Stefan Tappertzhofen

Nanobatteries in redox-based resistive switches require extension of memristor theory

Redox-based nanoionic resistive memory cells are one of the most promising emerging nanodevices for future information technology with applications for memory, logic and neuromorphic computing. Recently, the serendipitous discovery of the link between redox-based nanoionic-resistive memory cells and memristors and memristive devices has further intensified the research in this field. Here we show on both a theoretical and an experimental level that nanoionic-type memristive elements are inherently controlled by non-equilibrium states resulting in a nanobattery. As a result, the memristor theory must be extended to fit the observed non-zero-crossing I-V characteristics. The initial electromotive force of the nanobattery depends on the chemistry and the transport properties of the materials system but can also be introduced during redox-based nanoionic-resistive memory cell operations. The emf has a strong impact on the dynamic behaviour of nanoscale memories, and thus, its control is one of the key factors for future device development and accurate modelling.

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.

Beyond von Neumann—logic operations in passive crossbar arrays alongside memory operations

The realization of logic operations within passive crossbar memory arrays is a promising approach to expand the fields of application of such architectures. Material implication was recently suggested as the basic function of memristive crossbar junctions, and single bipolar resistive switches (BRS) as well as complementary resistive switches (CRS) were shown to be capable of realizing this logical functionality. Based on a systematic analysis of the Boolean functions, we demonstrate here that 14 of 16 Boolean functions can be realized with a single BRS or CRS cell in at most three sequential cycles. Since the read-out step is independent of the logic operation steps, the result of the logic operation is directly stored to memory, making logic-in-memory applications feasible.

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.

Quantum conductance and switching kinetics of AgI-based microcrossbar cells

Microcrossbar structured electrochemical metallization (ECM) cells based on silver iodide (AgI) solid electrolyte were fabricated and analyzed in terms of the resistive switching effect. The switching behavior implies the existence of quantized conductance higher than 78 µS which can be identified as a multiple of the single atomic point contact conductivity. The nonlinearity of the switching kinetics has been analyzed in detail. Fast switching in at least 50 ns was observed for short pulse measurements.

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.

Redox processes in silicon dioxide thin films using copper microelectrodes

Although SiO2 is a typical insulator, we demonstrate an electrochemical characteristic of the Cu/Cu+ oxidation at the interface with 30 nm thick silicon dioxide thin films studied by cyclic voltammetry. This study reveals the process of anodic oxidation and subsequent reduction of oxidized Cu ions injected in the SiO2 layer with special attention to the kinetics of the redox process. We estimated the diffusion coefficient and the mobility of Cu ions in SiO2. The results gain deeper insight in the processes involved during resistive switching of Cu/SiO2 based nonvolatile memory devices.

Capacity based nondestructive readout for complementary resistive switches.

Complementary resistive switches (CRS) were recently suggested to solve the sneak path problem of larger passive memory arrays. CRS cells consist of an antiserial setup of two bipolar resistive switching cells. The conventional destructive readout for CRS cells is based on a current measurement which makes a considerable call on the switching endurance. Here, we report a new approach for a nondestructive readout (NDRO) based on a capacity measurement. We suggest a concept of an alternative setup of a CRS cell in which both resistive switching cells have similar switching properties but are distinguishable by different capacities. The new approach has the potential of an energy saving and fast readout procedure without decreasing cycling performance and is not limited by the switching kinetics for integrated passive memory arrays.

Nanobattery Effect in RRAMs—Implications on Device Stability and Endurance

The impact of the recently discovered nanobattery effect on the switching, the endurance, and the retention of resistive random access memory devices is demonstrated. We show that the relaxation of the electromotive force voltage may lead to a shift of the resistance level for high resistive states, which is included into device modeling. Based on the extended memristive device model, which accounts for the nanobattery effects, endurance and retention problems can be explained.

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) .