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.     

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.     

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.     

Resistive switching effects in oxide sandwiched structures

Resistive switching (RS) behaviors have attracted great interest due to their promising potential for the data storage. Among various materials, oxide-based devices appear to be more advantageous considering their handy fabrication and compatibility with CMOS technology, though the underlying mechanism is still controversial due to the diversity of RS behaviors. In this review, we focus on the oxide-based RS memories, in which the working mechanism can be understood basically according to a so-called filament model. The filaments formation/rupture processes, approaches developed to detect and characterize filaments, several effective attempts to improve the performances of RS and the quantum conductance behaviors in oxide-based resistive random access memory (RRAM) devices are addressed, respectively.     

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.     

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.     

Synergies of Electrochemical Metallization and Valance Change in All‐Inorganic Perovskite Quantum Dots for Resistive Switching

The in‐depth understanding of ions' generation and movement inside all‐inorganic perovskite quantum dots (CsPbBr₃ QDs), which may lead to a paradigm to break through the conventional von Neumann bottleneck, is strictly limited. Here, it is shown that formation and annihilation of metal conductive filaments and Br^? ion vacancy filaments driven by an external electric field and light irradiation can lead to pronounced resistive‐switching effects. Verified by field‐emission scanning electron microscopy as well as energy‐dispersive X‐ray spectroscopy analysis, the resistive switching behavior of CsPbBr₃ QD‐based photonic resistive random‐access memory (RRAM) is initiated by the electrochemical metallization and valance change. By coupling CsPbBr₃ QD‐based RRAM with a p‐channel transistor, the novel application of an RRAM–gate field‐effect transistor presenting analogous functions of flash memory is further demonstrated. These results may accelerate the technological deployment of all‐inorganic perovskite QD‐based photonic resistive memory for successful logic application.     

Nanoscale Plasmon‐Enhanced Spectroscopy in Memristive Switches

Resistive switching memories are nonvolatile memory cells based on nano‐ionic redox processes and offer prospects for high scalability, ultrafast write and read access, and low power consumption. In two‐terminal cation based devices a nanoscale filament is formed in a switching material by metal ion migration from the anode to the cathode. However, the filament growth and dissolution mechanisms and the dynamics involved are still open questions, restricting device optimization. Here, a spectroscopic technique to optically characterize in situ the resistive switching effect is presented. Resistive switches arranged in a nanoparticle‐on‐mirror geometry are developed, exploiting the high sensitivity to morphological changes occurring in the tightly confined plasmonic hotspot within the switching material. The focus is on electrochemical metallization and the optical signatures detected over many cycles indicate incomplete removal of metal particles from the filament upon RESET and suggest that the filament can nucleate from different positions from cycle to cycle. The technique here is nondestructive and the measurements can be easily performed in tunable ambient conditions and with realistic cell geometries.     

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.     

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.     

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.     

Pseudohalide‐Induced 2D (CH3NH3)2PbI2(SCN)2 Perovskite for Ternary Resistive Memory with High Performance

Recently, organic–inorganic hybrid perovskites (OIHP) are studied in memory devices, but ternary resistive memory with three states based on OIHP is not achieved yet. In this work, ternary resistive memory based on hybrid perovskite is achieved with a high device yield (75%), much higher than most organic ternary resistive memories. The pseudohalide‐induced 2D (CH₃NH₃)₂PbI₂(SCN)₂ perovskite thin film is prepared by using a one‐step solution method and fabricated into Al/perovskite film/indium–tin oxide (glass substrate as well as flexible polyethylene terephthalate substrate) random resistive access memory (RRAM) devices. The three states have a conductivity ratio of 1:10³:10⁷, long retention over 10 000 s, and good endurance properties. The electrode area variation, impedance test, and current–voltage plotting show that the two resistance switches are attributable to the charge trap filling due to the effect of unscreened defect in 2D nanosheets and the formation of conductive filaments, respectively. This work paves way for stable perovskite multilevel RRAMs in ambient atmosphere.     

Diode-less bilayer oxide (WO(x)-NbO(x)) device for cross-point resistive memory applications

The combination of a threshold switching device and a resistive switching (RS) device was proposed to suppress the undesired sneak current for the integration of bipolar RS cells in a cross-point array type memory. A simulation for this hybrid-type device shows that the matching of key parameters between switch element and memory element is an important issue. Based on the threshold switching oxides, a conceptual structure with a simple metal-oxide?1-oxide?2-metal stack was provided to accommodate the evolution trend. We show that electroformed W-NbO(x)-Pt devices can simultaneously exhibit both threshold switching and memory switching. A qualitative model was suggested to elucidate the unique properties in a W-NbO(x)-Pt stack, where threshold switching is associated with a localized metal-insulator transition in the NbO(x) bulk, and the bipolar RS derives from a redox at the tip of the localized filament at the WO(x)-NbO(x) interface. Such a simple metal-oxide-metal structure, with functionally separated bulk and interface effects, provides a fabrication advantage for future high-density cross-point memory devices.     

