Metal-oxide interface reactions and their effect on integrated resistive/threshold switching in NbO x.

Reactive metal electrodes (Nb, Ti, Cr, Ta, and Hf) are shown to play an important role in controlling the volatile switching characteristics of metal/Nb2O5/Pt devices. In particular, devices are shown to exhibit stable threshold switching under negative bias but to have a response under positive bias that depends on the choice of metal. Three distinct responses are highlighted: Devices with Nb and Ti top electrodes are shown to exhibit stable threshold switching with symmetric characteristics for both positive and negative polarities; devices with Cr top electrodes are shown to exhibit stable threshold switching but with asymmetric hysteresis windows under positive and negative polarities; and devices with Ta and Hf electrodes are shown to exhibit an integrated threshold-memory (1S1M) response. Based on thermodynamic data and lumped element modelling these effects are attributed to the formation of a metal-oxide interlayer and its response to field-induced oxygen exchange. These results provide important insight into the physical origin of the switching response and pathways for engineering devices with reliable switching characteristics.

Anatomy of filamentary threshold switching in amorphous niobium oxide.

The threshold switching behavior of Pt/NbO x /TiN devices is investigated as a function device area and NbO x film thickness and shown to reveal important insight into the structure of the self-assembled switching region. The devices exhibit combined selector-memory (1S1R) behavior after an initial voltage-controlled forming process, but exhibit symmetric threshold switching when the RESET and SET currents are kept below a critical value. In this mode, the threshold and hold voltages are independent of the device area and film thickness but the threshold current (power), while independent of device area, decreases with increasing film thickness. These results are shown to be consistent with a structure in which the threshold switching volume is confined, both laterally and vertically, to the region between the residual memory filament and the TiN electrode, and where the memory filament has a core-shell structure comprising a metallic core and a semiconducting shell. The veracity of this structure is demonstrated by comparing experimental results with the predictions of a simple circuit model, and more detailed finite element simulations. These results provide further insight into the structure and operation of NbO x threshold switching devices that have application in emerging memory and neuromorphic computing fields.

Room temperature synthesis of HfO2/HfO x heterostructures by ion-implantation.

Implantation of Hf films with oxygen ions is shown to be an effective means of fabricating high-quality HfO2/HfO x heterostructures at room temperature, with the layer composition and thicknesses determined by the ion energy and fluence. Implantation with 3 keV O+ ions to a fluence of 1 × 1017 ions cm-2 produces a polycrystalline (monoclinic-) HfO2 layer extending from the surface to a depth of ∼12 nm, and an underlying graded HfO x layer extending an additional ∼7 nm, while implantation with 6 keV O to a similar fluence produces a near-stoichiometric surface layer of 7 nm thickness and a graded substoichiometric layer extending to depth of ∼30 nm. These structures are shown to be broadly consistent with oxygen range data but more detailed comparison with dynamic Monte Carlo simulations suggests that the near-surface region contains more oxygen than expected from collisional processes alone. The bandgap and dielectric strength of the HfO2 layer produced by 3 keV; 1 × 1017 ions cm-2 implant is shown to be indistinguishable from those of an amorphous film deposited by atomic layer deposition at 200 °C. The utility of these layers is demonstrated by studying the resistive switching properties of metal-oxide-metal test structures fabricated by depositing a top metal contact on the implanted film. These results demonstrate the suitability of ion-implantation for the synthesis of functional oxide layers at room temperature.

Coupling dynamics of Nb/Nb2O5 relaxation oscillators.

The coupling dynamics of capacitively coupled Nb/Nb2O5 relaxation oscillators are shown to exhibit rich collective behaviour depending on the negative differential resistance response of the individual devices, the operating voltage and the coupling capacitance. These coupled oscillators are shown to exhibit stable frequency and phase locking states at source voltages as low as 2.2 V, with frequency control in the range from 0.85 to 16.2 MHz and frequency tunability of ∼8 MHz V-1. The experimental realisation of such compact, scalable and low power coupled-oscillator systems is of particular significance for the development and implementation of large oscillator networks in non-Boolean computing architectures.

Biorealistic Neuronal Temperature-Sensitive Dynamics within Threshold Switching Memristors: Toward Neuromorphic Thermosensation.

Neuromorphic nanoelectronic devices that can emulate the temperature-sensitive dynamics of biological neurons are of great interest for bioinspired robotics and advanced applications such as in silico neuroscience. In this work, we demonstrate the biomimetic thermosensitive properties of two-terminal V3O5 memristive devices and showcase their similarity to the firing characteristics of thermosensitive biological neurons. The temperature-dependent electrical characteristics of V3O5-based memristors are used to understand the spiking response of a simple relaxation oscillator. The temperature-dependent dynamics of these oscillators are then compared with those of biological neurons through numerical simulations of a conductance-based neuron model, the Morris-Lecar neuron model. Finally, we demonstrate a robust neuromorphic thermosensation system inspired by biological thermoreceptors for bioinspired thermal perception and representation. These results not only demonstrate the biorealistic emulative potential of threshold-switching memristors but also establish V3O5 as a functional material for realizing solid-state neurons for neuromorphic computing and sensing applications.

