Topotactic Phase Transition Driving Memristive Behavior

Redox‐based memristive devices are one of the most attractive candidates for future nonvolatile memory applications and neuromorphic circuits, and their performance is determined by redox processes and the corresponding oxygen‐ion dynamics. In this regard, brownmillerite SrFeO_2.5 has been recently introduced as a novel material platform due to its exceptional oxygen‐ion transport properties for resistive‐switching memory devices. However, the underlying redox processes that give rise to resistive switching remain poorly understood. By using X‐ray absorption spectromicroscopy, it is demonstrated that the reversible redox‐based topotactic phase transition between the insulating brownmillerite phase, SrFeO_2.5, and the conductive perovskite phase, SrFeO₃, gives rise to the resistive‐switching properties of SrFeO_x memristive devices. Furthermore, it is found that the electric‐field‐induced phase transition spreads over a large area in (001) oriented SrFeO_2.5 devices, where oxygen vacancy channels are ordered along the in‐plane direction of the device. In contrast, (111)‐grown SrFeO_2.5 devices with out‐of‐plane oriented oxygen vacancy channels, reaching from the bottom to the top electrode, show a localized phase transition. These findings provide detailed insight into the resistive‐switching mechanism in SrFeO_x‐based memristive devices within the framework of metal–insulator topotactic phase transitions.     

Oxygen Exchange Processes between Oxide Memristive Devices and Water Molecules

Resistive switching based on transition metal oxide memristive devices is suspected to be caused by the electric‐field‐driven motion and internal redistribution of oxygen vacancies. Deriving the detailed mechanistic picture of the switching process is complicated, however, by the frequently observed influence of the surrounding atmosphere. Specifically, the presence or absence of water vapor in the atmosphere has a strong impact on the switching properties, but the redox reactions between water and the active layer have yet to be clarified. To investigate the role of oxygen and water species during resistive switching in greater detail, isotope labeling experiments in a N₂/H₂¹⁸O tracer gas atmosphere combined with time‐of‐flight secondary‐ion mass spectrometry are used. It is explicitly demonstrated that during the RESET operation in resistive switching SrTiO₃‐based memristive devices, oxygen is incorporated directly from water molecules or oxygen molecules into the active layer. In humid atmospheres, the reaction pathway via water molecules predominates. These findings clearly resolve the role of humidity as both oxidizing agent and source of protonic defects during the RESET operation.     

Electrically Controlled Nano and Micro Actuation in Memristive Switching Devices with On‐Chip Gas Encapsulation

Nanoactuators are a key component for developing nanomachinery. Here, an electrically driven device yielding actuation stresses exceeding 1 MPa withintegrated optical readout is demonstrated. 10 nm thick Al₂O₃ electrolyte films are sandwiched between graphene and Au electrodes. These allow reversible room‐temperature solid‐state redox reactions, producing Al metal and O₂ gas in a memristive‐type switching device. The resulting high‐pressure oxygen micro‐fuel reservoirs are encapsulated under the graphene, swelling to heights of up to 1 µm, which can be dynamically tracked by plasmonic rulers. Unlike standard memristors where the memristive redox reaction occurs in single or few conductive filaments, the mechanical deformation forces the creation of new filaments over the whole area of the inflated film. The resulting on–off resistance ratios reach 10⁸ in some cycles. The synchronization of nanoactuation and memristive switching in these devices is compatible with large‐scale fabrication and has potential for precise and electrically monitored actuation technology.     

一步掩膜法制备ZnO纳米线忆阻器

本文基于单根ZnO纳米线(NW),采用一步掩膜的方法制备了Au/ZnO NW/Au忆阻器。器件表现出无极性忆阻行为,开关比可达10~5以上。低阻态具有半导体导电特性,推测忆阻行为可能来源于ZnO NW表面氧空位形成的不连续导电丝的通断。一步掩膜法工艺简单,制备过程对器件污染少,因此是制备纳米线器件的有效方法。     

Multi‐Nonvolatile State Resistive Switching Arising from Ferroelectricity and Oxygen Vacancy Migration

