Photocatalytic Reduction of Graphene Oxide–TiO2 Nanocomposites for Improving Resistive‐Switching Memory Behaviors

Graphene oxide (GO)‐based resistive‐switching (RS) memories offer the promise of low‐temperature solution‐processability and high mechanical flexibility, making them ideally suited for future flexible electronic devices. The RS of GO can be recognized as electric‐field‐induced connection/disconnection of nanoscale reduced graphene oxide (RGO) conducting filaments (CFs). Instead of operating an electrical FORMING process, which generally results in high randomness of RGO CFs due to current overshoot, a TiO₂‐assisted photocatalytic reduction method is used to generate RGO‐domains locally through controlling the UV irradiation time and TiO₂ concentration. The elimination of the FORMING process successfully suppresses the RGO overgrowth and improved RS memory characteristics are achieved in graphene oxide–TiO₂ (Go‐TiO₂) nanocomposites, including reduced SET voltage, improved switching variability, and increased switching speed. Furthermore, the room‐temperature process of this method is compatible with flexible plastic substrates and the memory cells exhibit excellent flexibility. Experimental results evidence that the combined advantages of reducing the oxygen‐migration barrier and enhancing the local‐electric‐field with RGO‐manipulation are responsible for the improved RS behaviors. These results offer valuable insight into the role of RGO‐domains in GO memory devices, and also, this mild photoreduction method can be extended to the development of carbon‐based flexible electronics.     

Breaking the Current‐Retention Dilemma in Cation‐Based Resistive Switching Devices Utilizing Graphene with Controlled Defects

Cation‐based resistive switching (RS) devices, dominated by conductive filaments (CF) formation/dissolution, are widely considered for the ultrahigh density nonvolatile memory application. However, the current‐retention dilemma that the CF stability deteriorates greatly with decreasing compliance current makes it hard to decrease operating current for memory application and increase driving current for selector application. By centralizing/decentralizing the CF distribution, this current‐retention dilemma of cation‐based RS devices is broken for the first time. Utilizing the graphene impermeability, the cation injecting path to the RS layer can be well modulated by structure‐defective graphene, leading to control of the CF quantity and size. By graphene defect engineering, a low operating current (≈1 µA) memory and a high driving current (≈1 mA) selector are successfully realized in the same material system. Based on systematically materials analysis, the diameter of CF, modulated by graphene defect size, is the major factor for CF stability. Breakthrough in addressing the current‐retention dilemma will instruct the future implementation of high‐density 3D integration of RS memory immune to crosstalk issues.     

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.     

Biodegradable Natural Pectin‐Based Flexible Multilevel Resistive Switching Memory for Transient Electronics

Transient electronics that can physically vanish in solution can offer opportunities to address the ecological challenges for dealing with the rapidly growing electronic waste. As one important component, it is desirable that memory devices combined with the transient feature can also be developed as secrecy information storage systems besides the above advantage. Resistive switching (RS) memory is one of the most promising technologies for next‐generation memory. Herein, the biocompatible pectin extracted from natural orange peel is introduced to fabricate RS memory devices (Ag/pectin/indium tin oxides (ITO)), which exhibit excellent RS characteristics, such as forming free characteristic, low operating voltages (≈1.1 V), fast switching speed (<70 ns), long retention time (>10⁴ s), and multilevel RS behaviors. The device performance is not degraded after 10⁴ bending cycles, which will be beneficial for flexible memory applications. Additionally, instead of using acid solution, the Ag/pectin/ITO memory device can be dissolved rapidly in deionized water within 10 min thanks to the good solubility arising from ionization of its carboxylic groups, which shows promising application for green electronics. The present biocompatible memory devices based on natural pectin suggest promising material candidates toward enabling high‐density secure information storage systems applications, flexible electronics, and green electronics.     