Optically Tunable Electrical Oscillations in Oxide-Based Memristors for Neuromorphic Computing.

The application of hardware-based neural networks can be enhanced by integrating sensory neurons and synapses that enable direct input from external stimuli. This work reports direct optical control of an oscillatory neuron based on volatile threshold switching in V3O5. The devices exhibit electroforming-free operation with switching parameters that can be tuned by optical illumination. Using temperature-dependent electrical measurements, conductive atomic force microscopy (C-AFM), in situ thermal imaging, and lumped element modelling, it is shown that the changes in switching parameters, including threshold and hold voltages, arise from overall conductivity increase of the oxide film due to the contribution of both photoconductive and bolometric characteristics of V3O5, which eventually affects the oscillation dynamics. Furthermore, V3O5 is identified as a new bolometric material with a temperature coefficient of resistance (TCR) as high as -4.6% K-1 at 423 K. The utility of these devices is illustrated by demonstrating in-sensor reservoir computing with reduced computational effort and an optical encoding layer for spiking neural network (SNN), respectively, using a simulated array of devices.

Thermal transport in metal-NbOx-metal cross-point devices and its effect on threshold switching characteristics.

Volatile threshold switching and current-controlled negative differential resistance (NDR) in metal-oxide-metal (MOM) devices result from thermally driven conductivity changes induced by local Joule heating and are therefore influenced by the thermal properties of the device-structure. In this study, we investigate the effect of the metal electrodes on the threshold switching response of NbOx-based cross-point devices. The electroforming and switching characteristics are shown to be strongly influenced by the thickness and thermal conductivity of the top-electrode due to its effect on heat loss from the NbOx film. Specifically, we demonstrate a 40% reduction in threshold voltage and a 75% reduction in threshold power as the thickness of the top Au electrode is reduced from 125 nm to 25 nm, and a 24% reduction in threshold voltage and 64% reduction in threshold power when the Au electrode is replaced by a Pt electrode of the same thickness of NbOx film, due to its lower thermal conductivity. Lumped element and finite element modelling of the devices show that these improvements are due to a reduction in heat loss to the electrodes, which is dominated by lateral heat flow within the electrode. These results clearly demonstrate the importance of the electrodes in determining the electroforming and threshold switching characteristics of MOM cross point devices.

Effect of Interdiffusion and Crystallization on Threshold Switching Characteristics of Nb/Nb2O5/Pt Memristors.

The resistive switching response of two terminal metal/oxide/metal devices depends on the stoichiometry of the oxide film, and this is commonly controlled by using a reactive metal electrode to reduce the oxide layer. Here, we investigate compositional and structural changes induced in Nb/Nb2O5 bilayers by thermal annealing at temperatures in the range of 573-973 K and its effect on the volatile threshold switching characteristics of Nb/Nb2O5/Pt devices. Changes in the stoichiometry of the Nb and Nb2O5 films are determined by Rutherford backscattering spectrometry and energy-dispersive X-ray (EDX) mapping of sample cross sections, while the structure of the films is determined by X-ray diffraction, Raman spectroscopy, and transmission electron microscopy (TEM). Such analysis shows that the composition of the Nb and Nb2O5 layers is homogenized by interdiffusion at temperatures less than the crystallization temperature (i.e., >773 K) but that this effectively ceases once the films crystallize. This is explained by comparison with the predictions of a simple diffusion model which shows that the compositional changes are dominated by oxygen diffusion in the amorphous oxide, which is much faster than that in the crystalline phases. We further show that these compositional and structural changes have a significant effect on the electroforming and threshold switching characteristics of the devices, the most significant being a marked increase in their reliability and endurance after crystallization of the oxide films. Finally, we examine the effect of annealing on the quasistatic negative differential resistance characteristics and oscillator dynamics of devices and use a lumped element model to show that this is dominated by changes in the device capacitance resulting from interdiffusion.

Physical Origin of Negative Differential Resistance in V3 O5 and Its Application as a Solid-State Oscillator.

Oxides that exhibit an insulator-metal transition can be used to fabricate energy-efficient relaxation oscillators for use in hardware-based neural networks but there are very few oxides with transition temperatures above room temperature. Here the structural, electrical, and thermal properties of V3 O5 thin films and their application as the functional oxide in metal/oxide/metal relaxation oscillators are reported. The V3 O5 devices show electroforming-free volatile threshold switching and negative differential resistance (NDR) with stable (<3% variation) cycle-to-cycle operation. The physical mechanisms underpinning these characteristics are investigated using a combination of electrical measurements, in situ thermal imaging, and device modeling. This shows that conduction is confined to a narrow filamentary path due to self-confinement of the current distribution and that the NDR response is initiated at temperatures well below the insulator-metal transition temperature where it is dominated by the temperature-dependent conductivity of the insulating phase. Finally, the dynamics of individual and coupled V3 O5 -based relaxation oscillators is reported, showing that capacitively coupled devices exhibit rich non-linear dynamics, including frequency and phase synchronization. These results establish V3 O5 as a new functional material for volatile threshold switching and advance the development of robust solid-state neurons for neuromorphic computing.