Resistive switching phenomena form the basis of competing memory technologies. Among them, resistive switching, originating from oxygen vacancy migration (OVM), and ferroelectric switching offer two promising approaches. OVM in oxide films/heterostructures can exhibit high/low resistive state via conducting filament forming/deforming, while the resistive switching of ferroelectric tunnel junctions (FTJs) arises from barrier height or width variation while ferroelectric polarization reverses between asymmetric electrodes. Here the authors demonstrate a coexistence of OVM and ferroelectric induced resistive switching in a BaTiO₃ FTJ by comparing BaTiO₃ with SrTiO₃ based tunnel junctions. This coexistence results in two distinguishable loops with multi‐nonvolatile resistive states. The primary loop originates from the ferroelectric switching. The second loop emerges at a voltage close to the SrTiO₃ switching voltage, showing OVM being its origin. BaTiO₃ based devices with controlled oxygen vacancies enable us to combine the benefits of both OVM and ferroelectric tunneling to produce multistate nonvolatile memory devices.     

Resistive Switching Properties and Failure Behaviors of(Pt,Cu)/Amorphous ZrO_2/Pt Sandwich Structures

The effect of Pt and Cu electrodes on the resistive switching properties and failure behaviors of amorphous ZrO_2 ?lms were investigated. Compared with Cu/ZrO_2/Pt structures, the Pt/ZrO_2/Pt structures exhibit better resistive switching properties such as the higher resistance ratio of OFF/ON states, the longer switching cycles and narrow distribution of OFF state resistance(Roff). The switching mechanism in the Pt/ZrO_2/Pt structure can be attributed to the formation and rupture of oxygen vacancy ?laments; while in the Cu/Zr O2/Pt structure, there exist both oxygen vacancy ?laments and Cu ?laments. The formation of Cu?laments is related to the redox reaction of Cu electrode under the applied voltage. The inhomogeneous dispersive injection of Cu ions results in the dispersive Roff and signi?cant decrease of operate voltage.Schematic diagrams of the formation of conductive ?laments and the failure mechanism in the Cu/ZrO_2/Pt structures are also proposed.     

Atomic origin of the traps in memristive interface

In recent years,trap-related interfacial transport phenomena have received great attention owing to their potential applications in resistive switching devices and photo detectors.Not long ago,one new type of memristive interface that is composed of F-doped SnO2 and Bi2S3 nano-network layers has demonstrated a bivariate-continuous-tunable resistance with a swift response comparable to the one in neuron synapses and with a brain-like memorizing capability.However,the resistive mechanism is still not clearly understood because of lack of evidence,and the limited improvement in the development of the interfacial device.By combining I-V characterization,electron energy-loss spectroscopy,and firstprinciple calculation,we studied in detail the macro/micro features of the memristive interface using experimental and theoretical methods,and confirmed that its atomic origin is attributed to the traps induced by O-doping.This implies that impurity-doping might be an effective strategy for improving switching features and building new interfacial memristors.     

Multi-Wavelength-Recognizable Memristive Devices via Surface Plasmon Resonance Effect for Color Visual System

Photoelectric memristor has attracted many attentions thanks to their promising potential in optical communication chips and artificial vision systems. However, the implementation of an artificial visual system based on memristive devices remains a considerable challenge because most photoelectric memristors cannot recognize color. Herein, multi-wavelength recognizable memristive devices based on silver(Ag) nanoparticles (NPs) and porous silicon oxide (SiO_x) nanocomposites are presented. Rely on the effects of localized surface plasmon resonance (LSPR) and optical excitation of Ag NPs in SiO_x, the set voltage of the device can be gradually reduced. Moreover, the current overshoot problem is alleviated to suppress conducting filament overgrowth after visible light irradiation with different wavelengths, resulting in diverse low resistance states (LRS). Taking advantage of the characteristics of controlled switching voltage and LRS resistance distribution, color image recognition is finally realized in the present work. X-ray photoelectron spectroscopy (XPS) and conductive atomic force microscopy (C-AFM) show that the light irradiation plays an important role on resistive switching (RS) process: the photo-assisted Ag ionization leads to a significant reduction of set voltage and overshoot current. This work provides an effective method toward the development of multi-wavelength-recognizable memristive devices for future artificial color vision system.     

