range of tunable functionalities, such as conductivity and magnetism, that result from non-equilibrium growth conditions, are distinct from the bulk, and are heavily influenced by lattice disorder. [1] Order-disorder phase transitions are particularly important in A 2 B 2 O 7 compounds (where A and B are transition metal cations), which have been studied for use in solid oxide fuel cells (SOFCs), [2][3][4] advanced ferroelectric sensors, [5,6] and nuclear waste forms. [7] These materials represent model systems in which to examine the fundamental relationship between the introduction of point defects and lattice disorder, which together govern behavior.In the bulk, A 2 B 2 O 7 compounds can exhibit a range of structures from defected fluorite ( 3 Fd m) to cubic pyrochlore ( 3 Fd m) and monoclinic perovskite-like layered structure (P2 1 ), as the cation radius ratio (r A /r B ) increases. [8] During thin film growth, additional kinetic and substrate constraints can further change the energy landscape of the system and the resultant phase distribution. [5,9] This structural flexibility allows the pyrochlores to preserve their overall crystallinity during disordering of the cation sublattice by external stimuli, such as electric fields and energetic ion bombardment, making them promising candidates for SOFCs and nuclear waste forms. [10][11][12] Recently, Kreller et al. [13] have shown that ion irradiation may be used to controllably manipulate anti-site defect populations and resulting ion conduction at a fundamental level. Building upon this approach, ion irradiation applied to thin film heterostructures represents a promising route to examine how interface geometry and configuration mediate the evolution of local order. Furthermore, characterization using aberrationcorrected scanning transmission electron microscopy can provide direct insight into defect formation that can be linked to models.Decades of work on metals have shown that grain boundaries and other interfaces can significantly influence point defect transport and annihilation, [14] motivating the use of engineered nanostructured materials to mediate disordering processes. [15][16][17] While irradiation-induced structural disorder has been extensively studied in bulk pyrochlores, [7,12,18,19] less attention has been paid to the behavior of irradiated oxide thin film interfaces. Previous studies of epitaxial TiO 2 , [20,21] CeO 2 , [22,23] and BaTiO 3[24] films on SrTiO 3 have shown evidence for the presence of denuded zones in some interface configurations and not in others; these variations have been attributed to differences in defect kinetics and energetics of the interface and its component elements. The interface charge state Control of order-disorder phase transitions is a fundamental materials science challenge, underpinning the development of energy storage technologies such as solid oxide fuel cells and batteries, ultra-high temperature ceramics, and durable nuclear waste forms. At present, the development of promising complex oxides for these...