Direct Imaging of Ion Migration in Amorphous Oxide Electronic Synapses with Intrinsic Analog Switching Characteristics.

Amorphous metal oxides with analog resistive switching functions (i.e., continuous controllability of the electrical resistance) are gaining emerging interest due to their neuromorphic functionalities promising for energy efficient electronics. The mechanisms are currently attributed to field-driven migration of the constituent ions, but the applications are being hindered by the limited understanding of the physical mechanisms due to the difficulty in analyzing the causal ion migration, which occurs on a nanometer or even atomic scale. Here, the direct electrical transport measurement of analog resistive switching and ångström scale imaging of the causal ion migration is demonstrated in amorphous TaOx (a-TaOx) by conductive atomic force microscopy. Atomically flat thin films of a-TaOx, which is a practical material for commercial resistive random access memory, are fabricated in this study, and the mechanisms of the three known types of analog resistive switching phenomena (current-dependent set, voltage-dependent reset, and time-dependent switching) are directly visualized on the surfaces. The observations indicate that highly analog type of resistive switching can be induced in a-TaOx by inducing the continuous redox reactions for 2.0 < x < 2.5, which are characteristic of a-TaOx. The measurements also demonstrate drastic control of the switching stochasticity, which is attributable to controlled segregation of a metastable a-TaO2 phase. The findings provide direct clues for tuning the analog resistive switching characteristics of amorphous metal oxides and developing new functions for future neuromorphic computing.

Double gate operation of metal nanodot array based single electron device.

Multidot single-electron devices (SEDs) can enable new types of computing technologies, such as those that are reconfigurable and reservoir-computing. A self-assembled metal nanodot array film that is attached to multiple gates is a candidate for use in such SEDs for achieving high functionality. However, the single-electron properties of such a film have not yet been investigated in conjunction with optimally controlled multiple gates because of the structural complexity of incorporating many nanodots. In this study, Fe nanodot-array-based double-gate SEDs were fabricated by vacuum deposition, and their single-electron properties (modulated by the top- and bottom-gate voltages; VT and VB, respectively) were investigated. The phase of the Coulomb blockade oscillation systematically shifted with VT, indicating that the charge state of the single dot was controlled by both the gate voltages despite the metallic random multidot structure. This result demonstrates that the Coulomb blockade oscillation (originating from the dot in the multidot array) can be modulated by the two gates. The top and bottom gates affected the electronic state of the dot unevenly owing to the geometrical effect caused by the following: (1) vertically asymmetric dot shape and (2) variation of the dot size (including the surrounding dots). This is a characteristic feature of a nanodot array that uses self-assembled metal dots; for example, prepared by vacuum deposition. Such variations derived from a randomly distributed nanodot array will be useful in enhancing the functionality of multidot devices.

Stable and Tunable Current-Induced Phase Transition in Epitaxial Thin Films of Ca2RuO4.

Owing to the recent discovery of the current-induced metal-insulator transition and unprecedented electronic properties of the concomitant phases of calcium ruthenate Ca2RuO4, it is emerging as an important material. To further explore the properties, the growth of epitaxial thin films of Ca2RuO4 is receiving more attention, as high current densities can be applied to thin-film samples and the amount can be precisely controlled in an experimental environment. However, it is difficult to grow high-quality thin films of Ca2RuO4 due to the easy formation of the crystal defects originating from the sublimation of RuO4; therefore, the metal-insulator transition of Ca2RuO4 is typically not observed in the thin films. Herein, a stable current-induced metal-insulator transition is achieved in the high-quality thin films of Ca2RuO4 grown by solid-phase epitaxy under high growth temperatures and pressures. In the Ca2RuO4 thin films grown by ex situ annealing at >1200 °C and 1.0 atm, continuous changes in the resistance of over 2 orders of magnitude are induced by currents with a precise dependence of the resistance on the current amplitude. A hysteretic, abrupt resistive transition is also observed in the thin films from the resistance-temperature measurements conducted under constant-voltage (variable-current) conditions with controllability of the transition temperature. A clear resistive switching by the current-induced transition is demonstrated in the current-electric-field characteristics, and the switching currents and fields are shown to be very stable. These results represent a significant step toward understanding the high-current-density properties of Ca2RuO4 and the future development of Mott-electronic devices based on electricity-driven transitions.

Smooth Interfacial Scavenging for Resistive Switching Oxide via the Formation of Highly Uniform Layers of Amorphous TaOx.

We demonstrate that the inclusion of a Ta interfacial layer is a remarkably effective strategy for forming interfacial oxygen defects at metal/oxide junctions. The insertion of an interfacial layer of a reactive metal, that is, a "scavenging" layer, has been recently proposed as a way to create a high concentration of oxygen defects at an interface in redox-based resistive switching devices, and growing interest has been given to the underlying mechanism. Through structural and chemical analyses of Pt/metal/SrTiO3/Pt structures, we reveal that the rate and amount of oxygen scavenging are not directly determined by the formation free energies in the oxidation reactions of the scavenging metal and unveil the important roles of oxygen diffusibility. Active oxygen scavenging and highly uniform oxidation via scavenging are revealed for a Ta interfacial layer with high oxygen diffusibility. In addition, the Ta scavenging layer is shown to exhibit a highly uniform structure and to form a very flat interface with SrTiO3, which are advantageous for the fabrication of a steep metal/oxide contact.

Microstructural transitions in resistive random access memory composed of molybdenum oxide with copper during switching cycles.

The switching operation of a Cu/MoOx/TiN resistive random access memory (ReRAM) device was investigated using in situ transmission electron microscopy (TEM), where the TiN surface was slightly oxidized (ox-TiN). The relationship between the switching properties and the dynamics of the ReRAM microstructure was confirmed experimentally. The growth and/or shrinkage of the conductive filament (CF) can be classified into two set modes and two reset modes. These switching modes depend on the device's switching history, factors such as the amount of Cu inclusions in the MoOx layer and the CF geometry. High currents are needed to produce an observable change in the CF. However, sharp and stable switching behaviour can be achieved without requiring such a major change. The local region around the CF is thought to contribute to the ReRAM switching process.

Switching operation and degradation of resistive random access memory composed of tungsten oxide and copper investigated using in-situ TEM.

In-situ transmission electron microscopy (in-situ TEM) was performed to investigate the switching operation of a resistive random access memory (ReRAM) made of copper, tungsten oxide and titanium nitride (Cu/WOx/TiN). In the first Set (Forming) operation to initialize the device, precipitation appeared inside the WOx layer. It was presumed that a Cu conducting filament was formed, lowering the resistance (on-state). The Reset operation induced a higher resistance (the off-state). No change in the microstructure was identified in the TEM images. Only when an additional Reset current was applied after switching to the off-state could erasure of the filament be seen (over-Reset). Therefore, it was concluded that structural change relating to the resistance switch was localized in a very small area around the filament. With repeated switching operations and increasing operational current, the WOx/electrode interfaces became indistinct. At the same time, the resistance of the off-state gradually decreased. This is thought to be caused by Cu condensation at the interfaces because of leakage current through the area other than through the filament. This will lead to device degradation through mechanisms such as endurance failure. This is the first accelerated aging test of ReRAM achieved using in-situ TEM.