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ACS applied materials & interfaces 12(43), 48773-48780 (2020). doi:10.1021/acsami.0c13020, Published by American Chemical Society, Washington, DC

Memristive devices relying on redox-based resistive switching mechanisms represent promising candidates for the development of novel computing paradigms beyond von Neumann architecture. Recent advancements in understanding physicochemical phenomena underlying resistive switching have shed new light on the importance of an appropriate selection of material properties required to optimize the performance of devices. However, despite great attention has been devoted to unveiling the role of doping concentration, impurity type, adsorbed moisture, and catalytic activity at the interfaces, specific studies concerning the effect of the counter electrode in regulating the electronic flow in memristive cells are scarce. In this work, the influence of the metal-insulator Schottky interfaces in electrochemical metallization memory (ECM) memristive cell model systems based on single-crystalline ZnO nanowires (NWs) is investigated following a combined experimental and modeling approach. By comparing and simulating the electrical characteristics of single NW devices with different contact configurations and by considering Ag and Pt electrodes as representative of electrochemically active and inert electrodes, respectively, we highlight the importance of an appropriate choice of electrode materials by taking into account the Schottky barrier height and interface chemistry at the metal-insulator interfaces. In particular, we show that a clever choice of metal-insulator interfaces allows to reshape the hysteretic conduction characteristics of the device and to increase the device performance by tuning its resistance window. These results obtained from single NW-based devices provide new insights into the selection criteria for materials and interfaces in connection with the design of advanced ECM cells.

Neuromorphic computing aims at the realization of intelligent systems able to process information similarly to our brain. Brain-inspired computing paradigms have been implemented in crossbar arrays of memristive devices; however, this approach does not emulate the topology and the emergent behaviour of biological neuronal circuits, where the principle of self-organization regulates both structure and function. Here, we report on in materia reservoir computing in a fully memristive architecture based on self-organized nanowire networks. Thanks to the functional synaptic connectivity with nonlinear dynamics and fading memory properties, the designless nanowire complex network acts as a network-wide physical reservoir able to map spatio-temporal inputs into a feature space that can be analysed by a memristive resistive switching memory read-out layer. Computing capabilities, including recognition of spatio-temporal patterns and time-series prediction, show that the emergent memristive behaviour of nanowire networks allows in materia implementation of brain-inspired computing paradigms characterized by a reduced training cost.

Memristive devices based on a resistive switching mechanism are considered very promising for nonvolatile memory and unconventional computing applications, even though many details of the switching mechanisms are not yet fully understood. Here, we report a nanostructural study by means of high-resolution transmission electron microscopy and spectroscopy techniques of a Ag/ZnO/Pt memristive device. To ease the localization of the filament position for its characterization, we propose to use the guiding effect of regular perturbation arrays obtained by FIB technology to assist the filament formation. HRTEM and EDX were used to identify the composition and crystalline structure of the so-obtained conductive filaments and surrounding regions. It was determined that the conducting paths are composed mainly of monocrystalline Ag, which remains polycrystalline in some circumstances, including the zone where the switching occurs and at secondary filaments created at the grain boundaries of the polycrystalline ZnO matrix. We also observed that the ZnO matrix shows a degraded quality in the switching zone, while it remains unaltered in the rest of the memristive device.

Resistive switching (RS) devices based on self-assembled nanowires (NWs) and nanorods (NRs) represent a fascinating alternative to conventional devices with thin film structure. The high surface-to-volume ratio may indeed provide the possibility of modulating their functionalities through surface effects. However, devices based on NWs usually suffer from low resistive switching performances in terms of operating voltages, endurance and retention capabilities. In this work, we report on the resistive switching behaviour of ZnO NW arrays, grown by hydrothermal synthesis, that exhibit stable, bipolar resistive switching characterized by SET/RESET voltages lower than 3 V, endurance higher than 1100 cycles and resistance state retention of more than 105 s. The physical mechanism underlying these RS performances can be ascribed to nanoionic processes involving the formation/rupture of conductive paths assisted by oxygen-related species in the ZnO active layer. The reported results represent, to the best of our knowledge, the best resistive switching performances observed in ZnO NW arrays in terms of endurance and retention.

