The real structure of ε-Ga2O3 and its relation to κ-phase

A comprehensive study by high-resolution transmission electron microscopy (TEM) and X-ray diffraction (XRD) was carried out on Ga2O3 epilayers grown at low temperature (650 degrees C) by vapor phase epitaxy in order to investigate the real structure at the nanoscale. Initial XRD measurements showed that the films were of the so-called epsilon phase; i.e. they exhibited hexagonal P6(3)mc space group symmetry, characterized by disordered and partial occupation of the Ga sites. This work clarifies the crystal structure of Ga2O(3) layers deposited at low temperature at the nanoscale: TEM investigation demonstrates that the Ga atoms and vacancies are not randomly distributed, but actually possess ordering, with (110)-twinned domains of 5-10 nm size. Each domain has orthorhombic structure with Pna2(1) space group symmetry, referred to as kappa-Ga2O3. Further XRD analysis carried out on thicker samples (9-10 mu m) confirmed this finding and provided refined structural parameters. The six (110)-type twinned ordered domains together - if the domain size falls below the actual resolution of the probing techniques - can be misinterpreted as the disordered structure with its P6(3)mc space group symmetry usually referred to as epsilon-Ga2O3 in the current literature. The crystal structure of these Ga2O3 layers consists of an ABAC oxygen close-packed stacking, where Ga atoms occupy octahedral and tetrahedral sites in between, forming two types of polyhedral layers parallel to (001). The edge-sharing octahedra and the corner-sharing tetrahedra form zig-zag ribbons along the [100] direction. Anti-phase boundaries are common inside the domains. The polar character of the structure is confirmed, in agreement with the characteristics of the Pna2(1) space group and previous observations.