Nanoscale Topotactic Phase Transformation in SrFeOx Epitaxial Thin Films for High‐Density Resistive Switching Memory

Resistive switching (RS) memory has stayed at the forefront of next‐generation nonvolatile memory technologies. Recently, a novel class of transition metal oxides (TMOs), which exhibit reversible topotactic phase transformation between insulating brownmillerite (BM) phase and conducting perovskite (PV) phase, has emerged as promising candidate materials for RS memories. Nevertheless, the microscopic mechanism of RS in these TMOs is still unclear. Furthermore, RS devices with simultaneously high density and superior memory performance are yet to be reported. Here, using SrFeO_x as a model system, it is directly observed that PV SrFeO₃ nanofilaments are formed and extend almost through the BM SrFeO_2.5 matrix in the ON state and are ruptured in the OFF state, unambiguously revealing a filamentary RS mechanism. The nanofilaments are ≈10 nm in diameter, enabling to downscale Au/SrFeO_x/SrRuO₃ RS devices to the 100 nm range for the first time. These nanodevices exhibit good performance including ON/OFF ratio as high as ≈10⁴, retention time over 10⁵ s, and endurance up to 10⁷ cycles. This study significantly advances the understanding of the RS mechanism in TMOs exhibiting topotactic phase transformation, and it also demonstrates the potential of these materials for use in high‐density RS memories.     

Nanofilamentary resistive switching in binary oxide system; a review on the present status and outlook

This review article summarized the recent understanding of resistance switching (RS) behavior in several binary oxide thin film systems. Among the various RS materials and mechanisms, TiO(2) and NiO thin films in unipolar thermo-chemical switching mode are primarily dealt with. To facilitate the discussions, the RS was divided into three parts; electroforming, set and reset steps. After short discussions on the electrochemistry of 'electrolytic' oxide materials, the general and peculiar aspects of these RS systems and mechanism are elaborated. Although the RS behaviors and characteristics of these materials are primarily dependent on the repeated formation and rupture of the conducting filaments (CFs) at the nanoscale at a localized position, this mechanism appears to offer a basis for the understanding of other RS mechanisms which were originally considered to be irrelevant to the localized events. The electroforming and set switching phenomena were understood as the process of CF formation and rejuvenation, respectively, which are mainly driven by the thermally assisted electromigration and percolation (or even local phase transition) of defects, while the reset process was understood as the process of CF rupture where the thermal energy plays a more crucial role. This review also contains several remarks on the outlook of these resistance change devices as a semiconductor memory.     

Self‐Assembled Networked PbS Distribution Quantum Dots for Resistive Switching and Artificial Synapse Performance Boost of Memristors

With the advent of the era of big data, resistive random access memory (RRAM) has become one of the most promising nanoscale memristor devices (MDs) for storing huge amounts of information. However, the switching voltage of the RRAM MDs shows a very broad distribution due to the random formation of the conductive filaments. Here, self‐assembled lead sulfide (PbS) quantum dots (QDs) are used to improve the uniformity of switching parameters of RRAM, which is very simple comparing with other methods. The resistive switching (RS) properties of the MD with the self‐assembled PbS QDs exhibit better performance than those of MDs with pure‐Ga₂O₃ and randomly distributed PbS QDs, such as a reduced threshold voltage, uniformly distributed SET and RESET voltages, robust retention, fast response time, and low power consumption. This enhanced performance may be attributed to the ordered arrangement of the PbS QDs in the self‐assembled PbS QDs which can efficiently guide the growth direction for the conducting filaments. Moreover, biosynaptic functions and plasticity, are implemented successfully in the MD with the self‐assembled PbS QDs. This work offers a new method of improving memristor performance, which can significantly expand existing applications and facilitate the development of artificial neural systems.     

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.     

