A detailed understanding of the resistive switching mechanisms that operate in redox-based resistive random-access memories (ReRAM) is key to controlling these memristive devices and formulating appropriate design rules. Based on distinct fundamental switching mechanisms, two types of ReRAM have emerged: electrochemical metallization memories, in which the mobile species is thought to be metal cations, and valence change memories, in which the mobile species is thought to be oxygen anions (or positively charged oxygen vacancies). Here we show, using scanning tunnelling microscopy and supported by potentiodynamic current-voltage measurements, that in three typical valence change memory materials (TaO(x), HfO(x) and TiO(x)) the host metal cations are mobile in films of 2 nm thickness. The cations can form metallic filaments and participate in the resistive switching process, illustrating that there is a bridge between the electrochemical metallization mechanism and the valence change mechanism. Reset/Set operations are, we suggest, driven by oxidation (passivation) and reduction reactions. For the Ta/Ta2O5 system, a rutile-type TaO2 film is believed to mediate switching, and we show that devices can be switched from a valence change mode to an electrochemical metallization mode by introducing an intermediate layer of amorphous carbon.

Resistive switching memories based on the valence change mechanism have attracted great attention due to their potential use in future nanoelectronics. The working principle relies on ion migration in an oxide matrix and subsequent nanoscale redox processes leading to a resistance change. While switching from a low resistive to a high resistive state, different intermediate resistance levels can be programmed by changing the maximum applied voltage, making resistive switches highly interesting for multibit data storage and neuromorphic applications. To date, this phenomenon, which is known as gradual reset, has been reported in various experimental studies, but a comprehensive physical understanding of this key phenomenon is missing. Here, a combined experimental and numerical modeling approach is presented to address these issues. Time‐resolved pulse measurements are performed to study the reset kinetics in TaOx‐based nano‐crossbar structures. The results are analyzed using a 2D dynamic model of nonisothermal drift–diffusion transport in the mixed electronic–ionic conducting oxide including the effect of contact potential barriers. The model accurately describes the experimental data and provides physical insights into the processes determining the gradual reset. The gradual nature can be attributed to the temperature‐accelerated oxygen‐vacancy motion being governed by drift and diffusion processes approaching an equilibrium situation.

The local electronic properties of tantalum oxide (TaO x , 2 ≤ x ≤ 2.5) and strontium ruthenate (SrRuO 3 ) thin-film surfaces were studied under the influence of electric fields induced by a scanning tunneling microscope (STM) tip. The switching between different redox states in both oxides is achieved without the need for physical electrical contact by controlling the magnitude and polarity of the applied voltage between the STM tip and the sample surface. We demonstrate for TaO x films that two switching mechanisms operate. Reduced tantalum oxide shows resistive switching due to the formation of metallic Ta, but partial oxidation of the samples changes the switching mechanism to one mediated mainly by oxygen vacancies. For SrRuO 3 , we found that the switching mechanism depends on the polarity of the applied voltage and involves formation, annihilation, and migration of oxygen vacancies. Although TaO x and SrRuO 3 differ significantly in their electronic and structural properties, the resistive switching mechanisms could be elaborated based on STM measurements, proving the general capability of this method for studying resistive switching phenomena in different classes of transition metal oxides. KEYWORDS: resistive switching, strontium ruthenate, tantalum oxide, scanning tunneling microscopy, electric field effect R edox-based resistance switching random access memories (ReRAMs) are considered as the next-generation memory devices to replace the present flash-based technology.1,2 ReRAMs have a simple metal−solid electrolyte− metal architecture, storing binary code information using the change in the resistance induced by filament formation and rupture, defining the low-resistive ON state (also denoted as LRS) and the high-resistive OFF state (or HRS), respectively. High scalability, CMOS compatibility, switching times in the subnanosecond range, excellent endurance and retention, and low power consumption are key but otherwise difficult-toduplicate features of ReRAM devices.

The demand for highly scalable, low-power devices for data storage and logic operations is strongly stimulating research into resistive switching as a novel concept for future non-volatile memory devices. To meet technological requirements, it is imperative to have a set of material design rules based on fundamental material physics, but deriving such rules is proving challenging. Here, we elucidate both switching mechanism and failure mechanism in the valence-change model material SrTiO3, and on this basis we derive a design rule for failure-resistant devices. Spectromicroscopy reveals that the resistance change during device operation and failure is indeed caused by nanoscale oxygen migration resulting in localized valence changes between Ti4+ and Ti3+. While fast reoxidation typically results in retention failure in SrTiO3, local phase separation within the switching filament stabilizes the retention. Mimicking this phase separation by intentionally introducing retention-stabilization layers with slow oxygen transport improves retention times considerably.

Oxide-based metal-insulator-metal structures are of special interest for future resistive random-access memories. In such cells, redox processes on the nanoscale occur during resistive switching, which are initiated by the reversible movement of native donors, such as oxygen vacancies. The formation of these fi laments is mainly attributed to an enhanced oxygen diffusion due to Joule heating in an electric fi eld or due to electrical breakdown. Here, the development of a dendrite-like structure, which is induced by an avalanche discharge between the top electrode and the Ta 2 O 5-x layer, is presented, which occurs instead of a local breakdown between top and bottom electrode. The dendrite-like structure evolves primarily at structures with a pronounced interface adsorbate layer. Furthermore, local conductive atomic force microscopy reveals that the entire dendrite region becomes conductive. Via spectromicroscopy it is demonstrated that the subsequent switching is caused by a valence change between Ta 4+ and Ta 5+ , which takes place over the entire former Pt/Ta 2 O 5-x interface of the dendrite-like structure.