Electrochemical-Memristor-Based Artificial Neurons and Synapses-Fundamentals, Applications, and Challenges.

Artificial neurons and synapses are considered essential for the progress of the future brain-inspired computing, based on beyond von Neumann architectures. Here, a discussion on the common electrochemical fundamentals of biological and artificial cells is provided, focusing on their similarities with the redox-based memristive devices. The driving forces behind the functionalities and the ways to control them by an electrochemical-materials approach are presented. Factors such as the chemical symmetry of the electrodes, doping of the solid electrolyte, concentration gradients, and excess surface energy are discussed as essential to understand, predict, and design artificial neurons and synapses. A variety of two- and three-terminal memristive devices and memristive architectures are presented and their application for solving various problems is shown. The work provides an overview of the current understandings on the complex processes of neural signal generation and transmission in both biological and artificial cells and presents the state-of-the-art applications, including signal transmission between biological and artificial cells. This example is showcasing the possibility for creating bioelectronic interfaces and integrating artificial circuits in biological systems. Prospectives and challenges of the modern technology toward low-power, high-information-density circuits are highlighted.

Quantum Conductance in Memristive Devices: Fundamentals, Developments, and Applications.

Quantum effects in novel functional materials and new device concepts represent a potential breakthrough for the development of new information processing technologies based on quantum phenomena. Among the emerging technologies, memristive elements that exhibit resistive switching, which relies on the electrochemical formation/rupture of conductive nanofilaments, exhibit quantum conductance effects at room temperature. Despite the underlying resistive switching mechanism having been exploited for the realization of next-generation memories and neuromorphic computing architectures, the potentialities of quantum effects in memristive devices are still rather unexplored. Here, a comprehensive review on memristive quantum devices, where quantum conductance effects can be observed by coupling ionics with electronics, is presented. Fundamental electrochemical and physicochemical phenomena underlying device functionalities are introduced, together with fundamentals of electronic ballistic conduction transport in nanofilaments. Quantum conductance effects including quantum mode splitting, stability, and random telegraph noise are analyzed, reporting experimental techniques and challenges of nanoscale metrology for the characterization of memristive phenomena. Finally, potential applications and future perspectives are envisioned, discussing how memristive devices with controllable atomic-sized conductive filaments can represent not only suitable platforms for the investigation of quantum phenomena but also promising building blocks for the realization of integrated quantum systems working in air at room temperature.

Catalyst Interface Engineering for Improved 2D Film Lift-Off and Transfer.

The mechanisms by which chemical vapor deposited (CVD) graphene and hexagonal boron nitride (h-BN) films can be released from a growth catalyst, such as widely used copper (Cu) foil, are systematically explored as a basis for an improved lift-off transfer. We show how intercalation processes allow the local Cu oxidation at the interface followed by selective oxide dissolution, which gently releases the 2D material (2DM) film. Interfacial composition change and selective dissolution can thereby be achieved in a single step or split into two individual process steps. We demonstrate that this method is not only highly versatile but also yields graphene and h-BN films of high quality regarding surface contamination, layer coherence, defects, and electronic properties, without requiring additional post-transfer annealing. We highlight how such transfers rely on targeted corrosion at the catalyst interface and discuss this in context of the wider CVD growth and 2DM transfer literature, thereby fostering an improved general understanding of widely used transfer processes, which is essential to numerous other applications.

Self-assembled oxide films with tailored nanoscale ionic and electronic channels for controlled resistive switching.

Resistive switches are non-volatile memory cells based on nano-ionic redox processes that offer energy efficient device architectures and open pathways to neuromorphics and cognitive computing. However, channel formation typically requires an irreversible, not well controlled electroforming process, giving difficulty to independently control ionic and electronic properties. The device performance is also limited by the incomplete understanding of the underlying mechanisms. Here, we report a novel memristive model material system based on self-assembled Sm-doped CeO2 and SrTiO3 films that allow the separate tailoring of nanoscale ionic and electronic channels at high density (∼10(12) inch(-2)). We systematically show that these devices allow precise engineering of the resistance states, thus enabling large on-off ratios and high reproducibility. The tunable structure presents an ideal platform to explore ionic and electronic mechanisms and we expect a wide potential impact also on other nascent technologies, ranging from ionic gating to micro-solid oxide fuel cells and neuromorphics.