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。     

Supramolecular Framework Constructed by Dendritic Nanopolymer for Stable Flexible Perovskite Resistive Random-Access Memory

The 3D supramolecular framework (3D-SF) is constructed in this work through the hydrogen bond assisted self-assembly of spherical dendritic nanopolymer to regulate the flexibility, stability, and resistive switching (RS) performance of perovskite resistive random-access memory (RRAM). Herein, the 3D-SF network acts as the perovskite crystallization template to regulate the perovskite crystallization process due to its coordination interaction of functional groups with the perovskite grains, presenting the uniform, pinhole-free, and compact perovskite morphology for stable flexible RRAM. The 3D-SF network in situ stays at the perovskite intergranular boundaries to crosslink the perovskite grains. The RS performance of 3D-SF-modified perovskite RRAM device is evidently improved to the ON/OFF ratio of 10⁵, the cycle number of 500 times, and the data retention time of 10⁴ s. The 50-days exposure of unencapsulated RRAM device at ambient environment still makes the ON/OFF ratio to be kept at ≈10⁴, indicating the potential of long-term stable multilevel storage in the high-density data storage. The bending action under different radius also does not change the RS performance due to the excellent bending-resistant ability of 3D-SF-modified perovskite film. This work explores a novel polymer additive strategy to construct the 3D supramolecular framework for stable flexible perovskite optoelectronic devices.     

Effect of carrier screening on ZnO-based resistive switching memory devices

The carrier screening effect occurs commonly in dielectric materials. It reduces the electric potential gradient, thus negatively affecting the functionality of resistive random access memory (RRAM) devices. An Au/ZnO film/Al-doped ZnO device fabricated in this work exhibited no resistive switching (RS), which was attributed to the carrier screening effect. Therefore, annealing was used for alleviating the screening effect, significantly enhancing the RS property. In addition, different on/off ratios were obtained for various bias values, and the screening effect was accounted for by investigating electron transport mechanisms. Furthermore, different annealing temperatures were employed to modulate the free carrier concentration in ZnO films to alleviate the screening effect. The maximal on/off ratio reached 10⁵ at an annealing temperature of 600 °C, yielding the lowest number of free carriers and the weakest screening effect in ZnO films. This work investigates the screening effect in RS devices. The screening effect not only modulates the characteristics of memory devices but also provides insight into the mechanism of RS in these devices.

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Resistive Switching Behavior in Ferroelectric Heterostructures

Resistive random‐access memory (RRAM) is a promising candidate for next‐generation nonvolatile random‐access memory protocols. The information storage in RRAM is realized by the resistive switching (RS) effect. The RS behavior of ferroelectric heterostructures is mainly controlled by polarization‐dominated and defect‐dominated mechanisms. Under certain conditions, these two mechanisms can have synergistic effects on RS behavior. Therefore, RS performance can be effectively improved by optimizing ferroelectricity, conductivity, and interfacial structures. Many methods have been studied to improve the RS performance of ferroelectric heterostructures. Typical approaches include doping elements into the ferroelectric layer, controlling the oxygen vacancy concentration and optimizing the thickness of the ferroelectric layer, and constructing an insertion layer at the interface. Here, the mechanism of RS behavior in ferroelectric heterostructures is briefly introduced, and the methods used to improve RS performance in recent years are summarized. Finally, existing problems in this field are identified, and future development trends are highlighted.     

Collective Control of Potential-Constrained Oxygen Vacancies in Oxide Heterostructures for Gradual Resistive Switching

Filamentary resistive switching in oxides is one of the key strategies for developing next-generation non-volatile memory devices. However, despite numerous advantages, their practical applications in neuromorphic computing are still limited due to non-uniform and indeterministic switching behavior. Given the inherent stochasticity of point defect migration, the pursuit of reliable switching likely demands an innovative approach. Herein, a collective control of oxygen vacancies is introduced in LaAlO₃/SrTiO₃ (LAO/STO) heterostructures to achieve reliable and gradual resistive switching. By exploiting an electrostatic potential constraint in ultrathin LAO/STO heterostructures, the formation of conducting filaments is suppressed, but instead precisely control the concentration of oxygen vacancies. Since the conductance of the LAO/STO device is governed by the ensemble concentration of oxygen vacancies, not their individual probabilistic migrations, the resistive switching is more uniform and deterministic compared to conventional filamentary devices. It provides direct evidence for the collective control of oxygen vacancies by spectral noise analysis and modeling by Monte-Carlo simulation. As a proof of concept, the significantly-improved analog switching performance of the filament-free LAO/STO devices is demonstrated, revealing potential for neuromorphic applications. The results establish an approach to store information by point defect concentration, akin to biological ionic channels, for enhancing switching characteristics of oxide materials.     

