Low‐Dimensional Lead‐Free Inorganic Perovskites for Resistive Switching with Ultralow Bias

3D organic–inorganic and all‐inorganic lead halide perovskites have been intensively pursued for resistive switching memories in recent years. Unfortunately, instability and lead toxicity are two foremost challenges for their large‐scale commercial applications. Dimensional reduction and composition engineering are effective means to overcome these challenges. Herein, low‐dimensional inorganic lead‐free Cs₃Bi₂I₉ and CsBi₃I₁₀ perovskite‐like films are exploited for resistive switching memory applications. Both devices demonstrate stable switching with ultrahigh on/off ratios (≈10⁶), ultralow operation voltages (as low as 0.12 V), and self‐compliance characteristics. 0D Cs₃Bi₂I₉‐based device shows better retention time and larger reset voltage than the 2D CsBi₃I₁₀‐based device. Multilevel resistive switching behavior is also observed by modulating the current compliance, contributing to the device tunability. The resistive switching mechanism is hinged on the formation and rupture of conductive filaments of halide vacancies in the perovskite films, which is correlated with the formation of AgI_x layers at the electrode/perovskite interface. This study enriches the library of switching materials with all‐inorganic lead‐free halide perovskites and offers new insights on tuning the operation of solution‐processed memory devices.     

Enhancing Resistive Switching Performance and Ambient Stability of Hybrid Perovskite Single Crystals via Embedding Colloidal Quantum Dots

Hybrid organic‐inorganic halide perovskites are actively pursued for optoelectronic technologies, but the poor stability is the Achilles’ heel of these materials that hinders their applications. Very recently, it has been shown that lead sulfide (PbS) quantum dots (QDs) can form epitaxial interfaces with the perovskite matrix and enhance the overall stability. In this work, it is demonstrated that embedding QDs can significantly modify the transport property of pristine perovskite single crystals, endowing them with new functionalities besides being structurally robust and free from grain boundaries. Resistive switching memory devices are constructed using solution‐processed CH₃NH₃PbBr₃ (MAPbBr₃) perovskite single crystals and the QD‐embedded counterparts. It is found that QDs could significantly enhance the charge transport and reduce the current–voltage hysteresis. The pristine singe crystal device exhibits negative differential resistance, while the QD‐embedded crystals are featured with filament‐type switching behavior and much improved device stability. This study underscores the potential of QD‐embedded hybrid perovskites as a new media for advanced electronic devices.     

Size Dependence of Resistive Switching at Nanoscale Metal‐Oxide Interfaces

Size dependent variations in resistive switching using a metal‐semiconducting oxide model to examine the underlying mechanisms are reported. In the range of 20 nm to 200 nm, Au nanoparticle/SrTiO₃ interface transport properties are size dependent. The size dependence is attributed to the combination of geometric scaling and size‐dependent Schottky properties. After electroforming, the observed “eight‐wise” bipolar resistive hysteresis loop is modulated by trap/detrap process. The size‐dependent high resistance state is consistent with changes in both the interfacial area and Schottky properties. The low resistance state exhibits size independent resistance through the dominant fast conductive path. Detrapping requires more work for smaller interfaces due to the associated larger built‐in electric field.     

32 × 32 Crossbar Array Resistive Memory Composed of a Stacked Schottky Diode and Unipolar Resistive Memory

Various array types of 1‐diode and 1‐resistor stacked crossbar array (1D1R CA) devices composed of a Schottky diode (SD) (Pt/TiO₂/Ti/Pt) and a resistive switching (RS) memory cell (Pt/TiO₂/Pt) are fabricated and their performances are investigated. The unit cell of the 1D1R CA device shows high RS resistance ratio (≈10³ at 1.5 V) between low and high resistance state (LRS and HRS), and high rectification ratio (≈10⁵) between LRS and reverse‐state SD. It also shows a short RS time of <50 ns for SET (resistance transition from HRS to LRS), and ≈600 ns for RESET (resistance transition from LRS to HRS), as well as stable RS endurance and data retention characteristics. It is experimentally confirmed that the selected unit cell in HRS (logically the “off” state) is stably readable when it is surrounded by unselected LRS (logically the “on” state) cells, in an array of up to 32 × 32 cells. The SD, as a highly non‐linear resistor, appropriately controls the conducting path formation during the switching and protects the memory element from the noise during retention.     

