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.     

Nanoscale “Noise‐Source Switching” during the Optoelectronic Switching of Phase‐Separated Polymer Nanocomposites

A method is developed to directly map nanoscale “noise‐source switching” phenomena during the optoelectronic switching of phase‐separated polymer nanocomposites of tetrathiafulvalene (TTF) and phenyl‐C₆₁‐butyric acid methyl ester (PCBM) molecules dispersed in a polystyrene (PS) matrix. In the method, electrical current and noise maps of the nanocomposite film are recorded using a conducting nanoprobe, enabling the mapping of a conductivity and a noise‐source density. The results provide evidence for a repeated modulation in noise sources, a “noise‐source switching,” in each stage of a switching cycle. Interestingly, when the nanocomposite is “set” by a high bias, insulating PS‐rich phases shows a drastic decrease in a noise‐source density which becomes lower than that of conducting TTF‐PCBM‐rich phases. This can be attributed to a trap filling by charge carriers generated from a TTF (donor)–PCBM (acceptor) complex. In addition, when the film is exposed to UV, an optical switching occurs due to chemical reactions which lead to irreversible changes on the noise‐source density and conductivity. The method provides a new insight on noise‐source activities during the optoelectronic switching of polymer nanocomposites and thus can be a powerful tool for basic noise research and applications in organic memory devices.     

Atomically Thin Femtojoule Memristive Device

The morphology and dimension of the conductive filament formed in a memristive device are strongly influenced by the thickness of its switching medium layer. Aggressive scaling of this active layer thickness is critical toward reducing the operating current, voltage, and energy consumption in filamentary‐type memristors. Previously, the thickness of this filament layer has been limited to above a few nanometers due to processing constraints, making it challenging to further suppress the on‐state current and the switching voltage. Here, the formation of conductive filaments in a material medium with sub‐nanometer thickness formed through the oxidation of atomically thin two‐dimensional boron nitride is studied. The resulting memristive device exhibits sub‐nanometer filamentary switching with sub‐pA operation current and femtojoule per bit energy consumption. Furthermore, by confining the filament to the atomic scale, current switching characteristics are observed that are distinct from that in thicker medium due to the profoundly different atomic kinetics. The filament morphology in such an aggressively scaled memristive device is also theoretically explored. These ultralow energy devices are promising for realizing femtojoule and sub‐femtojoule electronic computation, which can be attractive for applications in a wide range of electronics systems that desire ultralow power operation.     

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.     

Vacancy‐Induced Synaptic Behavior in 2D WS2 Nanosheet–Based Memristor for Low‐Power Neuromorphic Computing

Memristors with nonvolatile memory characteristics have been expected to open a new era for neuromorphic computing and digital logic. However, existing memristor devices based on oxygen vacancy or metal‐ion conductive filament mechanisms generally have large operating currents, which are difficult to meet low‐power consumption requirements. Therefore, it is very necessary to develop new materials to realize memristor devices that are different from the mechanisms of oxygen vacancy or metal‐ion conductive filaments to realize low‐power operation. Herein, high‐performance and low‐power consumption memristors based on 2D WS₂ with 2H phase are demonstrated, which show fast ON (OFF) switching times of 13 ns (14 ns), low program current of 1 µA in the ON state, and SET (RESET) energy reaching the level of femtojoules. Moreover, the memristor can mimic basic biological synaptic functions. Importantly, it is proposed that the generation of sulfur and tungsten vacancies and electron hopping between vacancies are dominantly responsible for the resistance switching performance. Density functional theory calculations show that the defect states formed by sulfur and tungsten vacancies are at deep levels, which prevent charge leakage and facilitate the realization of low‐power consumption for neuromorphic computing application.     

Graphene oxide thin films for flexible nonvolatile memory applications

There has been strong demand for novel nonvolatile memory technology for low-cost, large-area, and low-power flexible electronics applications. Resistive memories based on metal oxide thin films have been extensively studied for application as next-generation nonvolatile memory devices. However, although the metal oxide based resistive memories have several advantages, such as good scalability, low-power consumption, and fast switching speed, their application to large-area flexible substrates has been limited due to their material characteristics and necessity of a high-temperature fabrication process. As a promising nonvolatile memory technology for large-area flexible applications, we present a graphene oxide based memory that can be easily fabricated using a room temperature spin-casting method on flexible substrates and has reliable memory performance in terms of retention and endurance. The microscopic origin of the bipolar resistive switching behavior was elucidated and is attributed to rupture and formation of conducting filaments at the top amorphous interface layer formed between the graphene oxide film and the top Al metal electrode, via high-resolution transmission electron microscopy and in situ X-ray photoemission spectroscopy. This work provides an important step for developing understanding of the fundamental physics of bipolar resistive switching in graphene oxide films, for the application to future flexible electronics.     

