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Electronic switches based on the migration of high-density point defects, or memristors, are poised to revolutionize post-digital electronics. Despite significant research, key mechanisms for filament formation and oxygen transport remain unresolved, hindering our ability to predict and design device properties. For example, experiments have achieved 10 orders of magnitude longer retention times than predicted by current models. Here, using electrical measurements, scanning probe microscopy, and first-principles calculations on tantalum oxide memristors, we reveal that the formation and stability of conductive filaments crucially depend on the thermodynamic stability of the amorphous oxygen-rich and oxygen-poor compounds, which undergo composition phase separation. Including the previously neglected effects of this amorphous phase separation reconciles unexplained discrepancies in retention and enables predictive design of key performance indicators such as retention stability. This result emphasizes non-ideal thermodynamic interactions as key design criteria in post-digital devices with defect densities substantially exceeding those of today’s covalent semiconductors. 

Memristor devices have been extensively studied as one of the most promising technologies for next-generation non-volatile memory. However, for the memristor devices to have a real technological impact, they must be densely packed in a large crossbar array (CBA) exceeding Gigabytes in size. Devising a selector device that is CMOS compatible, 3D stackable, and has a high non-linearity (NL) and great endurance is a crucial enabling ingredient to reach this goal. Tunneling based selectors are very promising in these aspects, but the mediocre NL value limits their applications in large passive crossbar arrays. In this work, we demonstrated a trilayer tunneling selector based on the Ge/Pt/TaN 1+x /Ta 2 O 5 /TaN 1+x /Pd layers that could achieve a NL of 3 × 10 5 , which is the highest NL achieved using a tunnel selector so far. The record-high tunneling NL is partially attributed to the bottom electrode's ultra-smoothness (BE) induced by a Ge/Pt layer. We further demonstrated the feasibility of 1S1R (1-selector 1-resistor) integration by vertically integrating a Pd/Ta 2 O 5 /Ru based memristor on top of the proposed selector. 

Abstract Ferroelectric materials exhibit spontaneous polarization that can be switched by electric field. Beyond traditional applications as nonvolatile capacitive elements, the interplay between polarization and electronic transport in ferroelectric thin films has enabled a path to neuromorphic device applications involving resistive switching. A fundamental challenge, however, is that finite electronic conductivity may introduce considerable power dissipation and perhaps destabilize ferroelectricity itself. Here, tunable microwave frequency electronic response of domain walls injected into ferroelectric lead zirconate titanate (PbZr_0.2Ti_0.8O₃) on the level of a single nanodomain is revealed. Tunable microwave response is detected through first‐order reversal curve spectroscopy combined with scanning microwave impedance microscopy measurements taken near 3 GHz. Contributions of film interfaces to the measured AC conduction through subtractive milling, where the film exhibited improved conduction properties after removal of surface layers, are investigated. Using statistical analysis and finite element modeling, we inferred that the mechanism of tunable microwave conductance is the variable area of the domain wall in the switching volume. These observations open the possibilities for ferroelectric memristors or volatile resistive switches, localized to several tens of nanometers and operating according to well‐defined dynamics under an applied field.