In this work, we report on the metal–insulator transition and electronic transport properties of single crystalline ZnO nanowires synthetized by means of Chemical Vapor Deposition. After evaluating the effect of adsorbed species on transport properties, the thermally activated conduction mechanism was investigated by temperature-dependent measurements in the range 81.7–250 K revealing that the electronic transport mechanism in these nanostructures is in good agreement with the presence of two thermally activated conduction channels. More importantly, it was observed that the electrical properties of ZnO NWs can be tuned from semiconducting to metallic-like as a function of temperature with a metal-to-insulator transition (MIT) observed at a critical temperature above room temperature (T c ∼ 365 K). Charge density and mobility were investigated by means of field effect measurements in NW field-effect transistor configuration. Results evidenced that the peculiar electronic transport properties of ZnO NWs are related to the high intrinsic n-type doping of these nanostructures that is responsible, at room temperature, of a charge carrier density that lays just below the critical concentration for the MIT. This work shows that native defects, Coulomb interactions and surface states influenced by adsorbed species can significantly influence charge transport in NWs.

Metal-semiconductor interfaces play a crucial role not only for regulating the electronic conduction mechanism but also in determining new functionalities in nanosized devices. In this work, we reported the investigation of the junction properties of single ZnO nanowires (NWs) asymmetrically contacted by means of a Pt electrochemically inert and a Cu electrochemically active electrode. At low applied voltages, these devices operate as diodes where the conduction mechanism was found to be dominated by the Schottky barrier at the Cu/ZnO interface. Junction parameters such as the Schottky barrier height, the ideality factor and the series resistance have been analyzed according to the thermionic emission theory. Different methods for parameter retrieval from I-V-T measurements are discussed and compared. A potential fluctuation model is considered in order to account for barrier inhomogeneities, revealing the presence of two Gaussian distribution of barrier heights. On the other hand, new device features arise from electrochemical dissolution and migration of Cu ions along the NW when high electric fields are implied. These electrochemical processes are underlaying the resistive switching and memristive behavior observed in single ZnO NWs, as suggested also by direct observation of Cu nanoclusters along the nanostructures after the switching events.

This work reports the fabrication of memristive devices based on iron oxide (Fe2O3) thin films grown by atomic layer deposition (ALD) using ferrocene as iron precursor and ozone as oxidant. An excellent control of the ALD process was achieved by using an experimental procedure based on a sequence of micro-pulses, which provided long residence time and homogeneous diffusion of precursors, allowing ALD of thin films with smooth morphology and crystallinity which was found to increase with layer thickness, at temperatures as low as 250 °C. The resistive switching of symmetric Pt/Fe2O3/Pt thin film devices exhibited bipolar mode with good stability and endurance. Multi-level switching was achieved via current and voltage control. It was proved that the ON state regime can be tuned by changing the current compliance while the OFF state can be changed to intermediate levels by decreasing the maximum voltage during RESET. The structural analysis of the switched oxide layer revealed the presence of nano-sized crystalline domains corresponding to different iron oxide phases, suggesting that Joule heating effects during I-V cycling are responsible for a crystallization process of the pristine amorphous layer.

The effect of laser irradiation on chemically vapor deposited (CVD) graphene was studied by analyzing the temporal evolution of Raman spectra acquired under various illumination conditions. The spectra showed that the normalized intensity of the defect-related peak increases with the square root of the exposure time and varies almost linearly with the laser power density. Furthermore, the hardness of graphene to radiation damage depends on its intrinsic structural quality. The results suggest that, contrary to the common belief, micro-Raman spectroscopy cannot be considered a noninvasive tool for the characterization of graphene. The experimental observations are compatible with a model that we derived from the interpretative approach of the Staebler–Wronski effect in hydrogenated amorphous silicon; this approach assumes that the recombination of photoexcited carriers induces the breaking of weak C–C bonds.

Resistive switching (RS) devices are considered as the most promising alternative to conventional random access memories. They interestingly offer effective properties in terms of device scalability, low power-consumption, fast read/write operations, high endurance and state retention. Moreover, neuromorphic circuits and synapse-like devices are envisaged with RS modeled as memristors, opening the route toward beyond-Von Neumann computing architectures and intelligent systems. This work investigates how the RS properties of zinc oxide thin films are related to both sputtering deposition process and device configuration, i.e. valence change memory and electrochemical metallization memory (ECM). Different devices, with an oxide thickness ranging from 50-250 nm, are fabricated and deeply characterized. The electrical characterization evidences that, differently from typical nanoscale amorphous oxides employed for resistive RAMs (HfO x , WO x , etc), sub-micrometric thicknesses of polycrystalline ZnO layers with ECM configuration are needed to achieve the most reliable devices. The obtained results are deeply discussed, correlating the RS mechanism to material nanostructure.