Nanoscale Resistive Switching in Amorphous Perovskite Oxide (a‐SrTiO3) Memristors

Memristive devices are the precursors to high density nanoscale memories and the building blocks for neuromorphic computing. In this work, a unique room temperature synthesized perovskite oxide (amorphous SrTiO₃: a‐STO) thin film platform with engineered oxygen deficiencies is shown to realize high performance and scalable metal‐oxide‐metal (MIM) memristive arrays demonstrating excellent uniformity of the key resistive switching parameters. a‐STO memristors exhibit nonvolatile bipolar resistive switching with significantly high (10³–10⁴) switching ratios, good endurance (>10⁶I–V sweep cycles), and retention with less than 1% change in resistance over repeated 10⁵ s long READ cycles. Nano‐contact studies utilizing in situ electrical nanoindentation technique reveal nanoionics driven switching processes that rely on isolatedly controllable nano‐switches uniformly distributed over the device area. Furthermore, in situ electrical nanoindentation studies on ultrathin a‐STO/metal stacks highlight the impact of mechanical stress on the modulation of non‐linear ionic transport mechanisms in perovskite oxides while confirming the ultimate scalability of these devices. These results highlight the promise of amorphous perovskite memristors for high performance CMOS/CMOL compatible memristive systems.     

Air‐Stable Cesium Lead Iodide Perovskite for Ultra‐Low Operating Voltage Resistive Switching

CsPbX₃ (X = halide, Cl, Br, or I) all‐inorganic halide perovskites (IHPs) are regarded as promising functional materials because of their tunable optoelectronic characteristics and superior stability to organic–inorganic hybrid halide perovskites. Herein, nonvolatile resistive switching (RS) memory devices based on all‐inorganic CsPbI₃ perovskite are reported. An air‐stable CsPbI₃ perovskite film with a thickness of only 200 nm is successfully synthesized on a platinum‐coated silicon substrate using low temperature all‐solution process. The RS memory devices of Ag/polymethylmethacrylate (PMMA)/CsPbI₃/Pt/Ti/SiO₂/Si structure exhibit reproducible and reliable bipolar switching characteristics with an ultralow operating voltage (<+0.2 V), high on/off ratio (>10⁶), reversible RS by pulse voltage operation (pulse duration < 1 ms), and multilevel data storage. The mechanical flexibility of the CsPbI₃ perovskite RS memory device on a flexible substrate is also successfully confirmed. With analyzing the influence of phase transition in CsPbI₃ on RS characteristics, a mechanism involving conducting filaments formed by metal cation migration is proposed to explain the RS behavior of the memory device. This study will contribute to the understanding of the intrinsic characteristics of IHPs for low‐voltage resistive switching and demonstrate the huge potential of them for use in low‐power consumption nonvolatile memory devices on next‐generation computing systems.     

Interface‐Engineered Amorphous TiO2‐Based Resistive Memory Devices

Crossbar‐type bipolar resistive memory devices based on low‐temperature amorphous TiO₂ (a‐TiO₂) thin films are very promising devices for flexible nonvolatile memory applications. However, stable bipolar resistive switching from amorphous TiO₂ thin films has only been achieved for Al metal electrodes that can have severe problems like electromigration and breakdown in real applications and can be a limiting factor for novel applications like transparent electronics. Here, amorphous TiO₂‐based resistive random access memory devices are presented that universally work for any configuration of metal electrodes via engineering the top and bottom interface domains. Both by inserting an ultrathin metal layer in the top interface region and by incorporating a thin blocking layer in the bottom interface, more enhanced resistance switching and superior endurance performance can be realized. Using high‐resolution transmission electron microscopy, point energy dispersive spectroscopy, and energy‐filtering transmission electron microscopy, it is demonstrated that the stable bipolar resistive switching in metal/a‐TiO₂/metal RRAM devices is attributed to both interface domains: the top interface domain with mobile oxygen ions and the bottom interface domain for its protection against an electrical breakdown.     

