For reproducible resistive switching in memristive devices, electroforming is a crucial process. However, a deeper understanding of the electroforming process is still lacking due to unavailability of a proper simulation tool. Here, we propose a physics-based compact model for the electroforming of valence change mechanism (VCM) memristive devices. The developed JART VCM Forming model is experimentally validated with the ZrOx-based memristive device. Furthermore, the electroforming process in different 1T1R memristive arrays is simulated with this model. The study shows that the electrical characteristics of each device in the array after the forming process are influenced by word/bit line series resistance. In addition, control effects depending on the channel width and applied gate voltage of transistor in the 1T1R cell are also investigated with the compact model simulation.

During the past decade, valence change memory (VCM) has been extensively studied due to its promising features, such as a high endurance and fast switching times. The information is stored in a high resistive state (HRS) and a low resistive state (LRS). It can also be operated in two different writing schemes, namely a unipolar switching mode (LRS and HRS are written at the same voltage polarity) and a bipolar switching mode (LRS and HRS are written at opposite voltage polarities). VCM, however, still suffers from a large variability during writing operations and also faults occur, which are not yet fully understood and, therefore, require a better understanding of the underlying fault mechanisms. In this study, a new intrinsic failure mechanism is identified, which prohibits RESET times (transition from LRS to HRS) faster than 400 ps and possibly also limits the endurance. We demonstrate this RESET speed limitation by measuring the RESET kinetics of two valence change memory devices (namely Pt/TaOx/Ta and Pt/ZrOx/Ta) in the time regime from 50 ns to 50 ps, corresponding to the fastest writing time reported for VCM. Faster RESET times were achieved by increasing the applied pulse voltage. Above a voltage threshold it was, however, no longer possible to reset both devices. Instead a unipolar SET (transition from HRS to LRS) event occurred, preventing faster RESET times. The occurrence of the unipolar SET is attributed to an oxygen exchange at the interface to the Pt electrode, which can be suppressed by introducing an oxygen blocking layer at this interface, which also allowed for 50 ps fast RESET times.

The inevitable variability within electronic devices causes strict constraints on operation, reliability and scalability of the circuit design. However, when a compromise arises among the different performance metrics, area, time and energy, variability then loosens the tight requirements and allows for further savings in an alternative design scope. To that end, unconventional computing approaches are revived in the form of approximate computing, particularly tuned for resource-constrained mobile computing. In this paper, a proof-of-concept of the approximate computing paradigm using memristors is demonstrated. Stochastic memristors are used as the main building block of probabilistic logic gates. As will be shown in this paper, the stochasticity of memristors’ switching characteristics is tightly bound to the supply voltage and hence to power consumption. By scaling of the supply voltage to appropriate levels stochasticity gets increased. In order to guide the design process of approximate circuits based on memristors a realistic device model needs to be elaborated with explicit emphasis of the probabilistic switching behavior. Theoretical formulation, probabilistic analysis, and simulation of the underlying logic circuits and operations are introduced. Moreover, the expected output behavior is verified with the experimental measurements of valence change memory cells. Hence, it is shown how the precision of the output is varied for the sake of the attainable gains at different levels of available design metrics. This approach represents the first proposition along with physical verification and mapping to real devices that combines stochastic memristors into unconventional computing approaches.

Though present in small amounts and migrating at low rates, intrinsic cation defects play a central role in governing the operational lifetime of oxide-ion conducting materials through slow degradation processes such as interdiffusion, kinetic demixing, grain growth, and creep. In this study, a new experimental approach to characterizing the behavior of such slow-moving, minority defects is presented. Diffusion is probed in samples with a constant cation-defect concentration well above the equilibrium values. This approach is applied to monoclinic hafnium dioxide, m-HfO2. To this end, nanocrystalline thin films of m-HfO2 were prepared by atomic layer deposition. Diffusion experiments with ZrO2 as a diffusion source were performed in the temperature range 1173 ≤ T/K ≤ 1323 in air. The Zr diffusion profiles obtained subsequently by secondary ion mass spectrometry exhibited the following two features: the first feature was attributed to slow bulk diffusion and the second was attributed to combined fast grain-boundary diffusion and slow bulk diffusion. The activation enthalpy of Zr diffusion in bulk HfO2 was found to be (2.1 ± 0.2) eV. This result is consistent with the density-functional-theory calculations of hafnium-vacancy migration in m-HfO2, which yield values of ∼2 eV for a specific path. The activation enthalpy of the grain-boundary diffusion of (2.1 ± 0.3) eV is equal to that for bulk diffusion. This behavior is interpreted in terms of enhanced cation diffusion along space-charge layers.

Memristive devices based on the valence change mechanism undergo an electroforming process before they can be switched repetitively between different resistance states. This electroforming process can already lead to device-to-device variability in a memristive array. Here, we propose a physics-based compact model for the electroforming process of filamentary memristive switches based on the valence change mechanism. The model is verified by experimental data of ZrO x -based devices. Using this model, the forming process of a whole memory array is investigated. It is shown that the parasitic IR-drop of the word and bit lines can influence the final state of the device after the electroforming process. In addition, the simulation results reveal that the location of the cell in the array influences the final state.