Magneto-Memristive Switching in a 2D Layer Antiferromagnet

Memristive devices whose resistance can be hysteretically switched by electric field or current are intensely pursued both for fundamental interest as well as potential applications in neuromorphic computing and phase-change memory. When the underlying material exhibits additional charge or spin order, the resistive states can be directly coupled, further allowing electrical control of the collective phases. The observation of abrupt, memristive switching of tunneling current in nanoscale junctions of ultrathin CrI₃, a natural layer antiferromagnet, is reported here. The coupling to spin order enables both tuning of the resistance hysteresis by magnetic field and electric-field switching of magnetization even in multilayer samples.     

Multilevel resistive switching and synaptic plasticity of nanoparticulated cobaltite oxide memristive device

Multilevel resistive switching(RS)is a key property to embrace the full potential of memristive devices for non-volatile memory and neuromorphic computing applications.In this study,we employed nanopar-ticulated cobaltite oxide(Co3O4)as a model material to demonstrate the multilevel RS and synaptic learning capabilities because of its multiple and stable redox state properties.The Pt/Co3O4/Pt memris-tive device exhibited tunable RS properties with respect to different voltages and compliance currents(CC)without the electroforming process.That is,the device showed voltage-dependent RS at a higher CC whereas CC-dependent RS was observed at lower CC.The device showed four different resistance states during endurance and retention measurements and non-volatile memory results indicated that the CC-based measurement had less variation.Besides,we investigated the basic and complex synap-tic plasticity properties using the analog current-voltage characteristics of the Pt/Co3O4/Pt device.In particular,we mimicked the potentiation-depression and four-spike time-dependent plasticity(STDP)rules such as asymmetric Hebbian,asymmetric anti-Hebbian,symmetric Hebbian,and symmetric anti-Hebbian learning rules.The results of the present work indicate that the cobaltite oxide is an excellent nanomaterial for both multilevel RS and neuromorphic computing applications.     

Correlation between evolution of resistive switching and oxygen vacancy configuration in La₀.₅Ca₀.₅MnO₃ based memristive devices

We here report a study of the correlation between the evolution of resistive switching and the oxygen vacancy configuration in La?.?Ca?.?MnO? (LCMO) based memristive devices. By taking advantage of LCMO located at a phase boundary of the metal-to-insulator transition, we observe the development of the high resistive states, depending upon not only the electrical pulse magnitude but also the switching cycles. We discuss the experimental results by an oxygen migration model that involves both single isolated and clustered oxygen vacancies, which are later verified using aberration-corrected scanning transmission electron microscopy.     

Resistive switching induced by metallic filaments formation through poly(3,4-ethylene-dioxythiophene):poly(styrenesulfonate)

We report the design and fabrication of Al/poly(3,4-ethylene-dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/Cu resistive memory devices that utilize the Cu redox reaction and conformational features of PEDOT:PSS to achieve resistive switching. The top Cu electrode acts as the source of the redox ions that are injected through the PEDOT:PSS layer during the forming process. The Cu filament is confirmed directly using the cross-sectional images of transmission electron microscopy and energy-dispersive X-ray spectroscopy. The resultant resistive memory devices can operate over a small voltage range, i.e., the switching-on threshold voltage is less than 1.5 V and the absolute value of the switching-off threshold voltage is less than 1.0 V. The on/off current ratio is as large as 1 × 10(4) and the two different resistance states can be maintained over 10(6) s. Moreover, the devices present good thermal stability that the resistive switching can be observed even at temperature up to 160 °C, at which the oxidation of the Cu top electrode is the failure factor. Furthermore, the cause of failure for Al/PEDOT:PSS/Cu memory devices at higher temperature is confirmed to be the oxidation of Cu top electrode.     

Complementary Resistive Switching Using Metal–Ferroelectric–Metal Tunnel Junctions

Complementary resistive switching (CRS) devices are receiving attention because they can potentially solve the current‐sneak and current‐leakage problems of memory arrays based on resistive switching (RS) elements. It is shown here that a simple anti‐serial connection of two ferroelectric tunnel junctions, based on BaTiO₃, with symmetric top metallic electrodes and a common, floating bottom nanometric film electrode, constitute a CRS memory element. It allows nonvolatile storage of binary states (“1” = “HRS+LRS” and “0” = “LRS+HRS”), where HRS (LRS) indicate the high (low) resistance state of each ferroelectric tunnel junction. Remarkably, these states have an identical and large resistance in the remanent state, characteristic of CRS. Here, protocols for writing information are reported and it is shown that non‐destructive or destructive reading schemes can be chosen by selecting the appropriate reading voltage amplitude. Moreover, this dual‐tunnel device has a significantly lower power consumption than a single ferroelectric tunnel junction to perform writing/reading functions, as is experimentally demonstrated. These findings illustrate that the recent impressive development of ferroelectric tunnel junctions can be further exploited to contribute to solving critical bottlenecks in data storage and logic functions implemented using RS elements.     