Donor‐Induced Performance Tuning of Amorphous SrTiO3 Memristive Nanodevices: Multistate Resistive Switching and Mechanical Tunability

Metal–oxide valence‐change memristive devices are the key contenders for the development of multilevel nonvolatile analog memories and neuromorphic computing architectures. Reliable low energy performance and tunability of nonlinear resistive switching dynamics are essential to streamline the high‐density circuit level integration of these devices. Here, manipulation of room temperature‐synthesized defect chemistry is employed to enhance and tune the switching characteristics of high‐performance amorphous SrTiO₃ (a‐STO) memristors. Substitutional donor (Nb) doping with low concentrations in the a‐STO oxide structure allows extensive improvements in energy requirements, stability, and controllability of the memristive performance, as well as field‐dependent multistate resistive switching. Evidence is presented that room temperature donor doping results in a modified insulator oxide where dislocation sites act as charge carrier modulators for low energy and multilevel operation. Finally, the performance of donor‐doped a‐STO‐based memristive nanodevices is showcased, with the possibility of mechanical modulation of the nonlinear memristive characteristics of these devices demonstrated. These results highlight the potential of donor‐doped a‐STO nanodevices for high‐density integration as analog memories and multifunctional alternative logic elements.     

Origin of the Ultra‐nonlinear Switching Kinetics in Oxide‐Based Resistive Switches

Experimental pulse length–pulse voltage studies of SrTiO₃ memristive cells are reported, which reveal nonlinearities in the switching kinetics of more than nine orders of magnitude. The results are interpreted using an electrothermal 2D finite element model. The nonlinearity arises from a temperature increase in a few‐nanometer‐thick disc‐shaped region at the Ti electrode and a corresponding exponential increase in oxygen‐vacancy mobility. The model fully reproduces the experimental data and it provides essential design rules for optimizing the cell concept of nanoionic resistive memories. The model is generic in nature: it is applicable to all those oxides which become n‐conducting upon chemical reduction and which show significant ion conductivity at elevated temperatures.     

Coexistence of Grain‐Boundaries‐Assisted Bipolar and Threshold Resistive Switching in Multilayer Hexagonal Boron Nitride

The use of 2D materials to improve the capabilities of electronic devices is a promising strategy that has recently gained much interest in both academia and industry. However, while the research in 2D metallic and semiconducting materials is well established, detailed knowledge and applications of 2D insulators are still scarce. In this paper, the presence of resistive switching (RS) in multilayer hexagonal boron nitride (h‐BN) is studied using different electrode materials, and a family of h‐BN‐based resistive random access memories with tunable capabilities is engineered. The devices show the coexistence of forming free bipolar and threshold‐type RS with low operation voltages down to 0.4 V, high current on/off ratio up to 10⁶, and long retention times above 10 h, as well as low variability. The RS is driven by the grain boundaries (GBs) in the polycrystalline h‐BN stack, which allow the penetration of metallic ions from adjacent electrodes. This reaction can be boosted by the generation of B vacancies, which are more abundant at the GBs. To the best of our knowledge, h‐BN is the first 2D material showing the coexistence of bipolar and threshold RS, which may open the door to additional functionalities and applications.     

Oxygen Ion Drift‐Induced Complementary Resistive Switching in Homo TiOx/TiOy/TiOx and Hetero TiOx/TiON/TiOx Triple Multilayer Frameworks

Developing a means by which to compete with commonly used Si‐based memory devices represents an important challenge for the realization of future three‐dimensionally stacked crossbar‐array memory devices with multifunctionality. Therefore, oxide‐based resistance switching memory (ReRAM), with its associated phenomena of oxygen ion drifts under a bias, is becoming increasingly important for use in nanoscalable crossbar arrays with an ideal memory cell size due to its simple metal–insulator–metal structure and low switching current of 10–100 μA. However, in a crossbar array geometry, one single memory element defined by the cross‐point of word and bit lines is highly susceptible to unintended leakage current due to parasitic paths around neighboring cells when no selective devices such as diodes or transistors are used. Therefore, the effective complementary resistive switching (CRS) features in all Ti‐oxide‐based triple layered homo Pt/TiO_x/TiO_y/TiO_x/Pt and hetero Pt/TiO_x/TiON/TiO_x/Pt geometries as alternative resistive switching matrices are reported. The possible resistive switching nature of the novel triple matrices is also discussed together with their electrical and structural properties. The ability to eliminate both an external resistor for efficient CRS operation and a metallic Pt middle electrode for further cost‐effective scalability will accelerate progress toward the realization of cross‐bar ReRAM in this framework.     

