Evolution of the conductive filament system in HfO₂-based memristors observed by direct atomic-scale imaging

The resistive switching effect in memristors typically stems from the formation and rupture of localized conductive filament paths, and HfO₂ has been accepted as one of the most promising resistive switching materials. However, the dynamic changes in the resistive switching process, including the composition and structure of conductive filaments, and especially the evolution of conductive filament surroundings, remain controversial in HfO₂-based memristors. Here, the conductive filament system in the amorphous HfO₂-based memristors with various top electrodes is revealed to be with a quasi-core-shell structure consisting of metallic hexagonal-Hf₆O and its crystalline surroundings (monoclinic or tetragonal HfO_x). The phase of the HfO_x shell varies with the oxygen reservation capability of the top electrode. According to extensive high-resolution transmission electron microscopy observations and ab initio calculations, the phase transition of the conductive filament shell between monoclinic and tetragonal HfO₂ is proposed to depend on the comprehensive effects of Joule heat from the conductive filament current and the concentration of oxygen vacancies. The quasi-core-shell conductive filament system with an intrinsic barrier, which prohibits conductive filament oxidation, ensures the extreme scalability of resistive switching memristors. This study renovates the understanding of the conductive filament evolution in HfO₂-based memristors and provides potential inspirations to improve oxide memristors for nonvolatile storage-class memory applications.