductor layer by x-ray diffraction. In this regard, x-ray diffraction is carried out such that data are taken at multiple phi angles. Data acquisition at multiple phi angles permits robust characterization of the film or layer subject to characterization, and such data may be utilized for process control and/or quality control. Additional methods for forming superconductive articles, and for characterizing same with XRD are also disclosed.