Configurable Resistive Switching between Memory and Threshold Characteristics for Protein‐Based Devices

The employ of natural biomaterials as the basic building blocks of electronic devices is of growing interest for biocompatible and green electronics. Here, resistive switching (RS) devices based on naturally silk protein with configurable functionality are demonstrated. The RS type of the devices can be effectively and exactly controlled by controlling the compliance current in the set process. Memory RS can be triggered by a higher compliance current, while threshold RS can be triggered by a lower compliance current. Furthermore, two types of memory devices, working in random access and WORM modes, can be achieved with the RS effect. The results suggest that silk protein possesses the potential for sustainable electronics and data storage. In addition, this finding would provide important guidelines for the performance optimization of biomaterials based memory devices and the study of the underlying mechanism behind the RS effect arising from biomaterials.     

Direct Observation of Conducting Nanofilaments in Graphene‐Oxide‐Resistive Switching Memory

Determining the presence of conducting filaments in resistive random access memory with nanoscale thin films is vital to unraveling resistive switching mechanisms. Bistable resistive switching within graphene‐oxide (GO)‐based resistive memory devices, recently developed by many research groups, has been generally explained by the formation and rupture of conducting filaments induced by the diffusion of metal or oxygen ions. Using a low‐voltage spherical aberration‐corrected transmission electron microscopy (TEM), we directly observe metallic nanofilaments formed at the amorphous top interface layer with the application of external voltages in an Al/GO/Al memory system. Atomic‐resolution TEM images acquired at an acceleration voltage of 80 kV clearly show that the conducting nanofilaments are composed of nanosized aluminum crystalline within the amorphous top interface layer after applying a negative bias (ON state). Simultaneously, we observe the change in the crystallinity of GO films by the back‐diffusion of oxygen ions. The oxygen‐deficient regions are clearly confirmed by energy‐filtered TEM oxygen elemental mapping. This work could provide strong evidence to confirm the resistive switching mechanism previously suggested by our group.     

Layered (C6H5CH2NH3)2CuBr4 Perovskite for Multilevel Storage Resistive Switching Memory

Although there have been attempts to use non‐lead based halide perovskite materials as insulating layers for resistive switching memory, the ratio of low resistance state (LRS) to high resistance state (HRS) ( = ON/OFF ratio) and/or endurance is reported to be mostly lower than 10³. Resistive switching memory characteristics of layered (BzA)₂CuBr₄ (BzA = C₆H₅CH₂NH₃) perovskite with high ON/OFF ratio and long endurance are reported here. The X‐ray diffraction (XRD) pattern of the deposited (BzA)₂CuBr₄ layer shows highly oriented (00l) planes perpendicular to a Pt substrate. An Ag/PMMA/(BzA)₂CuBr₄/Pt device shows bipolar switching behavior. A forming step at around +0.5 V is observed before the repeated bipolar switching at the SET voltage of +0.2 V and RESET voltage of ‐0.3 V. The ON/OFF ratio as high as =10⁸ is monitored along with an endurance of ≈2000 cycles and retention time over 1000 s. The high ON/OFF ratio enables multilevel storage characteristics as confirmed by changing the compliance currents. Ohmic conduction at the LRS and Schottky emission at HRS are involved in electrochemical metallization process. The bipolar resistive switching property is retained after storing the device at ambient condition under relative humidity of about 50% for 2 weeks, which indicates that (BzA)₂CuBr₄ is stable memory material.     