Analysis of the Bipolar Resistive Switching Behavior of a Biocompatible Glucose Film for Resistive Random Access Memory

Resistive random access memory (RRAM) devices are fabricated through a simple solution process using glucose, which is a natural biomaterial for the switching layer of RRAM. The fabricated glucose‐based RRAM device shows nonvolatile bipolar resistive switching behavior, with a switching window of 10³. In addition, the endurance and data retention capability of glucose‐based RRAM exhibit stable characteristics up to 100 consecutive cycles and 10⁴ s under constant voltage stress at 0.3 V. The interface between the top electrode and the glucose film is carefully investigated to demonstrate the bipolar switching mechanism of the glucose‐based RRAM device. The glucose based‐RRAM is also evaluated on a polyimide film to verify the possibility of a flexible platform. Additionally, a cross‐bar array structure with a magnesium electrode is prepared on various substrates to assess the degradability and biocompatibility for the implantable bioelectronic devices, which are harmless and nontoxic to the human body. It is expected that this research can provide meaningful insights for developing the future bioelectronic devices.     

Resistive switching mechanisms in random access memory devices incorporating transition metal oxides: TiO2, NiO and Pr0.7Ca0.3MnO3

Resistance change random access memory (RRAM) cells, typically built as MIM capacitor structures, consist of insulating layers I sandwiched between metal layers M, where the insulator performs the resistance switching operation. These devices can be electrically switched between two or more stable resistance states at a speed of nanoseconds, with long retention times, high switching endurance, low read voltage, and large switching windows. They are attractive candidates for next-generation non-volatile memory, particularly as a flash successor, as the material properties can be scaled to the nanometer regime. Several resistance switching models have been suggested so far for transition metal oxide based devices, such as charge trapping, conductive filament formation, Schottky barrier modulation, and electrochemical migration of point defects. The underlying fundamental principles of the switching mechanism still lack a detailed understanding, i.e. how to control and modulate the electrical characteristics of devices incorporating defects and impurities, such as oxygen vacancies, metal interstitials, hydrogen, and other metallic atoms acting as dopants. In this paper, state of the art ab initio theoretical methods are employed to understand the effects that filamentary types of stable oxygen vacancy configurations in TiO(2) and NiO have on the electronic conduction. It is shown that strong electronic interactions between metal ions adjacent to oxygen vacancy sites results in the formation of a conductive path and thus can explain the 'ON' site conduction in these materials. Implication of hydrogen doping on electroforming is discussed for Pr(0.7)Ca(0.3)MnO(3) devices based on electrical characterization and FTIR measurements.     

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.     

导电剂对锂离子电池性能的影响

综述了锂离子电池电极中添加不同的导电剂对电池性能的影响。用碳黑作为导电剂能明显改善电池的性能；采用具有特殊形状的碳丝则有更好的效果；采用电导率高的金属作为导电剂，可以使电池在大电流充放电时保持高容量和高循环效率；导电剂的含量对电池的性能也有明显的影响，过多则活性剂成分少，容量低；太少则导电性差，电池容易产生极化；导电剂的粒度和分散程度对电池的性能也有重要影响。此外，混料前对导电剂进行一些表面处理也能明显改善电池的循环性能。     

High‐Performance Solution‐Processed Organo‐Metal Halide Perovskite Unipolar Resistive Memory Devices in a Cross‐Bar Array Structure

Resistive random access memories can potentially open a niche area in memory technology applications by combining the advantages of the long endurance of dynamic random‐access memory and the long retention time of flash memories. Recently, resistive memory devices based on organo‐metal halide perovskite materials have demonstrated outstanding memory properties, such as a low‐voltage operation and a high ON/OFF ratio; such properties are essential requirements for low power consumption in developing practical memory devices. In this study, a nonhalide lead source is employed to deposit perovskite films via a simple single‐step spin‐coating method for fabricating unipolar resistive memory devices in a cross‐bar array architecture. These unipolar perovskite memory devices achieve a high ON/OFF ratio up to 10⁸ with a relatively low operation voltage, a large endurance, and long retention times. The high‐yield device fabrication based on the solution‐process demonstrated here will be a step toward achieving low‐cost and high‐density practical perovskite memory devices.     

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.     

