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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

Advanced materials interfaces 10(16), 2100915 (2021). doi:10.1002/admi.202100915, Published by Wiley-VCH, Weinheim

The knowledge of the spatial distribution of the electrical conductivity of metallic nanowire networks (NWN) is important for tailoring the performance in applications. This work focuses on Electrical Resistance Tomography (ERT), a technique that maps the electrical conductivity of a sample from several resistance measurements performed on its border. We show that ERT can be successfully employed for NWN characterisation if a dedicated measurement protocol is employed. When applied to other materials, ERT measurements are typically performed with a constant current excitation; we show that, because of the peculiar microscopic structure and behaviour of metallic NWN, a constant voltage excitation protocols is preferable. This protocol maximises the signal to noise ratio in the resistance measurements—and thus the accuracy of ERT maps—while preventing the onset of sample alterations.

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.

The physical mechanism involved in resistive switching phenomena occurring in devices based on ZnO nanowire (NW) arrays may vary considerably, also depending on the structure of the switching layer. In particular, it is shown here that the formation of a ZnO base layer between the metallic catalyst substrate and the NW, which is typical of CVD-grown ZnO NW arrays, should not be neglected when explaining the switching physical mechanism. The structural and electrical properties of this layer are investigated after the mechanical removal of NWs. Electrical measurements were performed in the presence of NWs and, after their removal, showed that the base alone exhibits resistive switching properties. The proposed switching mechanism is based on the creation/rupture of an oxygen vacancies conductive path along grain boundaries of the polycrystalline base. The creation of the filament is facilitated by the high concentration of vacancies at the grain boundaries that are oriented perpendicularly to the electrode...

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.

This letter deals with the compact modeling of the I-V characteristics of single crystalline ZnO nanowires (NW) attached to two metal electrodes (Pt and Ag). Starting from the standard model of electron transport in these structures based on the series combination of two back-to-back Schottky diodes, three different approaches which account for the role played by the NW series resistance are presented. The first approach considers a fixed potential drop across the NW, the second one involves the solution to the problem of a diode with linear and nonlinear series resistances using the Lambert W function, and the third one consists in a behavioral model with continuous first derivative suitable for circuit simulation environments. In the three cases, the proposed solutions are consistent with the observed electrical constraints both at low (linear I-V relationship) and high (current saturation) voltages.

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.

Surface and quantum confinement effects in one-dimensional systems such as ZnO nanowires are responsible for novel electrical properties, and can be exploited to tune electrical transport on the nanoscale. The investigation of new physical mechanisms for resistive switching can be fulfilled by studying metal/insulator/metal memristive devices that take advantage of the unique properties of one-dimensional nanoscale metal oxides. In particular, the mechanisms of resistive switching between multiple resistance states in such nanostructures can be associated with the variation of internal physical states. Here we demonstrate both experimentally and theoretically that core–shell structures based on polyacrylic acid coated ZnO nanowires exhibit a resistive switching behavior characterized by internal multiple resistance states, owing to the changes in surface states induced by redox reactions occurring at their surfaces. The introduction of a thin layer of polymer coating resulted in a resistive switching between more than two states. Specifically, the existence of two intermediate states in addition to the high and low resistance states was revealed during DC measurements in voltage sweep mode. All resistive states showed low variability over cycling. The mechanism of switching between multiple steps, as probed by density functional theory calculations, was associated with redox reactions involving species at the interface (e.g. methanal or hydroxyl groups), each characterized by a given redox potential. Therefore, multiple resistance states were induced by specific and stable threshold voltages, as shown experimentally.

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.