Biocompatible and Flexible Chitosan‐Based Resistive Switching Memory with Magnesium Electrodes

A flexible and transparent resistive switching memory based on a natural organic polymer for future flexible electronics is reported. The device has a coplanar structure of Mg/Ag‐doped chitosan/Mg on plastic substrate, which shows promising nonvolatile memory characteristics for flexible memory applications. It can be easily fabricated using solution processes on flexible substrates at room temperature and indicates reliable memory operations. The elucidated origin of the bipolar resistive switching behavior is attributed to trap‐related space‐charge‐limited conduction in high resistance state and filamentary conduction in low resistance state. The fabricated devices exhibit memory characteristics such as low power operation and long data retention. The proposed biocompatible memory device with transient electrodes is based on naturally abundant materials and is a promising candidate for low‐cost memory applications. Devices with natural substrates such as chitosan and rice paper are also fabricated for fully biodegradable resistive switching memory. This work provides an important step toward developing a flexible resistive switching memory with natural polymer films for application in flexible and biodegradable nanoelectronic devices.     

Resistive Switching in Bulk Silver Nanowire–Polystyrene Composites

Traditionally, bulk nanocomposites of electrically conducting particles and insulating polymers have been categorized as either insulating or conducting when the nanoparticle concentration is below or above the percolation threshold, respectively. Meanwhile, thin‐film polymer nanocomposites can exhibit resistive switching behavior appropriate for digital memory applications. Here, we present the first report of reversible resistive switching in bulk, glassy polymer nanocomposites. At compositions close to the electrical percolation threshold measured at low voltage, silver nanowire‐polystyrene nanocomposites demonstrate reversible resistive switching with increasing voltage at room temperature. Nanocomposites with compositions outside of this range exhibit either irreversible switching, or no switching at all. We propose that resistive switching in these materials is the result of the field‐induced formation of silver filaments that bridge adjacent nanowire clusters, extending the percolation network and decreasing the sample’s bulk resistivity. These findings break from the usual dichotomy of insulating or conducting properties in polymer nanocomposites and could inspire new devices that capitalize on this responsive behavior in these versatile materials.     

Electrode Dependence of Tunneling Electroresistance and Switching Stability in Organic Ferroelectric P(VDF‐TrFE)‐Based Tunnel Junctions

Ferroelectric tunnel junctions (FTJs) are promising candidates for nonvolatile memories and memristor‐based computing circuits. Thus far, most research has focused on FTJs with a perovskite oxide ferroelectric tunnel barrier. As the need for high‐temperature epitaxial film growth challenges the technological application of such inorganic junctions, more easily processable organic ferroelectrics can serve as alternative if large tunneling electroresistance (TER) and good switching durability would persist. This study reports on the performance of FTJs with a spin‐coated ferroelectric P(VDF‐TrFE) copolymer tunnel barrier. The use of three different bottom electrodes, indium tin oxide (ITO), La_0.67Sr_0.33MnO₃, (LSMO), and Nb‐doped SrTiO₃ (STO) are compared and it is shown that the polarity and magnitude of the TER effect depend on their conductivity. The largest TER of up to 10⁷% at room temperature is measured on FTJs with a semiconducting Nb‐doped STO electrode. This large switching effect is attributed to the formation of an extra barrier over the space charge region in the substrate. The organic FTJs exhibit good resistance retention and switching endurance up to 380 K, which is just below the ferroelectric Curie temperature of the P(VDF‐TrFE) barrier.     

A Versatile Light‐Switchable Nanorod Memory: Wurtzite ZnO on Perovskite SrTiO3

Integrating materials with distinct lattice symmetries and dimensions is an effective design strategy toward realizing novel devices with unprecedented functionalities, but many challenges remain in synthesis and device design. Here, a heterojunction memory made of wurtzite ZnO nanorods grown on perovskite Nb‐doped SrTiO₃ (NSTO) is reported, the electronic properties of which can be drastically reconfigured by applying a voltage and light. Despite of the distinct lattice structures of ZnO and NSTO, a consistent nature of single crystallinity is achieved in the heterojunctions via the low‐temperature solution‐based hydrothermal growth. In addition to a high and persistent photoconductivity, the ZnO/NSTO heterojunction diode can be turned into a versatile light‐switchable resistive switching memory with highly tunable ON and OFF states. The reversible modification of the effective interfacial energy barrier in the concurrent electronic and ionic processes most likely gives rise to the high susceptibility of the ZnO/NSTO heterojunction to external electric and optical stimuli. Furthermore, this facile synthesis route is promising to be generalized to other novel functional nanodevices integrating materials with diverse structures and properties.