Unveiling and mapping polymorphs in fluorite Y2TiO5 using 4D-STEM and unsupervised machine learning

Abstract

Y₂TiO₅ belongs to the Ln₂TiO₅ (Ln = lanthanide or Y) family of ceramic materials and exhibits a range of desirable material properties such as radiation tolerance, frustrated magnetism, and large dielectric constant. However, understanding the complex crystal structure of Y₂TiO₅ remains elusive, given that Y₂TiO₅ can adopt multiple polymorphs such as cubic, orthorhombic, and hexagonal phases within the lattice. In this work, we report a detailed structural analysis of Y₂TiO₅ using four-dimensional scanning transmission electron microscopy coupled with unsupervised machine learning. The pyrochlore nanodomains, characterized by the ordered arrangement of yttrium cations on the A site of their A₂BO₅ structure, are present within the matrix of a predominantly fluorite-structured Y₂TiO₅ along with a third polymorph, the hexagonal phase. The pyrochlore phase is found to form 2 nm boundary regions around hexagonal phase stacking faults, highlighting the potential influence of the hexagonal phase on the occurrence and distribution of the pyrochlore phase. Lastly, we identify a unique pyrochlore phase with asymmetric arrangement of cation ordering along a single planar direction. Our findings provide invaluable insights into the possible mechanisms stabilizing pyrochlore nanodomains within the fluorite lattice of Y₂TiO₅.