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.     

Memory and threshold resistance switching in Ni/NiO core-shell nanowires

We report on the first controlled alternation between memory and threshold resistance switching (RS) in single Ni/NiO core-shell nanowires by setting the compliance current (I(CC)) at room temperature. The memory RS is triggered by a high I(CC), while the threshold RS appears by setting a low I(CC), and the Reset process is achieved without setting a I(CC). In combination with first-principles calculations, the physical mechanisms for the memory and threshold RS are fully discussed and attributed to the formation of an oxygen vacancy (Vo) chain conductive filament and the electrical field induced breakdown without forming a conductive filament, respectively. Migration of oxygen vacancies can be activated by appropriate Joule heating, and it is energetically favorable to form conductive chains rather than random distributions due to the Vo-Vo interaction, which results in the nonvolatile switching from the off- to the on-state. For the Reset process, large Joule heating reorders the oxygen vacancies by breaking the Vo-Vo interactions and thus rupturing the conductive filaments, which are responsible for the switching from on- to off-states. This deeper understanding of the driving mechanisms responsible for the threshold and memory RS provides guidelines for the scaling, reliability, and reproducibility of NiO-based nonvolatile memory devices.     

A New Memristor with 2D Ti3C2Tx MXene Flakes as an Artificial Bio‐Synapse

Two‐dimensional (2D) materials have attracted extensive research interest in academia due to their excellent electrochemical properties and broad application prospects. Among them, 2D transition metal carbides (Ti₃C₂T_x) show semiconductor characteristics and are studied widely. However, there are few academic reports on the use of 2D MXene materials as memristors. In this work, reported is a memristor based on MXene Ti₃C₂T_x flakes. After electroforming, Al/Ti₃C₂T_x/Pt devices exhibit repeatable resistive switching (RS) behavior. More interestingly, the resistance of this device can be continuously modulated under the pulse sequence with 10 ns pulse width, and the pulse width of 10 ns is much lower than that in other reported work. Moreover, on the nanosecond scale, the transition from short‐term plasticity to long‐term plasticity is achieved. These two properties indicate that this device is favorable for ultrafast biological synapse applications and high‐efficiency training of neural networks. Through the exploration of the microstructure, Ti vacancies and partial oxidation are proposed as the origins of the physical mechanism of RS behavior. This work reveals that 2D MXene Ti₃C₂T_x flakes have excellent potential for use in memristor devices, which may open the door for more functions and applications.     

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.     

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.     

Improvement of resistive switching in Cu/ZnO/Pt sandwiches by weakening the randomicity of the formation/rupture of Cu filaments

We report an improvement in minimizing the dispersion of resistive switching (RS) parameters such as ON/OFF state resistances and switching voltages of Cu/ZnO/Pt structures in which ZnO films have been deposited at elevated temperature with N doping. This deposition process can enlarge the ZnO grain size and lessen grain boundaries while maintaining a high initial resistance since ZnO naturally shows n-type conductivity and N is a p-type dopant but with a low solubility. Cu filaments with a diameter of 15?nm are found to form at the ZnO grain boundaries. Therefore, fewer grain boundaries could depress the randomicity of the formation/rupture of Cu filaments and result in more stable RS performances. Such memory devices show a fast programming speed of 10?ns.     

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.