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.     

Phosphorene/ZnO Nano‐Heterojunctions for Broadband Photonic Nonvolatile Memory Applications

High‐performance photonic nonvolatile memory combining photosensing and data storage with low power consumption ensures the energy efficiency of computer systems. This study first reports in situ derived phosphorene/ZnO hybrid heterojunction nanoparticles and their application in broadband‐response photonic nonvolatile memory. The photonic nonvolatile memory consistently exhibits broadband response from ultraviolet (380 nm) to near infrared (785 nm), with controllable shifts of the SET voltage. The broadband resistive switching is attributed to the enhanced photon harvesting, a fast exciton separation, as well as the formation of an oxygen vacancy filament in the nano‐heterojunction. In addition, the device exhibits an excellent stability under air exposure compared with reported pristine phosphorene‐based nonvolatile memory. The superior antioxidation capacity is believed to originate from the fast transfer of lone‐pair electrons of phosphorene. The unique assembly of phosphorene/ZnO nano‐heterojunctions paves the way toward multifunctional broadband‐response data‐storage techniques.     

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.     

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.     

A Strategy to Design High‐Density Nanoscale Devices utilizing Vapor Deposition of Metal Halide Perovskite Materials

The demand for high memory density has increased due to increasing needs of information storage, such as big data processing and the Internet of Things. Organic–inorganic perovskite materials that show nonvolatile resistive switching memory properties have potential applications as the resistive switching layer for next‐generation memory devices, but, for practical applications, these materials should be utilized in high‐density data‐storage devices. Here, nanoscale memory devices are fabricated by sequential vapor deposition of organolead halide perovskite (OHP) CH₃NH₃PbI₃ layers on wafers perforated with 250 nm via‐holes. These devices have bipolar resistive switching properties, and show low‐voltage operation, fast switching speed (200 ns), good endurance, and data‐retention time >10⁵ s. Moreover, the use of sequential vapor deposition is extended to deposit CH₃NH₃PbI₃ as the memory element in a cross‐point array structure. This method to fabricate high‐density memory devices could be used for memory cells that occupy large areas, and to overcome the scaling limit of existing methods; it also presents a way to use OHPs to increase memory storage capacity.     

Hybrid Flexible Resistive Random Access Memory‐Gated Transistor for Novel Nonvolatile Data Storage

Here, a single‐device demonstration of novel hybrid architecture is reported to achieve programmable transistor nodes which have analogies to flash memory by incorporating a resistive switching random access memory (RRAM) device as a resistive switch gate for field effect transistor (FET) on a flexible substrate. A high performance flexible RRAM with a three‐layered structure is fabricated by utilizing solution‐processed MoS₂ nanosheets sandwiched between poly(methyl methacrylate) polymer layers. Gate coupling with the pentacene‐based transistor can be controlled by the RRAM memory state to produce a nonprogrammed state (inactive) and a programmed state (active) with a well‐defined memory window. Compared to the reference flash memory device based on the MoS₂ floating gate, the hybrid device presents robust access speed and retention ability. Furthermore, the hybrid RRAM‐gated FET is used to build an integrated logic circuit and a wide logic window in inverter logic is achieved. The controllable, well‐defined memory window, long retention time, and fast access speed of this novel hybrid device may open up new possibilities of realizing fully functional nonvolatile memory for high‐performance flexible electronics.     

Biological Spiking Synapse Constructed from Solution Processed Bimetal Core–Shell Nanoparticle Based Composites

Inspired by the highly parallel processing power and low energy consumption of the biological nervous system, the development of a neuromorphic computing paradigm to mimic brain‐like behaviors with electronic components based artificial synapses may play key roles to eliminate the von Neumann bottleneck. Random resistive access memory (RRAM) is suitable for artificial synapse due to its tunable bidirectional switching behavior. In this work, a biological spiking synapse is developed with solution processed Au@Ag core–shell nanoparticle (NP)‐based RRAM. The device shows highly controllable bistable resistive switching behavior due to the favorable Ag ions migration and filament formation in the composite film, and the good charge trapping and transport property of Au@Ag NPs. Moreover, comprehensive synaptic functions of biosynapse including paired‐pulse depression, paired‐pulse facilitation, post‐tetanic potentiation, spike‐time‐dependent plasticity, and the transformation from short‐term plasticity to long‐term plasticity are emulated. This work demonstrates that the solution processed bimetal core–shell nanoparticle‐based biological spiking synapse provides great potential for the further creation of a neuromorphic computing system.