Ultrasensitive Memristive Synapses Based on Lightly Oxidized Sulfide Films

For biological synapses, high sensitivity is crucial for transmitting information quickly and accurately. Compared to biological synapses, memristive ones show a much lower sensitivity to electrical stimuli since much higher voltages are needed to induce synaptic plasticity. Yet, little attention has been paid to enhancing the sensitivity of synaptic devices. Here, electrochemical metallization memory cells based on lightly oxidized ZnS films are found to show highly controllable memristive switching with an ultralow SET voltage of several millivolts, which likely originates from a two‐layer structure of ZnS films, i.e., the lightly oxidized and unoxidized layers, where the filament rupture/rejuvenation is confined to the two‐layer interface region several nanometers in thickness due to different ion transport rates in these two layers. Based on such devices, an ultrasensitive memristive synapse is realized where the synaptic functions of both short‐term plasticity and long‐term potentiation are emulated by applying electrical stimuli several millivolts in amplitude, whose sensitivity greatly surpasses that of biological synapses. The dynamic processes of memorizing and forgetting are mimicked through a 5 × 5 memristive synapse array. In addition, the ultralow operating voltage provides another effective solution to the relatively high energy consumption of synaptic devices besides reducing the operating current and pulse width.     

Electrochemical Tantalum Oxide for Resistive Switching Memories

Redox‐based resistive switching memories (ReRAMs) are strongest candidates for the next‐generation nonvolatile memories fulfilling the criteria for fast, energy efficient, and scalable green IT. These types of devices can also be used for selector elements, alternative logic circuits and computing, and memristive and neuromorphic operations. ReRAMs are composed of metal/solid electrolyte/metal junctions in which the solid electrolyte is typically a metal oxide or multilayer oxides structures. Here, this study offers an effective and cheap electrochemical approach to fabricate Ta/Ta₂O₅‐based devices by anodizing. This method allows to grow high‐quality and dense oxide thin films onto a metallic substrates with precise control over morphology and thickness. Electrochemical‐oxide‐based devices demonstrate superior properties, i.e., endurance of at least 10⁶ pulse cycles and/or 10³I–V sweeps maintaining a good memory window with a low dispersion in R_OFF and R_ON values, nanosecond fast switching, and data retention of at least 10⁴ s. Multilevel programing capability is presented with both I–V sweeps and pulse measurements. Thus, it is shown that anodizing has a great prospective as a method for preparation of dense oxide films for resistive switching memories.     

Controllable Organic Resistive Switching Achieved by One‐Step Integration of Cone‐Shaped Contact

Conductive filaments (CFs)‐based resistive random access memory possesses the ability of scaling down to sub‐nanoscale with high‐density integration architecture, making it the most promising nanoelectronic technology for reclaiming Moore's law. Compared with the extensive study in inorganic switching medium, the scientific challenge now is to understand the growth kinetics of nanoscale CFs in organic polymers, aiming to achieve controllable switching characteristics toward flexible and reliable nonvolatile organic memory. Here, this paper systematically investigates the resistive switching (RS) behaviors based on a widely adopted vertical architecture of Al/organic/indium‐tin‐oxide (ITO), with poly(9‐vinylcarbazole) as the case study. A nanoscale Al filament with a dynamic‐gap zone (DGZ) is directly observed using in situ scanning transmission electron microscopy (STEM) , which demonstrates that the RS behaviors are related to the random formation of spliced filaments consisting of Al and oxygen vacancy dual conductive channels growing through carbazole groups. The randomicity of the filament formation can be depressed by introducing a cone‐shaped contact via a one‐step integration method. The conical electrode can effectively shorten the DGZ and enhance the localized electric field, thus reducing the switching voltage and improving the RS uniformity. This study provides a deeper insight of the multiple filamentary mechanisms for organic RS effect.     