Physical Mechanism and Performance Factors of Metal Oxide Based Resistive Switching Memory:A Review

This review summarizes the mechanism and performance of metal oxide based resistive switching memory The origin of resistive switching(RS) behavior can be roughly classified into the conducting filament type and the interface type. Here,we adopt the filament type to study the metal oxide based resistive switching memory,which considers the migration of metallic cations and oxygen vacancies,as well as discuss two main mechanisms including the electrochemical metallization effect(ECM) and valence change memory effect(VCM). At the light of the influence of the electrode materials and switching layers on the RS characteristics,an overview has also been given on the performance parameters including the uniformity endurance,the retention,and the multi-layer storage. Especially,we mentioned ITO(indium tin oxide electrode and discussed the novel RS characteristics related with ITO. Finally,the challenges resistive random access memory(RRAM) device is facing,as well as the future development trend,are expressed.     

Observation of Resistive Switching Behavior in Crossbar Core–Shell Ni/NiO Nanowires Memristor

The crossbar structure of resistive random access memory (RRAM) is the most promising technology for the development of ultrahigh‐density devices for future nonvolatile memory. However, only a few studies have focused on the switching phenomenon of crossbar RRAM in detail. The main purpose of this study is to understand the formation and disruption of the conductive filament occurring at the crossbar center by real‐time transmission electron microscope observation. Core–shell Ni/NiO nanowires are utilized to form a cross‐structure, which restrict the position of the conductive filament to the crosscenter. A significant morphological change can be observed near the crossbar center, which results from the out‐diffusion and backfill of oxygen ions. Energy dispersive spectroscopy and electron energy loss spectroscopy demonstrate that the movement of the oxygen ions leads to the evolution of the conductive filament, followed by redox reactions. Moreover, the distinct reliability of the crossbar device is measured via ex situ experiments. In this work, the switching mechanism of the crossbar core–shell nanowire structure is beneficial to overcome the problem of nanoscale minimization. The experimental method shows high potential to fabricate high‐density RRAM devices, which can be applied to 3D stacked package technology and neuromorphic computing systems.     

Nanometer‐Scale Phase Transformation Determines Threshold and Memory Switching Mechanism

Creation of nanometer‐scale conductive filaments in resistive switching devices makes them appealing for advanced electrical applications. While in situ electrical probing transmission electron microscopy promotes fundamental investigations of how the conductive filament comes into existence, it does not provide proof‐of‐principle observations for the filament growth. Here, using advanced microscopy techniques, electrical, 3D compositional, and structural information of the switching‐induced conductive filament are described. It is found that during in situ probing microscopy of a Ag/TiO₂/Pt device showing both memory‐ and threshold‐switching characteristics, a crystalline Ag‐doped TiO₂ forms at vacant sites on the device surface and acts as the conductive filament. More importantly, change in filament morphology varying with applied compliance currents determines the underlying switching mechanisms that govern either memory or threshold response. When focusing more on threshold switching features, it is demonstrated that the structural disappearance of the filament arises at the end of the constricted region and leads to the spontaneous phase transformation from crystalline conductive state into an initial amorphous insulator. Use of the proposed method enables a new pathway for observing nanosized features in a variety of devices at the atomic scale in three dimensions.     

Highly Uniform Resistive Switching Properties of Solution‐Processed Silver‐Embedded Gelatin Thin Film

The silver‐embedded gelatin (AgG) thin film produced by the solution method of metal salts dissolved in gelatin is presented. Its simple fabrication method ensures the uniform distribution of Ag dots. Memory devices based on AgG exhibit good device performance, such as the ON/OFF ratio in excess of 10⁵ and the coefficient of variation in less of 50%. To further investigate the position of filament formation and the role of each element, current sensing atomic force microscopy (CSAFM) analysis as well as elemental line profiles across the two different conditions in the LRS and HRS are analyzed. The conductive and nonconductive regions in the current map of the CSAFM image show that the conductive filaments occur in the AgG layer around Ag dots. The migration of oxygen ions and the redox reaction of carbon are demonstrated to be the driving mechanism for the resistive switching of AgG memory devices. The results show that dissolving metal salts in gelatin is an effective way to achieve high‐performance organic–electronic applications.     