Thermal Conductivity of Amorphous NbOx Thin Films and Its Effect on Volatile Memristive Switching.

Metal-oxide-metal (MOM) devices based on niobium oxide exhibit threshold switching (or current-controlled negative differential resistance) due to thermally induced conductivity changes produced by Joule heating. A detailed understanding of the device characteristics therefore relies on an understanding of the thermal properties of the niobium oxide film and the MOM device structure. In this study, we use time-domain thermoreflectance to determine the thermal conductivity of amorphous NbOx films as a function of film composition and temperature. The thermal conductivity is shown to vary between 0.86 and 1.25 W·m-1·K-1 over the composition (x = 1.9 to 2.5) and temperature (293 to 453 K) ranges examined, and to increase with temperature for all compositions. The impact of these thermal conductivity variations on the quasistatic current-voltage (I-V) characteristics and oscillator dynamics of MOM devices is then investigated using a lumped-element circuit model. Understanding such effects is essential for engineering functional devices for nonvolatile memory and brain-inspired computing applications.

High Spatial Resolution Thermal Mapping of Volatile Switching in NbOx-Based Memristor Using In Situ Scanning Thermal Microscopy.

Temperature mapping by in situ thermoreflectance thermal imaging (TRTI) or midwave infrared spectroscopy has played an important role in understanding the origins of threshold switching and the effect of insulator-metal transitions in oxide-based memrsitive devices. In this study, we use scanning thermal microscopy (SThM) as an alternative thermal mapping technique that offers high spatial resolution imaging (∼100 nm) and is independent of material. Specifically, SThM is used to map the temperature distribution in NbOx-based cross-bar and nanovia devices with Pt top electrodes. The measurements on cross-bar devices reproduce the current redistribution and confinement processes previously observed by TRTI but without the need to coat the electrodes with a material of high thermo-reflectance coefficient (e.g., Au), while those on the nanovia devices highlight the spatial resolution of the technique. The measured temperature distributions are compared with those obtained from physics-based finite-element simulations and suggest that thermal boundary resistance plays an important role in heat transfer between the active device volume and the top electrode.

Engineering the Threshold Switching Response of Nb2O5-Based Memristors by Ti Doping.

Two terminal metal-oxide-metal devices based on niobium oxide thin films exhibit a wide range of non-linear electrical characteristics that have applications in hardware-based neuromorphic computing. In this study, we compare the threshold-switching and current-controlled negative differential resistance (NDR) characteristics of cross-point devices fabricated from undoped Nb2O5 and Ti-doped Nb2O5 and show that doping offers an effective means of engineering the device response for particular applications. In particular, doping is shown to improve the device reliability and to provide a means of tuning the threshold and hold voltages, the hysteresis window, and the magnitude of the negative differential resistance. Based on temperature-dependent current-voltage characteristics and lumped-element modelling, these effects are attributed to doping-induced reductions in the device resistance and its rate of change with temperature (i.e., the effective thermal activation energy for conduction). Significantly, these studies also show that a critical activation energy is required for devices to exhibit NDR, with doping providing an effective means of engineering the current-voltage characteristics. These results afford an improved understanding of the physical mechanisms responsible for threshold switching and provide new insights for designing devices for specific applications.

Electric Field- and Current-Induced Electroforming Modes in NbOx.

Electroforming is used to initiate the memristive response in metal/oxide/metal devices by creating a filamentary conduction path in the oxide film. Here, we use a simple photoresist-based detection technique to map the spatial distribution of conductive filaments formed in Nb/NbOx/Pt devices, and correlate these with current-voltage characteristics and in situ thermoreflectance measurements to identify distinct modes of electroforming in low- and high-conductivity NbOx films. In low-conductivity films, the filaments are randomly distributed within the oxide film, consistent with a field-induced weakest-link mechanism, while in high-conductivity films they are concentrated in the center of the film. In the latter case, the current-voltage characteristics and in situ thermoreflectance imaging show that electroforming is associated with current bifurcation into regions of low and high current density. This is supported by finite element modeling of the current distribution and shown to be consistent with predictions of a simple core-shell model of the current distribution. These results clearly demonstrate two distinct modes of electroforming in the same material system and show that the dominant mode depends on the conductivity of the film, with field-induced electroforming dominant in low-conductivity films and current bifurcation-induced electroforming dominant in high-conductivity films.