Complex oxide heterostructures provide access to emergent functional and structural phases which are not present in the bulk constituent materials. In this letter, we focus on Gd/La0.67Sr0.33CoO3 (LSCO) heterostructures due to the high oxygen ion conductivity, as well as the coupled magnetic and electronic properties of LSCO, which are strongly dependent on the oxygen stoichiometry. This combination of properties enable the ionic control of the functional properties of LSCO thin films through the presence of oxygen getter layers such as Gd. We utilize x-ray nanodiffraction to directly image the nanoscale morphology of LSCO thin films as they are progressively transformed from the equilibrium perovskite phase to the metastable brownmillerite (BM) phase with increasing Gd thickness. Our studies show the coexistence of perovskite and BM phases with a critical oxygen vacancy concentration threshold which leads to the formation of extended BM filaments. In addition to lateral phase separation, we observed phase separation within the film thickness possibly due to pinning of the perovskite and BM phases by the substrate/LSCO and Gd/LSCO interface, respectively. Our studies provide an unprecedented nanoscale survey of the phase separation in the cobaltites and shed light on the formation of the metastable BM phase.

Hard X-ray nanodiffraction provides a unique nondestructive technique to quantify local strain and structural inhomogeneities at nanometer length scales. However, sample mosaicity and phase separation can result in a complex diffraction pattern that can make it challenging to quantify nanoscale structural distortions. In this work, a k-means clustering algorithm was utilized to identify local maxima of intensity by partitioning diffraction data in a three-dimensional feature space of detector coordinates and intensity. This technique has been applied to X-ray nanodiffraction measurements of a patterned ferroelectric PbZr0.2Ti0.8O3 sample. The analysis reveals the presence of two phases in the sample with different lattice parameters. A highly heterogeneous distribution of lattice parameters with a variation of 0.02 Å was also observed within one ferroelectric domain. This approach provides a nanoscale survey of subtle structural distortions as well as phase separation in ferroelectric domains in a patterned sample.