What lies beneath? Investigations of atomic force microscopy-based nano-machining to reveal sub-surface ferroelectric domain configurations in ultrathin films

Multiferroic materials, encompassing simultaneous ferroelectric and ferromagnetic polarization states, are enticing mul ti-state materi al s for memory scal i ng beyond exi sti ng technol ogi es. Auri vi l l i us phase B6TFMO (Bi₆Ti_xFe_yMn_zO₁₈) is a unique room temperature multiferroic material that could ideally be suited to future production of revolutionary memory devices. As miniaturization of electronic devices continues, it is crucial to characterize ferroelectric domain configurations at very small (sub-10 nm) thickness. Direct liquid injection chemical vapor deposition allows for frontier development of ultrathin films at fundamental (close to unit cell) dimensions. However, layer-by-layer growth of ultrathin complex oxides is subject to the formation of surface contaminants and 2D islands and pits, which can obscure visualization of domain patterns using piezoresponse force microscopy (PFM). Herein, we apply force from a sufficiently stiff diamond cantilever while scanning over ultrathin films to perform atomic force microscopy (AFM)-based nano-machining of the surface layers. Subsequent lateral PFM imaging of sub-surface layers uncovers 45° orientated striped twin domains, entirely distinct from the randomly configured piezoresponse observed for the pristine film surface. Furthermore, our investigations indicate that these sub-surface domain structures persist along the in-plane directions throughout the film depth down to thicknesses of less than half of an Aurivillius phase unit cell (< 2.5 nm). Thus, AFM-based nano-machining in conjunction with PFM allows demonstration of stable in-plane ferroelectric domains at thicknesses lower than previously determined for multiferroic B6TFMO. These findings demonstrate the technological potential of Aurivillius phase B6TFMO for future miniaturized memory storage devices. Next-generation devices based on ultrathin multiferroic tunnel junctions are projected.