Nanoscale Plasmon-Enhanced Spectroscopy in Memristive Switches.

Resistive switching memories are nonvolatile memory cells based on nano-ionic redox processes and offer prospects for high scalability, ultrafast write and read access, and low power consumption. In two-terminal cation based devices a nanoscale filament is formed in a switching material by metal ion migration from the anode to the cathode. However, the filament growth and dissolution mechanisms and the dynamics involved are still open questions, restricting device optimization. Here, a spectroscopic technique to optically characterize in situ the resistive switching effect is presented. Resistive switches arranged in a nanoparticle-on-mirror geometry are developed, exploiting the high sensitivity to morphological changes occurring in the tightly confined plasmonic hotspot within the switching material. The focus is on electrochemical metallization and the optical signatures detected over many cycles indicate incomplete removal of metal particles from the filament upon RESET and suggest that the filament can nucleate from different positions from cycle to cycle. The technique here is nondestructive and the measurements can be easily performed in tunable ambient conditions and with realistic cell geometries.

Electrochemical dynamics of nanoscale metallic inclusions in dielectrics.

Nanoscale metal inclusions in or on solid-state dielectrics are an integral part of modern electrocatalysis, optoelectronics, capacitors, metamaterials and memory devices. The properties of these composite systems strongly depend on the size, dispersion of the inclusions and their chemical stability, and are usually considered constant. Here we demonstrate that nanoscale inclusions (for example, clusters) in dielectrics dynamically change their shape, size and position upon applied electric field. Through systematic in situ transmission electron microscopy studies, we show that fundamental electrochemical processes can lead to universally observed nucleation and growth of metal clusters, even for inert metals like platinum. The clusters exhibit diverse dynamic behaviours governed by kinetic factors including ion mobility and redox rates, leading to different filament growth modes and structures in memristive devices. These findings reveal the microscopic origin behind resistive switching, and also provide general guidance for the design of novel devices involving electronics and ionics.

Generic relevance of counter charges for cation-based nanoscale resistive switching memories.

Resistive switching memories (ReRAMs) are the major candidates for replacing the state-of-the-art memory technology in future nanoelectronics. These nonvolatile memory cells are based on nanoionic redox processes and offer prospects for high scalability, ultrafast write and read access, and low power consumption. The interfacial electrochemical reactions of oxidation and reduction of ions necessarily needed for resistive switching result inevitably in nonequilibrium states, which play a fundamental role in the processes involved during device operation. We report on nonequilibrium states in SiO2-based ReRAMs being induced during the resistance transition. It is demonstrated that the formation of metallic cations proceeds in parallel to reduction of moisture, supplied by the ambient. The latter results in the formation of an electromotive force in the range of up to 600 mV. The outcome of the study highlights the hitherto overlooked necessity of a counter charge/reaction to keep the charge electroneutrality in cation-transporting thin films, making it hard to analyze and compare experimental results under different ambient conditions such as water partial pressure. Together with the dependence of the electromotive force on the ambient, these results contribute to the microscopic understanding of the resistive switching phenomena in cation-based ReRAMs.

An associative capacitive network based on nanoscale complementary resistive switches for memory-intensive computing.

We report on the implementation of an Associative Capacitive Network (ACN) based on the nondestructive capacitive readout of two Complementary Resistive Switches (2-CRSs). ACNs are capable of performing a fully parallel search for Hamming distances (i.e. similarity) between input and stored templates. Unlike conventional associative memories where charge retention is a key function and hence, they require frequent refresh cycles, in ACNs, information is retained in a nonvolatile resistive state and normal tasks are carried out through capacitive coupling between input and output nodes. Each device consists of two CRS cells and no selective element is needed, therefore, CMOS circuitry is only required in the periphery, for addressing and read-out. Highly parallel processing, nonvolatility, wide interconnectivity and low-energy consumption are significant advantages of ACNs over conventional and emerging associative memories. These characteristics make ACNs one of the promising candidates for applications in memory-intensive and cognitive computing, switches and routers as binary and ternary Content Addressable Memories (CAMs) and intelligent data processing.