Engineering High‐Performance MoO2‐Based Nanomaterials with Supercapacity and Superhydrophobicity by Tuning the Raw Materials Source

Herein, a simple self‐assembly method is proposed for the fabrication of MoO₂‐based superhydrophobic material with record high contact angles (contact angle up to about 173°) for conductive metal oxides on hard/soft substrates. The spin‐coated surface demonstrates excellent oil–water separation efficiency (>98%) after 50 cycles and robust corrosion resistance after immersion into different pH solutions for 20 d. These water‐resistant coatings retain excellent superhydrophobicity after oil immersion, knife‐scratch, and long‐cycle sandpaper abrasion, which is not observed on most artificial surfaces. Meanwhile, the functionality switching from superhydrophobicity to supercapacity, which have an inverse relationship in aqueous solutions because of poor electrode wettability, is achieved simply by editing the raw materials source. Tuning of the raw materials leads to the same product MoO₂/graphitic carbon with different morphologies and functionalities. Different from superhydrophobic MoO₂/carbon ball flowers, MoO₂ nanotubes with carbon exhibit excellent supercapacity with a large gravimetric capacitance and great cycling stability.     

Temperature effects on the switching kinetics of a Cu-Ta2O5-based atomic switch

Voltage-current (I-V) measurements in a wide temperature range from 88 to 573 K demonstrated the effects of temperature on the switching behavior of a Cu/Ta(2)O(5)/Pt resistive memory cell that is referred to as a gapless-type atomic switch. After the forming process, the cells were SET from the OFF state to the ON state at a positive bias to the Cu electrode and then RESET from the ON state to the OFF state at a negative bias. In a previous study (Tsuruoka et al 2010 Nanotechnology 21 425205), it was demonstrated that the SET process corresponds to the reformation of a metal filament between the electrodes by the inhomogeneous nucleation and subsequent growth of Cu whereas the RESET process can be attributed to the Joule-heating-assisted dissolution of the metal filament. In the work described here, we observed that the voltages at which the cells are SET and RESET (SET and RESET voltages) decreased in magnitude with an increase in temperature. From calculations of the nucleation rate of Cu nuclei based on the classical nucleation theory, it was found that the observed temperature variation of the SET voltage is primarily determined by supersaturation in the vicinity of the Pt electrode, which is controlled by the application of positive bias. The supersaturation required for spontaneous growth of a Cu nucleus decreases with increasing temperature, resulting in lower SET voltages at higher temperatures. The RESET voltage is determined by the thermal stability of the metal filament formed. Moreover, using the temperature variation in cell resistances of the ON state, the growth speed of the Cu nucleus after the nucleation was found to decease with increasing temperature. These results are consistent with our switching model.     

Atomic switches: atomic-movement-controlled nanodevices for new types of computing

Atomic switches are nanoionic devices that control the diffusion of metal cations and their reduction/oxidation processes in the switching operation to form/annihilate a metal atomic bridge, which is a conductive path between two electrodes in the on-state. In contrast to conventional semiconductor devices, atomic switches can provide a highly conductive channel even if their size is of nanometer order. In addition to their small size and low on-resistance, their nonvolatility has enabled the development of new types of programmable devices, which may achieve all the required functions on a single chip. Three-terminal atomic switches have also been developed, in which the formation and annihilation of a metal atomic bridge between a source electrode and a drain electrode are controlled by a third (gate) electrode. Three-terminal atomic switches are expected to enhance the development of new types of logic circuits, such as nonvolatile logic. The recent development of atomic switches that use a metal oxide as the ionic conductive material has enabled the integration of atomic switches with complementary metal-oxide-semiconductor (CMOS) devices, which will facilitate the commercialization of atomic switches. The novel characteristics of atomic switches, such as their learning and photosensing abilities, are also introduced in the latter part of this review.     

Engineering Aptamer Switches for Multifunctional Stimulus-Responsive Nanosystems

Although RNA and DNA are best known for their capacity to encode biological information, it has become increasingly clear over the past few decades that these biomolecules are also capable of performing other complex functions, such as molecular recognition (e.g., aptamers) and catalysis (e.g., ribozymes). Building on these foundations, researchers have begun to exploit the predictable base-pairing properties of RNA and DNA in order to utilize nucleic acids as functional materials that can undergo a molecular “switching” process, performing complex functions such as signaling or controlled payload release in response to external stimuli including light, pH, ligand-binding and other microenvironmental cues. Although this field is still in its infancy, these efforts offer exciting potential for the development of biologically based “smart materials”. Herein, ongoing progress in the use of nucleic acids as an externally controllable switching material is reviewed. The diverse range of mechanisms that can trigger a stimulus response, and strategies for engineering those functionalities into nucleic acid materials are explored. Finally, recent progress is discussed in incorporating aptamer switches into more complex synthetic nucleic acid-based nanostructures and functionalized smart materials.