Filament-Free Bulk Resistive Memory Enables Deterministic Analogue Switching

Digital computing is nearing its physical limits as computing needs and energy consumption rapidly increase. Analogue-memory-based neuromorphic computing can be orders of magnitude more energy efficient at data-intensive tasks like deep neural networks, but has been limited by the inaccurate and unpredictable switching of analogue resistive memory. Filamentary resistive random access memory (RRAM) suffers from stochastic switching due to the random kinetic motion of discrete defects in the nanometer-sized filament. In this work, this stochasticity is overcome by incorporating a solid electrolyte interlayer, in this case, yttria-stabilized zirconia (YSZ), toward eliminating filaments. Filament-free, bulk-RRAM cells instead store analogue states using the bulk point defect concentration, yielding predictable switching because the statistical ensemble behavior of oxygen vacancy defects is deterministic even when individual defects are stochastic. Both experiments and modeling show bulk-RRAM devices using TiO_2-X switching layers and YSZ electrolytes yield deterministic and linear analogue switching for efficient inference and training. Bulk-RRAM solves many outstanding issues with memristor unpredictability that have inhibited commercialization, and can, therefore, enable unprecedented new applications for energy-efficient neuromorphic computing. Beyond RRAM, this work shows how harnessing bulk point defects in ionic materials can be used to engineer deterministic nanoelectronic materials and devices.     

Resistance switching study of stoichiometric ZrO2 films for non-volatile memory application

In this work, the advances in the resistance switching characteristics of stoichiometric ZrO₂ thin films were studied. The Al/ZrO₂/Al structure exhibits reliable and reproducible switching behaviours. The thickness dependence and electrode size effect was demonstrated and understood in terms of a combined model of conductive filament/carriers trapping. Analyses of current-voltage characteristics were performed and it is suggested that the resistive switching characteristics of the ZrO₂ film are governed by both the electrode/interface effect and the formation of conductive multi-filaments.     

Mediating Short‐Term Plasticity in an Artificial Memristive Synapse by the Orientation of Silica Mesopores

Memristive synapses based on resistive switching are promising electronic devices that emulate the synaptic plasticity in neural systems. Short‐term plasticity (STP), reflecting a temporal strengthening of the synaptic connection, allows artificial synapses to perform critical computational functions, such as fast response and information filtering. To mediate this fundamental property in memristive electronic devices, the regulation of the dynamic resistive change is necessary for an artificial synapse. Here, it is demonstrated that the orientation of mesopores in the dielectric silica layer can be used to modulate the STP of an artificial memristive synapse. The dielectric silica layer with vertical mesopores can facilitate the formation of a conductive pathway, which underlies a lower set voltage (≈1.0 V) compared to these with parallel mesopores (≈1.2 V) and dense amorphous silica (≈2.0 V). Also, the artificial memristive synapses with vertical mesopores exhibit the fastest current increase by successive voltage pulses. Finally, oriented silica mesopores are designed for varying the relaxation time of memory, and thus the successful mediation of STP is achieved. The implementation of mesoporous orientation provides a new perspective for engineering artificial synapses with multilevel learning and forgetting capability, which is essential for neuromorphic computing.     

Nanoscale Correlations between Metal–Insulator Transition and Resistive Switching Effect in Metallic Perovskite Oxides

Strongly correlated perovskite oxides are a class of materials with fascinating intrinsic physical functionalities due to the interplay of charge, spin, orbital ordering, and lattice degrees of freedom. Among the exotic phenomena arising from such an interplay, metal–insulator transitions (MITs) are fundamentally still not fully understood and are of large interest for novel nanoelectronics applications, such as resistive switching‐based memories and neuromorphic computing devices. In particular, rare‐earth nickelates and lanthanum strontium manganites are archetypical examples of bandwidth‐controlled and band‐filling‐controlled MIT, respectively, which are used in this work as a playground to correlate the switching characteristics of the oxides and their MIT properties by means of local probe techniques in a systematic manner. These findings suggest that an electric‐field‐induced MIT can be triggered in these strongly correlated systems upon generation of oxygen vacancies and establish that lower operational voltages and larger resistance ratios are obtained in those films where the MIT lies closer to room temperature. This work demonstrates the potential of using MITs in the next generation of nanoelectronics devices.