Switching kinetics of electrochemical metallization memory cells.

The strongly nonlinear switching kinetics of electrochemical metallization memory (ECM) cells are investigated using an advanced 1D simulation model. It is based on the electrochemical growth and dissolution of a Ag or Cu filament within a solid thin film and accounts for nucleation effects, charge transfer, and cation drift. The model predictions are consistent with experimental switching results of a time range of 12 orders of magnitude obtained from silver iodide (AgI) based ECM cells. By analyzing the simulation results the electrochemical processes limiting the switching kinetics are revealed. This study provides new insights into the understanding of the limiting electrochemical processes determining the switching kinetics of ECM cells.

Chemically-inactive interfaces in thin film Ag/AgI systems for resistive switching memories.

AgI nanoionics-based resistive switching memories were studied in respect to chemical stability of the Ag/AgI interface using x-ray absorption spectroscopy. The apparent dissolution of Ag films of thickness below some tens of nanometers and the loss of electrode/electrolyte contact was critically addressed. The results evidently show that there are no chemical interactions at the interface despite the high ionic mobility of Ag ions. Simulation results further show that Ag metal clusters can form in the AgI layer with intermediate-range order at least up to next-next nearest neighbors, suggesting that Ag can permeate into the AgI only in an aggregated form of metal crystallite.

Bond nature of active metal ions in SiO2-based electrochemical metallization memory cells.

Electrochemical metallization cells are candidates for the next-generation non-volatile memory devices based on resistive switching. Despite the intensive studies in recent years a microscopic model of the processes in these nanoscale electrochemical systems is still missing and the physicochemical properties of the active metal ions have been rarely reported. We examined the bonding characteristics of Cu(z+) and Ag(+) ions in SiO(2)-based cells using soft X-ray absorption spectroscopy. Whereas the Ag/SiO(2) interfaces showed no chemical interaction of Ag ions, the Cu/SiO(2) showed clear signatures of partial oxidation into two ionic species of Cu(2+) and Cu(+). The analyses on the orbital hybridization strength evidently showed that the Cu(2+)-O(2-) bonds in SiO(2) are much weaker than the Cu(+)-O(2-) bonds, analogous to the case of bulk CuO and Cu(2)O. This suggests that the Cu(2+) ions should be more mobile and with a dominating role in the process of resistive switching.

Direct observation of charge transfer in solid electrolyte for electrochemical metallization memory.

X-ray absorption spectroscopy study on an electrochemical metallization cell of GeS(x) :Ag shows clear experimental evidence of chemical ionization of the active metal atoms (Ag) and consequent transfer of charge to the electrolyte (GeS(x) ). The valence electron density and its change upon the Ag intercalation are depicted schematically as transparent waves on the Ge-S bond structure in amorphous GeS(x) .

Nanoionic transport and electrochemical reactions in resistively switching silicon dioxide.

The mobility of copper ions and redox reactions of Cu at the interface with SiO(2) being directly attributed to the resistive switching effect have been studied by cyclic voltammetry (CV). The electrode kinetics of the Cu(z+)/Cu redox reactions were analyzed suggesting the formation of both Cu(+) and Cu(2+) species. The ion mobility shows an unexpected strong dependence on the ion concentration indicating ion-ion interactions typical for concentrated solution conditions. Based on the standard reduction potentials for Cu(z+)/Cu we identified partial electrochemical redox reactions during oxidation and reduction. The results contribute to a detailed understanding of the resistive switching effect in Cu/SiO(2)/Pt cells and provide insight into electrochemically assisted diffusion of metal cations in oxides in general.