Ilia Valov opened discussion of the paper by Tony Kenyon: I saw that your device structures looked very similar to the device structures Elia Ambrosi showed yesterday (DOI: 10.1039/C8FD00106E). Your electrode was Mo, his was C. You didn't discuss the mechanism, do you suppose it's a similar mec

One of the key issues of resistive switching memory devices is the so called "forming" process, a one time process at a high voltage, which initializes the resistive switching at significantly lower voltages. With this study we identify the influence of the different layers - namely the insulating oxide layer (ZrO2 and Ta2O5) and the reactive ohmic electrode layer (Hf, Ta and Pt) - on the forming voltage and the pristine capacitance of the devices. For this, the forming voltage and pristine capacitance is measured in dependence of the oxide layer thickness with different electrodes. The different slopes of the forming voltage - thickness relation for different top electrodes give an indication that the reactive ohmic electrode is oxidized from the oxide layer underneath and that the degree of the oxidation depends on the thickness of the oxide layer as well as the materials used for the oxide and electrode layer. This finding could be confirmed by X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) measurements. From the electrical measurements and the TEM images the thickness of the oxidized electrode layer could be estimated. The degree of the oxidation depends on the oxygen affinity of the oxide and electrode material. The interface dependent (thickness independent) part of the forming voltage is determined by the material of the electrode. The magnitude of this interface voltage could be correlated to the oxide free energy of the electrode material. These results can support the ongoing research towards resistive switching memory devices with a very low forming voltage or forming free behaviour.

This study investigates resistive switching in amorphous undoped and Cr-doped vanadium oxide thin films synthesized by sputtering deposition at low oxygen partial pressure. Two different volatile threshold switching characteristics can occur as well as a non-volatile bipolar switching mechanism, depending on device stack symmetry and Cr-doping. The two threshold switching types are associated with different crystalline phases in the conduction filament created during an initial forming step. The first kind of threshold switching, observed for undoped vanadium oxide films, was, by its temperature dependence, proven to be associated with a thermally triggered insulator-to-metal transition in a crystalline VO2 phase, whereas the threshold switch observed in chromium doped films is stable up to 90 °C and shows characteristics of an electronically induced Mott transition. This different behaviour for undoped versus doped films has been attributed to an increased stability of V3+ due to the Cr3+ doping (as evidenced by X-ray photoelectron spectroscopy analysis), probably favouring the creation of a crystalline Cr-doped V2O3 phase (rather than a Cr-doped VO2 phase) during the energetic forming step. The symmetric Pt/a-(VCr)Ox/Pt device showing high temperature stable threshold switching may find interesting applications as a possible new selector device for resistive switching memory (ReRAM) crossbar arrays.

The properties of oxide-based resistive switching ReRAM devices depend critically on the thickness of the different layers of the device stack. Here we focus on the variation of the pristine resistance and the forming voltage with the thickness of the reactive oxygen exchange electrode layer. By means of electrical capacitance and X-ray photoelectron spectroscopy characterization, we show how this variation of the pristine properties is linked to the formation of (sub)stoichiometric oxide layers at the metal oxide/oxygen exchange layer interface. This insight provides guidelines for further device optimization.

Current-voltage characteristics of oxide-based resistive switching memories often show a pronounced asymmetry with respect to the voltage polarity in the high resistive state (HRS), where the HRS after the RESET is more conducting than the one before the SET. Here, we report that most of this HRS asymmetry is a volatile effect as the HRS obtained from a read operation differs from the one taken from the switching cycle at identical polarity and voltages. Transitions between the relaxed and the volatile excited states can be achieved via voltage sweeps, which are named subloops. The excited states are stable over time as long as a voltage is applied to the device and have a higher conductance than the stable relaxed state. Experimental data on the time and voltage dependence of the excitation and decay are presented for Ta/TaOx/Pt and Ta/ZrOx/Pt devices. The effect is not limited to one oxide or electrode material but is observed with different magnitudes (up to 10× current change) in several oxide systems. These observations describe an additional state variable of the memristive system that is controlled in a highly polarity dependent manner.

Renewable energy conversion and storage, and greenhouse gas emission-free technologies are within the primary tasks and challenges for the society. Hydrogen fuel, produced by alkaline water electrolysis is fulfilling all these demands, however the technology is economically feeble, limited by the slow rate of oxygen evolution reaction. Complex metal oxides were suggested to overcome this problem being low-cost efficient catalysts. However, the insufficient long-term stability, degradation of structure and electrocatalytic activity are restricting their utilization. Here we report on a new perovskite-based self-assembling material BaCo0.98Ti0.02O3-$\delta$:Co3O4 with superior performance, showing outstanding properties compared to current state-of-the-art materials without degeneration of its properties even at 353 K. By chemical and structural analysis the degradation mechanism was identified and modified by selective doping. Short-range order and chemical composition rather than long-range order are factors determining the outstanding performance. The derived general design rules can be used for further development of oxide-based electrocatalytic materials.

The ROFF to RON resistance ratio in metal-oxide based ReRAM is typically limited to 10-100 in average, which, due to the variability of the resistance states, results in overlapping distributions and read errors for larger memory arrays. The main issue is the maximum ROFF that can be obtained during the RESET process. In this work we identified a concomitant "eightwise" switching process that operates in parallel with the regular "counter-eightwise" VCM bipolar switching process in Ta2O5 ReRAM and that limits the maximum ROFF resistance. This coexisting switching process is associated with an oxygen exchange at the electronically active Pt/Ta2O5 interface, and can be suppressed by use of a thin carbon layer at the interface, as shown by the deep RESET characteristics of a novel TiN/Ta2O5/C/Pt ReRAM cell.